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Synergistically Stabilizing Zinc Anodes by Molybdenum Dioxide Coating and Tween 80 Electrolyte Additive for High-Performance Aqueous Zinc-Ion Batteries
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  • Nhat Anh Thieu
    Nhat Anh Thieu
    Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0000-0001-8274-6882
  • Wei Li*
    Wei Li
    Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0003-2802-7443
  • Xiujuan Chen
    Xiujuan Chen
    Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0000-0002-5921-3487
  • Qingyuan Li
    Qingyuan Li
    Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0000-0002-4296-9747
  • Qingsong Wang
    Qingsong Wang
    Bavarian Center for Battery Technology (BayBatt), Department of Chemistry, University of Bayreuth, Universitätsstrasse 30, 95447 Bayreuth, Germany
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    Orcidhttps://orcid.org/0000-0001-5879-8009
  • Murugesan Velayutham
    Murugesan Velayutham
    In Vivo Multifunctional Magnetic Resonance Center, Robert C. Byrd Health Sciences Center, West Virginia University, Morgantown, West Virginia 26506, United States
    Department of Biochemistry and Molecular Medicine, School of Medicine, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0009-0001-9751-538X
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    Zane M. Grady
    Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
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    Orcidhttps://orcid.org/0000-0001-7610-8905
  • Xuemei Li
    Xuemei Li
    Department of Chemical and Biomedical Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0009-0008-8978-7757
  • Wenyuan Li
    Wenyuan Li
    Department of Chemical and Biomedical Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0000-0002-8853-225X
  • Valery V. Khramtsov
    Valery V. Khramtsov
    In Vivo Multifunctional Magnetic Resonance Center, Robert C. Byrd Health Sciences Center, West Virginia University, Morgantown, West Virginia 26506, United States
    Department of Biochemistry and Molecular Medicine, School of Medicine, West Virginia University, Morgantown, West Virginia 26506, United States
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    Orcidhttps://orcid.org/0000-0001-6187-5546
  • David M. Reed
    David M. Reed
    Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
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    Orcidhttps://orcid.org/0000-0002-7012-9841
  • Xiaolin Li*
    Xiaolin Li
    Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0002-7728-0157
  • Xingbo Liu*
    Xingbo Liu
    Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0001-8720-7175
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2023, 15, 48, 55570–55586
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https://doi.org/10.1021/acsami.3c08474
Published November 21, 2023

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Recently, aqueous zinc-ion batteries (ZIBs) have become increasingly attractive as grid-scale energy storage solutions due to their safety, low cost, and environmental friendliness. However, severe dendrite growth, self-corrosion, hydrogen evolution, and irreversible side reactions occurring at Zn anodes often cause poor cyclability of ZIBs. This work develops a synergistic strategy to stabilize the Zn anode by introducing a molybdenum dioxide coating layer on Zn (MoO2@Zn) and Tween 80 as an electrolyte additive. Due to the redox capability and high electrical conductivity of MoO2, the coating layer can not only homogenize the surface electric field but also accommodate the Zn2+ concentration field in the vicinity of the Zn anode, thereby regulating Zn2+ ion distribution and inhibiting side reactions. MoO2 coating can also significantly enhance surface hydrophilicity to improve the wetting of electrolyte on the Zn electrode. Meanwhile, Tween 80, a surfactant additive, acts as a corrosion inhibitor, preventing Zn corrosion and regulating Zn2+ ion migration. Their combination can synergistically work to reduce the desolvation energy of hydrated Zn ions and stabilize the Zn anodes. Therefore, the symmetric cells of MoO2@Zn∥MoO2@Zn with optimal 1 mM Tween 80 additive in 1 M ZnSO4 achieve exceptional cyclability over 6000 h at 1 mA cm–2 and stability (>700 h) even at a high current density (5 mA cm–2). When coupling with the VO2 cathode, the full cell of MoO2@Zn∥VO2 shows a higher capacity retention (82.4%) compared to Zn∥VO2 (57.3%) after 1000 cycles at 5 A g–1. This study suggests a synergistic strategy of combining surface modification and electrolyte engineering to design high-performance ZIBs.

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1. Introduction

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Aqueous metal-ion batteries have many advantages, including higher ionic conductivity, cost-effectiveness, easier processing, and higher safety with aqueous electrolytes, which makes them a promising candidate for energy storage systems. (1) In this regard, aqueous zinc-ion batteries (ZIBs) have attracted intense interest due to the merits of Zn anodes with a high theoretical capacity (820 mAh g–1), low redox potential (−0.76 V vs. standard hydrogen electrode), low cost, inherent safety, low toxicity, and mature recyclability. (2,3) However, Zn metal anodes undergo dendritic issues due to inhomogeneous Zn2+ ion deposition and dissolution on the electrode surfaces. (3) Moreover, the Zn anode surface and electrolyte interaction can cause electrode corrosion. Corrosion of Zn anodes creates an irregular surface, causing uneven nucleation sites for Zn2+ ions and facilitating the hydrogen evolution reaction (HER) on such corroded Zn surfaces. (4) Then, some passivated byproducts, such as zinc sulfate hydroxide hydrate (Zn4SO4(OH)6·xH2O), can be formed during the electrochemical process. (3) Thus, Zn anodes suffer from poor electrochemical stability, low Coulombic efficiency (CE), short circuits, and limited cycle life, restricting the practical development of ZIBs. (5) Various strategies have been proposed to address these issues of Zn anodes, including modifying the anode surface, (6,7) optimizing the electrolyte composition, (8,9) constructing 3D-structured or alloyed anodes, (10,11) and fabricating functional separators. (12,13) Among them, the coating and electrolyte engineering strategies offer great potential for the practical application of Zn-ion batteries.
Constructing an artificial interface coating layer on the Zn anode surface effectively inhibits Zn dendrite formation and the electrochemical corrosion of Zn anodes. Two types of surface coating materials are commonly reported, including insulating and conductive materials. The use of nonconductive coating layers on the Zn anode surface, such as metal oxides, polymers, and inorganic compounds, can ensure uniform Zn deposition by guiding Zn2+ flux, and prevent corrosion by blocking free water with dissolved oxygen. (6,14,15) However, the high impedance of interfaces between these nonconductive artificial layers and Zn anodes may restrain the performance of ZIBs at high rates. (7) On the other hand, many conductive coating materials such as Cu, (7) Au, (16) MXene, (17) and porous carbon network, (18) can effectively homogenize the surface electric field and Zn2+ concentration field, inducing uniform Zn deposition. Although protective layers have effectively improved the electrochemical performance of ZIBs, some unavoidable limitations still restrict their practical applications. For example, surface modifications are usually produced using complex manufacturing processes, which may increase electron/ion transfer resistance. The coating may hinder the transport of ions to the Zn anode surface during Zn deposition. The exfoliation of the coating layer could occur during cycling due to the poor affinity between protective materials and Zn substrates. Furthermore, electrolyte optimization can suppress Zn anode issues, especially by adding various additives to the electrolyte. (8,9,19) In view of practical applications, the use of an electrolyte additive is a facile method to regulate the Zn anode-electrolyte interface. Adding additives can also stabilize Zn ions in electrolytes, and a homogeneous nucleation process can be achieved by the control of electrode–electrolyte interfaces due to the additives. (20) Nevertheless, these additives cannot completely hinder Zn anodes from contacting aqueous electrolytes, and some may even consume electrons from Zn anodes and be deteriorated (electrocatalytically oxidized/reduced), thereby decreasing the Coulombic efficiency and reversibility. (19) To avoid these issues, a protective layer is typically introduced to protect Zn anodes from reacting with electrolyte components.
As a result, an integrated strategy based on the synergistic effect of electrode surface engineering and electrolyte modification is a promising approach for stabilizing the Zn anode. Nevertheless, there is a need for more research on these synergistic effects and mechanisms of modification. This work introduces the integration of a molybdenum oxide coated Zn anode with the addition of Tween 80 additive to ZnSO4 electrolyte, giving rise to the synergistic protection for stabilizing the Zn anode. Molybdenum oxide has high chemical stability in acidic electrolytes, multiple metal center valences, and tunable oxygen nonstoichiometry leading to tailored oxygen vacancies, (21,22) which may be used as an artificial interface coating to engineer the electrochemistry of Zn. Particularly, molybdenum dioxide (MoO2) with a metallic nature possesses a high theoretical capacity (838 mAh g–1), narrow band gap (≈0.9 eV), outstanding conductivity (1.1 × 106 S·m–1 at 300 K in the form of thin film), high chemical and thermal stability, low toxicity, and cost-effectiveness. (23,24) Due to its one-dimensional (1D) tunnels for fast ion diffusion, MoO2 exhibits not only high electronic conductivity but also considerable ionic conductivity. (24) Although MoO2 has a less prominent presence in technology than MoO3, it has recently been identified as a promising anode material for lithium ion batteries (LIBs). (24−26) Since molybdenum (Mo) is a transition metal element with a unique flexibility in valences, nanostructured molybdenum dioxide (MoO2) exhibits high Li+ storage capacities because of its large redox capability of the multivalent Mo atoms. (25,26)
In this study, MoO2 nanoplates were used as the protective coating layer for stabilizing metallic Zn anodes in ZIBs with mildly acidic aqueous electrolytes. Due to the relatively high electrical conductivity of MoO2, the coating layer can homogenize the surface electric field and the Zn2+ concentration field in the vicinity of the Zn anode, thereby regulating Zn2+ ion distribution and inhibiting side reactions. On the other hand, Tween 80 (Tw80), a nonionic surfactant, has been used as a promising corrosion inhibitor for Zn in acidic solution in the corrosion field due to its hydrophobic main chain and abundant hydrophilic groups. (27−29) Therefore, the adsorption of Tw80 on the Zn surface may alter the corrosion-resistance property and interfacial chemical environment of Zn. Consequently, the MoO2 coating layer and Tw80 as an electrolyte additive could synergistically protect the Zn metal anodes for developing stable aqueous ZIBs. This work provides a new method combining the MoO2-based coating layer and nonionic surfactant additive for stabilizing Zn anodes for ZIBs.

2. Experimental Section

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2.1. Synthesis of MoO2

MoO2 was synthesized by thermal reduction from the MoO3 nanobelts. The details of the hydrothermal synthesis of MoO3 nanobelts are described in the Supporting Information. The as-prepared MoO3 was then placed inside a tube furnace (MTI Corporation) at 650 °C for 4 h in a mixture of N2 and H2 gas flow (95% N2 + 5% H2). After heating, the system was cooled to room temperature under a gas flow, and the obtained powder was MoO2. The other MoO2 control samples were prepared by similar thermal reduction for different durations (1, 8, and 12 h).

2.2. Preparation of MoO2-Coated Zn Anodes

Initially, a coating slurry was prepared by mixing MoO2 powder and carboxymethyl cellulose (CMC) with a weight ratio of 8:2 in DI water under magnetic stirring at room temperature overnight to obtain a homogeneous slurry. Next, abrasive papers were used to remove the oxidation layer from the bare Zn foils followed by ultrasonic cleaning with ethanol. Polished Zn foils were further used as either control samples or substrates for MoO2 coated Zn. In the following steps, the obtained slurry was cast onto clean Zn foils using a doctor blade method, then vacuum-dried overnight at 60 °C. The obtained MoO2-coated Zn foil was denoted as MoO2@Zn.

2.3. Synthesis of VO2 Nanorods and Preparation of Cathodes

A reported hydrothermal method was used to fabricate VO2 nanorods. (30) Typically, 1 g of V2O5 was added to 30 mL of deionized water and ethylene glycol mixture solution in a 3:2 volume ratio. The suspension mixture was vigorously stirred for 2 h and then was transferred into a Teflon-line autoclave for a hydrothermal reaction at 180 °C for 5 h. The obtained products were centrifuged, washed with deionized water and ethanol several times, and then dried in a vacuum oven at 80 °C overnight.
The cathode was fabricated by mixing VO2, super P conductive carbon, and CMC in a weight ratio of 7:2:1 with DI water as a solvent. The slurry was then cast on carbon paper and dried at 80 °C for 24 h in a vacuum oven. After drying, a 12 mm circular disk was punched from the sheet as a VO2 cathode.

2.4. Electrochemical Measurements

Bare Zn foil and MoO2@Zn were cut into 15 mm circular disks as electrodes. Glass microfiber sheets were cut into 16 mm circular disks as separators. The electrolytes used in this work are 1 M ZnSO4 and 1 M ZnSO4+1 mM Tw80 aqueous solutions, abbreviated as the ZnSO4 electrolyte and ZnSO4+1Tw80 electrolyte. For comparison, different concentrations (0.5, 5, and 10 mM) of Tw80 in a 1 M ZnSO4 aqueous solution were prepared and denoted as ZnSO4+0.5Tw80, ZnSO4+5Tw80, and ZnSO4+10Tw80 electrolytes, respectively. Coin cells (CR2032) were assembled with separators for symmetrical, half, and full cells. The electrochemical performances of these cells were evaluated using multichannel battery testing equipment (LAND CT2001). Symmetrical cells were assembled by using bare Zn or MoO2@Zn as working and counter electrodes. Different current densities of 1–10 mA cm–2 and an areal capacity of 1–5 mAh cm–2 were used for testing symmetric Zn∥Zn and MoO2@Zn∥MoO2@Zn cells. The Zn∥Cu, MoO2@Zn∥Cu, and MoO2@Zn∥MoO2@Cu half cells were prepared to evaluate the Coulombic efficiencies with Cu as a working electrode (diameter of 15 mm). Full cells were assembled by using bare Zn or MoO2@Zn anodes and VO2 cathodes. The mass loading of VO2 on the cathode is in the range of 1.4–2.1 mg cm–2. The full cells were cycled between 0.2 and 1.6 V vs Zn2+/Zn. Cyclic voltammetry (CV) curves were conducted on an electrochemical workstation (BioLogic, SP–300). Tafel plots and chronoamperometry (CA) curves were also performed under an electrochemical workstation (BioLogic, SP–300) with a three-electrode system including bare Zn or MoO2@Zn (1 cm × 1 cm) as working electrode, Pt wire as counter electrode, and saturated calomel electrode (SCE) as a reference electrode. The Tafel plots were recorded with a potential range of −0.3 to 0.3 V vs open circuit voltage (OCV) of the system at a scan rate of 1 mV s–1. An overpotential of −150 mV vs Zn2+/Zn was applied for testing CA curves. An optical microscope system (Keyence VHX–7000) recorded the homemade transparent cells’ plating/stripping process under an electrochemical workstation (Gamry Interface 5000E). To determine the activation energy (Ea) of the Zn deposition process, electrochemical impedance spectroscopy (EIS) tests of symmetric cells at different temperatures were carried out with the amplitude of 5 mV in the frequency range from 1 MHz to 0.05 Hz using a potentialstat (BioLogic VSP). The charge transfer resistance (Rct) was obtained by fitting the EIS curves with the modified Randles equivalent circuit model by using EC-Lab software. Then, eq 1 was used to calculate the Ea values, according to the Arrhenius equation:
1Rct=A⁡e−Ea/RT
(1)
where Rct is the charge transfer resistance obtained from the EIS spectra, R is the gas constant, and T is the thermodynamic temperature.

3. Results and Discussion

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The MoO2 was prepared by the thermal reduction of the hydrothermally synthesized MoO3 precursor in a H2/N2 atmosphere. The morphology changes from MoO3 to MoO2 can be observed by a scanning electron microscope (SEM), as shown in Figures 1a and S1. After the thermal treatment, MoO3 nanobelts are converted to MoO2 nanoplates, favorable for the rapid diffusion of metal ions. (31) The X-ray diffraction (XRD) pattern shows that MoO3 was reduced to MoO2 at 650 °C (Figure 1b). There are high index diffraction peaks observed at 2θ ≈ 26.5°, 37.5°, and 54.0° associated with reflection planes (1̅11), (2̅11), and (2̅22) of MoO2, which are similar to the previous report. (32) The sharp peaks show that the obtained monoclinic MoO2 from the reduction process possesses a high crystallinity. Further, X-ray photoelectron spectroscopy (XPS) analysis is used to verify the reduction of MoO3 to MoO2. The XPS survey spectra reveal the presence of Mo and O elements in both the MoO3 and MoO2 samples (Figure S2). A pair of peaks corresponding to Mo6+ are found in the XPS spectrum of Mo 3d in MoO3 (Figure 1c). Also, Figure 1c illustrates that the Mo 3d region of MoO2 contains three components, Mo6+, Mo5+, and Mo4+, consistent with the previous report. (33) The multivalent Mo in MoO2 indicates the reduction of MoO3 to MoO2. On the other hand, the O 1s spectrum of MoO3 exhibits the prominent peak at 531.1 eV, which corresponds to lattice oxygen (O2–), and the other two peaks (532.3 and 533.5 eV) are attributed to surface absorbed species (OH–, O–) (Figure 1d). (34) It is observed that the characteristic peaks of Mo6+ and the entire O 1s peak of MoO2 shifts to a lower level compared to that of MoO3, indicating that the coordination environment of Mo with O has changed (Figure 1c,d). (34) XPS results indicate that MoO2 may contain a mixture of Mo oxidation states between +6 and +4. This electronic configuration achieves a large electrical conductivity due to the concentration of free carriers, which effectively improves the electrochemical properties. (25)

Figure 1

Figure 1. (a) SEM image of synthesized MoO2. (b) Corresponding XRD patterns of MoO3 and MoO2. XPS spectra of MoO3 and MoO2 in (c) Mo 3d and (d) O 1s spectrum. (e) Mo K-edge XANES spectra of the synthesized MoO3 and MoO2 with the reference spectra of MoO3, MoO2, and Mo. (f) EPR spectra of MoO3 and MoO2 and background signals from the Dewar.

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X-ray absorption spectroscopy (XAS) measurement is then performed in the Mo K-edge region for the as-prepared MoO3 and MoO2 samples to confirm the reduction of MoO3 to MoO2. A comparison of the X-ray absorption near edge structure (XANES) spectra of MoO3 and MoO2 is shown in Figure 1e. Accordingly, the XANES spectrum of the as-prepared MoO3 shows the pre-edge absorption at ≈20004.2 eV, almost identical to the reference MoO3 (≈20004.9 eV), suggesting a similar structure to orthorhombic α-MoO3. (35) The pre-edge is associated with the electronic transition from 1s to 4d in systems with tetragonal symmetry, such as MoO3, and is not observed in MoO2 because Mo is coordinated by regular octahedra. (36) The pre-edge peak of the synthesized-MoO2 is significantly reduced, and the absorption edge shifts to lower energy, resulting in a spectrum closely resembling monoclinic MoO2. (36) The reason is that a phase transition occurs from orthorhombic α-MoO3 with a distorted octahedral geometry to symmetric HyMoO3–x suboxide with low-valence Mo atoms. (36) These results indicate the reduction of Mo6+ ions in MoO3 to lower oxidation states (Mo5+, Mo4+) in MoO2 due to the removal of oxygen and accompanied by partial reduction. This spectral change is consistent with both XRD and Mo 3d XPS results. Additionally, MoO3 shows a broad electron paramagnetic resonance (EPR) peak at g = 1.954 (Figure 1f), which corresponds to EPR active Mo5+ centers/species. The hyperfine coupling/splitting corresponds to Mo isotopes with I = 5/2 (natural abundance) is not resolved. (37) However, no EPR signal was observed for the MoO2 sample. This result suggests that this sample contains more than one ferromagnetic cluster/domain, which is due to the ferroelectric/metallic materials of MoO2 in nature. (38) The magnetic interaction between the centers leads to ferromagnetic coupling and the metallic nature of the materials. The metallic nature of the materials did not allow the microwave to pass through the samples in the EPR cavity and dampened the resonance condition. Therefore, the MoO2 sample showed no EPR signal.
A MoO2 layer was then coated on polished Zn foil (MoO2@Zn) by a facile doctor-blade method. Figure 2a shows MoO2@Zn maintaining identical crystallographic orientation as bare Zn foil with characteristic peaks of MoO2 at 2θ ≈ 26.5° and 37.6°. While the original bare Zn has several ridges and holds on the surface (Figure S3), MoO2@Zn demonstrates a surface densely covered with MoO2 nanoplates with a thickness of 20 μm shown in the SEM images and energy dispersive X-ray spectroscopy (EDS) mapping (Figure 2b–d). The electrochemical stability of Zn in 1 M ZnSO4 is then investigated, focusing on the effects of the MoO2 coating and Tw80 electrolyte additive, as 1 M ZnSO4 is more industrially relevant than costly zinc triflate and other high-concentration electrolytes. The symmetric cells were assembled to evaluate the cycling stability of Zn plating/stripping at different current densities and capacities. Figure 2e exhibits the long-term cycling of bare Zn and MoO2@Zn symmetric cells with and without Tw80 electrolyte additives at 1 mA cm–2 for 1 mAh cm–2. In a blank ZnSO4 electrolyte, the Zn symmetric cell maintains a short lifespan for less than 50 h, while the MoO2@Zn symmetric cell exhibits improved stability for ca. 100 h. Despite the longer lifetime of symmetric cells provided by MoO2@Zn electrodes compared with bare Zn electrodes, the cycle life has not been significantly improved. With the addition of 1 mM Tw80 in the ZnSO4 electrolyte, the Zn symmetric cell shows excellent stability up to 4000 h. Nevertheless, the bare Zn electrodes remain directly in contact with water in the electrolyte, resulting in a possibility of HER forming or corrosion, which would adversely affect cell performance. Interestingly, the MoO2@Zn symmetric cell with the Tw80 electrolyte additive achieves an extended cycle life of 6000 h. It is observed that bare Zn and MoO2@Zn electrodes show an obvious Zn dendrite after 50 cycles in the blank ZnSO4 electrolyte (Figure S4a,d), while no apparent dendrites are observed on the surface of bare Zn and MoO2@Zn in ZnSO4+1Tw80 electrolyte after 50 cycles (Figure S4b,e). As exhibited in the XRD pattern (Figure S4c), a prominent peak at 2θ ≈ 8.07° and other peaks at 2θ ≈ 16.22° and 24.44° of Zn4SO4(OH)6·xH2O (ZSOH) are observed for the bare Zn electrode after 50 cycles in blank ZnSO4 electrolyte, while applying the MoO2 coating layer could reduce the ZSOH intensity peaks (Figure S4f). On the other hand, no obvious ZSOH could be found on the XRD patterns of both electrodes in the ZnSO4+1Tw80 electrolyte after 50 cycles. Based on the results, MoO2 alone can slightly prevent the formation of byproducts, whereas combining MoO2@Zn with the Tw80 additive can significantly inhibit corrosion. Therefore, the combination of using the MoO2 coating layer incorporating the Tw80 additive can ensure the stability of Zn electrodes.

Figure 2

Figure 2. (a) XRD patterns of bare Zn and MoO2@Zn. SEM images of MoO2@Zn at the (b) cross-section and (c) surface with (d) corresponding EDS mapping. (e) Cycling performance of bare Zn and MoO2@Zn symmetric cells using ZnSO4 and ZnSO4+1Tw80 electrolytes at 1 mA cm–2–1 mAh cm–2. (f) Rate performance of symmetric cells using ZnSO4+1Tw80 electrolyte. (g) Cycling performance of bare Zn and MoO2@Zn symmetric cells using ZnSO4+1Tw80 electrolyte at a high current density–capacity of 5 mA cm–2–5 mAh cm–2. (h) Voltage profiles of bare Zn and MoO2@Zn symmetric cells with ZnSO4 electrolyte containing Tw80 additive for testing under alternate 10 continuous stripping/plating cycles and 10 h resting.

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Figure S5 compares the voltage profile between bare Zn and MoO2@Zn symmetric cells in the ZnSO4+1Tw80 electrolyte. In the initial cycle, the voltage hysteresis of two cells displays the same value (∼110 mV). As the cycle number increased, the voltage of the MoO2@Zn symmetric cell remains relatively stable, while the voltage of the bare Zn cell slightly drops after 100 cycles. At cycle 2001, a slight drop to 95.8 mV could be observed in the MoO2@Zn cell, and the bare Zn cell shows a polarization. Moreover, the rate performance of bare Zn and MoO2@Zn symmetric cells using ZnSO4+1Tw80 electrolyte is evaluated at different current densities from 1 to 10 mA cm–2 with a fixed capacity of 1 mAh cm–2 (Figure 2f). A sudden short circuit occurs in the Zn symmetric cell when the current density is increased to 10 mA cm–2. In contrast, the MoO2@Zn symmetric cell exhibits excellent performance even at 10 mA cm–2. Afterward, when the current density is returned to 1 mA cm–2, the MoO2@Zn symmetric cell shows an excellent reversible stability of 3000 h with prominent resilience. The MoO2@Zn symmetric cells also demonstrate higher stability than Zn symmetric cells when the current density increases to 5 mA cm–2 (Figure 2g) and 10 mA cm–2 (Figure S6) at a fixed capacity of 5 mAh cm–2. These results indicate the great protective effect of the Tw80 additive and MoO2 coating on Zn electrodes. Furthermore, the shelving and restoring abilities of symmetric cells with bare Zn and MoO2@Zn anodes containing ZnSO4+1Tw80 electrolyte are also compared by alternate cycling and resting evaluation (Figure 2h). The symmetric cell of MoO2@Zn is stable for 3000 h with an average overpotential of 110 mV. Conversely, the bare Zn anode produces an apparent fluctuation in the polarization voltage, which culminates in cell failure after 320 h. When switching between cycling and resting conditions, the MoO2@Zn electrode shows a stable voltage response, indicating excellent corrosion resistance and resilience. Thus, the MoO2@Zn anode using the ZnSO4+1Tw80 electrolyte additive extensively stabilizes the Zn electrode and ensures a prolonged life for the cell. Table S1 compared our work’s test conditions and electrochemical performance with those previously reported by others, indicating that the MoO2@Zn electrode with Tw80-assisted electrolyte delivers superior and competitive performance at a wide range of current density-capacity in symmetric cells.
To verify the effect of Tw80 on regulating the electrode–electrolyte interface, experiments using MoO2@Zn symmetric cells were conducted. With a fixed concentration of 1 mM Tw80, the concentration of ZnSO4 is increased to 2 M to explore the effect of the salt concentration on the system. According to Figure S7a, the lifespan of the MoO2@Zn symmetric cell using 2 M ZnSO4 shows a stability performance of over 1000 h, six times less than that of the cell using 1 M ZnSO4. It is known that increasing the electrolyte concentration could result in a decrease in solvent molecules surrounding the Zn2+ ions, altering the solvation structures and the transport of cations and anions. (39,40) Increased concentrations also increase the viscosity of the solution, leading to a decrease in the ionic conductivity in the electrolyte. These reasons could account for the shorter performance of symmetric cells using 2 M ZnSO4 than that using 1 M ZnSO4. A further investigation on Tw80 concentration is explored to verify the optimization of Tw80 concentration varied from 0.5 to 10 mM (0.5Tw80 to 10Tw80) using MoO2@Zn symmetric cells at 5 mA cm–2–5 mAh cm–2. As shown in Figure S7b, the MoO2@Zn symmetric cell using ZnSO4+1Tw80 exhibits exceptional stability for 705 h. With a slight decrease in Tw80 content to 0.5 mM, the cell also performs well at 650 h. However, the lifespan of cells significantly decreases as the concentration of Tw80 increases to 5 and 10 mM. Figure S8 demonstrates the XRD patterns at the plating (P) and stripping (S) states of MoO2@Zn symmetric cells using different Tw80 concentrations after 100 cycles. At the plating state, the cell using 1 mM Tw80 shows the highest intensity of the MoO2 characteristic peak at 2θ ≈ 26.2°, meaning that the MoO2 coating on the Zn surface maintains a more incredible amount compared to the other cells. In addition, the formation of ZSOH byproduct is discovered at the stripping state. Although ZSOH is discovered in all cells, the cell using 1 mM Tw80 demonstrates the smallest amount of ZSOH. The reason is that a lower concentration (0.5 mM) may not sufficiently suppress water-induced corrosion because of the uncontrollable nucleation process caused by the partially covered Zn foil and incompletely complexed Zn2+ ions. (39) Nevertheless, excessive Tw80 additives (5 and 10 mM) could result in increasing voltage hysteresis. A high energy barrier may exist for Zn deposition due to the smaller ionic conductivity and an adsorption layer caused by the excess Tw80 content. (19) Thus, the content of additives in the electrolyte should be as small as possible to prevent deterioration of the energy density. Figure S9 shows the corresponding morphology of the MoO2@Zn electrode by using different Tw80 concentrations after cycling. After 100 cycles, the MoO2@Zn electrode using 1 mM Tw80 maintains a dense MoO2 coating layer on the surface. However, for other electrodes using 0.5, 5, and 10 mM Tw80, some Zn or ZSOH flakes appear on the top surface. Consequently, 1 M ZnSO4 incorporating 1 mM Tw80 is optimal for the stability of Zn electrodes.
MoO2 was selected due to its excellent chemical stability in mildly acidic electrolytes and relatively high electronic conductivity. To better understand the unique effects of combining the MoO2-coating layer and Tw80 electrolyte additive on the electrochemical performance improvement, TiO2, and WO2 were chosen as the alternative coating materials on Zn anodes in the presence of the Tw80 additive. The stability of symmetric cells of TiO2 and WO2 coated Zn was conducted at high current densities of 5 mA cm–2 and 10 mA cm–2 with a fixed areal capacity of 5 mAh cm–2 using the ZnSO4+1Tw80 electrolyte, as shown in Figure S10. The cycling stability of TiO2@Zn and WO2@Zn symmetric cells at both current densities is inferior to that of MoO2@Zn symmetric cells. Furthermore, TiO2@Zn cells seem to show a higher polarization. Although both have good chemical stability in acidic solutions, TiO2 is a semiconductor with relatively low electrical conductivity at room temperature, while WO2 is an analogue of MoO2 with relatively high electrical conductivity among metal oxides. (41,42) The low electrical conductivity of TiO2 may not effectively help to make the electric field distribution uniform over the coated Zn surface and thus leads to lower stability and higher polarization at high current densities. The chemistries of MoO2 and WO2 have many similarities, however, WO2 is less stable in acidic solutions than MoO2. (43) Therefore, the relatively high electrical conductivity of WO2 can reduce the coated cell polarization but cannot ensure high cycling stability. Therefore, in this work, MoO2 has the unique features of high chemical stability and relatively high electrical conductivity, which makes MoO2 a promising coating material when combined with the use of the Tw80 additive. Also, MoO2 is known for its good electrical conductivity, which makes it potentially useful in battery applications. (23,24,44) The effect of the electrical conductivity of MoO2 on Zn anode protection was evaluated by comparing the electrical conductivities of MoO2 and MoO3 and the electrochemical stability of Zn anodes coated with them. The MoO2 pellet shows a conductivity range of 23–24 S cm–1 at room temperature, while the MoO3 pellet exhibits a conductivity of less than 3.26 × 10–13 S cm–1. This result is consistent with the finding that MoO2 has a metallic conducting property with a high electrical conductivity, while MoO3 has a semiconductor property with a low electrical conductivity. (45) Similar to other conductive coating materials for Zn anodes, the conductive MoO2 coating may homogeneously regulate Zn2+ flux and maintain a stable electric field on Zn anode surface to optimize Zn plating/stripping processes. (7,16,17) The electrochemical stabilities of MoO3 and MoO2-coated Zn symmetric cells are compared. As shown in Figure S11, the MoO3@Zn symmetric cell shows higher polarization and a much shorter cycling lifetime than the MoO2@Zn counterpart.
The extent of reduction of the MoO2 coating layer also plays a crucial role in the electrochemical stability of Zn. Symmetric cells MoO2@Zn with different reduction times (1, 4, 8, and 12 h) were assembled with ZnSO4+1Tw80 electrolyte to investigate their electrochemical performances. The symmetric cell using MoO2(4 h)@Zn delivers the highest stability at 1 mA cm–2 and 5 mA cm–2 (Figure S12). Figure S13a illustrates that reduced MoO2 at 1 h exhibits the mixture of MoO3 and MoO2 phases. With the increase in reduction time, the MoO2 phase becomes dominant, and the characteristic peaks of MoO3 are reduced (at 4, 8, and 12 h). Meanwhile, EPR results show that MoO2 samples at longer reduction times also contain more than one ferromagnetic cluster/domain similar to MoO2(4 h), demonstrating that different thermal reduction treatment time could change the oxygen coordination of Mo5+ center/site in MoO2 (Figure S13b). Also, the morphology of MoO2 becomes more coarsened with increasing reduction time (Figures 1a and S13c–e). The increased agglomeration results in a decreased surface area of the reduced MoO2, leading to the reduction of electrochemical performance. (46) As a result, symmetric cells of MoO2(4 h)@Zn exhibit the most prolonged cycling stability at both low and high current densities, suggesting excellent reversibility of Zn plating/stripping. It is proposed that MoO2(4 h) is optimal for both high capacity and stable cyclability, attributed to the smallest crystallite size or the lowest crystalline nature. Therefore, despite the dominant phase of MoO2(8 h) and MoO2 (12 h) being MoO2, the symmetric cells exhibit a higher overpotential and shorter stability than MoO2(4 h), implying that the tailored surface structure could affect the energy barrier for the Zn2+ ions against desolvation and deposition. (47) This will be discussed later.
To explore the interfacial reactions that result in the formation of byproduct and dendrite, the phases of cycled electrodes at plating and stripping states after longer cycling were examined using XRD. As exhibited in the XRD pattern (Figure 3a), a prominent peak at 2θ ≈ 8.07° and other peaks at 2θ ≈ 16.22° and 24.44° of ZSOH are also discovered at plated and stripped forms of bare Zn electrode after 500 cycles. Conversely, no obvious peaks of ZSOH are observed at the plating state of MoO2@Zn, while weak ZSOH peaks at 2θ ≈ 8.07°, 12.23°, and 24.44° are detected at the stripping state (Figure 3b). XRD analysis reveals significant differences between cycled Zn electrodes and MoO2@Zn electrodes in the crystallographic orientation after plating. While the plated MoO2@Zn electrode shows the dominance of the (002) plane to form Zn deposits with horizontal orientation preferentially, the plated bare Zn electrode exhibits the (101) crystal facet exposure and significantly increased the (100) plane, which is easy to form dendrite deposition. (48) It is also observed that the dominance of (101) orientation for the pristine MoO2@Zn sample (Figure 2a) is preserved after the complete stripping of the MoO2@Zn electrode, which suggests that the Zn plating/stripping process is highly reversible. (15)

Figure 3

Figure 3. XRD patterns of cycled (a) bare Zn and (b) MoO2@Zn electrodes at plating (P) and stripping (S) states. SEM images and EDS analysis after cycling for 500 cycles at the plating state of (c) bare Zn and (d) MoO2@Zn. SEM images and EDS analysis after cycling for 500 cycles at stripping state of (e) bare Zn and (f) MoO2@Zn. The cells were cycled in a ZnSO4+1Tw80 electrolyte.

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SEM morphology analysis of cycled electrodes also confirms the hypothesis based on the XRD results. As shown in Figure S3, the inherent surface defects of bare Zn, such as holes, are detrimental to the Zn plating/stripping stability since they can capture hydrogen gas generated from corrosion, thereby promoting the HER, and inducing the inhomogeneous local electric field due to the high surface energy and inhomogeneity. Consequently, several flakes appear on the surface of the bare Zn anode after 500 cycles, indicating uneven Zn plating and stripping (Figure 3c,e). In contrast, these protrusions are not evident on the surface of the MoO2@Zn electrodes (Figure 3d,f). The EDS elemental maps display that Mo and the O elements dominate the MoO2@Zn after cycling, while the surface of bare Zn anode after cycling contains S elements (14:21 at. %) arising from ZSOH. Thus, the MoO2 coating layer serves as a stable protective layer on Zn surface to minimize the direct contact between Zn electrodes and the electrolyte and suppress side reactions.
The exchange current density (i0) values of bare Zn and MoO2@Zn in different electrolytes were explored via the Tafel plots to determine the regulation of Zn2+ ion kinetics. (49) Note that a low i0 suggests the suppressed corrosion and Zn plating-stripping kinetics simultaneously, as both involve the similar electrochemical Zn redox reactions. (50) Therefore, a proper i0 is preferred to achieve the trade-off. As shown in Figures 4a and S14, the addition of Tw80 can lower i0 values for bare Zn and MoO2@Zn, suggesting that Tw80, as a corrosion inhibitor, can restrain the corrosion of Zn. On the other hand, the MoO2 coating layer can increase i0 in both electrolytes (ZnSO4 and ZnSO4+1Tw80), suggesting that MoO2 can improve the electrochemical redox kinetics of electrolyte–anode interface which is favorable for plating and stripping of Zn anodes. (51) Therefore, the combination of Tw80 and MoO2 coating can help to achieve a balance between inhibiting corrosion and ensuring sufficient electrochemical redox kinetics of the electrolyte–anode interface. To investigate the stability of electrodes in the electrolytes under resting conditions, bare Zn and MoO2@Zn plates were immersed in aqueous ZnSO4-based electrolytes with or without Tw80 to reveal the corrosion inhibition capability of the coating layer combined with Tw80 (Figure S15). Upon soaking in electrolyte for 30 days, the MoO2@Zn surface in blank ZnSO4 is severely corroded as evidenced by the color change from brown to white, while the surface of MoO2@Zn in ZnSO4+1Tw80 is negligibly changed (Figure S16).

Figure 4

Figure 4. (a) Tafel plots of MoO2@Zn electrodes in blank ZnSO4 and ZnSO4+1Tw80 electrolytes. (b) CA curves of MoO2@Zn electrodes in blank ZnSO4 and ZnSO4+1Tw80 electrolytes. (c) Calculated activation energy of Zn2+ desolvation of different MoO2 coating layers via the Arrhenius equation. Voltage-capacity profiles of (d) Zn||Cu, (e) MoO2@Zn||Cu, and (f) MoO2@Zn||MoO2@Cu half cells. Coulombic efficiency of (g) Zn||Cu, MoO2@Zn||Cu in blank ZnSO4 electrolyte and (h) Zn||Cu, MoO2@Zn||Cu, and MoO2@Zn||MoO2@Cu half cells in ZnSO4+1Tw80 electrolyte.

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CA curves are further analyzed to determine changes in reaction kinetics when Zn2+ is deposited under a constant overpotential of −150 mV. In a blank ZnSO4 electrolyte, the CA curve of MoO2@Zn exhibits an initial decrease in the cathodic current density in the first seconds and then shows the increase of the current density with the cathodic Zn deposition time (Figure 4b). This initial decrease (minus sign only represents the cathodic current direction) is caused due to the formation of a depletion layer close to the working electrode. (52,53) Then, the continuous increase of the current density is due to the increased surface area caused by the growth of deposited Zn. The results imply that only the MoO2-coating layer could not fully hinder the dendritic formation of electrodeposited Zn. On the other hand, a smaller initial current density is observed for bare Zn, and the current density increases over time in blank ZnSO4 electrolyte (Figure S17a), indicating that Zn dendrites are forming and gradually growing on the surface of the Zn anode. (54,55) Moreover, bare Zn in ZnSO4+1Tw80 electrolyte (Figure S17b) shows an initial decrease and later increase in current density similar to MoO2@Zn in blank ZnSO4 electrolyte, indicating that only the Tw80 additive could not fully impede Zn dendrites. However, the current density of MoO2@Zn in ZnSO4-containing Tw80 electrolyte decreases in a few seconds and then demonstrates a steady current–time behavior (Figures 4b and S17b), (54,56,57) confirming the promotion of uniform Zn deposition and effective inhibition of Zn dendrite growth in the plating process of Zn2+ ions by combining the MoO2 coating layer and Tw80 electrolyte additive.
Additionally, the influences of the MoO2 coating layer and Tw80 additive on the Zn anode interfaces were evaluated. Contact angle measurements were conducted to examine the effects of the MoO2 coating and Tw80 additive on the wettability of Zn. Figure S18a illustrates that the bare Zn exhibited a relatively large contact angle of 87.8° in a ZnSO4 solution. The addition of Tw80 in ZnSO4 solution reduced the contact angle to 47.9° (Figure S18b), enhancing the hydrophilicity of the Zn surface. Thus, Tw80, as a nonionic surfactant, can help to improve the surface wettability between Zn electrode and electrolyte, (58) which may assist in the uniform distribution of Zn2+ ions. Meanwhile, the MoO2 coating layer plays a more pronounced role in significantly reducing the contact angle to almost 0° in the solutions with and without Tw80 (Figure S18c,d), making the coated Zn surface superhydrophilic in the electrolyte possibly by enhancing the surface roughness or heterogeneity. (59,60) It has been reported that the electrode wettability plays a role in the final Zn deposition pattern and high surface hydrophilicity will result in more uniform Zn2+ flux across the surface of MoO2@Zn anodes, contributing to homogeneous Zn nucleation and growth. (61) Consequently, the MoO2 coating provides improved electrolyte–anode interfaces and hence enhances Zn2+ transport kinetics.
Furthermore, MoO2 coating can significantly enhance surface hydrophilicity to improve the wetting of electrolyte on the Zn electrode, which is beneficial for reducing the desolvation energy of hydrated Zn ions. (61) To determine the activation energy of Zn2+ desolvation under the protection of diverse MoO2 coatings, EIS measurements of diverse MoO2@Zn symmetric cells in ZnSO4+1Tw80 electrolyte were conducted at the temperature range from 30 to 60 °C. At a given temperature, the EIS curves show that the charge-transfer resistance (Rct) increased with the extended reduction time of MoO2 (Figure S19a–c), suggesting improved charge transfer kinetics in the MoO2(4 h)@Zn cells. Based on the Arrhenius equation (Supporting Information), the desolvation activation energy (Ea) can be obtained. The calculated activation energy (Ea) of Zn2+ desolvation with MoO2(4 h)@Zn is lower than that of MoO2(8 h)@Zn and MoO2(12 h)@Zn in 1 M ZnSO4 with Tw80 (Figure 4c). The reduced Ea of MoO2(4 h)@Zn demonstrates that MoO2(4 h) coating layer can facilitate rapid Zn2+ desolvation and enhance Zn2+ transfer and deposition kinetics. (11−13) Additionally, adding the Tw80 additive reduces Rct in MoO2@Zn symmetric cells (Figure S19a,d). Moreover, a slight decrease in the Ea value is observed in both bare Zn and MoO2-coated Zn based symmetric cells with the addition of Tw80 in the electrolyte, while the MoO2 coating layer can further decrease the Ea value (Figure S20). The combination of the MoO2 coating layer and Tw80 additive can lower the activation energy of Zn2+ desovlation, enhance the Zn deposition, and thus facilitate the desolvation-reduction process of hydrated Zn ions. (12,13)
The Zn∥Cu half cells are used to investigate the electrochemical reversibility of bare Zn and MoO2@Zn in the ZnSO4+Tw80 electrolyte. As shown in Figure S21, the initial nucleation overpotential increased from 0.1997 to 0.2696 V after being coated with MoO2. A higher nucleation overpotential indicates that the MoO2 coating layer reduces the transfer kinetics of Zn2+ ions, which is beneficial for refining deposited particles and achieving uniform Zn deposition, consistent with previous reports. (40,62) The Coulombic efficiency is also examined to evaluate the reversibility of Zn plating/stripping. The CE values of Zn||Cu, MoO2@Zn||Cu, and MoO2@Zn||MoO2@Cu cells using ZnSO4+1Tw80 electrolytes are investigated to evaluate the sustainability of the anode behavior by measuring Zn plating/stripping at 1 mA cm–2. Figure 4d–f shows the voltage profiles of bare Zn and MoO2@Zn anodes. In the initial cycles of the plating/stripping process, a lattice fitting phase (or reshaped Zn coordination) would occur, resulting in relatively low CE. (15) At different cycles, the voltage profiles of Zn||Cu cells exhibit significant jitter (Figure 4d) because of the nonuniform reshaping of the surface and the formation of “dead Zn” on Cu foil. (15) Also, MoO2@Zn||Cu and MoO2@Zn||MoO2@Cu cells demonstrate stable voltage profiles at increasing cycle numbers (Figure 4e,f), suggesting an enhancement of surface protection for the plating/stripping process. Therefore, the MoO2 coating layer substantially enhances the CE.
A comparison of CE between blank ZnSO4 and ZnSO4+1Tw80 electrolytes is also conducted to verify the effect of the Tw80 additive on enhancing the reversibility and stability of Zn plating/stripping (Figure 4g,h). The CE of the bare Zn electrode in blank ZnSO4 electrolyte quickly decays after 88 cycles, indicating the irregular Zn deposition on Cu foil. On the stable cyclability of bare Zn could be maintained over 118 cycles with the Tw80 additive in ZnSO4 electrolyte, which is attributed to the effective regulation of Tw80 on Zn plating/stripping processes. Moreover, while the CE of MoO2@Zn cell with ZnSO4+1Tw80 electrolyte remains stable over 500 cycles, the cell using blank ZnSO4 electrolyte remains relatively stable for 150 cycles and then continuously fluctuates in the following cycles, possibly due to the dendrite formation, byproducts, and other side reactions. As demonstrated by XRD patterns, characteristic peaks of Zn metal can be observed after deposition on Cu foil (Figure S22). The results show that the Zn deposit in ZnSO4+1Tw80 electrolyte has a higher intensity ratio of (002) peak to (101) peak, I(002)/I(101) than that in blank ZnSO4 electrolytes (1.69 and 1.03), which indicates that the ZnSO4+1Tw80 electrolyte facilitates a preferential orientation of Zn (002) plane. (63) Due to this change in texture orientation, the Zn deposited on the electrodes in the ZnSO4+1Tw80 electrolyte will be more homogeneous and flatter. Thus, the Tw80 additive can help stabilize the CE.
In situ optical microscopy was further employed on transparent cells to investigate the protective effect of the Tw80 additive and MoO2 layer on the plating and stripping of the Zn anodes. The fabricated transparent cell is shown in Figure S23. The transparent cells are plated for 30 min and then stripped for 30 min at 2 mA cm–2. In a blank ZnSO4 electrolyte, numerous Zn nuclei are unevenly distributed on the edge and surface of bare Zn foil after 10 min (Figure 5a and Video S1). It took 30 min for the small protrusion to grow into a prominent Zn dendrite at the exact location. Meanwhile, severe corrosion signs are observed on the Zn surface, and their areas increase as the plating duration increases. In the subsequent stripping process, dendrite growth and corrosion continuously occur on the electrode edge and surface, especially in the area adjacent to the Zn dendrites. According to these observations, the bare Zn electrode using a blank ZnSO4 electrolyte exhibits uneven electrodeposition, high corrosion, and weak reversibility. For the bare Zn electrode in a ZnSO4+1Tw80 electrolyte, dark spots exist on the surface after 10 min, and their sizes increase as plating proceeds, demonstrating that dendrite growth could occur on the electrode surface (Figure 5b and Video S2). There are also signs of corrosion on the surface of the bare Zn electrode. Besides, the bare Zn electrode surface becomes brighter during the subsequent stripping process, resulting in continuously ununiform Zn dissolution. However, the edge of bare Zn using ZnSO4+1Tw80 maintains a smooth and flat shape during the plating/stripping process, indicating that the Tw80 additive can support diminishing dendrite growth. The MoO2@Zn electrode is also plated/stripped in blank ZnSO4 electrolyte, showing that the surface is almost as smooth as the initial process, and very few dendrites could be observed at the edge after plating/stripping for 30 min (Figure 5c and Video S3). On the contrary, no apparent dendrite growth and corrosion are observed on the MoO2@Zn electrode using ZnSO4+1Tw80 electrolyte, benefiting from the induced uniform deposition effect of MoO2 coating (Figure 5d and Video S4). All of the above results confirm that the combination of MoO2 coating with Tw80 additive has synergistic protection on Zn electrodes, effectively homogenizing Zn nucleation and suppressing dendrite growth.

Figure 5

Figure 5. In situ optical microscope observation of Zn plating/stripping process for bare Zn using (a) blank ZnSO4 electrolyte and (b) ZnSO4 containing Tw80 electrolyte at 2 mA cm–2 for 30 min. In situ optical microscope observation of Zn plating/stripping process for MoO2@Zn electrodes using (c) blank ZnSO4 electrolyte and (d) ZnSO4 containing Tw80 electrolyte at 2 mA cm–2 for 30 min.

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A detailed mechanism for the contribution of the Tw80 additive and MoO2 coating to the regulation of Zn2+ ions deposition behavior is presented in Figure 6. It is noticeable that bare Zn foil in an aqueous electrolyte is unstable during the plating/stripping process. According to the “tip effect”, anode surfaces become rough during the initial nucleation process owing to the deposition of Zn2+ ions. (64) Due to the principle of minimizing surface energy and exposed surface area, Zn2+ ions adsorbed on the surface tend to diffuse laterally along the surface and generate Zn dendrites. With repeated plating cycles, the Zn2+ ions are preferably deposited on the initial dendrites, causing an inhomogeneous electric field distribution. Thus, considerable harmful Zn dendrites are formed on the anode surface (Figure 6a). Since the Zn2+ ions are coordinated with H2O molecules in ZnSO4 aqueous solution, hydride Zn2+ ions ([Zn(H2O)6]2+) are the main form of Zn2+ ions in the solution, which provides a high desolvation energy of Zn2+ ions. (64) However, [Zn(H2O)6]2+ ions could result in a deprotonation process, creating OH– and H+. The produced H+ ions cause the HER on the surface of the anode because of its higher redox potential compared with that of Zn deposition. The generated OH– ions incorporate H2O molecules to induce corrosion and increase the local pH value by passivating the anode surface to form byproducts (ZSOH). These factors would result in inferior cycling performance and low CEs of ZIBs. Also, the above-mentioned results indicate that only MoO2 coatings cannot completely enhance long-term stability for the following reasons: (1) A single MoO2 coating layer cannot effectively and durably inhibit corrosion, and (2) it is not an ideally hermetical coating layer that can eliminate electrolyte penetration and corrosion, which may not fully prevent the formation of byproducts and HER.

Figure 6

Figure 6. Schematic diagrams of Zn2+ ions deposition behaviors in aqueous electrolytes (a) bare Zn in blank ZnSO4 electrolyte, (b) bare Zn in blank ZnSO4 containing Tw80 electrolyte, and (c) MoO2-coated Zn in ZnSO4 electrolyte containing Tw80 electrolyte. (d) XANES spectra of MoO2@Zn electrodes after plating and stripping in ZnSO4+1Tw80 electrolyte.

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An effective electrolyte additive for stabilizing the Zn/electrolyte interface is introduced in this work by using Tw80, which is a low-cost and nonionic surfactant. Notably, the Tw80 additive provides promising inhibitors against Zn corrosion in a sulfate solution. (27,28) First, hydrophilic groups in Tw80 (Figure S24) can form strong hydrogen bonds with water molecules, thereby decreasing the solvation interaction between Zn2+ ions and H2O molecules and facilitating the desolvation process of hydrated Zn2+ ions. (9) Second, the hydrophobic alkyl chains in Tw80 have a negative inductive effect, leading to the increase of electron density at the oxygen atom along the alkyl chain, thus stabilizing the interaction between Zn and O (on Tw80) and mitigating H2O contact with the anode to enhance the protection efficiency. (27) In the corrosion field, the surfactant like Tw80, as a corrosion inhibitor, makes its hydrophilic portion adsorbed on the metal/metal oxide surface and a second layer (or multiple layers) may form with their hydrophobic tail adjacent to each other in an increased concentration, which can decrease the interfacial tension at the solid–water interface and contact angle and thus enhance the wettability. (58,65) Based on results of contact angle measurement and EIS under different temperatures (Figures S18–S20), Tw80 can also slightly increase surface hydrophilicity to reduce the desolvation energy of hydrated Zn ions. Thus, Tw80 can act as a corrosion inhibitor to prevent Zn corrosion and side reactions (Figure 6b). Although the Tw80 additive is an effective corrosion inhibitor, dendrites, HER, and byproducts could gradually develop on the bare Zn surface due to the direct contact between the electrolyte and electrode surface. Then, polarization linear sweep voltammetry (LSV) was performed to further examine the effect of the MoO2 coating layer and Tw80 additive on suppressing HER. Figure S25 shows the LSV curves of bare Zn in blank ZnSO4 electrolyte, and MoO2@Zn in ZnSO4 electrolyte without Tw80 and with Tw80. The MoO2 coating layer can slightly increase the hydrogen evolution overpotential, thereby retarding the HER during cycling in blank ZnSO4. In addition, the overpotential apparently increases when the MoO2 coating layer is combined with the Tw80 additive, indicating that the combination of MoO2@Zn and Tw80 additive is most effective in suppressing HER. Therefore, the combination of the MoO2 coating layer and the Tw80 additive can synergistically work to significantly prevent corrosion and side reactions for stabilizing Zn (Figure 6c).
To study the redox behavior of MoO2 on protective Zn electrode, Mo K-edge XANES spectra were collected for cycled MoO2@Zn electrodes at 5 mA cm–2 after the first cycle at both plating/stripping processes (Figure 6d). It is observed that during cycling, the absorption edge of XANES spectra of MoO2@Zn electrodes exhibits similar properties except for a slight energy position shift, implying no change in the structure. Specifically, during plating, the edge position shifts to the lower energy suggesting the slightly reduced Mo valence, possibly because MoO2 may accommodate a small quantity of Zn2+, similar to the reported Li+ insertion into the MoO2 lattice. (66) After the stripping, the XANES spectrum demonstrates a slight shift of the absorption edge to a higher energy position closer to the initial state (MoO2), implying a recovery of the Mo valence state. (66) This result indicates a redox reversibility of Mo in the MoO2 coating layer during the Zn2+ insertion (plating) and extraction (stripping) processes in MoO2. This mechanism of Zn2+ insertion/extraction into/from MoO2 may differ from that of MoO3 conversion in LIBs. (66,67) The Zn-ion storage process for MoO2 is similar to that of previously reported MoOx for Zn2+ storage, (67) as follows:
MoO2+xZn2++2xe−⇆ZnxMoO2
(2)
The MoO2 coating layer with slight Zn2+ accommodation capability may help to make the Zn2+ concentration field more homogeneously distributed in the vicinity of the Zn anode and avoid a large concentration gradient, which may facilitate the uniform deposition of Zn.
To further investigate the advantages of the MoO2 coating layer and Tw80 additive on Zn anode protection, full cells were assembled by using VO2 as cathodes. The characterizations of VO2 are displayed in Figure S26. A nanorod morphology of VO2 is observed in the SEM image. The XRD pattern matches well with the standard card (PDF no. 00–031–1438), confirming the monoclinic phase and purity of the synthesized VO2. As shown in Figure 7a, the CV curves at 0.1 mV s–1 for the full cell with bare Zn and MoO2@Zn anodes in blank ZnSO4 and ZnSO4+1Tw80 electrolytes are compared within a voltage window of 0.2–1.6 V versus Zn2+/Zn. All cells exhibit two pairs of reduction and oxidation peaks, suggesting a two-step Zn2+ ion intercalation and deintercalation reactions mechanism during the charge/discharge process, which has been previously reported. (68,69) The CV curves of the four samples have no considerable difference in the shape, suggesting that the addition of the Tw80 electrolyte additive and MoO2 coating layer has no significant effect on the intercalation/deintercalation processes. When Tw80 is added to the Zn∥VO2 cell, the peaks are shifted (Figure S27a). However, the CV curves of MoO2@Zn∥VO2 cells in different electrolytes are almost overlapped, which implies that the redox reaction of the VO2 cathode is not affected by the coating layer (Figure S27b). Additionally, MoO2@Zn∥VO2 cells in different electrolytes demonstrate lower potential separation and higher response current than bare Zn anode (Figure 7a), indicating better reversibility and electrochemical activity, which may be due to the faster kinetics of Zn2+ intercalation and weaker side reactions. (70) Figure 7b displays the cycling performance of Zn∥VO2 and MoO2@Zn∥VO2 full cells with blank ZnSO4 and ZnSO4+1Tw80 electrolytes at a current density of 1 A g–1. The cell using the MoO2@Zn anode in ZnSO4+1Tw80 electrolyte shows the best cycling stability with an initial discharge capacity of 228.3 mAh g–1 and capacity retention of 85.2% after 300 cycles, while the capacity retention decreases rapidly to 39.9% after cycling for the cell with a bare Zn anode. In contrast, the capacity of Zn∥VO2 cell in blank ZnSO4 drops to <10 mAh g–1 after 210 cycles and the MoO2@Zn∥VO2 cell exhibits a capacity retention of 34.8% after 300 cycles. The galvanostatic charge/discharge profiles (GCD) of full cells are shown in Figures 7c,d and S28. Likewise, the full cells with ZnSO4 and ZnSO4+1Tw80 electrolytes display a similar charge/discharge behavior. The cells using ZnSO4+1Tw80 electrolyte can sustain a much longer cycle lifespan and much better stability than those using a blank ZnSO4 electrolyte. The results demonstrate that the combination of the MoO2@Zn anode and Tw80 electrolyte additive could prolong the lifetime of Zn∥VO2 full cells.

Figure 7

Figure 7. Zn∥VO2 and MoO2@Zn∥VO2 full cells performance with (a) CV curves at a scan rate of 0.1 mV s–1. (b) Long-term cycling performance at 1 A g–1. GCD curves of different cycles of Zn∥VO2 and MoO2@Zn∥VO2 full cells using (c) ZnSO4 and (d) ZnSO4+1Tw80 electrolytes at a current density of 1 A g–1. (e) Rate performance from 0.5–10 A g–1. (f) Cycling stability at a high current density of 5 A g–1.

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Additionally, the rate performance of the full cell with the MoO2@Zn anode is superior to that of the cell with the bare Zn anode in different electrolytes as the current density increases from 1 to 10 A g–1 (Figure 7c). Even at a high current density of 10 A g–1, the MoO2@Zn∥ZnSO4+1Tw80∥VO2 full cell demonstrates a large initial capacity of 171.4 mAh g–1, while Zn∥ ZnSO4+1Tw80∥VO2 and MoO2@Zn∥ZnSO4∥VO2 show the capacity below 100 mAh g–1 and the capacity of Zn∥ZnSO4∥VO2 is less than 50 mAh g–1. Upon long-term cycling at a current density of 5 A g–1, the MoO2@Zn∥ZnSO4+1Tw80∥VO2 cell maintains outstanding performance with a high retained capacity of 105.6 mAh g–1 and superior capacity retention of 82.4% after 1000 cycles (Figure 7d). Conversely, the specific capacity of the Zn∥ZnSO4+1Tw80∥VO2 cell is reduced to 57.7 mAh g–1, corresponding to a capacity retention of 57.3%. At 5 A g–1, Zn∥VO2 and MoO2@Zn∥VO2 cells using blank ZnSO4 display the same electrochemical performance trend for 1000 cycles. However, the capacity retention of these full cells drops quickly to 59.3% and 31.2%, respectively. Significantly increasing the current density to 10 A g–1, the MoO2@Zn∥VO2 cell in the Tw80-assisted electrolyte system maintains an exceptionally stable performance (Figure S29). Overall, the outstanding electrochemical performances of the Zn anodes can be attributed to the effective inhibition of corrosion, HER, and dendrite formation in the presence of the MoO2 layer incorporating Tw80 electrolyte additive.

4. Conclusion

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In summary, this work proposed a new approach to developing a highly stable Zn anode by combining a surface coating layer and an electrolyte additive. The combination of MoO2 coating layer and the Tw80 additive can synergistically work to significantly prevent corrosion and side reactions. It can also reduce the desolvation energy of hydrated Zn ions during cycling, promoting uniform Zn2+ stripping/plating and improving the cell electrochemical performances. Benefiting from the dual synergistic effects of the MoO2 coating layer and Tw80 additive, the MoO2@Zn anode exhibits excellent electrochemical stability in a 1 M ZnSO4 electrolyte. The MoO2@Zn anode shows ultralong cycling stability in symmetric cells over 6000 h at 1 mA cm–2 for 1 mAh cm–2. The symmetric cells also show long-term stability over 705 h, even at a high current density of 5 mA cm–2 and areal capacity of 5 mAh cm–2. Especially, the full cells exhibit a high capacity of 105.6 mAh g–1 after 1000 cycles with outstanding rate performance (171.4 mAh g–1 at 10 A g–1). This work provides a method of combining the artificial coating layer and electrolyte additive to stabilize Zn for high-performance aqueous ZIBs.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c08474.

  • Experimental section; SEM images of synthesized MoO3 and bare Zn electrode; XPS survey spectra of MoO3 and MoO2; voltage profiles of bare Zn and MoO2@Zn symmetric cells at different cycles; cycling performance of bare Zn and MoO2@Zn symmetric cells under high current density, MoO2@Zn symmetric cells with different electrolytes, MoO3@Zn and different MoO2@Zn symmetric cells; characterization of MoO2@Zn electrodes after cycling with different electrolytes (SEM images and XRD results); characterization of different MoO2 (SEM images and XRD, EPR results); contact angles of bare Zn and MoO2@Zn with different electrolytes; optical images of MoO2@Zn soaking in different electrolytes and corresponding XRD patterns and SEM images; EIS spectra at different temperatures, calculated activation energy, Tafel plots, CA curves of different electrodes in different electrolytes; XRD results of bare Cu foils after Zn deposition in different electrolytes and corresponding peak intensity ratio; digital image of transparent cell using for optical in situ microscope observation; structure of Tween 80; characterization of the VO2 cathode (SEM image and XRD result) and corresponding electrochemical performance of Zn∥VO2 and MoO2@Zn∥VO2 full cells in different electrolytes (PDF)

  • Video S1: In situ optical microscope testing of bare Zn electrode in blank ZnSO4 electrolyte (MP4)

  • Video S2: In situ optical microscope testing of MoO2@Zn electrode in blank ZnSO4 electrolyte (MP4)

  • Video S3: In situ optical microscope testing of bare Zn electrode in ZnSO4-containing Tween 80 electrolyte (MP4)

  • Video S4: In situ optical microscope testing of MoO2@Zn electrode in ZnSO4-containing Tween 80 electrolyte (MP4)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Authors
  • Authors
    • Nhat Anh Thieu - Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0000-0001-8274-6882
    • Xiujuan Chen - Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0000-0002-5921-3487
    • Qingyuan Li - Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0000-0002-4296-9747
    • Qingsong Wang - Bavarian Center for Battery Technology (BayBatt), Department of Chemistry, University of Bayreuth, Universitätsstrasse 30, 95447 Bayreuth, Germany;  Orcidhttps://orcid.org/0000-0001-5879-8009
    • Murugesan Velayutham - In Vivo Multifunctional Magnetic Resonance Center, Robert C. Byrd Health Sciences Center, West Virginia University, Morgantown, West Virginia 26506, United States;  Department of Biochemistry and Molecular Medicine, School of Medicine, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0009-0001-9751-538X
    • Zane M. Grady - Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States;  Orcidhttps://orcid.org/0000-0001-7610-8905
    • Xuemei Li - Department of Chemical and Biomedical Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0009-0008-8978-7757
    • Wenyuan Li - Department of Chemical and Biomedical Engineering, Benjamin M. Statler College of Engineering and Mineral Resources, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0000-0002-8853-225X
    • Valery V. Khramtsov - In Vivo Multifunctional Magnetic Resonance Center, Robert C. Byrd Health Sciences Center, West Virginia University, Morgantown, West Virginia 26506, United States;  Department of Biochemistry and Molecular Medicine, School of Medicine, West Virginia University, Morgantown, West Virginia 26506, United States;  Orcidhttps://orcid.org/0000-0001-6187-5546
    • David M. Reed - Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States;  Orcidhttps://orcid.org/0000-0002-7012-9841
  • Author Contributions

    N.A.T. and W.L. contributed equally to this work. N.A.T.: Designed the experiments and methodology, synthesized materials, conducted material characterizations and electrochemical measurements, analyzed the data, prepared the figures, wrote the original draft of manuscript, revised the finalized manuscript. W.L.: Conceived the idea, designed the experiments and methodology, prepared the experimental setups, carried out the sample synthesis, material characterization, and electrochemical measurements, analyzed the data, prepared the figures, wrote the original draft of manuscript, revised and polished the manuscript, contributed to the funding acquisition, led and supervised the whole research activity planning and execution, managed and coordinated the project. X.C.: Carried out material characterizations and electrochemical measurements, reviewed, edited, and commented on the manuscript. Q.L.: Contributed to the synchrotron XAS sample preparation and analyzed the XAS data, reviewed and commented on the manuscript. Q.W.: Carried out the synchrotron XAS characterization, contributed to the XAS data analysis and visualization, reviewed and commented on the manuscript. M.V.: Carried out the EPR measurement, analyzed the EPR data, contributed to writing of the EPR discussion section and data presentation, reviewed and commented on the manuscript. Z.M.G.: Carried out the EIS measurement at different temperatures and contact angle testing, analyzed the EIS data, contributed to preparation of EIS figures and writing of the EIS discussion section, reviewed and commented on the manuscript. X.L.: Carried out the electrical conductivity measurement and analyzed the data, reviewed the manuscript. W.L.: Prepared the conductivity testing setup, carried out the electrical conductivity measurement and analyzed the data, reviewed the manuscript. V.V.K.: Provided the EPR resources, reviewed the manuscript. D.M.R.: Provided the electrochemical measurement resources, contributed to the funding acquisition, reviewed and commented on the manuscript. X.L.: Supervised the whole research activity planning and execution, managed and coordinated the project, provided the electrochemical measurement resources, contributed to the funding acquisition, reviewed and commented on the manuscript. X.L.: Led and supervised the whole research activity planning and execution, acquired the funding, administered the project, reviewed and commented on the manuscript.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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The work was sponsored by the U.S. Department of Energy (DOE), Office of Electricity (OE), under contract DE-AC06-76LO1830 through Pacific Northwest National Laboratory (No. 539057). We thank the Manager of OE Energy Storage Program, Dr. Imre Gyuk, for the support and technical guidance. Parts of this research were carried out at PETRA III (Deutsches Elektronen-Synchrotron, DESY, Hamburg, Germany) and assistance from Dr. Edmund Welter is gratefully acknowledged. Beamtime was allocated for proposal I-20221092. We acknowledge the use of the WVU Shared Research Facilities. We thank Dr. Xuefei Gao who was at University of North Carolina at Chapel Hill for technical discussion of Tween 80 properties. We also thank Guy Cordonier and Dr. Konstantinos A. Sierros at West Virginia University for their assistance with contact angle measurements.

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    Advanced Functional Materials (2020), 30 (43), 2003932CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Zn dendrites growth and poor cycling stability are significant challenges for rechargeable aq. Zn batteries. Zn metal deposition-dissoln. in aq. electrolytes is typically detd. by Zn anode-electrolyte interfaces. In this work, the role of a long-chain polyethylene oxide (PEO) polymer as a multifunctional electrolyte additive in stabilizing Zn metal anodes is reported. PEO mols. suppress Zn2+ ion transfer kinetics and regulate Zn2+ ion concn. in the vicinity of Zn anodes through interactions between ether groups of PEO and Zn2+ ions. The suppressed Zn2+ ion transfer kinetics and homogeneous Zn2+ ion distribution at the interface promotes dendrite-free homogeneous Zn deposition. In addn., electrochem. inert PEO mols. adsorbed onto Zn anodes can protect the anode surfaces from H2+ generation and, thereby, enhance their electrochem. stability. Stable cycling over 3000 h and high reversibility (Coulombic efficiency > 99.5%) of Zn anodes is demonstrated in 1 M ZnSO4 electrolyte with 0.5 wt% PEO. This finding provides helpful insights into the mechanism of Zn metal anodes stabilization by low-cost multifunctional polymer electrolyte additives that stabilize interfacial reactions.
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  9. 9
    Zhou, M.; Chen, H.; Chen, Z.; Hu, Z.; Wang, N.; Jin, Y.; Yu, X.; Meng, H. Nonionic Surfactant Coconut Diethanol Amide Inhibits the Growth of Zinc Dendrites for More Stable Zinc-Ion Batteries. ACS Appl. Energy Mater. 2022, 5, 7590– 7599,  DOI: 10.1021/acsaem.2c01048
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    9
    Nonionic Surfactant Coconut Diethanol Amide Inhibits the Growth of Zinc Dendrites for More Stable Zinc-Ion Batteries
    Zhou, Ming; Chen, Hongzhan; Chen, Zehai; Hu, Zehao; Wang, Nan; Jin, Yanshuo; Yu, Xiang; Meng, Hui
    ACS Applied Energy Materials (2022), 5 (6), 7590-7599CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Uncontrollable growth of zinc dendrites and byproducts has become the main factor which limits the life of zinc-ion batteries. Herein, we reported a nonionic surfactant, coconut diethanolamide (CDA), which can be applied as an electrolyte additive. It not only effectively suppresses zinc graft growth and promotes uniform growth of zinc dendrites but also efficiently inhibits the generation of side reactions and byproducts. When CDA is added to the electrolyte, the life of the battery has been significantly improved (1580 h). Compared with an electrolyte without CDA (100 h), its life has grown more than 10 times. CDA can adsorb on the surface of the zinc electrode to form a protective layer by its special mol. structure. Therefore, zinc ions will have a higher barrier for deposition, and there should be induced uniform deposition. Moreover, the Cu/Zn cell shows 98% av. Coulomb efficiency in the electrolyte with CDA after about 620 h. In addn., after long-term cycles, the addn. of CDA enables the MnO2/Zn cell to show 85% capacity retention and 98% av. Coulomb efficiency. The electrolyte additives reported in this study will provide a more convenient and environmentally friendly way to effectively solve the problem of zinc branches.
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  10. 10
    Qian, Y.; Meng, C.; He, J.; Dong, X. A Lightweight 3D Zn@Cu Nanosheets@activated Carbon Cloth as Long-Life Anode with Large Capacity for Flexible Zinc Ion Batteries. J. Power Sources 2020, 480, 228871  DOI: 10.1016/j.jpowsour.2020.228871
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    10
    A lightweight 3D Zn@Cu nanosheets@activated carbon cloth as long-life anode with large capacity for flexible zinc ion batteries
    Qian, Yong; Meng, Chen; He, Jinxin; Dong, Xia
    Journal of Power Sources (2020), 480 (), 228871CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Zinc metal is actively developed as the most potential next generation anode material for aq. rechargeable batteries. However, Zn deposition and uncontrollable dendrite growth of metallic Zn anodes during cycles lead to poor cycle performance and coulombic efficiency, hindering their practical application. Constructing a three-dimensional (3D) current collector has been demonstrated to significantly inhibit the formation of zinc dendrites. Herein, a lightwt. 3D flexible Zn plating/stripping scaffold, Cu nanosheets grown on activated carbon cloth (Cu nanosheets@ACC), is prepd. by an electrochem. deposition technol. Compared with activated carbon cloth (ACC), Cu nanosheets@ACC current collector delivers higher special surface area and cond. Besides, Cu nanosheets layer not only can provide numerous, uniformly distributed Zn deposition sites but also can significantly decrease Zn nucleation overpotential. As a consequence, Zn@Cu nanosheets@ACC (Zn grown on Cu nanosheets@ACC) anode delivers a highly reversible Zn plating/stripping behavior with satisfactory cyclic stability rather than uncontrollable Zn dendrites growth. Moreover, a zinc ion battery based on the Zn@Cu nanosheets@ACC anode and MnO2@ACC (MnO2 grown on ACC) cathode presents high av. coulombic efficiency (97.9%) and excellent cycling stability (94.8%) over 1000 cycles at 1 A/g as well as satisfactory mech. properties, displaying great potential for long-life flexible zinc ion batteries.
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  11. 11
    Xie, S.; Li, Y.; Dong, L. Stable Anode-Free Zinc-Ion Batteries Enabled by Alloy Network-Modulated Zinc Deposition Interface. J. Energy Chem. 2023, 76, 32– 40,  DOI: 10.1016/j.jechem.2022.08.040
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    11
    Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface
    Xie, Shiyin; Li, Yang; Dong, Liubing
    Journal of Energy Chemistry (2023), 76 (), 32-40CODEN: JECOFG; ISSN:2095-4956. (Science Press)
    Newly-proposed anode-free zinc-ion batteries (ZIBs) are promising to remarkably enhance the energy d. of ZIBs, but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability. Herein, we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs. The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes. Consequently, the alloy network-modulated zinc deposition interface realizes high-Coulombic efficiency of 99.2% and high stability. As proof, Zn//Zn sym. cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 mA/cm2 and 1200 h at 5 mA/cm2, significantly superior to Zn//Zn sym. cells with unmodified zinc deposition interface (whose operation lifetime is shorter than 50 h). Meanwhile, Zn3V3O8 cathode-based ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes. As expected, the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8 cathodes to deliver superior cycling stability, better than most currently-reported anode-free ZIBs. This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.
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  12. 12
    Wang, Z.; Dong, L.; Huang, W.; Jia, H.; Zhao, Q.; Wang, Y.; Fei, B.; Pan, F. Simultaneously Regulating Uniform Zn2+ Flux and Electron Conduction by MOF/rGO Interlayers for High-Performance Zn Anodes. Nano-Micro Lett. 2021, 13, 73,  DOI: 10.1007/s40820-021-00594-7
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    12
    Simultaneously regulating uniform Zn2+ flux and electron conduction by MOF/rGO interlayers for high-performance Zn anodes
    Wang, Ziqi; Dong, Liubing; Huang, Weiyuan; Jia, Hao; Zhao, Qinghe; Wang, Yidi; Fei, Bin; Pan, Feng
    Nano-Micro Letters (2021), 13 (), 73CODEN: NLAEBV; ISSN:2150-5551. (Nano-Micro Letters)
    Owing to the merits of low cost, high safety and environmental benignity, rechargeable aq. Zn-based batteries (ZBs) have gained tremendous attention in recent years. Nevertheless, the poor reversibility of Zn anodes that originates from dendrite growth, surface passivation and corrosion, severely hinders the further development of ZBs. To tackle these issues, here we report a Janus separator based on a Zn-ion conductive metal-org. framework (MOF) and reduced graphene oxide (rGO), which is able to regulate uniform Zn2+ flux and electron conduction simultaneously during battery operation. Facilitated by the MOF/rGO bifunctional interlayers, the Zn anodes demonstrate stable plating/stripping behavior (over 500 h at 1 mA cm-2), high Coulombic efficiency (99.2% at 2 mA cm-2 after 100 cycles) and reduced redox barrier. Moreover, it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface. Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells, which deliver nearly 100% capacity retention after 2000 cycles at 4 A g-1 and high power d. over 10 kW kg-1. This work provides a feasible route to the high-performance Zn anodes for ZBs.
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  13. 13
    Li, Y.; Peng, X.; Li, X.; Duan, H.; Xie, S.; Dong, L.; Kang, F. Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc-Based Energy Storage. Adv. Mater. 2023, 35, 2300019  DOI: 10.1002/adma.202300019
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    13
    Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc-Based Energy Storage
    Li, Yang; Peng, Xinya; Li, Xu; Duan, Huan; Xie, Shiyin; Dong, Liubing; Kang, Feiyu
    Advanced Materials (Weinheim, Germany) (2023), 35 (18), 2300019CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Ultrathin separators are indispensable to high-energy-d. zinc-ion batteries (ZIBs), but their easy failure caused by zinc dendrites poses a great challenge. Herein, 23μm-thick functional ultrathin separators (FUSs), realizing superb electrochem. stability of zinc anodes and outstanding long-term durability of ultrathin separators, are reported. In the FUSs, an ultrathin but mechinal strong nanoporous membrane substrate benefits fast and flux-homogenized Zn2+ transport, while a metal-org. framework (MOF)-derived C/Cu nanocomposite decoration layer provides rich low-barrier zinc nucleation sites, thereby synergistically stabilizing zinc anodes to inhibit zinc dendrites and dendrite-caused separator failure. Investigation of the zinc affinity of the MOF-derived C/Cu nanocomposites unravels the high zincophilicity of heteroatom-contg. C/Cu interfaces. Zinc anodes coupled with the FUSs present superior electrochem. stability, whose operation lifetime exceeds 2000 h at 1 mA cm-2 and 600 h at 10 mA cm-2, 40-50 times longer than that of the zinc anodes using glass-fiber separators. The reliability of the FUSs in ZIBs and zinc-ion hybrid supercapacitors is also validated. This work proposes a new strategy to stabilize zinc anodes and provides theor. guidance in developing ultrathin separators for high-energy-d. zinc-based energy storage.
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  14. 14
    Kang, L.; Cui, M.; Jiang, F.; Gao, Y.; Luo, H.; Liu, J.; Liang, W.; Zhi, C. Nanoporous CaCO3 Coatings Enabled Uniform Zn Stripping/Plating for Long-Life Zinc Rechargeable Aqueous Batteries. Adv. Energy Mater. 2018, 8, 1801090  DOI: 10.1002/aenm.201801090
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    Chen, X.; Li, W.; Hu, S.; Akhmedov, N. G.; Reed, D.; Li, X.; Liu, X. Polyvinyl Alcohol Coating Induced Preferred Crystallographic Orientation in Aqueous Zinc Battery Anodes. Nano Energy 2022, 98, 107269  DOI: 10.1016/j.nanoen.2022.107269
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    15
    Polyvinyl alcohol coating induced preferred crystallographic orientation in aqueous zinc battery anodes
    Chen, Xiujuan; Li, Wei; Hu, Shanshan; Akhmedov, Novruz G.; Reed, David; Li, Xiaolin; Liu, Xingbo
    Nano Energy (2022), 98 (), 107269CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    The development of rechargeable aq. zinc batteries is mainly hindered by the Zn anode, which suffers from dendrite growth, corrosion, hydrogen evolution, and surface passivation. Herein, a thin polyvinyl alc. (PVA) coating layer on Zn anode has enabled dendrite-free, long-life aq. Zn batteries by effectively regulating the interfacial ion diffusion and inducing the homogeneous Zn nucleation and deposition of stacked plates with preferentially crystallog. orientation along (002)Zn planes. The PVA@Zn anode achieved an ultralong cycle lifespan of thousands of hours at 0.25 and 1 mA cm-2. Outstanding durability under a deep cycling capacity (5 mA h cm-2), high c.d. (10 mA cm-2), and long duration conditions were achieved. The superior cyclability of PVA@Zn anode was also demonstrated in PVA@Zn//V2O5 full cells. The insights of PVA induced Zn deposition with preferred crystal orientation and interfacial regulation shed light on the future development of stable Zn anodes.
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  16. 16
    Cui, M.; Xiao, Y.; Kang, L.; Du, W.; Gao, Y.; Sun, X.; Zhou, Y.; Li, X.; Li, H.; Jiang, F.; Zhi, C. Quasi-Isolated Au Particles as Heterogeneous Seeds To Guide Uniform Zn Deposition for Aqueous Zinc-Ion Batteries. ACS Appl. Energy Mater. 2019, 2, 6490– 6496,  DOI: 10.1021/acsaem.9b01063
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    16
    Quasi-Isolated Au Particles as Heterogeneous Seeds To Guide Uniform Zn Deposition for Aqueous Zinc-Ion Batteries
    Cui, Mangwei; Xiao, Yan; Kang, Litao; Du, Wei; Gao, Yanfeng; Sun, Xueqin; Zhou, Yanli; Li, Xiangming; Li, Hongfei; Jiang, Fuyi; Zhi, Chunyi
    ACS Applied Energy Materials (2019), 2 (9), 6490-6496CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    As a promising anode for aq. batteries, Zn metal shows a no. of attractive advantages such as low cost, low redox potential, high capacity, and environmental benignity. Nevertheless, the quick growth of dendrites/protrusions on the "hostless" Zn anodes not only enlarges batteries' internal resistance but also causes sudden shorting failure by piercing separators. Herein, we report a novel heterogeneous seed method to guide the morphol. evolution of plated Zn. The heterogeneous seeds are sputtering-deposited quasi-isolated nano-Au particles (Au-NPs) that enable a uniform and stable Zn-plating/stripping process on the anodes. Tested on Zn|Zn sym. cells, the Au-nanoparticle (NP) decorated Zn anodes (NA-Zn) demonstrate much better cycling stability than the bare ones (92 vs 2000 h). In NA-Zn|CNT/MnO2 batteries, this heterogeneous seed prolongs the lifetime of the device from ∼480 cycles up to 2000 cycles. This work offers a facile and promising Zn dendrite/protrusion suppressing route for the achievement of long-life Zn-ion batteries.
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  17. 17
    Zhang, N.; Huang, S.; Yuan, Z.; Zhu, J.; Zhao, Z.; Niu, Z. Direct Self-Assembly of MXene on Zn Anodes for Dendrite-Free Aqueous Zinc-Ion Batteries. Angew. Chem., Int. Ed. 2021, 60, 2861– 2865,  DOI: 10.1002/anie.202012322
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    17
    Direct Self-Assembly of MXene on Zn Anodes for Dendrite-Free Aqueous Zinc-Ion Batteries
    Zhang, Nannan; Huang, Shuo; Yuan, Zishun; Zhu, Jiacai; Zhao, Zifang; Niu, Zhiqiang
    Angewandte Chemie, International Edition (2021), 60 (6), 2861-2865CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Metallic zinc is a promising anode candidate of aq. zinc-ion batteries owing to its high theor. capacity and low redox potential. However, Zn anodes usually suffer from dendrite and side reactions, which will degrade their cycle stability and reversibility. Herein, we developed an in situ spontaneously reducing/assembling strategy to assemble a ultrathin and uniform MXene layer on the surface of Zn anodes. The MXene layer endows the Zn anode with a lower Zn nucleation energy barrier and a more uniformly distributed elec. field through the favorable charge redistribution effect in comparison with pure Zn. Therefore, MXene-integrated Zn anode exhibits obviously low voltage hysteresis and excellent cycling stability with dendrite-free behaviors, ensuring the high capacity retention and low polarization potential in zinc-ion batteries.
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  18. 18
    Wang, A.; Zhou, W.; Huang, A.; Chen, M.; Chen, J.; Tian, Q.; Xu, J. Modifying the Zn Anode with Carbon Black Coating and Nanofibrillated Cellulose Binder: A Strategy to Realize Dendrite-Free Zn-MnO2 Batteries. J. Colloid Interface Sci. 2020, 577, 256– 264,  DOI: 10.1016/j.jcis.2020.05.102
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    18
    Modifying the Zn anode with carbon black coating and nanofibrillated cellulose binder: A strategy to realize dendrite-free Zn-MnO2 batteries
    Wang, Anran; Zhou, Weijun; Huang, Aixiang; Chen, Minfeng; Chen, Jizhang; Tian, Qinghua; Xu, Junling
    Journal of Colloid and Interface Science (2020), 577 (), 256-264CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
    Aq. zinc-ion batteries have received significant attention due to their low cost and high safety. However, the unsatisfactory cycling performances caused by the dendritic growth on the Zn anode limit their practical applications. Herein, we propose to modify the conventional Zn foil anode by using carbon black coating and nanofibrillated cellulose binder. The carbon black can form an elec. conductive network, thus greatly enlarging the electroactive surface area, while the nanofibrillated cellulose can act as an electrolyte reservoir to facilitate charge transports. Thanks to that, the modified anode can significantly eliminate the dendritic growth and side reactions, therefore ensuring excellent interface stability with the electrolyte even at a com.-level areal capacity of 5 mAh g-1. With the modified anode, the Zn-MnO2 battery gives a high capacity retention of 87.4% after 1000 cycles, much higher than that with the unmodified Zn foil (42.6%). This study discloses a facile, scalable, and cost-effective strategy to achieve dendrite-free metal electrodes towards great cyclability.
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  19. 19
    Xu, J.; Lv, W.; Yang, W.; Jin, Y.; Jin, Q.; Sun, B.; Zhang, Z.; Wang, T.; Zheng, L.; Shi, X.; Sun, B.; Wang, G. In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries. ACS Nano 2022, 16, 11392– 11404,  DOI: 10.1021/acsnano.2c05285
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    19
    In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries
    Xu, Jing; Lv, Wenli; Yang, Wang; Jin, Yang; Jin, Qianzheng; Sun, Bin; Zhang, Zili; Wang, Tianyi; Zheng, Linfeng; Shi, Xiaolong; Sun, Bing; Wang, Guoxiu
    ACS Nano (2022), 16 (7), 11392-11404CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    The strong activity of water mols. causes a series of parasitic side reactions on Zn anodes in the aq. electrolytes. Herein, we introduce silk fibroin (SF) as a multifunctional electrolyte additive for aq. zinc-ion (Zn-ion) batteries. The secondary structure transformation of SF mols. from α-helixes to random coils in the aq. electrolytes allows them to break the hydrogen bond network among free water mols. and participate in Zn2+ ion solvation structure. The SF mols. released from the [Zn(H2O)4(SF)]2+ solvation sheath appear to be gradually adsorbed on the surface of Zn anodes and in situ form a hydrostable and self-healable protective film. This SF-based protective film not only shows strong Zn2+ ion affinity to promote homogeneous Zn deposition but also has good insulating behavior to suppress parasitic reactions. Benefiting from these multifunctional advantages, the cycle life of the Zn||Zn sym. cells reaches over 1600 h in SF-contg. ZnSO4 electrolytes. In addn., by adopting a potassium vanadate cathode, the full cell shows excellent cycling stability for 1000 cycles at 3 A g-1. The in situ construction of a protective film on the Zn anode from natural protein mols. provides an effective strategy to achieve high-performance Zn metal anodes for Zn-ion batteries.
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  20. 20
    Zhao, X.; Dong, N.; Yan, M.; Pan, H. Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries. ACS Appl. Mater. Interfaces 2023, 15, 4053– 4060,  DOI: 10.1021/acsami.2c19022
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    20
    Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries
    Zhao, Xuesong; Dong, Ning; Yan, Mengdie; Pan, Huilin
    ACS Applied Materials & Interfaces (2023), 15 (3), 4053-4060CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    A robust solid electrolyte interface (SEI) is crucial to widen the electrochem. stability window of the electrolyte and enable sustainably stable electrode reactions in aq. Zn ion batteries. Different from the SEI in nonaq. electrolytes, it is of great importance to form a functional and stable SEI due to parasitic reactions with water in aq. Zn ion batteries. However, the concrete SEI formation in aq. electrolytes has been elusive so far. Here, we regulate and unravel the decompn. mechanisms of org. Zn salts at the Zn anode-electrolyte interface in the widely studied zinc triflate-based aq. electrolytes. By introducing a buffering adsorption layer with an optimal concn. of acetate anions, the uncontrollable decompn. of org. zinc triflate salt is greatly inhibited on Zn anodes, resulting in a stable interface. The av. Coulombic efficiency of the Zn anode thus can reach as high as 99.95% and stable cycling for 4200 h. With the cooperation of buffering adsorption layers, the tetra-Et ammonium trifluoromethanesulfonate additive as the decompn. promoter could further regulate the decompn. of triflate anions for the formation of robust SEI layers for Zn anodes in electrolytes with a dil. salt concn. Zn-polyaniline (PANI) full cells demonstrate stable cycling with controlled N/P ratios in such electrolytes. This work proposes an insightful perspective on rational regulation of the decompn. pathway of electrolyte components by forming a stable electrode-electrolyte interface for improved electrochem. performance of aq. Zn ion batteries.
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  21. 21
    Kim, H.-S.; Cook, J.-B.; Lin, H.; Ko, J.-S.; Tolbert, S.-H.; Ozolins, V.; Dunn, B. Oxygen Vacancies Enhance Pseudocapacitive Charge Storage Properties of MoO3-x. Nat. Mater. 2017, 16, 454– 462,  DOI: 10.1038/nmat4810
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    21
    Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3-x
    Kim, Hyung-Seok; Cook, John B.; Lin, Hao; Ko, Jesse S.; Tolbert, Sarah H.; Ozolins, Vidvuds; Dunn, Bruce
    Nature Materials (2017), 16 (4), 454-460CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    The short charging times and high power capabilities assocd. with capacitive energy storage make this approach an attractive alternative to batteries. One limitation of electrochem. capacitors is their low energy d. and for this reason, there is widespread interest in pseudocapacitive materials that use Faradaic reactions to store charge. One candidate pseudocapacitive material is orthorhombic MoO3 (α-MoO3), a layered compd. with a high theor. capacity for lithium (279 mA h g-1 or 1,005 C g-1). Here, we report on the properties of reduced α-MoO3-x(R-MoO3-x) and compare it with fully oxidized α-MoO3 (F-MoO3). The introduction of oxygen vacancies leads to a larger interlayer spacing that promotes faster charge storage kinetics and enables the α-MoO3 structure to be retained during the insertion and removal of Li ions. The higher specific capacity of the R-MoO3-x is attributed to the reversible formation of a significant amt. of Mo4+ following lithiation. This study underscores the potential importance of incorporating oxygen vacancies into transition metal oxides as a strategy for increasing the charge storage kinetics of redox-active materials.
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  22. 22
    Jung, Y.-S.; Lee, S.; Ahn, D.; Dillon, A.-C.; Lee, S.-H. Electrochemical Reactivity of Ball-Milled MoO3-y as Anode Materials for Lithium-Ion Batteries. J. Power Sources 2009, 188, 286– 291,  DOI: 10.1016/j.jpowsour.2008.11.125
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    22
    Electrochemical reactivity of ball-milled MoO3-y as anode materials for lithium-ion batteries
    Jung, Yoon S.; Lee, Sangkyoo; Ahn, Dongjoon; Dillon, Anne C.; Lee, Se-Hee
    Journal of Power Sources (2009), 188 (1), 286-291CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    The electrochem. reactivity of ball-milled MoO3 powders was studied in Li rechargeable cells. High-energy ball-milling converts highly-cryst. MoO3 bulk powders into partially reduced low-cryst. MoO3-y materials with a reduced particle size. Both bulk and ball-milled MoO3 exhibit a 1st discharge capacity beyond 1100 mAh g-1 when tested in the 0-3 V (vs. Li/Li+) range, which is indicative of a complete conversion reaction. Partial redn. caused by ball-milling results in a redn. in the conversion reaction. Addnl., incomplete reoxidn. during subsequent charge gave MoO2 instead of MoO3, which in turn affects the reactivity in subsequent cycles. As compared to bulk MoO3, ball-milled MoO3-y showed significantly enhanced cycle performance (bulk: 27.6% charge capacity retention at the 10th cycle vs. ball-milled for 8 h: 64.4% at the 35th cycle), which can be attributed to the nano-texture wherein nanometer-sized particles aggregate to form secondary ones.
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  23. 23
    Wang, B.; Yan, J.; Zhang, Y.; Ye, M.; Yang, Y.; Li, C. C. In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable “Rocking-Chair” Zinc-Ion Batteries. Adv. Funct. Mater. 2021, 31, 2102827  DOI: 10.1002/adfm.202102827
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    23
    In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable "Rocking-Chair" Zinc-Ion Batteries
    Wang, Bo; Yan, Jianping; Zhang, Yufei; Ye, Minghui; Yang, Yang; Li, Cheng Chao
    Advanced Functional Materials (2021), 31 (30), 2102827CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Aq. zinc-ion batteries (ZIBs) have attracted significant attention due to their intrinsic safety, cost-effectiveness, and environmental friendliness. However, the common zinc metal anode suffers from zinc dendrite formation, self-corrosion, and surface passivation, which impede the further application of aq. ZIBs. Herein, carbon-inserted molybdenum dioxide (MoO2) materials with laminated structure are designed as novel intercalation-type anodes for ZIBs by combination of interlayer engineering and in situ carbonization of aniline guest in molybdenum trioxide interlayers. The uniform dispersion of carbon layers in laminated MoO2 not only provide fast transportation paths for electron but also strengthen the framework of MoO2, leading to high structural integration during high-rate cycling. Benefiting from the unique structural design, the carbon-inserted MoO2 electrode exhibits high initial Coulombic efficiency, excellent cycling stability, and outstanding rate capability. Multiple ex situ characterizations reveal its excellent electrochem. stability is derived from reversible intercalation mechanism and ultrastable structural framework. Furthermore, the rocking-chair zinc-ion full battery assembled with the zinc pre-intercalated Na3V2(PO4)2O2F cathode presents excellent stability and ultralong lifespan with a high capacity retention of 91% over 8000 cycles.
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  24. 24
    Zhu, Y.; Ji, X.; Cheng, S.; Chern, Z.-Y.; Jia, J.; Yang, L.; Luo, H.; Yu, J.; Peng, X.; Wang, J.; Zhou, W.; Liu, M. Fast Energy Storage in Two-Dimensional MoO2 Enabled by Uniform Oriented Tunnels. ACS Nano 2019, 13, 9091– 9099,  DOI: 10.1021/acsnano.9b03324
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    24
    Fast Energy Storage in Two-Dimensional MoO2 Enabled by Uniform Oriented Tunnels
    Zhu, Yuanyuan; Ji, Xu; Cheng, Shuang; Chern, Zhao-Ying; Jia, Jin; Yang, Lufeng; Luo, Haowei; Yu, Jiayuan; Peng, Xinwen; Wang, Jenghan; Zhou, Weijia; Liu, Meilin
    ACS Nano (2019), 13 (8), 9091-9099CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    While pseudocapacitive electrodes have potential to store more energy than elec. double-layer capacitive electrodes, their rate capability is often limited by the sluggish kinetics of the Faradaic reactions or poor electronic and ionic cond. Unlike most transition-metal oxides, MoO2 is a very promising material for fast energy storage, attributed to its unusually high electronic and ionic cond.; the 1-dimensional tunnel is ideally suited for fast ionic transport. Here, we report our findings in prepn. and characterization of ultrathin MoO2 sheets with oriented tunnels as a pseudocapacitive electrode for fast charge storage/release. A composite electrode consisting of MoO2 and 5 wt.% GO demonstrates a capacity of 1097 C/g at 2 mV/s and 390 C/g at 1000 mV/s while maintaining ∼80% of the initial capacity after 10,000 cycles at 50 mV/s, due to minimal change in structural features of the MoO2 during charge/discharge, except a small vol. change (∼14%), as revealed from operando Raman spectroscopy, x-ray analyses, and d. functional theory calcns. The vol. change during cycling is highly reversible, implying high structural stability and long cycling life.
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  25. 25
    Wang, H.; Li, T.; Hashem, A. M.; Abdel-Ghany, A. E.; El-Tawil, R. S.; Abuzeid, H. M.; Coughlin, A.; Chang, K.; Zhang, S.; El-Mounayri, H.; Tovar, A.; Zhu, L.; Julien, C. M. Nanostructured Molybdenum-Oxide Anodes for Lithium-Ion Batteries: An Outstanding Increase in Capacity. Nanomaterials 2022, 12, 13,  DOI: 10.3390/nano12010013
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    25
    Nanostructured Molybdenum-Oxide Anodes for Lithium-Ion Batteries: An Outstanding Increase in Capacity
    Wang, Hua; Li, Tianyi; Hashem, Ahmed M.; Abdel-Ghany, Ashraf E.; El-Tawil, Rasha S.; Abuzeid, Hanaa M.; Coughlin, Amanda; Chang, Kai; Zhang, Shixiong; El-Mounayri, Hazim; Tovar, Andres; Zhu, Likun; Julien, Christian M.
    Nanomaterials (2022), 12 (1), 13CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
    This work aimed at synthesizing MoO3 and MoO2 by a facile and cost-effective method using ext. of orange peel as a biol. chelating and reducing agent for ammonium molybdate. Calcination of the precursor in air at 450°C yielded the stochiometric MoO3 phase, while calcination in vacuum produced the reduced form MoO2 as evidenced by X-ray powder diffraction, Raman scattering spectroscopy, and XPS results. Scanning and transmission electron microscopy images showed different morphologies and sizes of MoOx particles. MoO3 formed platelet particles that were larger than those obsd. for MoO2. MoO3 showed stable thermal behavior until approx. 800°C, whereas MoO2 showed wt. gain at approx. 400°C due to the fact of re-oxidn. and oxygen uptake and, hence, conversion to stoichiometric MoO3. Electrochem., traditional performance was obsd. for MoO3, which exhibited a high initial capacity with steady and continuous capacity fading upon cycling. On the contrary, MoO2 showed completely different electrochem. behavior with less initial capacity but an outstanding increase in capacity upon cycling, which reached 1600 mAh g-1 after 800 cycles. This outstanding electrochem. performance of MoO2 may be attributed to its higher surface area and better elec. cond. as obsd. in surface area and impedance investigations.
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  26. 26
    Zhou, Y.; Geng, C. A MoO2 Sheet as a Promising Electrode Material: Ultrafast Li-Diffusion and Astonishing Li-Storage Capacity. Nanotechnology 2017, 28, 105402  DOI: 10.1088/1361-6528/aa56d0
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    26
    A MoO2 sheet as a promising electrode material: ultrafast Li-diffusion and astonishing Li-storage capacity
    Zhou, Yungang; Geng, Cheng
    Nanotechnology (2017), 28 (10), 105402/1-105402/8CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
    The potential of MoO2 crystal as an electrode material is reported, and nanostructural MoO2 systems, including nanoparticles, nanospheres, nanobelts and nanowires, were synthesized and proved to be advanced electrode materials. A two-dimensional (2D) geometric structure represents an extreme of surface-to-vol. ratio, and thus is more suitable as an electrode material in general. Stimulated by the recent fabrication of 2D MoO2, we adopted an ab initio mol. dynamics simulation and d. functional theory calcn. to study the stability and electrochem. properties of a MoO2 sheet. Identified by a phonon dispersion curve and potential energy curve calcns., the MoO2 sheet proved to be dynamically and thermally stable. After lithiation, similar to most promising 2D structures, we found that a Li atom can strongly adsorb on a MoO2 sheet, and the lithiated MoO2 sheet presented excellent metallic properties. Note that, compared with most promising 2D structures, we unexpectedly revealed that the diffusion barrier of the Li atom on the MoO2 sheet was much lower and the storage capacity of the MoO2 sheet was much larger. The calcd. energy barrier for the diffusion of Li on the MoO2 sheet was only 75 meV, and, due to multilayer adsorption, the theor. capacity of the MoO2 sheet can reach up to 2513 mA h g-1 . Benefiting from general properties, such as strong Li-binding and excellent cond., and unique phenomena, such as ultrafast diffusion capacity and astonishing storage capacity, we highlight a new promising electrode material for the Li-ion battery.
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  27. 27
    Hazazi, O. A. Water Soluble Non-Toxic Organic Zinc Corrosion Inhibitors in Acidic Solution. Chem. Sci. Rev. Lett. 2015, 4, 965– 978
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    Water soluble non-toxic organic zinc corrosion inhibitors in acidic solution
    Hazazi, Omar A.
    Chemical Science Review and Letters (2015), 4 (16), 965-978CODEN: CSRLBV; ISSN:2278-6783. (Aufau Periodicals)
    The corrosion inhibition of Zn was investigated in acidic solns. using some polysorbate compds. (tweens) as environmentally safe corrosion inhibitors. The corrosion rate was calcd. in the absence and presence of the corrosion inhibitor using various techniques. The corrosion inhibition process was found to depend on the adsorption of the tween mols. on the metal surface as supported by their influence on the ethanol oxidn. at Pt electrode using cyclic voltammetric technique. Electrochem. measurements indicated that all the additives behave as mixed-type inhibitors. The corrosion inhibition efficiency was found to depend on the concn. of the tween and its structure.
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  28. 28
    Bawazeer, T. M.; Defrawy, A. M. E.; El-Shafei, A. A. Corrosion Inhibition of Zinc in Sodium Sulphate Solution Using Nonionic Surfactants of Tween Series: Experimental and Theoretical Study. Colloids Surf. A 2017, 520, 694– 700,  DOI: 10.1016/j.colsurfa.2017.02.025
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    28
    Corrosion inhibition of zinc in sodium sulphate solution using nonionic surfactants of tween series: Experimental and theoretical study
    Bawazeer, Tahani M.; El Defrawy, Ahmed M.; El-Shafei, A. A.
    Colloids and Surfaces, A: Physicochemical and Engineering Aspects (2017), 520 (), 694-700CODEN: CPEAEH; ISSN:0927-7757. (Elsevier B.V.)
    The effects of three tween compds. have been tested as corrosion inhibitors of a zinc surface in 0.1 M of sodium sulfate (Na2SO4) using potentiodynamic, potentiostatic transient in addn. to the Electrochem. Impedance Spectroscopy (EIS) method. The efficiency of the inhibitory effect of these additives was found to decrease in the order: Tween-60 > Tween-80 > Tween-20. These compds. were selected based on their active surface property and high mol. wt. as well as their soly. in aq. media. Cyclic voltammetry (CV) was used to evaluate their effect on the ethanol oxidn. The exptl. results were discussed and the correlation between the outcomes and inhibition properties towards Zn pitting corrosion was accomplished. Finally, quantum chem. descriptors of the tween derivs. that relate to their performance as regards corrosion inhibition efficiency have been detd. and found to be in good agreement with the exptl. results.
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  29. 29
    Wang, D.-Y.; Nie, B.-L.; Li, H.-J.; Zhang, W.-W.; Wu, Y.-C. Anticorrosion Performance of Grape Seed Proanthocyanidins Extract and Tween-80 for Mild Steel in Hydrochloric Acid Medium. J. Mol. Liq. 2021, 331, 115799  DOI: 10.1016/j.molliq.2021.115799
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    29
    Anticorrosion performance of grape seed proanthocyanidins extract and Tween-80 for mild steel in hydrochloric acid medium
    Wang, Dan-Yang; Nie, Bo-Li; Li, Hui-Jing; Zhang, Wei-Wei; Wu, Yan-Chao
    Journal of Molecular Liquids (2021), 331 (), 115799CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
    Grape seed proanthocyanidins ext. (GSPE) is extd. from grape seeds, the waste of the grape consumption, based on a three-level three-factor response surface methodol. (RSM). An eco-friendly corrosion inhibitor composed of GSPE and Tween-80 has been developed for mild steel in 1 M hydrochloric acid, whose inhibition performance is evaluated by using wt. loss test, electrochem. investigations, and surface morphol. anal. The mixt. of GSPE and Tween-80 mixt. improves the corrosion inhibition of mild steel compared to individual inhibitors (i.e., 96.48% vs. 77.68%/88.57%), reflecting a synergistic action between GSPE and Tween-80. Adsorption isotherm and kinetic parameters indicate that the adsorption follows Langmuir isotherm, and involves both physisorption and chemisorption. Potentiodynamic polarization (PDP) study shows that the GSPE-Tween-80 mixt. acts as a mixed type inhibitor and mainly inhibits the anodic process. Surface morphol. by scanning electron microscope (SEM), energy dispersive x-ray spectroscopy (EDX) and XPS help to confirm the presence of the GSPE-Tween-80 mixt. on the mild steel surface. Quantum chem. (QC) calcn. and mol. dynamics (MD) simulations studies further supported the exptl. results.
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  30. 30
    Li, Z.; Ganapathy, S.; Xu, Y.; Zhou, Z.; Sarilar, M.; Wagemaker, M. Mechanistic Insight into the Electrochemical Performance of Zn/VO2 Batteries with an Aqueous ZnSO4 Electrolyte. Adv. Energy Mater. 2019, 9, 1900237  DOI: 10.1002/aenm.201900237
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    Liu, X.; Yang, J.; Hou, W.; Wang, J.; Nuli, Y. Highly Reversible Lithium-ions Storage of Molybdenum Dioxide Nanoplates for High Power. ChemSusChem 2015, 8, 2621– 2624,  DOI: 10.1002/cssc.201500574
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    Highly Reversible Lithium-ions Storage of Molybdenum Dioxide Nanoplates for High Power Lithium-ion Batteries
    Liu, Xiaolin; Yang, Jun; Hou, Wenhua; Wang, Jiulin; Nuli, Yanna
    ChemSusChem (2015), 8 (16), 2621-2624CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Herein, MoO2 nanoplates were facilely prepd. through a hydrothermal process by using MoO3 microbelts as the intercalation host. The obtained MoO2 nanoplates manifest excellent electrochem. properties when the discharge cutoff voltage is simply set at 1.0 V to preclude the occurrence of conversion reactions. Its initial reversible capacity reaches 251 mAh/g, which is larger than that of Li4Ti5O12, at a current rate of 0.2 C. The av. capacity decay is only 0.0465 mAh/g per cycle, with a coulombic efficiency of 99.5% (from the 50th cycle onward) for 2000 cycles at 1 C. Also, this MoO2 electrode demonstrates an outstanding high power performance. When the current rate is increased from 0.2 to 50 C, ∼54% of the capacity is retained. The superior electrochem. performance can be attributed to the metallic cond. of MoO2, short Li+ diffusion distance in the nanoplates, and reversible cryst. phase conversion of the addn.-type reaction of MoO2. The prepd. MoO2 nanoplates may hopefully replace their currently used analogs, such as Li4Ti5O12, in high power lithium-ion batteries.
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    Kumar Sen, U.; Shaligram, A.; Mitra, S. Intercalation Anode Material for Lithium Ion Battery Based on Molybdenum Dioxide. ACS Appl. Mater. Interfaces 2014, 6, 14311– 14319,  DOI: 10.1021/am503605u
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    Intercalation Anode Material for Lithium Ion Battery Based on Molybdenum Dioxide
    Kumar Sen, Uttam; Shaligram, Apoorv; Mitra, Sagar
    ACS Applied Materials & Interfaces (2014), 6 (16), 14311-14319CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    MoO2 is one of the most studied anode systems in lithium ion batteries. Previously, the reaction of MoO2 with lithium via conversion reaction has been widely studied. The present study highlights the possible application of MoO2 as an intercalation-based anode material to improve the safety of lithium ion batteries. Nanobelts of MoO2 are prepd. by redn. of MoO3 nanobelts under hydrogen atm. The intercalation behavior of MoO2 is specially focused upon by limiting the charge-discharge cycling to narrow potential window of 1.0 to 2.2 V vs Li/Li+ to avoid conversion reaction. An excellent electrochem. stability over 200 cycles is achieved at a current rate of 100 mAh g-1. A phase transformation from monoclinic to orthorhombic to monoclinic is obsd. during the lithiation process, which is reversible during delithiation process and is confirmed by ex-situ XRD and electrochem. impedance spectroscopy. To further demonstrate the viability of MoO2 as a com. anode material, MoO2 is tested in a full-cell configuration against LiFePO4. The full-cell assembly is cycled for 100 cycles and stable performance is obsd. The combination showed an energy d. of 70 Wh kg-1 after 100 cycles.
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    Han, X.; Gerke, C. S.; Banerjee, S.; Zubair, M.; Jiang, J.; Bedford, N. M.; Miller, E. M.; Thoi, V. S. Strategic Design of MoO2 Nanoparticles Supported by Carbon Nanowires for Enhanced Electrocatalytic Nitrogen Reduction. ACS Energy Lett. 2020, 5, 3237– 3243,  DOI: 10.1021/acsenergylett.0c01857
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    Strategic Design of MoO2 Nanoparticles Supported by Carbon Nanowires for Enhanced Electrocatalytic Nitrogen Reduction
    Han, Xu; Gerke, Carter S.; Banerjee, Soumyodip; Zubair, Muhammad; Jiang, Junjie; Bedford, Nicholas M.; Miller, Elisa M.; Thoi, V. Sara
    ACS Energy Letters (2020), 5 (10), 3237-3243CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    Ammonia is an industrially relevant chem. that can be directly synthesized from water and air using renewable energy through the electrochem. nitrogen redn. reaction (NRR). However, because of the inert nature of nitrogen, current attempts at synthesizing ammonia under aq. conditions result in low selectivity and yield rates. The poor electrocatalytic performance is mainly attributed to competing hydrogen evolution, underexposed active sites, inadequate electrode contact, and poor stabilization/destabilization of key reaction intermediates. Herein, a catalyst is presented composed of MoO2 with surface vacancies dispersed over conductive carbon nanowires that mitigates these obstacles for NRR by providing a high surface area with stable catalytic sites and an underlying conductive support, where a variety of X-ray spectroscopy techniques are used to characterize the MoO2 catalyst. This uniquely engineered catalyst exhibits exceptional Faradaic efficiencies of > 30% and yields of 21.2μg h-1 mg-1 at a low potential of -0.1 V vs. RHE under ambient aq. conditions.
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    Luo, Z.; Miao, R.; Huan, T. D.; Mosa, I. M.; Poyraz, A. S.; Zhong, W.; Cloud, J. E.; Kriz, D. A.; Thanneeru, S.; He, J.; Zhang, Y.; Ramprasad, R.; Suib, S. L. Mesoporous MoO3–x Material as an Efficient Electrocatalyst for Hydrogen Evolution Reactions. Adv. Energy Mater. 2016, 6, 1600528  DOI: 10.1002/aenm.201600528
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    Li, J.; Ye, Y.; Ye, L.; Su, F.; Ma, Z.; Huang, J.; Xie, H.; Doronkin, D. E.; Zimina, A.; Grunwaldt, J. D.; Zhou, Y. Sunlight Induced Photo-Thermal Synergistic Catalytic CO2 Conversion: Via Localized Surface Plasmon Resonance of MoO3–x. J. Mater. Chem. A 2019, 7, 2821– 2830,  DOI: 10.1039/C8TA10922B
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    Sunlight induced photo-thermal synergistic catalytic CO2 conversion via localized surface plasmon resonance of MoO3-x
    Li, Jue; Ye, Yinghao; Ye, Liqun; Su, Fengyun; Ma, Zhaoyu; Huang, Jindi; Xie, Haiquan; Doronkin, Dmitry E.; Zimina, Anna; Grunwaldt, Jan-Dierk; Zhou, Ying
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (6), 2821-2830CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Photocatalytic conversion of CO2 to solar fuels is considered an alternative approach for simultaneously mitigating the greenhouse effect and solving energy shortage. The efficient light harvesting and the thermochem. conversion have been demanding quests in photocatalysis due to the relatively low solar energy utilization efficiency. In this work, oxygen vacancies are induced in MoO3 for improving photo-thermal CO2 redn. efficiency by capturing near-IR (NIR) photons. The localized surface plasmon resonance (LSPR) of MoO3-x triggered by oxygen vacancies enables the efficient capture of NIR photons. Addnl., oxygen vacancies can promote the carrier sepn., improve CO2 adsorption on the defective surface and lower the barrier of CO2 hydrogenation during the conversion process. As a result, MoO3-x displayed dramatically enhanced photo-thermal synergistic CO2 redn. under simulated sunlight (UV-Vis-IR) irradn. than MoO3. The amt. of CO produced by MoO3-x can reach 10.3 μmol g-1 h-1, which is 20 times higher than that of MoO3 (0.52 μmol g-1 h-1). And the CH4 prodn. of MoO3-x can reach 2.08 μmol g-1 h-1, which is 52 times higher than that of MoO3 (0.04 μmol g-1 h-1). In situ FT-IR and theor. calcns. also proved the enhanced activity of MoO3-x. This work highlights the significance of defect engineering for improving the photo-thermal catalytic conversion of CO2.
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    Kuwahara, Y.; Mihogi, T.; Hamahara, K.; Kusu, K.; Kobayashi, H.; Yamashita, H. A Quasi-Stable Molybdenum Sub-Oxide with Abundant Oxygen Vacancies That Promotes CO2 Hydrogenation to Methanol. Chem. Sci. 2021, 12, 9902– 9915,  DOI: 10.1039/D1SC02550C
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    36
    A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol
    Kuwahara, Yasutaka; Mihogi, Takashi; Hamahara, Koji; Kusu, Kazuki; Kobayashi, Hisayoshi; Yamashita, Hiromi
    Chemical Science (2021), 12 (29), 9902-9915CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    Prodn. of methanol from anthropogenic carbon dioxide (CO2) is a promising chem. process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, redn. of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/HxMoO3-y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat-1 h-1 in liq.-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200°C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Expts. and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance IR Fourier transform (DRIFT) spectroscopy and d. functional theory (DFT) calcns. reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable HxMoO3-y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissocn. sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the exptl. and computational studies, an oxygen-vacancy-mediated "reverse Mars-van Krevelen (M-vK)" mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion.
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    Kuwahara, Y.; Mihogi, T.; Hamahara, K.; Kusu, K.; Kobayashi, H.; Yamashita, H. A Quasi-Stable Molybdenum Sub-Oxide with Abundant Oxygen Vacancies That Promotes CO2 Hydrogenation to Methanol. Chem. Sci. 2021, 12, 9902– 9915,  DOI: 10.1039/D1SC02550C
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    37
    A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol
    Kuwahara, Yasutaka; Mihogi, Takashi; Hamahara, Koji; Kusu, Kazuki; Kobayashi, Hisayoshi; Yamashita, Hiromi
    Chemical Science (2021), 12 (29), 9902-9915CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    Prodn. of methanol from anthropogenic carbon dioxide (CO2) is a promising chem. process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, redn. of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/HxMoO3-y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat-1 h-1 in liq.-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200°C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Expts. and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance IR Fourier transform (DRIFT) spectroscopy and d. functional theory (DFT) calcns. reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable HxMoO3-y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissocn. sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the exptl. and computational studies, an oxygen-vacancy-mediated "reverse Mars-van Krevelen (M-vK)" mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion.
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  38. 38
    Thakur, P.; Cezar, J. C.; Brookes, N. B.; Choudhary, R. J.; Prakash, R.; Phase, D. M.; Chae, K. H.; Kumar, R. Direct Observation of Oxygen Induced Room Temperature Ferromagnetism in MoO2 Thin Films by X-Ray Magnetic Circular Dichroism Characterizations. Appl. Phys. Lett. 2009, 94, 062501  DOI: 10.1063/1.3080679
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    Direct observation of oxygen induced room temperature ferromagnetism in MoO2 thin films by x-ray magnetic circular dichroism characterizations
    Thakur, P.; Cezar, J. C.; Brookes, N. B.; Choudhary, R. J.; Prakash, Ram; Phase, D. M.; Chae, K. H.; Kumar, Ravi
    Applied Physics Letters (2009), 94 (6), 062501/1-062501/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
    We report the element specific polarized near edge x-ray absorption fine structure (NEXAFS) and x-ray magnetic CD (XMCD) expts. on well characterized undoped MoO2 thin films that show ferromagnetism at room temp. The polarization dependent of O K edge NEXAFS spectra indicate a strong hybridization of O 2p-4d Mo orbitals followed by a strong anisotropy in the electronic properties. An unquenched orbital magnetic moment within the O 2p shell is clearly evident from the XMCD O K edge, which is ferromagnetically coupled to the neighboring Mo moments as confirmed by Mo M3,2 edge XMCD expt. (c) 2009 American Institute of Physics.
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  39. 39
    Xie, K.; Ren, K.; Sun, C.; Yang, S.; Tong, M.; Yang, S.; Liu, Z.; Wang, Q. Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte Additive for Uniform Zinc Deposition. ACS Appl. Energy Mater. 2022, 5, 4170– 4178,  DOI: 10.1021/acsaem.1c03558
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    Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte Additive for Uniform Zinc Deposition
    Xie, Kaixuan; Ren, Kaixin; Sun, Chuang; Yang, Shuna; Tong, Minman; Yang, Shun; Liu, Zhifang; Wang, Qinghong
    ACS Applied Energy Materials (2022), 5 (4), 4170-4178CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Zn-ion batteries are re-evaluated as a potential choice to address the safety issue and cost concerns of current energy storage systems. Unfortunately, further application is severely hindered by low coulombic efficiency and poor cycle life, which are caused by the undesirable dendrite growth and side reactions on metal Zn anode. Herein, EDTA (EDTA) is employed as an electrolyte additive to solve the problem. The functional groups of EDTA adsorption layer on Zn foil results in refined grains by providing abundant nucleation sites for initial deposition and further induces uniform and flat Zn deposition without dendrites. Moreover, the chelation of EDTA with Zn2+ changes the coordination environment of hydrated Zn2+ and suppresses the side reactions. The smooth deposition of Zn endows the Zn anodes with super stability in both sym. cells and Zn-V2O5 full cells. This work provides a simple and feasible approach for solving anode issues in high-performance and safe Zn-ion batteries.
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    Li, T. C.; Lim, Y.; Li, X. L.; Luo, S.; Lin, C.; Fang, D.; Xia, S.; Wang, Y.; Yang, H. Y. A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage. Adv. Energy Mater. 2022, 12, 2103231  DOI: 10.1002/aenm.202103231
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    A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage
    Li, Tian Chen; Lim, YewVon; Li, Xue Liang; Luo, Songzhu; Lin, Congjian; Fang, Daliang; Xia, Sunwen; Wang, Ye; Yang, Hui Ying
    Advanced Energy Materials (2022), 12 (15), 2103231CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
    The benefits of Zn, despite many of its performance advantages (e.g., high theor. capacity and low redox potential), are compromised by severe side reactions and Zn dendrite growth in aq. electrolytes, due to the coordinated H2O within the Zn2+-solvation sheath and reactive free water in the bulk electrolyte. Unlike most efforts focused on costly super-concd. electrolytes and single additive species, a universal strategy is proposed to boost Zn reversibility in dil. electrolytes via adding carbonyl-contg. org. solvents. Based on exptl. investigations and multiscale simulations, the representative electrolyte with a N-methyl-2-pyrrolidone polar additive is proved to assist in structural reshaping of Zn2+-solvation and stabilizing the hydrogen bond network of water. This synergy is instrumental in contributing to suppressed water-induced parasitic reactions and dendrite formation, which enables high av. coulombic efficiency of 99.7% over 1000 cycles in an Zn/Cu asym. cell, and an ultralong cycling lifespan of 2000 cycles with 99.4% capacity retention in a Zn/VS2@SS full cell. Even with an elevated cathodic mass loading (up to 9.5 mg cm-2), the cycling stability is still maintained. The proposed strategy provides new insight into electrolyte additive design and sheds light on high-performance Zn-ion batteries.
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    Ben-Dor, L.; Shimony, Y. Crystal structure, magnetic susceptibility and electrical conductivity of pure and NiO-doped MoO2 and WO2. Mater. Res. Bull. 1974, 9, 837– 844,  DOI: 10.1016/0025-5408(74)90120-2
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    Crystal structure, magnetic susceptibility, and electrical conductivity of pure and nickel(II) oxide-doped molybdenum(IV) oxide and tungsten(IV) oxide
    Ben-Dor, L.; Shimony, Y.
    Materials Research Bulletin (1974), 9 (6), 837-44CODEN: MRBUAC; ISSN:0025-5408.
    Single crystals of MoO2 and WO2, pure and doped with NiO, were grown by chem. transport with I as the transporting agent. X-ray diffraction showed the crystals to be monoclinic. Doping up to 5% does not change the crystallog. consts. The pure crystals are weakly paramagnetic (χM < 100 × 10-6 emu), but doping raises the susceptibility markedly, to ∼2500 × 10-6 emu. These materials are metallic conductors, with room-temp. resistivities of ∼10-4-10-3 Ω-cm, decreasing by an order of magnitude at liq.-N temp. Doping substantially lowers the cond.
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    Kaiser, F.; Simon, P.; Burkhardt, U.; Kieback, B.; Grin, Y.; Veremchuk, I. Spark Plasma Sintering of Tungsten Oxides WOx (2.50 ≤ x ≤ 3): Phase Analysis and Thermoelectric Properties. Crystals 2017, 7, 271,  DOI: 10.3390/cryst7090271
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    Spark plasma sintering of tungsten oxides WOx (2.50 ≤ x ≤ 3): phase analysis and thermoelectric properties
    Kaiser, Felix; Simon, Paul; Burkhardt, Ulrich; Kieback, Bernd; Grin, Yuri; Veremchuk, Igor
    Crystals (2017), 7 (9), 271/1-271/14CODEN: CRYSBC; ISSN:2073-4352. (MDPI AG)
    The solid-state reaction of WO3 with W was studied in order to clarify the phase formation in the binary system W-O around the compn. WOx (2.50 ≤ x ≤ 3) during spark plasma sintering (SPS). A new phase "WO" is obsd. in the range 2.72 ≤ × ≤ 2.90 which might have the compn. W12O34. The influence of the compn. on the thermoelec. properties was investigated for 2.72 ≤ × ≤ 3. The Seebeck coeff., elec. cond. and electronic thermal cond. are continuously tunable with the oxygen-to-tungsten ratio. The phase formation mainly affects the lattice thermal cond. κlat which is significantly reduced until 700 K for the sample with the compn. × ≤ 2.84, which contains the phases W12O34 and "WO". In single-phase WO and multi-phase WOx materials (2.90 ≤ × ≤ 3), which contain crystallog. shear plane phases, a similar reduced κlat is obsd. only below 560 K and 550 K, resp. Therefore, the compn. range × < 2.90 in which the pentagonal column structural motif is formed might be more suitable for decreasing the lattice thermal cond. at high temps.
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    Horkans, J.; Shafer, M. W. An Investigation of the Electrochemistry of a Series of Metal Dioxides with Rutile-Type Structure MoO2, WO2, ReO2, RuO2, OsO2, and IrO2. J. Electrochem. Soc. 1977, 124, 1202,  DOI: 10.1149/1.2133528
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    An investigation of the electrochemistry of a series of metal dioxides with rutile-type structure: Molybdenum dioxide, tungsten dioxide, rhenium dioxide, osmium dioxide and iridium dioxide
    Horkans, Jean; Shafer, M. W.
    Journal of the Electrochemical Society (1977), 124 (8), 1202-7CODEN: JESOAN; ISSN:0013-4651.
    Six transition metal dioxides, MoO2, WO2, ReO2, RuO2, OsO2, and IrO2, were examd. as electrodes in H2SO4 soln. The oxides MoO2, WO2, ReO2, and RuO2 have broad current-potential profiles, indicating the formation of a surface layer which can exist over a range of compns. Steady-state measurements of O redn. showed catalytic activities which were low compared to common O catalysts such as Pt, but of the same order as other oxide catalysts. Activities were lowest for WO2 and ReO2, which form resistive surface layers of a higher oxide. The only material studied which was sufficienty stable to allow measurement of both O evolution and O redn. was RuO2. The current-potential profiles of OsO2 and IrO2 are characterized by distinct changes of oxidn. state. These oxides were not sufficiently stable to allow the measurement of O redn.
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    Ma, J.; Fu, J.; Niu, M.; Quhe, R. MoO2 and Graphene Heterostructure as Promising Flexible Anodes for Lithium-Ion Batteries. Carbon 2019, 147, 357– 363,  DOI: 10.1016/j.carbon.2019.03.006
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    MoO2 and graphene heterostructure as promising flexible anodes for lithium-ion batteries
    Ma, Jiachen; Fu, Jia; Niu, Mengqi; Quhe, Ruge
    Carbon (2019), 147 (), 357-363CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)
    Two-dimensional van der Waals heterostructures hold great promise to create lithium-ion batteries with large energy d., large power d., and long cycle life. In this work, we investigate the MoO2/graphene heterostructure as anodes for lithium-ion batteries by first principles calcns. It is found that the MoO2/graphene heterostructure possesses enhanced elec. cond., high theor. specific capacity (1411 mAh•g-1), and small diffusion barriers (77 meV). Meanwhile, the flexibility of graphene eliminates the irreversible deformation of MoO2 during the charge-discharge process. These characteristics render the MoO2/graphene heterostructure a stable and efficient Li ion storage performance.
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    De Melo, O.; González, Y.; Climent-Font, A.; Galán, P.; Ruediger, A.; Sánchez, M.; Calvo-Mola, C.; Santana, G.; Torres-Costa, V. Optical and Electrical Properties of MoO2 and MoO3 Thin Films Prepared from the Chemically Driven Isothermal Close Space Vapor Transport Technique. J. Phys.: Condens. Matter 2019, 31, 295703  DOI: 10.1088/1361-648X/ab18e2
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    Optical and electrical properties of MoO2 and MoO3 thin films prepared from the chemically driven isothermal close space vapor transport technique
    de Melo, O.; Gonzalez, Y.; Climent-Font, A.; Galan, P.; Ruediger, A.; Sanchez, M.; Calvo-Mola, C.; Santana, G.; Torres-Costa, V.
    Journal of Physics: Condensed Matter (2019), 31 (29), 295703CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
    Chem.-driven isothermal close space vapor transport was used to prep. pure MoO2 thin films which were eventually converted to MoO3 by annealing in air. According to temp.-dependent Raman measurements, the MoO2/MoO3 phase transformation occurs at 225-350° while no other phases were detected during the transition. A clear change in compn. as well as noticeable modifications of the band gap and the absorption coeff. confirmed the conversion from MoO2 to MoO3. An extensive characterization of these 2 pure phases was carried out. In particular, a procedure was developed to det. the dispersion relation of the refractive index of MoO2 from the shift of the interference fringes of the used SiO2/Si substrate. The obtained data of the refractive index was cor. taking into account the porosity of the samples calcd. from elastic backscattering spectrometry. The Debye temp. and the residual resistivity were extd. from the elec. resistivity temp. dependence using the Bloch-Gruneisen equation. MoO3 converted samples presented a very high resistivity and a typical semiconducting behavior. They also showed intense and broad luminescence spectra composed by several contributions whose temp. behavior was examd. Also, surface photovoltage spectra were taken and their relation with the luminescence is discussed.
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    Enneti, R. K.; Wolfe, T. A. Agglomeration during Reduction of MoO3. Int. J. Refract. Metals Hard. Mater. 2012, 31, 47– 50,  DOI: 10.1016/j.ijrmhm.2011.09.004
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    Agglomeration during reduction of MoO3
    Enneti, Ravi K.; Wolfe, Thomas A.
    International Journal of Refractory Metals & Hard Materials (2012), 31 (), 47-50CODEN: IRMME3; ISSN:0958-0611. (Elsevier Ltd.)
    Mo powder was manufd. in a two step process starting from MoO3. The first step redn. of MoO3 to MoO2 was carried out in rotary calciners. Agglomeration of powder occurs during this redn. stage resulting in several manufg. issues. The evolution of agglomeration during the redn. of MoO3 was investigated in the current study. As-received MoO3 and MoO3 milled for 0.5 h were used as the starting powders. The powders were reduced at 550, 650, and 750° in a hydrogen atm. The starting and reduced powders at various temps. were analyzed using BET surface area, XRD, and SEM techniques. The surface area of the reduced powders was monitored for quantifying the degree of agglomeration. The surface area was found to be min. for the samples reduced at 650°. SEM observations confirmed the agglomeration of powders during redn. process. XRD anal. showed complete redn. of MoO3 to MoO2 at 650 and 750°. The agglomeration of the powders was either due to melting of eutectic formed between MoO3 and Mo4O11 or due to partial melting of MoO3. The redn. of MoO3 is recommended to be completed at a low temp. to prevent agglomeration of the oxide powders.
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    Zhang, S.; Wang, G.; Jin, J.; Zhang, L.; Wen, Z.; Yang, J. Self-Catalyzed Decomposition of Discharge Products on the Oxygen Vacancy Sites of MoO3 Nanosheets for Low-Overpotential Li-O2 Batteries. Nano Energy 2017, 36, 186– 196,  DOI: 10.1016/j.nanoen.2017.04.038
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    Self-catalyzed decomposition of discharge products on the oxygen vacancy sites of MoO3 nanosheets for low-overpotential Li-O2 batteries
    Zhang, Sanpei; Wang, Gan; Jin, Jun; Zhang, Linlin; Wen, Zhaoyin; Yang, Jianhua
    Nano Energy (2017), 36 (), 186-196CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    The efficient reversible formation of discharge products for Li-O2 batteries is still challenging. Meanwhile, the question of the nature of the discharge products and their decompn. mechanism are still remain. Implanting oxygen vacancies on the metal oxides can create neg.-charge surface to provide strong adsorption of active oxygen and at the same time, the exposed metal sites can serve as an efficient substrate for decompd. reaction of discharge products. In this work, we apply the graphene-like MoO3 ultrathin nanosheets as a matrix. By controlling the redn. time, the MoO3 nanosheets with different concn. of oxygen vacancy are obtained. Exptl. results reveal that the MoO3 nanosheets with the high-concn. oxygen vacancies can significantly decrease the overpotential and get enhanced electrochem. response, namely, a low overpotential of ∼0.5 V can be delivered with ultra-stable cycles (over 60 cycles). Moreover, the Li-O2 batteries demonstrate an interesting four-step discharge and charge process. XPS, X-ray diffraction, transmission electron microscopy and electron energy-loss spectroscopy analyses are carried out for the four typical states of the cathode to reveal the reaction mechanism for the unique electrochem. behavior.
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    Du, W.; Yan, J.; Cao, C.; Li, C. C. Electrocrystallization Orientation Regulation of Zinc Metal Anodes: Strategies and Challenges. Energy Storage Mater. 2022, 52, 329– 354,  DOI: 10.1016/j.ensm.2022.07.046
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    Wu, Z.; Li, M.; Tian, Y.; Chen, H.; Zhang, S.-J.; Sun, C.; Li, C.; Kiefel, M.; Lai, C.; Lin, Z.; Zhang, S. Cyclohexanedodecol-Assisted Interfacial Engineering for Robust and High-Performance Zinc Metal Anode. Nano-Micro Lett. 2022, 14, 110,  DOI: 10.1007/s40820-022-00846-0
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    Cyclohexanedodecol-assisted interfacial engineering for robust and high-performance zinc metal anode
    Wu, Zhenzhen; Li, Meng; Tian, Yuhui; Chen, Hao; Zhang, Shao-Jian; Sun, Chuang; Li, Chengpeng; Kiefel, Milton; Lai, Chao; Lin, Zhan; Zhang, Shanqing
    Nano-Micro Letters (2022), 14 (), 110CODEN: NLAEBV; ISSN:2150-5551. (Nano-Micro Letters)
    Aq. zinc-ion batteries (AZIBs) can be one of the most promising electrochem. energy storage devices for being non-flammable, low-cost, and sustainable. However, the challenges of AZIBs, including dendrite growth, hydrogen evolution, corrosion, and passivation of zinc anode during charging and discharging processes, must be overcome to achieve high cycling performance and stability in practical applications. In this work, we utilize a dual-functional org. additive cyclohexanedodecol (CHD) to firstly establish [Zn(H2O)5(CHD)]2+ complex ion in an aq. Zn electrolyte and secondly build a robust protection layer on the Zn surface to overcome these dilemmas. Systematic expts. and theor. calcns. are carried out to interpret the working mechanism of CHD. At a very low concn. of 0.1 mg mL-1 CHD, long-term reversible Zn plating/stripping could be achieved up to 2200 h at 2 mA cm-2, 1000 h at 5 mA cm-2, and 650 h at 10 mA cm-2 at the fixed capacity of 1 mAh cm-2. When matched with V2O5 cathode, the resultant AZIBs full cell with the CHD-modified electrolyte presents a high capacity of 175 mAh g-1 with the capacity retention of 92% after 2000 cycles under 2 A g-1. Such a performance could enable the commercialization of AZIBs for applications in grid energy storage and industrial energy storage.
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    He, X.; Bresser, D.; Passerini, S.; Baakes, F.; Krewer, U.; Lopez, J.; Mallia, C. T.; Shao-Horn, Y.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Soto, F. A.; Ponce, V.; Seminario, J. M.; Balbuena, P. B.; Jia, H.; Xu, W.; Xu, Y.; Wang, C.; Horstmann, B.; Amine, R.; Su, C.-C.; Shi, J.; Amine, K.; Winter, M.; Latz, A.; Kostecki, R. The Passivity of Lithium Electrodes in Liquid Electrolytes for Secondary Batteries. Nat. Rev. Mater. 2021, 6, 1036– 1052,  DOI: 10.1038/s41578-021-00345-5
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    The passivity of lithium electrodes in liquid electrolytes for secondary batteries
    He, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, Robert
    Nature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)
    Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
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    Wang, X.; Meng, J.; Lin, X.; Yang, Y.; Zhou, S.; Wang, Y.; Pan, A. Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings. Adv. Funct. Mater. 2021, 31, 2106114  DOI: 10.1002/adfm.202106114
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    Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings
    Wang, Xia; Meng, Junping; Lin, Xuguang; Yang, Yadi; Zhou, Shuang; Wang, Yaping; Pan, Anqiang
    Advanced Functional Materials (2021), 31 (48), 2106114CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The uneven electrodeposition and inferior corrosion resistance are the fundamental obstacles to achieve stable Zn metal anodes. The features of the electrode surface/interface are closely correlated with the properties. Herein, the Zn surface with more exposed (002)Zn planes is modified through a simple acid-etching approach. The in situ generated zinc compds. form an interface layer with strong adhesion to the Zn electrode, which can enhance the Zn2+ ion kinetics and regulate the deposition/dissoln. behaviors. A variety of acids with functional cations are selected, among which the phosphoric acid etches the Zn with a higher extent of texturing and generates a more compact layer. The obtained zinc phosphate@Zn electrode enables stable cycling and fast kinetics in sym. and full Zn metal batteries. This study provides a new example of combined surface and interface modification toward high-performance aq. zinc metal anodes.
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    Rana, A.; Thakare, A.; Kumar, N.; Mukherjee, B.; Torris, A.; Das, B.; Ogale, S.; Banerjee, A. Mitigating Dendrite Formation on a Zn Electrode in Aqueous Zinc Chloride by the Competitive Surface Chemistry of an Imidazole Additive. ACS Appl. Mater. Interfaces 2023, 15, 23093– 23103,  DOI: 10.1021/acsami.3c01310
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    Mitigating dendrite formation on a Zn electrode in aqueous zinc chloride by the competitive surface chemistry of an imidazole additive
    Rana, Ashutosh; Thakare, Anup; Kumar, Nikhil; Mukherjee, Buddhadev; Torris, Arun; Das, Bidisa; Ogale, Satishchandra; Banerjee, Abhik
    ACS Applied Materials & Interfaces (2023), 15 (19), 23093-23103CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Electrochem. energy storage systems are crit. in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technol., since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a redn. potential of -0.76 V vs SHE) has a significantly higher theor. volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via exptl. (kinetics and imaging) and theor. d. functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concn. of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addn. of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-sym. cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomog. reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn sym. cells. It is obsd. that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the prodn. of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calcns. conform well with the stated exptl. observations.
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    Mitha, A.; Yazdi, A. Z.; Ahmed, M.; Chen, P. Surface Adsorption of Polyethylene Glycol to Suppress Dendrite Formation on Zinc Anodes in Rechargeable Aqueous Batteries. ChemElectroChem. 2018, 5, 2409– 2418,  DOI: 10.1002/celc.201800572
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    53
    Surface Adsorption of Polyethylene Glycol to Suppress Dendrite Formation on Zinc Anodes in Rechargeable Aqueous Batteries
    Mitha, Aly; Yazdi, Alireza Z.; Ahmed, Moin; Chen, Pu
    ChemElectroChem (2018), 5 (17), 2409-2418CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Aq. metal batteries routinely suffer from the dendritic growth at the anode, leading to significant capacity fading and ultimately, battery failure from short-circuit. Herein, we utilize polyethylene glycol to regulate dendrite growth and improve the long-term cycling stability of an aq. rechargeable lithium/zinc battery. PEG200 in the electrolyte decreases the corrosion and chronoamperometric current densities of the zinc electrode up to four-fold. Batteries with pre-grown dendrites also perform significantly better when PEG is present in the electrolyte (41.4 mAh g-1 vs. 7.9 mAh g-1 after 1000 cycles). X-ray diffraction and electron microscopy studies show that dendrites in the PEG-contg. electrolyte have been inhibited, leading to much smaller/smoother surface features than those of the control. The facile prepn. process of the aq. electrolyte combined with low cost and vast performance improvement in batteries of all sizes indicates high upscaling viability.
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    Jian, Q.; Wan, Y.; Lin, Y.; Ni, M.; Wu, M.; Zhao, T. A Highly Reversible Zinc Anode for Rechargeable Aqueous Batteries. ACS Appl. Mater. Interfaces 2021, 13, 52659– 52669,  DOI: 10.1021/acsami.1c15628
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    A Highly Reversible Zinc Anode for Rechargeable Aqueous Batteries
    Jian, Qinping; Wan, Yuhan; Lin, Yanke; Ni, Meng; Wu, Maochun; Zhao, Tianshou
    ACS Applied Materials & Interfaces (2021), 13 (44), 52659-52669CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Zinc metal holds a great potential as an anode material for next-generation aq. batteries due to its suitable redox potential, high specific capacity, and low cost. However, the uncontrollable dendrite growth and detrimental side reactions with electrolytes hinder the practical application of this type of electrodes. To tackle the issues, an ultrathin (~ 1μm) sulfonated poly(ether ether ketone) (SPEEK) solid-electrolyte interphase (SEI) is constructed onto the Zn anode surface by a facile spin-coating method. We demonstrate that the polymeric SEI simultaneously blocks the water mols. and anions, uniformizes the ion flux, and facilitates the desolvation process of Zn2+ ions, thus effectively suppressing the side reactions and Zn dendrite formation. As a result, the newly developed Zn@SPEEK anode enables a sym. cell to stably operate over 1000 cycles at 5 mA cm-2 without degrdn. Moreover, with the Zn anode paired with a MnO2 cathode, the full cell exhibits an improved Coulombic efficiency (over 99% at 0.1 A g-1), a superior rate capability (127 mA h g-1 at 2 A g-1), and excellent cycling stability (capacity retention of 70% over 1000 cycles at 1 A g-1). This work provides a facile yet effective strategy to address the crit. challenges in Zn anodes, paving the way for the development of high-performance rechargeable aq. batteries.
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    Shi, W.; Song, Z.; Wang, J.; Li, Q.; An, Q. Phytic Acid Conversion Film Interfacial Engineering for Stabilizing Zinc Metal Anode. Chem. Eng. J. 2022, 446, 137295  DOI: 10.1016/j.cej.2022.137295
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    Phytic acid conversion film interfacial engineering for stabilizing zinc metal anode
    Shi, Wenchao; Song, Zhenjun; Wang, Junjun; Li, Qi; An, Qinyou
    Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 446 (Part_4), 137295CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Due to the high safety and low cost, aq. zinc ion batteries (ZIBs) have attracted more and more attention and are expected to become the next generation energy storage system. However, the cycle lifespan of ZIBs is limited due to the issues of zinc (Zn) dendrites and side reactions, which seriously hinders their further development. Herein, a simple interfacial engineering strategy was designed in which a layer of dense phytic acid (PA) conversion film was constructed on the surface of Zn metal (Zn@PA). The film can inhibit the direct contact between Zn metal and electrolyte, reducing side reactions. Moreover, it can effectively regulate the Zn ions deposition behavior to realize the compact Zn deposition owing to its strong adsorption and extremely low barrier migration of Zn ions, thus significantly extending the cycle lifespan of Zn anode. As proof, the assembled Zn@PA sym. cell exhibited a long-cycle lifespan of 3900 h at a c.d. of 1 mA cm-2. In addn., the Zn@PA-MnO2 full cell showed no capacity decay during 500 cycles at a c.d. of 1 A g-1. Most importantly, it can retain a high discharge specific capacity of 110.6 mAh g-1 after 30,000 cycles at a high c.d. of 5 A g-1. The remarkable effects of the strategy show its application prospect in high-rate and long-life ZIBs.
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    Zhu, J.; Deng, W.; Yang, N.; Xu, X.; Huang, C.; Zhou, Y.; Zhang, M.; Yuan, X.; Hu, J.; Li, C.; Li, R. Biomolecular Regulation of Zinc Deposition to Achieve Ultra-Long Life and High-Rate Zn Metal Anodes. Small 2022, 18, 2202509  DOI: 10.1002/smll.202202509
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    Biomolecular Regulation of Zinc Deposition to Achieve Ultra-Long Life and High-Rate Zn Metal Anodes
    Zhu, Jinlin; Deng, Wenjun; Yang, Na; Xu, Xianqi; Huang, Chao; Zhou, Yi; Zhang, Man; Yuan, Xinran; Hu, Jun; Li, Chang; Li, Rui
    Small (2022), 18 (29), 2202509CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Aq. zinc-ion batteries (ZIBs) have been extensively studied due to their inherent safety and high energy d. for large-scale energy storage. However, the practical application is significantly limited by the growing Zn dendrites on metallic Zn anode during cycling. Herein, an environmental biomol. electrolyte additive, fibroin (FI), is proposed to guide the homogeneous Zn deposition and stabilize Zn anode. This work demonstrates that the FI mols. with abundant electron-rich groups (NH, OH, and CO) can anchor on Zn anode surface to provide more nucleation sites and suppress the side reactions, and the strong interaction with water mols. can simultaneously regulate the Zn2+ coordination environment facilitating the uniform deposition of Zn. As a consequence, only 0.5 wt% FI additive enables a highly reversible Zn plating/stripping over 4000 h at 1 mA cm-2, indicating a sufficient advance in performance over state-of-the-art Zn anodes. Furthermore, when applied to a full battery (NaVO/Zn), the cell exhibits excellent capacity retention of 98.4% after 1000 cycles as well as high Coulombic efficiency of 99%, whereas the cell only operates for 68 cycles without FI additive. This work offers a non-toxic, low-cost, effective additive strategy to solve dendrites problems and achieve long-life and high-performance rechargeable aq. ZIBs.
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    Su, T.-T.; Wang, K.; Shao, C.-Y.; Le, J.-B.; Ren, W.-F.; Sun, R.-C. Surface Control Behavior toward Crystal Regulation and Anticorrosion Capacity for Zinc Metal Anodes. ACS Appl. Mater. Interfaces 2023, 15, 20040– 20052,  DOI: 10.1021/acsami.2c22477
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    Surface Control Behavior toward Crystal Regulation and Anticorrosion Capacity for Zinc Metal Anodes
    Su, Ting-Ting; Wang, Ke; Shao, Chang-You; Le, Jia-Bo; Ren, Wen-Feng; Sun, Run-Cang
    ACS Applied Materials & Interfaces (2023), 15 (16), 20040-20052CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    The com. application of high-safety aq. zinc (Zn) secondary batteries is hindered by the poor cycling life of Zn metal anodes. Here we propose a dendrite growth and hydrogen evolution corrosion reaction mechanism from the binding energy of the deposited crystal plane on the Zn surface and the adsorption energy of H2O mols. on different crystal planes as well as the binding energy of H2O mols. with Zn2+ ions. The biomass-based alkyl polyglucoside (APG) surfactant is adopted as an electrolyte additive of 0.15% to regulate the preferential growth of a parallel Zn(002) plane and enhance the anticorrosion ability of Zn metal anodes. The robust binding and adsorption energies of APG with Zn2+ ions in the aq. electrolyte and the Zn(002) plane on Zn surface generate a synergistic effect to increase the concn. of Zn2+ ions on the APG-adsorbed Zn(002) plane, endowing the continuous growth of the preferential parallel Zn(002) plane and the excellent anticorrosion capacity. Accordingly, the long-term cycle stability of 4000 h can be achieved for Zn anodes with APG additives, which is better than that with pure ZnSO4 electrolyte. With the addn. of APG in the anolyte electrolyte, Zn-I2 full cells display excellent cycling performance (70 mAh g-1 after 20000 cycles) as compared with that without APG additives.
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    Zhu, Y.; Free, M. L.; Woollam, R.; Durnie, W. A Review of Surfactants as Corrosion Inhibitors and Associated Modeling. Prog. Mater. Sci. 2017, 90, 159– 223,  DOI: 10.1016/j.pmatsci.2017.07.006
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    A review of surfactants as corrosion inhibitors and associated modeling
    Zhu, Yakun; Free, Michael L.; Woollam, Richard; Durnie, William
    Progress in Materials Science (2017), 90 (), 159-223CODEN: PRMSAQ; ISSN:0079-6425. (Elsevier Ltd.)
    Surfactants have been commonly used as corrosion inhibitors for the protection of metallic materials against corrosion. The amphiphilic nature of surfactant mols. creates an affinity for adsorption at interfaces such as metal/metal oxide-water interface. The adsorption of surfactant on metals and metal oxides creates a barrier that can inhibit corrosion. The properties of surfactant and the interaction of surfactant with metal or metal oxide and the surrounding soln. environments det. the level of adsorption and corrosion inhibition. Understanding and modeling the behavior of surfactants in corrosive environments is crit. to optimal utilization of surfactants as corrosion inhibitors. This review of surfactants as corrosion inhibitors is designed to provide systemic evaluation of various phys. and chem. properties of surfactants, surfactant behaviors in corrosive environments, and their influence in corrosion inhibition, which can be used to improve the effectiveness with which surfactants are used as corrosion inhibitors in a variety of environments. Progress in the development of various predictive models, including semi-empirical models, mechanistic models, and multiphysics models, are reviewed for the evaluation and prediction of surfactant properties and surfactant corrosion inhibition efficiency. Applications of these models to exptl. design and anal., surfactant design and selection, and lifetime prediction are also discussed.
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    Dong, N.; Zhao, X.; Yan, M.; Li, H.; Pan, H. Synergetic Control of Hydrogen Evolution and Ion-Transport Kinetics Enabling Zn Anodes with High-Areal-Capacity. Nano Energy 2022, 104, 107903  DOI: 10.1016/j.nanoen.2022.107903
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    Synergetic control of hydrogen evolution and ion-transport kinetics enabling Zn anodes with high-areal-capacity
    Dong, Ning; Zhao, Xuesong; Yan, Mengdie; Li, Hong; Pan, Huilin
    Nano Energy (2022), 104 (Part_A), 107903CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    Intrinsic uneven Zn deposition-dissoln. and hydrogen evolution reaction (HER) induce poor reversibility and limited cycle life of Zn anodes, which thus restrict the practical application of rechargeable aq. Zn batteries. In this work, a synergistic strategy of porous indium (In) coating layer combined with a polyacrylamide (PAM) polymer layer for Zn anodes is proposed to provide large HER overpotential while facilitating fast and homogeneous Zn2+ transport at the electrode-electrolyte interface. The corrosion reaction and Zn dendrite growth are simultaneously prevented at high utilization of Zn anodes. The optimal ZnIn-PAM electrodes demonstrate outstanding cycling stability at ultra-high c.d. and areal capacity (10 mA cm-2, 10 mAh cm-2, Zn utilization: 57%) for over 400 h, and long-term lifespan for over 1700 h at 5 mA cm-2 and 5 mAh cm-2 (Zn utilization: 28.5%) with only ∼50 mV overpotential. Coupled with electrolytic manganese dioxide cathode, the full cell delivers ultra-long lifespan of 10000 cycles with capacity decay rate of 0.006% per cycle at 5 C. This work provides useful perspective for exploring synergetic strategies to address the limited cycling stability of Zn metal-based aq. batteries for practical use.
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    Zhou, W.; Chen, M.; Tian, Q.; Chen, J.; Xu, Z.; Wong, C.-P. Cotton-Derived Cellulose Film as a Dendrite-Inhibiting Separator to Stabilize the Zinc Metal Anode of Aqueous Zinc Ion Batteries. Energy Storage Mater. 2022, 44, 57– 65,  DOI: 10.1016/j.ensm.2021.10.002
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    Zhang, Y.; Chen, P.; Li, M.; Li, S.; Yue, Y.; Wang, Y.; Xie, S.; Zhou, W. Highly Reversible, Dendrite-Free and Low-Polarization Zn Metal Anodes Enabled by a Thin SnO2 Layer for Aqueous Zn-Ion Batteries. J. Mater. Chem. A 2023, 11, 14333– 14344,  DOI: 10.1039/D3TA01415K
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    Highly reversible, dendrite-free and low-polarization Zn metal anodes enabled by a thin SnO2 layer for aqueous Zn-ion batteries
    Zhang, Yuejuan; Chen, Penghui; Li, Mingming; Li, Shaoqing; Yue, Ying; Wang, Yanchun; Xie, Sishen; Zhou, Weiya
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2023), 11 (26), 14333-14344CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Aq. Zn-ion batteries (AZIBs) are attractive for next-generation renewable and secure energy storage systems due to their high safety and low cost. However, dendrite growth and side reactions of Zn metal anodes severely limit their practical applications. Moreover, polarization is an important but easily overlooked factor hampering the development of AZIBs. Herein, a zincophilic, hydrophilic, and thin (∼100 nm) SnO2 protective layer is reported to remodel the Zn anode/electrolyte interface via a simple spin-coating approach. The SnO2 layer effectively inhibits the growth of the dendrites, which prolongs the lifetime of Zn anodes to 3900 h. It also alleviates the side reactions and endows Zn‖Cu cells with a high Coulombic efficiency of 99.3% over 2000 cycles. Meanwhile, the SnO2 layer presents fast Zn deposition kinetics to ensure reversible Zn anodes at high current/capacity by decreasing electrochem. polarization and concn. polarization. Consequently, SnO2/Zn anodes exhibit a high cumulative capacity of 4.5 A h cm-2 at an ultrahigh current of 30 mA cm-2 with a low overpotential of 90 mV and even 3.2 A h cm-2 at a high capacity of 4 mA h cm-2 and high current of 8 mA cm-2. Prototype SnO2/Zn‖δ-MnO2 full cells also obtain higher capacities and capacity retention (96.9% after 500 cycles at 2C) than bare Zn. This work offers new insights for ensuring the reversibility and durability of Zn anodes with low polarization at high current/capacity and provides a promising way to promote the practical application of AZIBs.
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    Wang, T.; Xi, Q.; Li, Y.; Fu, H.; Hua, Y.; Shankar, E. G.; Kakarla, A. K.; Yu, J. S. Regulating Dendrite-Free Zinc Deposition by Red Phosphorous-Derived Artificial Protective Layer for Zinc Metal Batteries. Adv. Sci. 2022, 9, 2200155  DOI: 10.1002/advs.202200155
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    Regulating Dendrite-Free Zinc Deposition by Red Phosphorous-Derived Artificial Protective Layer for Zinc Metal Batteries
    Wang, Tian; Xi, Qiao; Li, Yifan; Fu, Hao; Hua, Yongbin; Shankar, Edugulla Girija; Kakarla, Ashok Kumar; Yu, Jae Su
    Advanced Science (Weinheim, Germany) (2022), 9 (18), 2200155CODEN: ASDCCF; ISSN:2198-3844. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Rational architecture design of the artificial protective layer on the zinc (Zn) anode surface is a promising strategy to achieve uniform Zn deposition and inhibit the uncontrolled growth of Zn dendrites. Herein, a red phosphorous-derived artificial protective layer combined with a conductive N-doped carbon framework is designed to achieve dendrite-free Zn deposition. The Zn-phosphorus (ZnP) solid soln. alloy artificial protective layer is formed during Zn plating. Meanwhile, the dynamic evolution mechanism of the ZnP on the Zn anode is successfully revealed. The concn. gradient of the electrolyte on the electrode surface can be redistributed by this protective layer, thereby achieving a uniform Zn-ion flux. The fabricated Zn sym. battery delivers a dendrite-free plating/stripping for 1100 h at the c.d. of 2.0 mA cm-2. Furthermore, aq. Zn//MnO2 full cell exhibits a reversible capacity of 200 mAh g-1 after 350 cycles at 1.0 A g-1. This study suggests an effective soln. for the suppression of Zn dendrites in Zn metal batteries, which is expected to provide a deep insight into the design of high-performance rechargeable aq. Zn-ion batteries.
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    Wang, M.; Wu, X.; Yang, D.; Zhao, H.; He, L.; Su, J.; Zhang, X.; Yin, X.; Zhao, K.; Wang, Y.; Wei, Y. A Colloidal Aqueous Electrolyte Modulated by Oleic Acid for Durable Zinc Metal Anode. Chem. Eng. J. 2023, 451, 138589  DOI: 10.1016/j.cej.2022.138589
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    A colloidal aqueous electrolyte modulated by oleic acid for durable zinc metal anode
    Wang, Meiling; Wu, Xiaoyu; Yang, Di; Zhao, Hainan; He, Li; Su, Jiaran; Zhang, Xu; Yin, Xiuxiu; Zhao, Kangning; Wang, Yizhan; Wei, Yingjin
    Chemical Engineering Journal (Amsterdam, Netherlands) (2023), 451 (Part_1), 138589CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Continuous dendrites growth, as well as corrosion and side reactions of Zn metal anode seriously hinder the development of aq. zinc ion batteries. To address these issues, oleic acid (OA) is dispersed into a 2 M ZnSO4 soln. to form a novel colloidal Zn-ion electrolyte. The non-sol. OA surfactant doesn't coordinate with Zn2+ and the water solvent. Instead, it works as a "temporary electrolyte additive" during initial stage of battery processing. After, the OA additive is bonded to Zn metal forming an OA adsorption layer on the anode surface. This hydrophobic OA adsorption layer can not only regulate Zn deposition with parallel orientation of the Zn (002) plane to the Zn foil substrate leading to a flat Zn metal anode, but also isolate direct contact of water with Zn thus inhibiting the harmful side reactions on the Zn anode. Consequently, this colloidal electrolyte enables highly reversible Zn deposition with Coulombic efficiency of 99.63% and cycle life over 3340 cycles. This strategy of in-situ facet engineering and interface modification of Zn metal anode using colloidal electrolyte presents a new perspective toward design of high-performance aq. zinc ion batteries.
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    Cao, Z.; Zhuang, P.; Zhang, X.; Ye, M.; Shen, J.; Ajayan, P. M. Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc Ion Batteries. Adv. Energy Mater. 2020, 10, 2001599  DOI: 10.1002/aenm.202001599
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    Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc Ion Batteries
    Cao, Ziyi; Zhuang, Peiyuan; Zhang, Xiang; Ye, Mingxin; Shen, Jianfeng; Ajayan, Pulickel M.
    Advanced Energy Materials (2020), 10 (30), 2001599CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
    A review. Ongoing interest is focused on aq. zinc ion batteries (ZIBs) for mass-prodn. energy storage systems as a result of their affordability, safety, and high energy d. Ensuring the stability of the electrode/electrolyte interface is of particular importance for prolonging the cycling ability to meet the practical requirements of rechargeable batteries. Zinc anodes exhibit poor cycle life and low coulombic efficiency, stemming from the severe dendrite growth, and irreversible byproducts such as H2 and inactive ZnO. Great efforts have recently been devoted to zinc anode protection for designing high-performance ZIBs. However, the intrinsic origins of zinc plating/striping are poorly understood, which greatly delay its potential applications. Rather than focusing on battery metrics, this review delves deeply into the underlying science that triggers the deposition/dissoln. of zinc ions. Furthermore, recent advances in modulating the zinc coordination environment, uniforming interfacial elec. fields, and inducing zinc deposition are highlighted and summarized. Finally, perspectives and suggestions are provided for designing highly stable zinc anodes for the industrialization of the aq. rechargeable ZIBs in the near future.
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    Li, X. H.; Deng, S. D.; Fu, H.; Mu, G. N. Inhibition Action of Tween-80 on the Corrosion of Cold Rolled Steel in Sulfuric Acid. Mater. Corros. 2009, 60, 969– 976,  DOI: 10.1002/maco.200905217
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    Inhibition action of Tween-80 on the corrosion of cold rolled steel in sulfuric acid
    Li, X. H.; Deng, S. D.; Fu, H.; Mu, G. N.
    Materials and Corrosion (2009), 60 (12), 969-976CODEN: MTCREQ; ISSN:0947-5117. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The inhibition action of a nonionic surfactant of tween-80 on the corrosion of cold rolled steel (CRS) in sulfuric acid (H2SO4) has been investigated by wt. loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the CRS surface conditions. The results show that tween-80 is a good inhibitor in 1.0 M H2SO4, and its adsorption obeys Langmuir adsorption isotherm. Effects of temp. (20-50 °C) and acid concn. (0.5-7.0 M) on the inhibition action were investigated. Polarization curves show that tween-80 is a mixed-type inhibitor in sulfuric acid, but prominently inhibits the cathodic reaction. The results obtained from wt. loss and potentiodynamic polarization are consistent, and the inhibition action could also be evidenced by AFM images.
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    Shin, S.; Yoon, J.; Kim, E.; Yoon, W.-S.; Shin, H. High Capacity and Reversibility of Oxygen-Vacancy-Controlled MoO3 on Cu in Li-Ion Batteries: Unveiling Storage Mechanism in Binder-Free MoO3–x Anodes. Energy Technol. 2020, 8, 1901502  DOI: 10.1002/ente.201901502
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    High Capacity and Reversibility of Oxygen-Vacancy-Controlled MoO3 on Cu in Li-Ion Batteries: Unveiling Storage Mechanism in Binder-Free MoO3-x Anodes
    Shin, Sooeun; Yoon, Jaesang; Kim, Eunsoo; Yoon, Won-Sub; Shin, Hyunjung
    Energy Technology (Weinheim, Germany) (2020), 8 (6), 1901502CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)
    MoO3 has great potential as an electrode for lithium-ion batteries due to its unique layered structure that can host Li+. Despite high theor. capacity (≈1117 mAh g-1), MoO3 is not widely used simply because of poor rate capability due to lower electronic cond. and severe pulverization. The Li-storage mechanism in MoO3 is also still unclear. Herein, oxygen-vacancy-controlled MoO3 is used without any addnl. binders and conductive materials to directly examine the Li-storage mechanism on MoO3-x. Li-storage capacity based on the reversible formation/decompn. of solid-electrolyte interphase (SEI) films and the transformation of MoO3-x to amorphous Li2MoO3 is demonstrated. The surfaces of MoO3-x are conjugated with Cu2O nanoparticles via annealing at 200°C. Cu2O acts as an effective catalyst for the formation of SEI films and the reversible reaction of MoO3-x with Li+ ions. As a result, Cu2OoO3-x exhibits a charge capacity of 1100 mAh g-1 after the second cycle and maintains a high reversible capacity, whereas MoO3-x exhibits a charge capacity of 900 mAh g-1 and fades to 590 mAh g-1 after 100 cycles at 1 A g-1.
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    Wang, S.; Lu, S.; Yang, X.; Liu, X. Pseudocapacitive MoOx Anode Material with Super-High Rate and Ultra-Long Cycle Properties for Aqueous Zinc Ion Batteries. J. Electroanal. Chem. 2021, 882, 115033  DOI: 10.1016/j.jelechem.2021.115033
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    Pseudocapacitive MoOx anode material with super-high rate and ultra-long cycle properties for aqueous zinc ion batteries
    Wang, Sai; Lu, Shaowei; Yang, Xu; Liu, Xingmin
    Journal of Electroanalytical Chemistry (2021), 882 (), 115033CODEN: JECHES; ISSN:1873-2569. (Elsevier B.V.)
    Aq. Zn-ion batteries (AZIBs) are widely concerned and considered as promising candidates for grid-scale energy storage systems due to the simple and feasible prepn. process together with the demonstrated electrochem. properties, but it is still a tremendous challenge to develop new-type anode materials which can effectively overcome the Zn dendrites formation and low use efficiency of the typical Zn metal anodes, not to mention the ones with outstanding rate and cycle properties. Herein, for the 1st time, monoclinic MoOx is verified to be a novel and promising pseudocapacitive anode material for aq. Zn-ion batteries and the MoOx shows excellent Zn ion storage abilities-esp. at 10 A g-1, including ideal av. potential of 0.53 V (vs. Zn2+/Zn), high discharge/charge capacities of 82.5/82.0 mAh g-1 and cycling life of 30,000 cycles. Further, Zn ion storage mechanism of the as proposed monoclinic MoOx is also studied and deduced to be: MoOx + yZn2++2ye-.dblharw. ZnyMoOx.
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    Photovoltaics are an important source of renewable energy, but due to the intermittent nature of insolation, solar cells usually need to be connected to rechargeable batteries, electrochem. capacitors or other energy storage devices, which adds to the complexity and cost of these systems. In this work, a cathode design for photo-rechargeable zinc-ion batteries (photo-ZIBs) is reported, that is inherently capable of harvesting sunlight to recharge without the need for external solar cells. The proposed photocathodes, comprising a composite of vanadium dioxide nanorods and reduced graphene oxide, are engineered to provide the necessary charge sepn. and storage for photocharging under illumination. The photo-ZIBs achieve capacities of ≈282 mAh g-1 in the dark and ≈315 mAh -1 under illumination, at 200 mA g-1, demonstrating the use of light not only to charge the devices, but addnl. to enhance their capacity. The photo-ZIBs also demonstrate enhanced high-rate capabilities under illumination, as well as a capacity retention of ≈90% over 1000 cycles. The proposed photo-ZIBs are considered a promising new technol. for addressing energy poverty, due to their high performance and inherent cost-efficiency and safety.
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    Long-life and low-polarization Zn metal anodes enabled by a covalent triazine framework coating
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This article is cited by 5 publications.

  1. Hyun-Woo Kim, Eunyoung Cho, Myung-Jun Kwak, Jeongin Lee, Hosik Lee, Chihyun Hwang, Hyun-Kon Song. Porphyrinic N 4 channels of zinc ions for the electrochemical reversibility of zinc plating/stripping. Materials Horizons 2025, 3 https://doi.org/10.1039/D4MH01088D
  2. Xueqing Hu, Bastola Narayan, Nibagani Naresh, Iman Pinnock, Yijia Zhu, Xiaopeng Liu, Tianlei Wang, Bing Li, Ivan P. Parkin, Buddha Deka Boruah. Ferroelectric Interfaces for Dendrite Prevention in Zinc‐Ion Batteries. Small 2024, 20 (49) https://doi.org/10.1002/smll.202403555
  3. Mengjuan Chen, Yimeng Cui, Wenfeng Liu, Zhenpu Shi, Hongyu Dong, Hongyun Yue, Zhaoxia Cao, Zhansheng Lu, Shuting Yang, Yanhong Yin. Ti 4 O 7 coating creates a highly stable Zn anode for aqueous zinc-ion batteries. Inorganic Chemistry Frontiers 2024, 11 (15) , 4748-4756. https://doi.org/10.1039/D4QI00808A
  4. Liansheng Li, Chun Chen, Pengyu Meng, Yijie Zhang, Qinghua Liang. A Water‐Insoluble Yttrium‐Based Complex as Dual‐Ionic Electrolyte Additive for Stable Aqueous Zinc Metal Batteries. Advanced Functional Materials 2024, 17 https://doi.org/10.1002/adfm.202406965
  5. Songhe Zheng, Jianping Chen, Ting Wu, Ruimin Li, Xiaoli Zhao, Yajun Pang, Zhenghui Pan. Rational Design of Ni-Doped V2O5@3D Ni Core/Shell Composites for High-Voltage and High-Rate Aqueous Zinc-Ion Batteries. Materials 2024, 17 (1) , 215. https://doi.org/10.3390/ma17010215
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  • Abstract

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    Figure 1

    Figure 1. (a) SEM image of synthesized MoO2. (b) Corresponding XRD patterns of MoO3 and MoO2. XPS spectra of MoO3 and MoO2 in (c) Mo 3d and (d) O 1s spectrum. (e) Mo K-edge XANES spectra of the synthesized MoO3 and MoO2 with the reference spectra of MoO3, MoO2, and Mo. (f) EPR spectra of MoO3 and MoO2 and background signals from the Dewar.

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    Figure 2

    Figure 2. (a) XRD patterns of bare Zn and MoO2@Zn. SEM images of MoO2@Zn at the (b) cross-section and (c) surface with (d) corresponding EDS mapping. (e) Cycling performance of bare Zn and MoO2@Zn symmetric cells using ZnSO4 and ZnSO4+1Tw80 electrolytes at 1 mA cm–2–1 mAh cm–2. (f) Rate performance of symmetric cells using ZnSO4+1Tw80 electrolyte. (g) Cycling performance of bare Zn and MoO2@Zn symmetric cells using ZnSO4+1Tw80 electrolyte at a high current density–capacity of 5 mA cm–2–5 mAh cm–2. (h) Voltage profiles of bare Zn and MoO2@Zn symmetric cells with ZnSO4 electrolyte containing Tw80 additive for testing under alternate 10 continuous stripping/plating cycles and 10 h resting.

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    Figure 3

    Figure 3. XRD patterns of cycled (a) bare Zn and (b) MoO2@Zn electrodes at plating (P) and stripping (S) states. SEM images and EDS analysis after cycling for 500 cycles at the plating state of (c) bare Zn and (d) MoO2@Zn. SEM images and EDS analysis after cycling for 500 cycles at stripping state of (e) bare Zn and (f) MoO2@Zn. The cells were cycled in a ZnSO4+1Tw80 electrolyte.

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    Figure 4

    Figure 4. (a) Tafel plots of MoO2@Zn electrodes in blank ZnSO4 and ZnSO4+1Tw80 electrolytes. (b) CA curves of MoO2@Zn electrodes in blank ZnSO4 and ZnSO4+1Tw80 electrolytes. (c) Calculated activation energy of Zn2+ desolvation of different MoO2 coating layers via the Arrhenius equation. Voltage-capacity profiles of (d) Zn||Cu, (e) MoO2@Zn||Cu, and (f) MoO2@Zn||MoO2@Cu half cells. Coulombic efficiency of (g) Zn||Cu, MoO2@Zn||Cu in blank ZnSO4 electrolyte and (h) Zn||Cu, MoO2@Zn||Cu, and MoO2@Zn||MoO2@Cu half cells in ZnSO4+1Tw80 electrolyte.

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    Figure 5

    Figure 5. In situ optical microscope observation of Zn plating/stripping process for bare Zn using (a) blank ZnSO4 electrolyte and (b) ZnSO4 containing Tw80 electrolyte at 2 mA cm–2 for 30 min. In situ optical microscope observation of Zn plating/stripping process for MoO2@Zn electrodes using (c) blank ZnSO4 electrolyte and (d) ZnSO4 containing Tw80 electrolyte at 2 mA cm–2 for 30 min.

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    Figure 6

    Figure 6. Schematic diagrams of Zn2+ ions deposition behaviors in aqueous electrolytes (a) bare Zn in blank ZnSO4 electrolyte, (b) bare Zn in blank ZnSO4 containing Tw80 electrolyte, and (c) MoO2-coated Zn in ZnSO4 electrolyte containing Tw80 electrolyte. (d) XANES spectra of MoO2@Zn electrodes after plating and stripping in ZnSO4+1Tw80 electrolyte.

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    Figure 7

    Figure 7. Zn∥VO2 and MoO2@Zn∥VO2 full cells performance with (a) CV curves at a scan rate of 0.1 mV s–1. (b) Long-term cycling performance at 1 A g–1. GCD curves of different cycles of Zn∥VO2 and MoO2@Zn∥VO2 full cells using (c) ZnSO4 and (d) ZnSO4+1Tw80 electrolytes at a current density of 1 A g–1. (e) Rate performance from 0.5–10 A g–1. (f) Cycling stability at a high current density of 5 A g–1.

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  • References

    This article references 70 other publications.

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      Abstr.: Rechargeable aq. zinc-ion batteries (ZIBs) have resurged in large-scale energy storage applications due to their intrinsic safety, affordability, competitive electrochem. performance, and environmental friendliness. Extensive efforts have been devoted to exploring high-performance cathodes and stable anodes. However, many fundamental issues still hinder the development of aq. ZIBs. Here, we critically review and assess the energy storage chemistries of aq. ZIBs for both cathodes and anodes. First, this review presents a comprehensive understanding of the cathode charge storage chem., probes the existing deficiencies in mechanism verification, and analyzes contradictions between the exptl. results and proposed mechanisms. Then, a detailed summary of the representative cathode materials and corresponding comparative discussion is provided with typical cases encompassing structural features, electrochem. properties, existing drawbacks, and feasible remedies. Subsequently, the fundamental chem. properties, remaining challenges, and improvement strategies of both Zn metal and non-Zn anodes are presented to thoroughly explore the energy storage chem. of ZIBs and pursue the development of high-performance ZIBs. Furthermore, the progress of mechanistic characterization techniques and theor. simulation methods used for ZIBs is timely reviewed. Finally, we provide our perspectives, crit. anal., and insights on the remaining challenges and future directions for development of aq. ZIBs. Graphical Abstr.: [graphic not available: see fulltext].
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      Aq. Zn/MnO2 batteries have attracted considerable attention for large-scale energy storage application owing to their low cost, high safety and environmental friendliness. However, MnO2 cathodes still suffer from the inferior utilization and deficient cyclability at a wide range of current densities. Integrating MnO2 with conductive carbon is promising to overcome the challenges. Unfortunately, the required use of strongly oxidative acids or expensive plasma to functionalize the inherently hydrophobic carbon makes it an obstacle for scalable prodn. Herein, the hierarchical core-shell carbon nanofiber(CNF)@MnO2 (MOC) nanowires were synthesized by using a facile, controllable and scalable approach combining simple grinding and low-temp. wet-chem. reaction. A synergistic effect was demonstrated for the MOC cathode in Zn-ion batteries (ZIBs). The conductive CNF backbone significantly boosts the electron transfer kinetics, while ultrathin MnO2 nanosheets provide large electrode/electrolyte interfacial contact areas and facilitate the ionic diffusion. Addnl., the intimate contact between CNFs and MnO2 synergistically renders an interconnected network with high electronic and ionic cond. and flexibility to minimize structural collapse and strain of vol. variation upon cycling. The favorable synergistic effect ensures the high capacity, long shelf life, enhanced rate capability and extraordinary cycling stability of MOC. It shows a high capacity of 221 mAh g-1 after 700 cycles at 200 mA g-1. Even at 3000 mA g-1, it still maintains 130 mAh g-1 after 2750 cycles without obvious capacity decay. Featuring the exceptional electrochem. performance, rational design for synergy and low-cost manufg., the developed MOC cathode is promising for cost-efficient and high-performance ZIBs.
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      Batteries (Basel, Switzerland) (2023), 9 (1), 41CODEN: BATTAT; ISSN:2313-0105. (MDPI AG)
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      A review. Water electrolysis is a promising technol. for sustainable energy conversion and storage of intermittent and fluctuating renewable energy sources and prodn. of high-purity hydrogen for fuel cells and various industrial applications. Low-temp. electrochem. water splitting technologies include alk., proton exchange membrane, and anion exchange membrane water electrolyzes, which normally consist of two coupled half reactions: the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Despite the advances over decades, formidable challenges still exist and hinder the practical application of large-scale, energy-efficient, and economically viable water electrolysis, including large energy penalty, sluggish kinetics, high cost of precious metal based electrocatalysts, possible H2/O2 gas crossover, difficulty in storage, and distribution of H2. Herein, we first briefly introduce the fundamentals of water electrolysis, summarize the recommended standardized electrochem. characterization protocols, and demonstrate the metrics and key performance indicators that are used to evaluate the performances of HER and OER electrocatalysts and electrolyzer cells. Then, we present six new strategies to mitigate the tech. challenges in conventional water electrolysis. These emerging strategies for disruptive innovation of water electrolysis technol. include overall water electrolysis based on bifunctional nonprecious electrocatalysts (or pre-catalysts), magnetic field-assisted water electrolysis, decoupled water electrolysis, hybrid water electrolysis, acid/alk. asym. electrolyte electrolysis, and tandem water electrolysis. Finally, the remaining challenges, perspectives and future directions are discussed. This review will provide guidance and inspire more endeavours to deepen the mechanistic understanding and advance the development of water electrolysis.
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      Dong, Ning; Zhang, Fenglin; Pan, Huilin
      Chemical Science (2022), 13 (28), 8243-8252CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Rechargeable aq. Zn batteries have been widely investigated in recent years due to the merits of high safety and low cost. However inevitable dendrite growth, corrosion and hydrogen evolution of Zn anodes severely compromise the practical lifespan of rechargeable Zn batteries. Despite the encouraging improvements for Zn anodes reported in the literature, the comprehensive understanding of Zn anodes under practical conditions is still often neglected. In this article, we focus on the "less-discussed" but critically important points for rechargeable aq. Zn batteries, including revisit of the relationship between the coulombic efficiency and lifespan of Zn anodes, the rational control of the pH environment in the vicinity of Zn anodes, the design of appropriate aq. separators and the relevant estn. of practical energy d. for aq. Zn batteries. It concludes that energy d. of 60-80 W h kg-1 for aq. Zn batteries should be realistic in practice with appropriate cell design. We also propose practical tech. recommendations for the rational development of aq. Zn batteries based on research experience from the community and our group. We hope this article offers readers more practical insights into the future development of aq. Zn batteries as competitive technol. for practical use.
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      Dai, L.; Wang, T.; Jin, B.; Liu, N.; Niu, Y.; Meng, W.; Gao, Z.; Wu, X.; Wang, L.; He, Z. γ-Al2O3 Coating Layer Confining Zinc Dendrite Growth for High Stability Aqueous Rechargeable Zinc-Ion Batteries. Surf. Coat. Technol. 2021, 427, 127813  DOI: 10.1016/j.surfcoat.2021.127813
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      γ-Al2O3 coating layer confining zinc dendrite growth for high stability aqueous rechargeable zinc-ion batteries
      Dai, Lei; Wang, Tingting; Jin, Boxuan; Liu, Na; Niu, Yifei; Meng, Wenhao; Gao, Ziming; Wu, Xianwen; Wang, Ling; He, Zhangxing
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      Zinc is a widely used anode material for zinc-ion batteries. However, the problems of dendrites and side reactions faced by the metal zinc anode limit its cycle stability and service life. Surface modification is a simple and effective strategy for prepairing high-performance anodes. Here, we used a simple method to coat the γ-Al2O3 on surface of metal zinc as an artificial protective layer for the anode/electrolyte. γ-Al2O3 coating can guide the uniform deposition of zinc ions. The coating has good hydrophilicity, which is conducive to accelerate ion transmission. In addn., the importance of controlling the thickness of protective layer on surface of zinc metal anode to obtain good electrochem. performance is emphasized. The appropriate thickness of Al2O3 coating ensures the rapid migration of zinc ions and improves the uniformity of zinc plating/stripping, which is conducive to more uniform zinc nucleation and high-quality deposition. Therefore, the discharge capacity of Zn@Al2O3-15 full cell at a c.d. of 0.3 A g-1 is 174.3 mAh g-1, which is much higher than that of bare zinc cell (71.8 mAh g-1). This work has certain ref. significance for the development of anode coating strategies in zinc-ion batteries.
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      Xie, S.; Li, Y.; Li, X.; Zhou, Y.; Dang, Z.; Rong, J.; Dong, L. Stable Zinc Anodes Enabled by Zincophilic Cu Nanowire Networks. Nano-Micro Lett. 2022, 14, 39,  DOI: 10.1007/s40820-021-00783-4
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      Stable zinc anodes enabled by zincophilic Cu nanowire networks
      Xie, Shiyin; Li, Yang; Li, Xu; Zhou, Yujun; Dang, Ziqi; Rong, Jianhua; Dong, Liubing
      Nano-Micro Letters (2022), 14 (), 39CODEN: NLAEBV; ISSN:2150-5551. (Nano-Micro Letters)
      Zn-based electrochem. energy storage (EES) systems have received tremendous attention in recent years, but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions (e.g., corrosion and hydrogen evolution). Herein, we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects. According to exptl. results, COMSOL simulation and d. functional theory calcns., the Cu nanowire networks covering on zinc anode surface not only homogenize the surface elec. field and Zn2+ concn. field, but also inhibit side reactions through their hydrophobic feature. Meanwhile, facets and edge sites of the Cu nanowires, esp. the latter ones, are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition. Consequently, the Cu nanowire networksprotected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities (e.g., 10 mA cm-2 and 5 mAh cm-2), remarkably superior to bare zinc anodes and most of currently reported zinc anodes, thereby enabling Zn-based EES devices to possess high capacity, 16,000-cycle lifespan and rapid charge/discharge ability. This work provides new thoughts to realize long-life and high-rate zinc anodes.
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      Jin, Y.; Han, K. S.; Shao, Y.; Sushko, M. L.; Xiao, J.; Pan, H.; Liu, J. Stabilizing Zinc Anode Reactions by Polyethylene Oxide Polymer in Mild Aqueous Electrolytes. Adv. Funct. Mater. 2020, 30, 2003932  DOI: 10.1002/adfm.202003932
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      Stabilizing Zinc Anode Reactions by Polyethylene Oxide Polymer in Mild Aqueous Electrolytes
      Jin, Yan; Han, Kee Sung; Shao, Yuyan; Sushko, Maria L.; Xiao, Jie; Pan, Huilin; Liu, Jun
      Advanced Functional Materials (2020), 30 (43), 2003932CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Zn dendrites growth and poor cycling stability are significant challenges for rechargeable aq. Zn batteries. Zn metal deposition-dissoln. in aq. electrolytes is typically detd. by Zn anode-electrolyte interfaces. In this work, the role of a long-chain polyethylene oxide (PEO) polymer as a multifunctional electrolyte additive in stabilizing Zn metal anodes is reported. PEO mols. suppress Zn2+ ion transfer kinetics and regulate Zn2+ ion concn. in the vicinity of Zn anodes through interactions between ether groups of PEO and Zn2+ ions. The suppressed Zn2+ ion transfer kinetics and homogeneous Zn2+ ion distribution at the interface promotes dendrite-free homogeneous Zn deposition. In addn., electrochem. inert PEO mols. adsorbed onto Zn anodes can protect the anode surfaces from H2+ generation and, thereby, enhance their electrochem. stability. Stable cycling over 3000 h and high reversibility (Coulombic efficiency > 99.5%) of Zn anodes is demonstrated in 1 M ZnSO4 electrolyte with 0.5 wt% PEO. This finding provides helpful insights into the mechanism of Zn metal anodes stabilization by low-cost multifunctional polymer electrolyte additives that stabilize interfacial reactions.
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    9. 9
      Zhou, M.; Chen, H.; Chen, Z.; Hu, Z.; Wang, N.; Jin, Y.; Yu, X.; Meng, H. Nonionic Surfactant Coconut Diethanol Amide Inhibits the Growth of Zinc Dendrites for More Stable Zinc-Ion Batteries. ACS Appl. Energy Mater. 2022, 5, 7590– 7599,  DOI: 10.1021/acsaem.2c01048
      9
      Nonionic Surfactant Coconut Diethanol Amide Inhibits the Growth of Zinc Dendrites for More Stable Zinc-Ion Batteries
      Zhou, Ming; Chen, Hongzhan; Chen, Zehai; Hu, Zehao; Wang, Nan; Jin, Yanshuo; Yu, Xiang; Meng, Hui
      ACS Applied Energy Materials (2022), 5 (6), 7590-7599CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Uncontrollable growth of zinc dendrites and byproducts has become the main factor which limits the life of zinc-ion batteries. Herein, we reported a nonionic surfactant, coconut diethanolamide (CDA), which can be applied as an electrolyte additive. It not only effectively suppresses zinc graft growth and promotes uniform growth of zinc dendrites but also efficiently inhibits the generation of side reactions and byproducts. When CDA is added to the electrolyte, the life of the battery has been significantly improved (1580 h). Compared with an electrolyte without CDA (100 h), its life has grown more than 10 times. CDA can adsorb on the surface of the zinc electrode to form a protective layer by its special mol. structure. Therefore, zinc ions will have a higher barrier for deposition, and there should be induced uniform deposition. Moreover, the Cu/Zn cell shows 98% av. Coulomb efficiency in the electrolyte with CDA after about 620 h. In addn., after long-term cycles, the addn. of CDA enables the MnO2/Zn cell to show 85% capacity retention and 98% av. Coulomb efficiency. The electrolyte additives reported in this study will provide a more convenient and environmentally friendly way to effectively solve the problem of zinc branches.
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    10. 10
      Qian, Y.; Meng, C.; He, J.; Dong, X. A Lightweight 3D Zn@Cu Nanosheets@activated Carbon Cloth as Long-Life Anode with Large Capacity for Flexible Zinc Ion Batteries. J. Power Sources 2020, 480, 228871  DOI: 10.1016/j.jpowsour.2020.228871
      10
      A lightweight 3D Zn@Cu nanosheets@activated carbon cloth as long-life anode with large capacity for flexible zinc ion batteries
      Qian, Yong; Meng, Chen; He, Jinxin; Dong, Xia
      Journal of Power Sources (2020), 480 (), 228871CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Zinc metal is actively developed as the most potential next generation anode material for aq. rechargeable batteries. However, Zn deposition and uncontrollable dendrite growth of metallic Zn anodes during cycles lead to poor cycle performance and coulombic efficiency, hindering their practical application. Constructing a three-dimensional (3D) current collector has been demonstrated to significantly inhibit the formation of zinc dendrites. Herein, a lightwt. 3D flexible Zn plating/stripping scaffold, Cu nanosheets grown on activated carbon cloth (Cu nanosheets@ACC), is prepd. by an electrochem. deposition technol. Compared with activated carbon cloth (ACC), Cu nanosheets@ACC current collector delivers higher special surface area and cond. Besides, Cu nanosheets layer not only can provide numerous, uniformly distributed Zn deposition sites but also can significantly decrease Zn nucleation overpotential. As a consequence, Zn@Cu nanosheets@ACC (Zn grown on Cu nanosheets@ACC) anode delivers a highly reversible Zn plating/stripping behavior with satisfactory cyclic stability rather than uncontrollable Zn dendrites growth. Moreover, a zinc ion battery based on the Zn@Cu nanosheets@ACC anode and MnO2@ACC (MnO2 grown on ACC) cathode presents high av. coulombic efficiency (97.9%) and excellent cycling stability (94.8%) over 1000 cycles at 1 A/g as well as satisfactory mech. properties, displaying great potential for long-life flexible zinc ion batteries.
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    11. 11
      Xie, S.; Li, Y.; Dong, L. Stable Anode-Free Zinc-Ion Batteries Enabled by Alloy Network-Modulated Zinc Deposition Interface. J. Energy Chem. 2023, 76, 32– 40,  DOI: 10.1016/j.jechem.2022.08.040
      11
      Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface
      Xie, Shiyin; Li, Yang; Dong, Liubing
      Journal of Energy Chemistry (2023), 76 (), 32-40CODEN: JECOFG; ISSN:2095-4956. (Science Press)
      Newly-proposed anode-free zinc-ion batteries (ZIBs) are promising to remarkably enhance the energy d. of ZIBs, but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability. Herein, we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs. The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes. Consequently, the alloy network-modulated zinc deposition interface realizes high-Coulombic efficiency of 99.2% and high stability. As proof, Zn//Zn sym. cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 mA/cm2 and 1200 h at 5 mA/cm2, significantly superior to Zn//Zn sym. cells with unmodified zinc deposition interface (whose operation lifetime is shorter than 50 h). Meanwhile, Zn3V3O8 cathode-based ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes. As expected, the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8 cathodes to deliver superior cycling stability, better than most currently-reported anode-free ZIBs. This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.
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    12. 12
      Wang, Z.; Dong, L.; Huang, W.; Jia, H.; Zhao, Q.; Wang, Y.; Fei, B.; Pan, F. Simultaneously Regulating Uniform Zn2+ Flux and Electron Conduction by MOF/rGO Interlayers for High-Performance Zn Anodes. Nano-Micro Lett. 2021, 13, 73,  DOI: 10.1007/s40820-021-00594-7
      12
      Simultaneously regulating uniform Zn2+ flux and electron conduction by MOF/rGO interlayers for high-performance Zn anodes
      Wang, Ziqi; Dong, Liubing; Huang, Weiyuan; Jia, Hao; Zhao, Qinghe; Wang, Yidi; Fei, Bin; Pan, Feng
      Nano-Micro Letters (2021), 13 (), 73CODEN: NLAEBV; ISSN:2150-5551. (Nano-Micro Letters)
      Owing to the merits of low cost, high safety and environmental benignity, rechargeable aq. Zn-based batteries (ZBs) have gained tremendous attention in recent years. Nevertheless, the poor reversibility of Zn anodes that originates from dendrite growth, surface passivation and corrosion, severely hinders the further development of ZBs. To tackle these issues, here we report a Janus separator based on a Zn-ion conductive metal-org. framework (MOF) and reduced graphene oxide (rGO), which is able to regulate uniform Zn2+ flux and electron conduction simultaneously during battery operation. Facilitated by the MOF/rGO bifunctional interlayers, the Zn anodes demonstrate stable plating/stripping behavior (over 500 h at 1 mA cm-2), high Coulombic efficiency (99.2% at 2 mA cm-2 after 100 cycles) and reduced redox barrier. Moreover, it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface. Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells, which deliver nearly 100% capacity retention after 2000 cycles at 4 A g-1 and high power d. over 10 kW kg-1. This work provides a feasible route to the high-performance Zn anodes for ZBs.
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    13. 13
      Li, Y.; Peng, X.; Li, X.; Duan, H.; Xie, S.; Dong, L.; Kang, F. Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc-Based Energy Storage. Adv. Mater. 2023, 35, 2300019  DOI: 10.1002/adma.202300019
      13
      Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc-Based Energy Storage
      Li, Yang; Peng, Xinya; Li, Xu; Duan, Huan; Xie, Shiyin; Dong, Liubing; Kang, Feiyu
      Advanced Materials (Weinheim, Germany) (2023), 35 (18), 2300019CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Ultrathin separators are indispensable to high-energy-d. zinc-ion batteries (ZIBs), but their easy failure caused by zinc dendrites poses a great challenge. Herein, 23μm-thick functional ultrathin separators (FUSs), realizing superb electrochem. stability of zinc anodes and outstanding long-term durability of ultrathin separators, are reported. In the FUSs, an ultrathin but mechinal strong nanoporous membrane substrate benefits fast and flux-homogenized Zn2+ transport, while a metal-org. framework (MOF)-derived C/Cu nanocomposite decoration layer provides rich low-barrier zinc nucleation sites, thereby synergistically stabilizing zinc anodes to inhibit zinc dendrites and dendrite-caused separator failure. Investigation of the zinc affinity of the MOF-derived C/Cu nanocomposites unravels the high zincophilicity of heteroatom-contg. C/Cu interfaces. Zinc anodes coupled with the FUSs present superior electrochem. stability, whose operation lifetime exceeds 2000 h at 1 mA cm-2 and 600 h at 10 mA cm-2, 40-50 times longer than that of the zinc anodes using glass-fiber separators. The reliability of the FUSs in ZIBs and zinc-ion hybrid supercapacitors is also validated. This work proposes a new strategy to stabilize zinc anodes and provides theor. guidance in developing ultrathin separators for high-energy-d. zinc-based energy storage.
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    14. 14
      Kang, L.; Cui, M.; Jiang, F.; Gao, Y.; Luo, H.; Liu, J.; Liang, W.; Zhi, C. Nanoporous CaCO3 Coatings Enabled Uniform Zn Stripping/Plating for Long-Life Zinc Rechargeable Aqueous Batteries. Adv. Energy Mater. 2018, 8, 1801090  DOI: 10.1002/aenm.201801090
      There is no corresponding record for this reference.
    15. 15
      Chen, X.; Li, W.; Hu, S.; Akhmedov, N. G.; Reed, D.; Li, X.; Liu, X. Polyvinyl Alcohol Coating Induced Preferred Crystallographic Orientation in Aqueous Zinc Battery Anodes. Nano Energy 2022, 98, 107269  DOI: 10.1016/j.nanoen.2022.107269
      15
      Polyvinyl alcohol coating induced preferred crystallographic orientation in aqueous zinc battery anodes
      Chen, Xiujuan; Li, Wei; Hu, Shanshan; Akhmedov, Novruz G.; Reed, David; Li, Xiaolin; Liu, Xingbo
      Nano Energy (2022), 98 (), 107269CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      The development of rechargeable aq. zinc batteries is mainly hindered by the Zn anode, which suffers from dendrite growth, corrosion, hydrogen evolution, and surface passivation. Herein, a thin polyvinyl alc. (PVA) coating layer on Zn anode has enabled dendrite-free, long-life aq. Zn batteries by effectively regulating the interfacial ion diffusion and inducing the homogeneous Zn nucleation and deposition of stacked plates with preferentially crystallog. orientation along (002)Zn planes. The PVA@Zn anode achieved an ultralong cycle lifespan of thousands of hours at 0.25 and 1 mA cm-2. Outstanding durability under a deep cycling capacity (5 mA h cm-2), high c.d. (10 mA cm-2), and long duration conditions were achieved. The superior cyclability of PVA@Zn anode was also demonstrated in PVA@Zn//V2O5 full cells. The insights of PVA induced Zn deposition with preferred crystal orientation and interfacial regulation shed light on the future development of stable Zn anodes.
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    16. 16
      Cui, M.; Xiao, Y.; Kang, L.; Du, W.; Gao, Y.; Sun, X.; Zhou, Y.; Li, X.; Li, H.; Jiang, F.; Zhi, C. Quasi-Isolated Au Particles as Heterogeneous Seeds To Guide Uniform Zn Deposition for Aqueous Zinc-Ion Batteries. ACS Appl. Energy Mater. 2019, 2, 6490– 6496,  DOI: 10.1021/acsaem.9b01063
      16
      Quasi-Isolated Au Particles as Heterogeneous Seeds To Guide Uniform Zn Deposition for Aqueous Zinc-Ion Batteries
      Cui, Mangwei; Xiao, Yan; Kang, Litao; Du, Wei; Gao, Yanfeng; Sun, Xueqin; Zhou, Yanli; Li, Xiangming; Li, Hongfei; Jiang, Fuyi; Zhi, Chunyi
      ACS Applied Energy Materials (2019), 2 (9), 6490-6496CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      As a promising anode for aq. batteries, Zn metal shows a no. of attractive advantages such as low cost, low redox potential, high capacity, and environmental benignity. Nevertheless, the quick growth of dendrites/protrusions on the "hostless" Zn anodes not only enlarges batteries' internal resistance but also causes sudden shorting failure by piercing separators. Herein, we report a novel heterogeneous seed method to guide the morphol. evolution of plated Zn. The heterogeneous seeds are sputtering-deposited quasi-isolated nano-Au particles (Au-NPs) that enable a uniform and stable Zn-plating/stripping process on the anodes. Tested on Zn|Zn sym. cells, the Au-nanoparticle (NP) decorated Zn anodes (NA-Zn) demonstrate much better cycling stability than the bare ones (92 vs 2000 h). In NA-Zn|CNT/MnO2 batteries, this heterogeneous seed prolongs the lifetime of the device from ∼480 cycles up to 2000 cycles. This work offers a facile and promising Zn dendrite/protrusion suppressing route for the achievement of long-life Zn-ion batteries.
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    17. 17
      Zhang, N.; Huang, S.; Yuan, Z.; Zhu, J.; Zhao, Z.; Niu, Z. Direct Self-Assembly of MXene on Zn Anodes for Dendrite-Free Aqueous Zinc-Ion Batteries. Angew. Chem., Int. Ed. 2021, 60, 2861– 2865,  DOI: 10.1002/anie.202012322
      17
      Direct Self-Assembly of MXene on Zn Anodes for Dendrite-Free Aqueous Zinc-Ion Batteries
      Zhang, Nannan; Huang, Shuo; Yuan, Zishun; Zhu, Jiacai; Zhao, Zifang; Niu, Zhiqiang
      Angewandte Chemie, International Edition (2021), 60 (6), 2861-2865CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Metallic zinc is a promising anode candidate of aq. zinc-ion batteries owing to its high theor. capacity and low redox potential. However, Zn anodes usually suffer from dendrite and side reactions, which will degrade their cycle stability and reversibility. Herein, we developed an in situ spontaneously reducing/assembling strategy to assemble a ultrathin and uniform MXene layer on the surface of Zn anodes. The MXene layer endows the Zn anode with a lower Zn nucleation energy barrier and a more uniformly distributed elec. field through the favorable charge redistribution effect in comparison with pure Zn. Therefore, MXene-integrated Zn anode exhibits obviously low voltage hysteresis and excellent cycling stability with dendrite-free behaviors, ensuring the high capacity retention and low polarization potential in zinc-ion batteries.
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    18. 18
      Wang, A.; Zhou, W.; Huang, A.; Chen, M.; Chen, J.; Tian, Q.; Xu, J. Modifying the Zn Anode with Carbon Black Coating and Nanofibrillated Cellulose Binder: A Strategy to Realize Dendrite-Free Zn-MnO2 Batteries. J. Colloid Interface Sci. 2020, 577, 256– 264,  DOI: 10.1016/j.jcis.2020.05.102
      18
      Modifying the Zn anode with carbon black coating and nanofibrillated cellulose binder: A strategy to realize dendrite-free Zn-MnO2 batteries
      Wang, Anran; Zhou, Weijun; Huang, Aixiang; Chen, Minfeng; Chen, Jizhang; Tian, Qinghua; Xu, Junling
      Journal of Colloid and Interface Science (2020), 577 (), 256-264CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
      Aq. zinc-ion batteries have received significant attention due to their low cost and high safety. However, the unsatisfactory cycling performances caused by the dendritic growth on the Zn anode limit their practical applications. Herein, we propose to modify the conventional Zn foil anode by using carbon black coating and nanofibrillated cellulose binder. The carbon black can form an elec. conductive network, thus greatly enlarging the electroactive surface area, while the nanofibrillated cellulose can act as an electrolyte reservoir to facilitate charge transports. Thanks to that, the modified anode can significantly eliminate the dendritic growth and side reactions, therefore ensuring excellent interface stability with the electrolyte even at a com.-level areal capacity of 5 mAh g-1. With the modified anode, the Zn-MnO2 battery gives a high capacity retention of 87.4% after 1000 cycles, much higher than that with the unmodified Zn foil (42.6%). This study discloses a facile, scalable, and cost-effective strategy to achieve dendrite-free metal electrodes towards great cyclability.
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    19. 19
      Xu, J.; Lv, W.; Yang, W.; Jin, Y.; Jin, Q.; Sun, B.; Zhang, Z.; Wang, T.; Zheng, L.; Shi, X.; Sun, B.; Wang, G. In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries. ACS Nano 2022, 16, 11392– 11404,  DOI: 10.1021/acsnano.2c05285
      19
      In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries
      Xu, Jing; Lv, Wenli; Yang, Wang; Jin, Yang; Jin, Qianzheng; Sun, Bin; Zhang, Zili; Wang, Tianyi; Zheng, Linfeng; Shi, Xiaolong; Sun, Bing; Wang, Guoxiu
      ACS Nano (2022), 16 (7), 11392-11404CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      The strong activity of water mols. causes a series of parasitic side reactions on Zn anodes in the aq. electrolytes. Herein, we introduce silk fibroin (SF) as a multifunctional electrolyte additive for aq. zinc-ion (Zn-ion) batteries. The secondary structure transformation of SF mols. from α-helixes to random coils in the aq. electrolytes allows them to break the hydrogen bond network among free water mols. and participate in Zn2+ ion solvation structure. The SF mols. released from the [Zn(H2O)4(SF)]2+ solvation sheath appear to be gradually adsorbed on the surface of Zn anodes and in situ form a hydrostable and self-healable protective film. This SF-based protective film not only shows strong Zn2+ ion affinity to promote homogeneous Zn deposition but also has good insulating behavior to suppress parasitic reactions. Benefiting from these multifunctional advantages, the cycle life of the Zn||Zn sym. cells reaches over 1600 h in SF-contg. ZnSO4 electrolytes. In addn., by adopting a potassium vanadate cathode, the full cell shows excellent cycling stability for 1000 cycles at 3 A g-1. The in situ construction of a protective film on the Zn anode from natural protein mols. provides an effective strategy to achieve high-performance Zn metal anodes for Zn-ion batteries.
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    20. 20
      Zhao, X.; Dong, N.; Yan, M.; Pan, H. Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries. ACS Appl. Mater. Interfaces 2023, 15, 4053– 4060,  DOI: 10.1021/acsami.2c19022
      20
      Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries
      Zhao, Xuesong; Dong, Ning; Yan, Mengdie; Pan, Huilin
      ACS Applied Materials & Interfaces (2023), 15 (3), 4053-4060CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      A robust solid electrolyte interface (SEI) is crucial to widen the electrochem. stability window of the electrolyte and enable sustainably stable electrode reactions in aq. Zn ion batteries. Different from the SEI in nonaq. electrolytes, it is of great importance to form a functional and stable SEI due to parasitic reactions with water in aq. Zn ion batteries. However, the concrete SEI formation in aq. electrolytes has been elusive so far. Here, we regulate and unravel the decompn. mechanisms of org. Zn salts at the Zn anode-electrolyte interface in the widely studied zinc triflate-based aq. electrolytes. By introducing a buffering adsorption layer with an optimal concn. of acetate anions, the uncontrollable decompn. of org. zinc triflate salt is greatly inhibited on Zn anodes, resulting in a stable interface. The av. Coulombic efficiency of the Zn anode thus can reach as high as 99.95% and stable cycling for 4200 h. With the cooperation of buffering adsorption layers, the tetra-Et ammonium trifluoromethanesulfonate additive as the decompn. promoter could further regulate the decompn. of triflate anions for the formation of robust SEI layers for Zn anodes in electrolytes with a dil. salt concn. Zn-polyaniline (PANI) full cells demonstrate stable cycling with controlled N/P ratios in such electrolytes. This work proposes an insightful perspective on rational regulation of the decompn. pathway of electrolyte components by forming a stable electrode-electrolyte interface for improved electrochem. performance of aq. Zn ion batteries.
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    21. 21
      Kim, H.-S.; Cook, J.-B.; Lin, H.; Ko, J.-S.; Tolbert, S.-H.; Ozolins, V.; Dunn, B. Oxygen Vacancies Enhance Pseudocapacitive Charge Storage Properties of MoO3-x. Nat. Mater. 2017, 16, 454– 462,  DOI: 10.1038/nmat4810
      21
      Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3-x
      Kim, Hyung-Seok; Cook, John B.; Lin, Hao; Ko, Jesse S.; Tolbert, Sarah H.; Ozolins, Vidvuds; Dunn, Bruce
      Nature Materials (2017), 16 (4), 454-460CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      The short charging times and high power capabilities assocd. with capacitive energy storage make this approach an attractive alternative to batteries. One limitation of electrochem. capacitors is their low energy d. and for this reason, there is widespread interest in pseudocapacitive materials that use Faradaic reactions to store charge. One candidate pseudocapacitive material is orthorhombic MoO3 (α-MoO3), a layered compd. with a high theor. capacity for lithium (279 mA h g-1 or 1,005 C g-1). Here, we report on the properties of reduced α-MoO3-x(R-MoO3-x) and compare it with fully oxidized α-MoO3 (F-MoO3). The introduction of oxygen vacancies leads to a larger interlayer spacing that promotes faster charge storage kinetics and enables the α-MoO3 structure to be retained during the insertion and removal of Li ions. The higher specific capacity of the R-MoO3-x is attributed to the reversible formation of a significant amt. of Mo4+ following lithiation. This study underscores the potential importance of incorporating oxygen vacancies into transition metal oxides as a strategy for increasing the charge storage kinetics of redox-active materials.
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    22. 22
      Jung, Y.-S.; Lee, S.; Ahn, D.; Dillon, A.-C.; Lee, S.-H. Electrochemical Reactivity of Ball-Milled MoO3-y as Anode Materials for Lithium-Ion Batteries. J. Power Sources 2009, 188, 286– 291,  DOI: 10.1016/j.jpowsour.2008.11.125
      22
      Electrochemical reactivity of ball-milled MoO3-y as anode materials for lithium-ion batteries
      Jung, Yoon S.; Lee, Sangkyoo; Ahn, Dongjoon; Dillon, Anne C.; Lee, Se-Hee
      Journal of Power Sources (2009), 188 (1), 286-291CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The electrochem. reactivity of ball-milled MoO3 powders was studied in Li rechargeable cells. High-energy ball-milling converts highly-cryst. MoO3 bulk powders into partially reduced low-cryst. MoO3-y materials with a reduced particle size. Both bulk and ball-milled MoO3 exhibit a 1st discharge capacity beyond 1100 mAh g-1 when tested in the 0-3 V (vs. Li/Li+) range, which is indicative of a complete conversion reaction. Partial redn. caused by ball-milling results in a redn. in the conversion reaction. Addnl., incomplete reoxidn. during subsequent charge gave MoO2 instead of MoO3, which in turn affects the reactivity in subsequent cycles. As compared to bulk MoO3, ball-milled MoO3-y showed significantly enhanced cycle performance (bulk: 27.6% charge capacity retention at the 10th cycle vs. ball-milled for 8 h: 64.4% at the 35th cycle), which can be attributed to the nano-texture wherein nanometer-sized particles aggregate to form secondary ones.
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    23. 23
      Wang, B.; Yan, J.; Zhang, Y.; Ye, M.; Yang, Y.; Li, C. C. In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable “Rocking-Chair” Zinc-Ion Batteries. Adv. Funct. Mater. 2021, 31, 2102827  DOI: 10.1002/adfm.202102827
      23
      In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable "Rocking-Chair" Zinc-Ion Batteries
      Wang, Bo; Yan, Jianping; Zhang, Yufei; Ye, Minghui; Yang, Yang; Li, Cheng Chao
      Advanced Functional Materials (2021), 31 (30), 2102827CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Aq. zinc-ion batteries (ZIBs) have attracted significant attention due to their intrinsic safety, cost-effectiveness, and environmental friendliness. However, the common zinc metal anode suffers from zinc dendrite formation, self-corrosion, and surface passivation, which impede the further application of aq. ZIBs. Herein, carbon-inserted molybdenum dioxide (MoO2) materials with laminated structure are designed as novel intercalation-type anodes for ZIBs by combination of interlayer engineering and in situ carbonization of aniline guest in molybdenum trioxide interlayers. The uniform dispersion of carbon layers in laminated MoO2 not only provide fast transportation paths for electron but also strengthen the framework of MoO2, leading to high structural integration during high-rate cycling. Benefiting from the unique structural design, the carbon-inserted MoO2 electrode exhibits high initial Coulombic efficiency, excellent cycling stability, and outstanding rate capability. Multiple ex situ characterizations reveal its excellent electrochem. stability is derived from reversible intercalation mechanism and ultrastable structural framework. Furthermore, the rocking-chair zinc-ion full battery assembled with the zinc pre-intercalated Na3V2(PO4)2O2F cathode presents excellent stability and ultralong lifespan with a high capacity retention of 91% over 8000 cycles.
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    24. 24
      Zhu, Y.; Ji, X.; Cheng, S.; Chern, Z.-Y.; Jia, J.; Yang, L.; Luo, H.; Yu, J.; Peng, X.; Wang, J.; Zhou, W.; Liu, M. Fast Energy Storage in Two-Dimensional MoO2 Enabled by Uniform Oriented Tunnels. ACS Nano 2019, 13, 9091– 9099,  DOI: 10.1021/acsnano.9b03324
      24
      Fast Energy Storage in Two-Dimensional MoO2 Enabled by Uniform Oriented Tunnels
      Zhu, Yuanyuan; Ji, Xu; Cheng, Shuang; Chern, Zhao-Ying; Jia, Jin; Yang, Lufeng; Luo, Haowei; Yu, Jiayuan; Peng, Xinwen; Wang, Jenghan; Zhou, Weijia; Liu, Meilin
      ACS Nano (2019), 13 (8), 9091-9099CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      While pseudocapacitive electrodes have potential to store more energy than elec. double-layer capacitive electrodes, their rate capability is often limited by the sluggish kinetics of the Faradaic reactions or poor electronic and ionic cond. Unlike most transition-metal oxides, MoO2 is a very promising material for fast energy storage, attributed to its unusually high electronic and ionic cond.; the 1-dimensional tunnel is ideally suited for fast ionic transport. Here, we report our findings in prepn. and characterization of ultrathin MoO2 sheets with oriented tunnels as a pseudocapacitive electrode for fast charge storage/release. A composite electrode consisting of MoO2 and 5 wt.% GO demonstrates a capacity of 1097 C/g at 2 mV/s and 390 C/g at 1000 mV/s while maintaining ∼80% of the initial capacity after 10,000 cycles at 50 mV/s, due to minimal change in structural features of the MoO2 during charge/discharge, except a small vol. change (∼14%), as revealed from operando Raman spectroscopy, x-ray analyses, and d. functional theory calcns. The vol. change during cycling is highly reversible, implying high structural stability and long cycling life.
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    25. 25
      Wang, H.; Li, T.; Hashem, A. M.; Abdel-Ghany, A. E.; El-Tawil, R. S.; Abuzeid, H. M.; Coughlin, A.; Chang, K.; Zhang, S.; El-Mounayri, H.; Tovar, A.; Zhu, L.; Julien, C. M. Nanostructured Molybdenum-Oxide Anodes for Lithium-Ion Batteries: An Outstanding Increase in Capacity. Nanomaterials 2022, 12, 13,  DOI: 10.3390/nano12010013
      25
      Nanostructured Molybdenum-Oxide Anodes for Lithium-Ion Batteries: An Outstanding Increase in Capacity
      Wang, Hua; Li, Tianyi; Hashem, Ahmed M.; Abdel-Ghany, Ashraf E.; El-Tawil, Rasha S.; Abuzeid, Hanaa M.; Coughlin, Amanda; Chang, Kai; Zhang, Shixiong; El-Mounayri, Hazim; Tovar, Andres; Zhu, Likun; Julien, Christian M.
      Nanomaterials (2022), 12 (1), 13CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
      This work aimed at synthesizing MoO3 and MoO2 by a facile and cost-effective method using ext. of orange peel as a biol. chelating and reducing agent for ammonium molybdate. Calcination of the precursor in air at 450°C yielded the stochiometric MoO3 phase, while calcination in vacuum produced the reduced form MoO2 as evidenced by X-ray powder diffraction, Raman scattering spectroscopy, and XPS results. Scanning and transmission electron microscopy images showed different morphologies and sizes of MoOx particles. MoO3 formed platelet particles that were larger than those obsd. for MoO2. MoO3 showed stable thermal behavior until approx. 800°C, whereas MoO2 showed wt. gain at approx. 400°C due to the fact of re-oxidn. and oxygen uptake and, hence, conversion to stoichiometric MoO3. Electrochem., traditional performance was obsd. for MoO3, which exhibited a high initial capacity with steady and continuous capacity fading upon cycling. On the contrary, MoO2 showed completely different electrochem. behavior with less initial capacity but an outstanding increase in capacity upon cycling, which reached 1600 mAh g-1 after 800 cycles. This outstanding electrochem. performance of MoO2 may be attributed to its higher surface area and better elec. cond. as obsd. in surface area and impedance investigations.
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    26. 26
      Zhou, Y.; Geng, C. A MoO2 Sheet as a Promising Electrode Material: Ultrafast Li-Diffusion and Astonishing Li-Storage Capacity. Nanotechnology 2017, 28, 105402  DOI: 10.1088/1361-6528/aa56d0
      26
      A MoO2 sheet as a promising electrode material: ultrafast Li-diffusion and astonishing Li-storage capacity
      Zhou, Yungang; Geng, Cheng
      Nanotechnology (2017), 28 (10), 105402/1-105402/8CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
      The potential of MoO2 crystal as an electrode material is reported, and nanostructural MoO2 systems, including nanoparticles, nanospheres, nanobelts and nanowires, were synthesized and proved to be advanced electrode materials. A two-dimensional (2D) geometric structure represents an extreme of surface-to-vol. ratio, and thus is more suitable as an electrode material in general. Stimulated by the recent fabrication of 2D MoO2, we adopted an ab initio mol. dynamics simulation and d. functional theory calcn. to study the stability and electrochem. properties of a MoO2 sheet. Identified by a phonon dispersion curve and potential energy curve calcns., the MoO2 sheet proved to be dynamically and thermally stable. After lithiation, similar to most promising 2D structures, we found that a Li atom can strongly adsorb on a MoO2 sheet, and the lithiated MoO2 sheet presented excellent metallic properties. Note that, compared with most promising 2D structures, we unexpectedly revealed that the diffusion barrier of the Li atom on the MoO2 sheet was much lower and the storage capacity of the MoO2 sheet was much larger. The calcd. energy barrier for the diffusion of Li on the MoO2 sheet was only 75 meV, and, due to multilayer adsorption, the theor. capacity of the MoO2 sheet can reach up to 2513 mA h g-1 . Benefiting from general properties, such as strong Li-binding and excellent cond., and unique phenomena, such as ultrafast diffusion capacity and astonishing storage capacity, we highlight a new promising electrode material for the Li-ion battery.
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    27. 27
      Hazazi, O. A. Water Soluble Non-Toxic Organic Zinc Corrosion Inhibitors in Acidic Solution. Chem. Sci. Rev. Lett. 2015, 4, 965– 978
      27
      Water soluble non-toxic organic zinc corrosion inhibitors in acidic solution
      Hazazi, Omar A.
      Chemical Science Review and Letters (2015), 4 (16), 965-978CODEN: CSRLBV; ISSN:2278-6783. (Aufau Periodicals)
      The corrosion inhibition of Zn was investigated in acidic solns. using some polysorbate compds. (tweens) as environmentally safe corrosion inhibitors. The corrosion rate was calcd. in the absence and presence of the corrosion inhibitor using various techniques. The corrosion inhibition process was found to depend on the adsorption of the tween mols. on the metal surface as supported by their influence on the ethanol oxidn. at Pt electrode using cyclic voltammetric technique. Electrochem. measurements indicated that all the additives behave as mixed-type inhibitors. The corrosion inhibition efficiency was found to depend on the concn. of the tween and its structure.
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    28. 28
      Bawazeer, T. M.; Defrawy, A. M. E.; El-Shafei, A. A. Corrosion Inhibition of Zinc in Sodium Sulphate Solution Using Nonionic Surfactants of Tween Series: Experimental and Theoretical Study. Colloids Surf. A 2017, 520, 694– 700,  DOI: 10.1016/j.colsurfa.2017.02.025
      28
      Corrosion inhibition of zinc in sodium sulphate solution using nonionic surfactants of tween series: Experimental and theoretical study
      Bawazeer, Tahani M.; El Defrawy, Ahmed M.; El-Shafei, A. A.
      Colloids and Surfaces, A: Physicochemical and Engineering Aspects (2017), 520 (), 694-700CODEN: CPEAEH; ISSN:0927-7757. (Elsevier B.V.)
      The effects of three tween compds. have been tested as corrosion inhibitors of a zinc surface in 0.1 M of sodium sulfate (Na2SO4) using potentiodynamic, potentiostatic transient in addn. to the Electrochem. Impedance Spectroscopy (EIS) method. The efficiency of the inhibitory effect of these additives was found to decrease in the order: Tween-60 > Tween-80 > Tween-20. These compds. were selected based on their active surface property and high mol. wt. as well as their soly. in aq. media. Cyclic voltammetry (CV) was used to evaluate their effect on the ethanol oxidn. The exptl. results were discussed and the correlation between the outcomes and inhibition properties towards Zn pitting corrosion was accomplished. Finally, quantum chem. descriptors of the tween derivs. that relate to their performance as regards corrosion inhibition efficiency have been detd. and found to be in good agreement with the exptl. results.
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    29. 29
      Wang, D.-Y.; Nie, B.-L.; Li, H.-J.; Zhang, W.-W.; Wu, Y.-C. Anticorrosion Performance of Grape Seed Proanthocyanidins Extract and Tween-80 for Mild Steel in Hydrochloric Acid Medium. J. Mol. Liq. 2021, 331, 115799  DOI: 10.1016/j.molliq.2021.115799
      29
      Anticorrosion performance of grape seed proanthocyanidins extract and Tween-80 for mild steel in hydrochloric acid medium
      Wang, Dan-Yang; Nie, Bo-Li; Li, Hui-Jing; Zhang, Wei-Wei; Wu, Yan-Chao
      Journal of Molecular Liquids (2021), 331 (), 115799CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
      Grape seed proanthocyanidins ext. (GSPE) is extd. from grape seeds, the waste of the grape consumption, based on a three-level three-factor response surface methodol. (RSM). An eco-friendly corrosion inhibitor composed of GSPE and Tween-80 has been developed for mild steel in 1 M hydrochloric acid, whose inhibition performance is evaluated by using wt. loss test, electrochem. investigations, and surface morphol. anal. The mixt. of GSPE and Tween-80 mixt. improves the corrosion inhibition of mild steel compared to individual inhibitors (i.e., 96.48% vs. 77.68%/88.57%), reflecting a synergistic action between GSPE and Tween-80. Adsorption isotherm and kinetic parameters indicate that the adsorption follows Langmuir isotherm, and involves both physisorption and chemisorption. Potentiodynamic polarization (PDP) study shows that the GSPE-Tween-80 mixt. acts as a mixed type inhibitor and mainly inhibits the anodic process. Surface morphol. by scanning electron microscope (SEM), energy dispersive x-ray spectroscopy (EDX) and XPS help to confirm the presence of the GSPE-Tween-80 mixt. on the mild steel surface. Quantum chem. (QC) calcn. and mol. dynamics (MD) simulations studies further supported the exptl. results.
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    30. 30
      Li, Z.; Ganapathy, S.; Xu, Y.; Zhou, Z.; Sarilar, M.; Wagemaker, M. Mechanistic Insight into the Electrochemical Performance of Zn/VO2 Batteries with an Aqueous ZnSO4 Electrolyte. Adv. Energy Mater. 2019, 9, 1900237  DOI: 10.1002/aenm.201900237
      There is no corresponding record for this reference.
    31. 31
      Liu, X.; Yang, J.; Hou, W.; Wang, J.; Nuli, Y. Highly Reversible Lithium-ions Storage of Molybdenum Dioxide Nanoplates for High Power. ChemSusChem 2015, 8, 2621– 2624,  DOI: 10.1002/cssc.201500574
      31
      Highly Reversible Lithium-ions Storage of Molybdenum Dioxide Nanoplates for High Power Lithium-ion Batteries
      Liu, Xiaolin; Yang, Jun; Hou, Wenhua; Wang, Jiulin; Nuli, Yanna
      ChemSusChem (2015), 8 (16), 2621-2624CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Herein, MoO2 nanoplates were facilely prepd. through a hydrothermal process by using MoO3 microbelts as the intercalation host. The obtained MoO2 nanoplates manifest excellent electrochem. properties when the discharge cutoff voltage is simply set at 1.0 V to preclude the occurrence of conversion reactions. Its initial reversible capacity reaches 251 mAh/g, which is larger than that of Li4Ti5O12, at a current rate of 0.2 C. The av. capacity decay is only 0.0465 mAh/g per cycle, with a coulombic efficiency of 99.5% (from the 50th cycle onward) for 2000 cycles at 1 C. Also, this MoO2 electrode demonstrates an outstanding high power performance. When the current rate is increased from 0.2 to 50 C, ∼54% of the capacity is retained. The superior electrochem. performance can be attributed to the metallic cond. of MoO2, short Li+ diffusion distance in the nanoplates, and reversible cryst. phase conversion of the addn.-type reaction of MoO2. The prepd. MoO2 nanoplates may hopefully replace their currently used analogs, such as Li4Ti5O12, in high power lithium-ion batteries.
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    32. 32
      Kumar Sen, U.; Shaligram, A.; Mitra, S. Intercalation Anode Material for Lithium Ion Battery Based on Molybdenum Dioxide. ACS Appl. Mater. Interfaces 2014, 6, 14311– 14319,  DOI: 10.1021/am503605u
      32
      Intercalation Anode Material for Lithium Ion Battery Based on Molybdenum Dioxide
      Kumar Sen, Uttam; Shaligram, Apoorv; Mitra, Sagar
      ACS Applied Materials & Interfaces (2014), 6 (16), 14311-14319CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      MoO2 is one of the most studied anode systems in lithium ion batteries. Previously, the reaction of MoO2 with lithium via conversion reaction has been widely studied. The present study highlights the possible application of MoO2 as an intercalation-based anode material to improve the safety of lithium ion batteries. Nanobelts of MoO2 are prepd. by redn. of MoO3 nanobelts under hydrogen atm. The intercalation behavior of MoO2 is specially focused upon by limiting the charge-discharge cycling to narrow potential window of 1.0 to 2.2 V vs Li/Li+ to avoid conversion reaction. An excellent electrochem. stability over 200 cycles is achieved at a current rate of 100 mAh g-1. A phase transformation from monoclinic to orthorhombic to monoclinic is obsd. during the lithiation process, which is reversible during delithiation process and is confirmed by ex-situ XRD and electrochem. impedance spectroscopy. To further demonstrate the viability of MoO2 as a com. anode material, MoO2 is tested in a full-cell configuration against LiFePO4. The full-cell assembly is cycled for 100 cycles and stable performance is obsd. The combination showed an energy d. of 70 Wh kg-1 after 100 cycles.
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    33. 33
      Han, X.; Gerke, C. S.; Banerjee, S.; Zubair, M.; Jiang, J.; Bedford, N. M.; Miller, E. M.; Thoi, V. S. Strategic Design of MoO2 Nanoparticles Supported by Carbon Nanowires for Enhanced Electrocatalytic Nitrogen Reduction. ACS Energy Lett. 2020, 5, 3237– 3243,  DOI: 10.1021/acsenergylett.0c01857
      33
      Strategic Design of MoO2 Nanoparticles Supported by Carbon Nanowires for Enhanced Electrocatalytic Nitrogen Reduction
      Han, Xu; Gerke, Carter S.; Banerjee, Soumyodip; Zubair, Muhammad; Jiang, Junjie; Bedford, Nicholas M.; Miller, Elisa M.; Thoi, V. Sara
      ACS Energy Letters (2020), 5 (10), 3237-3243CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      Ammonia is an industrially relevant chem. that can be directly synthesized from water and air using renewable energy through the electrochem. nitrogen redn. reaction (NRR). However, because of the inert nature of nitrogen, current attempts at synthesizing ammonia under aq. conditions result in low selectivity and yield rates. The poor electrocatalytic performance is mainly attributed to competing hydrogen evolution, underexposed active sites, inadequate electrode contact, and poor stabilization/destabilization of key reaction intermediates. Herein, a catalyst is presented composed of MoO2 with surface vacancies dispersed over conductive carbon nanowires that mitigates these obstacles for NRR by providing a high surface area with stable catalytic sites and an underlying conductive support, where a variety of X-ray spectroscopy techniques are used to characterize the MoO2 catalyst. This uniquely engineered catalyst exhibits exceptional Faradaic efficiencies of > 30% and yields of 21.2μg h-1 mg-1 at a low potential of -0.1 V vs. RHE under ambient aq. conditions.
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    34. 34
      Luo, Z.; Miao, R.; Huan, T. D.; Mosa, I. M.; Poyraz, A. S.; Zhong, W.; Cloud, J. E.; Kriz, D. A.; Thanneeru, S.; He, J.; Zhang, Y.; Ramprasad, R.; Suib, S. L. Mesoporous MoO3–x Material as an Efficient Electrocatalyst for Hydrogen Evolution Reactions. Adv. Energy Mater. 2016, 6, 1600528  DOI: 10.1002/aenm.201600528
      There is no corresponding record for this reference.
    35. 35
      Li, J.; Ye, Y.; Ye, L.; Su, F.; Ma, Z.; Huang, J.; Xie, H.; Doronkin, D. E.; Zimina, A.; Grunwaldt, J. D.; Zhou, Y. Sunlight Induced Photo-Thermal Synergistic Catalytic CO2 Conversion: Via Localized Surface Plasmon Resonance of MoO3–x. J. Mater. Chem. A 2019, 7, 2821– 2830,  DOI: 10.1039/C8TA10922B
      35
      Sunlight induced photo-thermal synergistic catalytic CO2 conversion via localized surface plasmon resonance of MoO3-x
      Li, Jue; Ye, Yinghao; Ye, Liqun; Su, Fengyun; Ma, Zhaoyu; Huang, Jindi; Xie, Haiquan; Doronkin, Dmitry E.; Zimina, Anna; Grunwaldt, Jan-Dierk; Zhou, Ying
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (6), 2821-2830CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Photocatalytic conversion of CO2 to solar fuels is considered an alternative approach for simultaneously mitigating the greenhouse effect and solving energy shortage. The efficient light harvesting and the thermochem. conversion have been demanding quests in photocatalysis due to the relatively low solar energy utilization efficiency. In this work, oxygen vacancies are induced in MoO3 for improving photo-thermal CO2 redn. efficiency by capturing near-IR (NIR) photons. The localized surface plasmon resonance (LSPR) of MoO3-x triggered by oxygen vacancies enables the efficient capture of NIR photons. Addnl., oxygen vacancies can promote the carrier sepn., improve CO2 adsorption on the defective surface and lower the barrier of CO2 hydrogenation during the conversion process. As a result, MoO3-x displayed dramatically enhanced photo-thermal synergistic CO2 redn. under simulated sunlight (UV-Vis-IR) irradn. than MoO3. The amt. of CO produced by MoO3-x can reach 10.3 μmol g-1 h-1, which is 20 times higher than that of MoO3 (0.52 μmol g-1 h-1). And the CH4 prodn. of MoO3-x can reach 2.08 μmol g-1 h-1, which is 52 times higher than that of MoO3 (0.04 μmol g-1 h-1). In situ FT-IR and theor. calcns. also proved the enhanced activity of MoO3-x. This work highlights the significance of defect engineering for improving the photo-thermal catalytic conversion of CO2.
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    36. 36
      Kuwahara, Y.; Mihogi, T.; Hamahara, K.; Kusu, K.; Kobayashi, H.; Yamashita, H. A Quasi-Stable Molybdenum Sub-Oxide with Abundant Oxygen Vacancies That Promotes CO2 Hydrogenation to Methanol. Chem. Sci. 2021, 12, 9902– 9915,  DOI: 10.1039/D1SC02550C
      36
      A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol
      Kuwahara, Yasutaka; Mihogi, Takashi; Hamahara, Koji; Kusu, Kazuki; Kobayashi, Hisayoshi; Yamashita, Hiromi
      Chemical Science (2021), 12 (29), 9902-9915CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Prodn. of methanol from anthropogenic carbon dioxide (CO2) is a promising chem. process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, redn. of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/HxMoO3-y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat-1 h-1 in liq.-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200°C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Expts. and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance IR Fourier transform (DRIFT) spectroscopy and d. functional theory (DFT) calcns. reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable HxMoO3-y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissocn. sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the exptl. and computational studies, an oxygen-vacancy-mediated "reverse Mars-van Krevelen (M-vK)" mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion.
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    37. 37
      Kuwahara, Y.; Mihogi, T.; Hamahara, K.; Kusu, K.; Kobayashi, H.; Yamashita, H. A Quasi-Stable Molybdenum Sub-Oxide with Abundant Oxygen Vacancies That Promotes CO2 Hydrogenation to Methanol. Chem. Sci. 2021, 12, 9902– 9915,  DOI: 10.1039/D1SC02550C
      37
      A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol
      Kuwahara, Yasutaka; Mihogi, Takashi; Hamahara, Koji; Kusu, Kazuki; Kobayashi, Hisayoshi; Yamashita, Hiromi
      Chemical Science (2021), 12 (29), 9902-9915CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Prodn. of methanol from anthropogenic carbon dioxide (CO2) is a promising chem. process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, redn. of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/HxMoO3-y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat-1 h-1 in liq.-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200°C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Expts. and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance IR Fourier transform (DRIFT) spectroscopy and d. functional theory (DFT) calcns. reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable HxMoO3-y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissocn. sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the exptl. and computational studies, an oxygen-vacancy-mediated "reverse Mars-van Krevelen (M-vK)" mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion.
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    38. 38
      Thakur, P.; Cezar, J. C.; Brookes, N. B.; Choudhary, R. J.; Prakash, R.; Phase, D. M.; Chae, K. H.; Kumar, R. Direct Observation of Oxygen Induced Room Temperature Ferromagnetism in MoO2 Thin Films by X-Ray Magnetic Circular Dichroism Characterizations. Appl. Phys. Lett. 2009, 94, 062501  DOI: 10.1063/1.3080679
      38
      Direct observation of oxygen induced room temperature ferromagnetism in MoO2 thin films by x-ray magnetic circular dichroism characterizations
      Thakur, P.; Cezar, J. C.; Brookes, N. B.; Choudhary, R. J.; Prakash, Ram; Phase, D. M.; Chae, K. H.; Kumar, Ravi
      Applied Physics Letters (2009), 94 (6), 062501/1-062501/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
      We report the element specific polarized near edge x-ray absorption fine structure (NEXAFS) and x-ray magnetic CD (XMCD) expts. on well characterized undoped MoO2 thin films that show ferromagnetism at room temp. The polarization dependent of O K edge NEXAFS spectra indicate a strong hybridization of O 2p-4d Mo orbitals followed by a strong anisotropy in the electronic properties. An unquenched orbital magnetic moment within the O 2p shell is clearly evident from the XMCD O K edge, which is ferromagnetically coupled to the neighboring Mo moments as confirmed by Mo M3,2 edge XMCD expt. (c) 2009 American Institute of Physics.
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    39. 39
      Xie, K.; Ren, K.; Sun, C.; Yang, S.; Tong, M.; Yang, S.; Liu, Z.; Wang, Q. Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte Additive for Uniform Zinc Deposition. ACS Appl. Energy Mater. 2022, 5, 4170– 4178,  DOI: 10.1021/acsaem.1c03558
      39
      Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte Additive for Uniform Zinc Deposition
      Xie, Kaixuan; Ren, Kaixin; Sun, Chuang; Yang, Shuna; Tong, Minman; Yang, Shun; Liu, Zhifang; Wang, Qinghong
      ACS Applied Energy Materials (2022), 5 (4), 4170-4178CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Zn-ion batteries are re-evaluated as a potential choice to address the safety issue and cost concerns of current energy storage systems. Unfortunately, further application is severely hindered by low coulombic efficiency and poor cycle life, which are caused by the undesirable dendrite growth and side reactions on metal Zn anode. Herein, EDTA (EDTA) is employed as an electrolyte additive to solve the problem. The functional groups of EDTA adsorption layer on Zn foil results in refined grains by providing abundant nucleation sites for initial deposition and further induces uniform and flat Zn deposition without dendrites. Moreover, the chelation of EDTA with Zn2+ changes the coordination environment of hydrated Zn2+ and suppresses the side reactions. The smooth deposition of Zn endows the Zn anodes with super stability in both sym. cells and Zn-V2O5 full cells. This work provides a simple and feasible approach for solving anode issues in high-performance and safe Zn-ion batteries.
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    40. 40
      Li, T. C.; Lim, Y.; Li, X. L.; Luo, S.; Lin, C.; Fang, D.; Xia, S.; Wang, Y.; Yang, H. Y. A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage. Adv. Energy Mater. 2022, 12, 2103231  DOI: 10.1002/aenm.202103231
      40
      A Universal Additive Strategy to Reshape Electrolyte Solvation Structure toward Reversible Zn Storage
      Li, Tian Chen; Lim, YewVon; Li, Xue Liang; Luo, Songzhu; Lin, Congjian; Fang, Daliang; Xia, Sunwen; Wang, Ye; Yang, Hui Ying
      Advanced Energy Materials (2022), 12 (15), 2103231CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      The benefits of Zn, despite many of its performance advantages (e.g., high theor. capacity and low redox potential), are compromised by severe side reactions and Zn dendrite growth in aq. electrolytes, due to the coordinated H2O within the Zn2+-solvation sheath and reactive free water in the bulk electrolyte. Unlike most efforts focused on costly super-concd. electrolytes and single additive species, a universal strategy is proposed to boost Zn reversibility in dil. electrolytes via adding carbonyl-contg. org. solvents. Based on exptl. investigations and multiscale simulations, the representative electrolyte with a N-methyl-2-pyrrolidone polar additive is proved to assist in structural reshaping of Zn2+-solvation and stabilizing the hydrogen bond network of water. This synergy is instrumental in contributing to suppressed water-induced parasitic reactions and dendrite formation, which enables high av. coulombic efficiency of 99.7% over 1000 cycles in an Zn/Cu asym. cell, and an ultralong cycling lifespan of 2000 cycles with 99.4% capacity retention in a Zn/VS2@SS full cell. Even with an elevated cathodic mass loading (up to 9.5 mg cm-2), the cycling stability is still maintained. The proposed strategy provides new insight into electrolyte additive design and sheds light on high-performance Zn-ion batteries.
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    41. 41
      Ben-Dor, L.; Shimony, Y. Crystal structure, magnetic susceptibility and electrical conductivity of pure and NiO-doped MoO2 and WO2. Mater. Res. Bull. 1974, 9, 837– 844,  DOI: 10.1016/0025-5408(74)90120-2
      41
      Crystal structure, magnetic susceptibility, and electrical conductivity of pure and nickel(II) oxide-doped molybdenum(IV) oxide and tungsten(IV) oxide
      Ben-Dor, L.; Shimony, Y.
      Materials Research Bulletin (1974), 9 (6), 837-44CODEN: MRBUAC; ISSN:0025-5408.
      Single crystals of MoO2 and WO2, pure and doped with NiO, were grown by chem. transport with I as the transporting agent. X-ray diffraction showed the crystals to be monoclinic. Doping up to 5% does not change the crystallog. consts. The pure crystals are weakly paramagnetic (χM < 100 × 10-6 emu), but doping raises the susceptibility markedly, to ∼2500 × 10-6 emu. These materials are metallic conductors, with room-temp. resistivities of ∼10-4-10-3 Ω-cm, decreasing by an order of magnitude at liq.-N temp. Doping substantially lowers the cond.
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    42. 42
      Kaiser, F.; Simon, P.; Burkhardt, U.; Kieback, B.; Grin, Y.; Veremchuk, I. Spark Plasma Sintering of Tungsten Oxides WOx (2.50 ≤ x ≤ 3): Phase Analysis and Thermoelectric Properties. Crystals 2017, 7, 271,  DOI: 10.3390/cryst7090271
      42
      Spark plasma sintering of tungsten oxides WOx (2.50 ≤ x ≤ 3): phase analysis and thermoelectric properties
      Kaiser, Felix; Simon, Paul; Burkhardt, Ulrich; Kieback, Bernd; Grin, Yuri; Veremchuk, Igor
      Crystals (2017), 7 (9), 271/1-271/14CODEN: CRYSBC; ISSN:2073-4352. (MDPI AG)
      The solid-state reaction of WO3 with W was studied in order to clarify the phase formation in the binary system W-O around the compn. WOx (2.50 ≤ x ≤ 3) during spark plasma sintering (SPS). A new phase "WO" is obsd. in the range 2.72 ≤ × ≤ 2.90 which might have the compn. W12O34. The influence of the compn. on the thermoelec. properties was investigated for 2.72 ≤ × ≤ 3. The Seebeck coeff., elec. cond. and electronic thermal cond. are continuously tunable with the oxygen-to-tungsten ratio. The phase formation mainly affects the lattice thermal cond. κlat which is significantly reduced until 700 K for the sample with the compn. × ≤ 2.84, which contains the phases W12O34 and "WO". In single-phase WO and multi-phase WOx materials (2.90 ≤ × ≤ 3), which contain crystallog. shear plane phases, a similar reduced κlat is obsd. only below 560 K and 550 K, resp. Therefore, the compn. range × < 2.90 in which the pentagonal column structural motif is formed might be more suitable for decreasing the lattice thermal cond. at high temps.
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    43. 43
      Horkans, J.; Shafer, M. W. An Investigation of the Electrochemistry of a Series of Metal Dioxides with Rutile-Type Structure MoO2, WO2, ReO2, RuO2, OsO2, and IrO2. J. Electrochem. Soc. 1977, 124, 1202,  DOI: 10.1149/1.2133528
      43
      An investigation of the electrochemistry of a series of metal dioxides with rutile-type structure: Molybdenum dioxide, tungsten dioxide, rhenium dioxide, osmium dioxide and iridium dioxide
      Horkans, Jean; Shafer, M. W.
      Journal of the Electrochemical Society (1977), 124 (8), 1202-7CODEN: JESOAN; ISSN:0013-4651.
      Six transition metal dioxides, MoO2, WO2, ReO2, RuO2, OsO2, and IrO2, were examd. as electrodes in H2SO4 soln. The oxides MoO2, WO2, ReO2, and RuO2 have broad current-potential profiles, indicating the formation of a surface layer which can exist over a range of compns. Steady-state measurements of O redn. showed catalytic activities which were low compared to common O catalysts such as Pt, but of the same order as other oxide catalysts. Activities were lowest for WO2 and ReO2, which form resistive surface layers of a higher oxide. The only material studied which was sufficienty stable to allow measurement of both O evolution and O redn. was RuO2. The current-potential profiles of OsO2 and IrO2 are characterized by distinct changes of oxidn. state. These oxides were not sufficiently stable to allow the measurement of O redn.
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    44. 44
      Ma, J.; Fu, J.; Niu, M.; Quhe, R. MoO2 and Graphene Heterostructure as Promising Flexible Anodes for Lithium-Ion Batteries. Carbon 2019, 147, 357– 363,  DOI: 10.1016/j.carbon.2019.03.006
      44
      MoO2 and graphene heterostructure as promising flexible anodes for lithium-ion batteries
      Ma, Jiachen; Fu, Jia; Niu, Mengqi; Quhe, Ruge
      Carbon (2019), 147 (), 357-363CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)
      Two-dimensional van der Waals heterostructures hold great promise to create lithium-ion batteries with large energy d., large power d., and long cycle life. In this work, we investigate the MoO2/graphene heterostructure as anodes for lithium-ion batteries by first principles calcns. It is found that the MoO2/graphene heterostructure possesses enhanced elec. cond., high theor. specific capacity (1411 mAh•g-1), and small diffusion barriers (77 meV). Meanwhile, the flexibility of graphene eliminates the irreversible deformation of MoO2 during the charge-discharge process. These characteristics render the MoO2/graphene heterostructure a stable and efficient Li ion storage performance.
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    45. 45
      De Melo, O.; González, Y.; Climent-Font, A.; Galán, P.; Ruediger, A.; Sánchez, M.; Calvo-Mola, C.; Santana, G.; Torres-Costa, V. Optical and Electrical Properties of MoO2 and MoO3 Thin Films Prepared from the Chemically Driven Isothermal Close Space Vapor Transport Technique. J. Phys.: Condens. Matter 2019, 31, 295703  DOI: 10.1088/1361-648X/ab18e2
      45
      Optical and electrical properties of MoO2 and MoO3 thin films prepared from the chemically driven isothermal close space vapor transport technique
      de Melo, O.; Gonzalez, Y.; Climent-Font, A.; Galan, P.; Ruediger, A.; Sanchez, M.; Calvo-Mola, C.; Santana, G.; Torres-Costa, V.
      Journal of Physics: Condensed Matter (2019), 31 (29), 295703CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
      Chem.-driven isothermal close space vapor transport was used to prep. pure MoO2 thin films which were eventually converted to MoO3 by annealing in air. According to temp.-dependent Raman measurements, the MoO2/MoO3 phase transformation occurs at 225-350° while no other phases were detected during the transition. A clear change in compn. as well as noticeable modifications of the band gap and the absorption coeff. confirmed the conversion from MoO2 to MoO3. An extensive characterization of these 2 pure phases was carried out. In particular, a procedure was developed to det. the dispersion relation of the refractive index of MoO2 from the shift of the interference fringes of the used SiO2/Si substrate. The obtained data of the refractive index was cor. taking into account the porosity of the samples calcd. from elastic backscattering spectrometry. The Debye temp. and the residual resistivity were extd. from the elec. resistivity temp. dependence using the Bloch-Gruneisen equation. MoO3 converted samples presented a very high resistivity and a typical semiconducting behavior. They also showed intense and broad luminescence spectra composed by several contributions whose temp. behavior was examd. Also, surface photovoltage spectra were taken and their relation with the luminescence is discussed.
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    46. 46
      Enneti, R. K.; Wolfe, T. A. Agglomeration during Reduction of MoO3. Int. J. Refract. Metals Hard. Mater. 2012, 31, 47– 50,  DOI: 10.1016/j.ijrmhm.2011.09.004
      46
      Agglomeration during reduction of MoO3
      Enneti, Ravi K.; Wolfe, Thomas A.
      International Journal of Refractory Metals & Hard Materials (2012), 31 (), 47-50CODEN: IRMME3; ISSN:0958-0611. (Elsevier Ltd.)
      Mo powder was manufd. in a two step process starting from MoO3. The first step redn. of MoO3 to MoO2 was carried out in rotary calciners. Agglomeration of powder occurs during this redn. stage resulting in several manufg. issues. The evolution of agglomeration during the redn. of MoO3 was investigated in the current study. As-received MoO3 and MoO3 milled for 0.5 h were used as the starting powders. The powders were reduced at 550, 650, and 750° in a hydrogen atm. The starting and reduced powders at various temps. were analyzed using BET surface area, XRD, and SEM techniques. The surface area of the reduced powders was monitored for quantifying the degree of agglomeration. The surface area was found to be min. for the samples reduced at 650°. SEM observations confirmed the agglomeration of powders during redn. process. XRD anal. showed complete redn. of MoO3 to MoO2 at 650 and 750°. The agglomeration of the powders was either due to melting of eutectic formed between MoO3 and Mo4O11 or due to partial melting of MoO3. The redn. of MoO3 is recommended to be completed at a low temp. to prevent agglomeration of the oxide powders.
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    47. 47
      Zhang, S.; Wang, G.; Jin, J.; Zhang, L.; Wen, Z.; Yang, J. Self-Catalyzed Decomposition of Discharge Products on the Oxygen Vacancy Sites of MoO3 Nanosheets for Low-Overpotential Li-O2 Batteries. Nano Energy 2017, 36, 186– 196,  DOI: 10.1016/j.nanoen.2017.04.038
      47
      Self-catalyzed decomposition of discharge products on the oxygen vacancy sites of MoO3 nanosheets for low-overpotential Li-O2 batteries
      Zhang, Sanpei; Wang, Gan; Jin, Jun; Zhang, Linlin; Wen, Zhaoyin; Yang, Jianhua
      Nano Energy (2017), 36 (), 186-196CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      The efficient reversible formation of discharge products for Li-O2 batteries is still challenging. Meanwhile, the question of the nature of the discharge products and their decompn. mechanism are still remain. Implanting oxygen vacancies on the metal oxides can create neg.-charge surface to provide strong adsorption of active oxygen and at the same time, the exposed metal sites can serve as an efficient substrate for decompd. reaction of discharge products. In this work, we apply the graphene-like MoO3 ultrathin nanosheets as a matrix. By controlling the redn. time, the MoO3 nanosheets with different concn. of oxygen vacancy are obtained. Exptl. results reveal that the MoO3 nanosheets with the high-concn. oxygen vacancies can significantly decrease the overpotential and get enhanced electrochem. response, namely, a low overpotential of ∼0.5 V can be delivered with ultra-stable cycles (over 60 cycles). Moreover, the Li-O2 batteries demonstrate an interesting four-step discharge and charge process. XPS, X-ray diffraction, transmission electron microscopy and electron energy-loss spectroscopy analyses are carried out for the four typical states of the cathode to reveal the reaction mechanism for the unique electrochem. behavior.
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    48. 48
      Du, W.; Yan, J.; Cao, C.; Li, C. C. Electrocrystallization Orientation Regulation of Zinc Metal Anodes: Strategies and Challenges. Energy Storage Mater. 2022, 52, 329– 354,  DOI: 10.1016/j.ensm.2022.07.046
      There is no corresponding record for this reference.
    49. 49
      Wu, Z.; Li, M.; Tian, Y.; Chen, H.; Zhang, S.-J.; Sun, C.; Li, C.; Kiefel, M.; Lai, C.; Lin, Z.; Zhang, S. Cyclohexanedodecol-Assisted Interfacial Engineering for Robust and High-Performance Zinc Metal Anode. Nano-Micro Lett. 2022, 14, 110,  DOI: 10.1007/s40820-022-00846-0
      49
      Cyclohexanedodecol-assisted interfacial engineering for robust and high-performance zinc metal anode
      Wu, Zhenzhen; Li, Meng; Tian, Yuhui; Chen, Hao; Zhang, Shao-Jian; Sun, Chuang; Li, Chengpeng; Kiefel, Milton; Lai, Chao; Lin, Zhan; Zhang, Shanqing
      Nano-Micro Letters (2022), 14 (), 110CODEN: NLAEBV; ISSN:2150-5551. (Nano-Micro Letters)
      Aq. zinc-ion batteries (AZIBs) can be one of the most promising electrochem. energy storage devices for being non-flammable, low-cost, and sustainable. However, the challenges of AZIBs, including dendrite growth, hydrogen evolution, corrosion, and passivation of zinc anode during charging and discharging processes, must be overcome to achieve high cycling performance and stability in practical applications. In this work, we utilize a dual-functional org. additive cyclohexanedodecol (CHD) to firstly establish [Zn(H2O)5(CHD)]2+ complex ion in an aq. Zn electrolyte and secondly build a robust protection layer on the Zn surface to overcome these dilemmas. Systematic expts. and theor. calcns. are carried out to interpret the working mechanism of CHD. At a very low concn. of 0.1 mg mL-1 CHD, long-term reversible Zn plating/stripping could be achieved up to 2200 h at 2 mA cm-2, 1000 h at 5 mA cm-2, and 650 h at 10 mA cm-2 at the fixed capacity of 1 mAh cm-2. When matched with V2O5 cathode, the resultant AZIBs full cell with the CHD-modified electrolyte presents a high capacity of 175 mAh g-1 with the capacity retention of 92% after 2000 cycles under 2 A g-1. Such a performance could enable the commercialization of AZIBs for applications in grid energy storage and industrial energy storage.
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    50. 50
      He, X.; Bresser, D.; Passerini, S.; Baakes, F.; Krewer, U.; Lopez, J.; Mallia, C. T.; Shao-Horn, Y.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Soto, F. A.; Ponce, V.; Seminario, J. M.; Balbuena, P. B.; Jia, H.; Xu, W.; Xu, Y.; Wang, C.; Horstmann, B.; Amine, R.; Su, C.-C.; Shi, J.; Amine, K.; Winter, M.; Latz, A.; Kostecki, R. The Passivity of Lithium Electrodes in Liquid Electrolytes for Secondary Batteries. Nat. Rev. Mater. 2021, 6, 1036– 1052,  DOI: 10.1038/s41578-021-00345-5
      50
      The passivity of lithium electrodes in liquid electrolytes for secondary batteries
      He, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, Robert
      Nature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)
      Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
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    51. 51
      Wang, X.; Meng, J.; Lin, X.; Yang, Y.; Zhou, S.; Wang, Y.; Pan, A. Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings. Adv. Funct. Mater. 2021, 31, 2106114  DOI: 10.1002/adfm.202106114
      51
      Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings
      Wang, Xia; Meng, Junping; Lin, Xuguang; Yang, Yadi; Zhou, Shuang; Wang, Yaping; Pan, Anqiang
      Advanced Functional Materials (2021), 31 (48), 2106114CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The uneven electrodeposition and inferior corrosion resistance are the fundamental obstacles to achieve stable Zn metal anodes. The features of the electrode surface/interface are closely correlated with the properties. Herein, the Zn surface with more exposed (002)Zn planes is modified through a simple acid-etching approach. The in situ generated zinc compds. form an interface layer with strong adhesion to the Zn electrode, which can enhance the Zn2+ ion kinetics and regulate the deposition/dissoln. behaviors. A variety of acids with functional cations are selected, among which the phosphoric acid etches the Zn with a higher extent of texturing and generates a more compact layer. The obtained zinc phosphate@Zn electrode enables stable cycling and fast kinetics in sym. and full Zn metal batteries. This study provides a new example of combined surface and interface modification toward high-performance aq. zinc metal anodes.
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    52. 52
      Rana, A.; Thakare, A.; Kumar, N.; Mukherjee, B.; Torris, A.; Das, B.; Ogale, S.; Banerjee, A. Mitigating Dendrite Formation on a Zn Electrode in Aqueous Zinc Chloride by the Competitive Surface Chemistry of an Imidazole Additive. ACS Appl. Mater. Interfaces 2023, 15, 23093– 23103,  DOI: 10.1021/acsami.3c01310
      52
      Mitigating dendrite formation on a Zn electrode in aqueous zinc chloride by the competitive surface chemistry of an imidazole additive
      Rana, Ashutosh; Thakare, Anup; Kumar, Nikhil; Mukherjee, Buddhadev; Torris, Arun; Das, Bidisa; Ogale, Satishchandra; Banerjee, Abhik
      ACS Applied Materials & Interfaces (2023), 15 (19), 23093-23103CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Electrochem. energy storage systems are crit. in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technol., since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a redn. potential of -0.76 V vs SHE) has a significantly higher theor. volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via exptl. (kinetics and imaging) and theor. d. functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concn. of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addn. of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-sym. cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomog. reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn sym. cells. It is obsd. that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the prodn. of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calcns. conform well with the stated exptl. observations.
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    53. 53
      Mitha, A.; Yazdi, A. Z.; Ahmed, M.; Chen, P. Surface Adsorption of Polyethylene Glycol to Suppress Dendrite Formation on Zinc Anodes in Rechargeable Aqueous Batteries. ChemElectroChem. 2018, 5, 2409– 2418,  DOI: 10.1002/celc.201800572
      53
      Surface Adsorption of Polyethylene Glycol to Suppress Dendrite Formation on Zinc Anodes in Rechargeable Aqueous Batteries
      Mitha, Aly; Yazdi, Alireza Z.; Ahmed, Moin; Chen, Pu
      ChemElectroChem (2018), 5 (17), 2409-2418CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Aq. metal batteries routinely suffer from the dendritic growth at the anode, leading to significant capacity fading and ultimately, battery failure from short-circuit. Herein, we utilize polyethylene glycol to regulate dendrite growth and improve the long-term cycling stability of an aq. rechargeable lithium/zinc battery. PEG200 in the electrolyte decreases the corrosion and chronoamperometric current densities of the zinc electrode up to four-fold. Batteries with pre-grown dendrites also perform significantly better when PEG is present in the electrolyte (41.4 mAh g-1 vs. 7.9 mAh g-1 after 1000 cycles). X-ray diffraction and electron microscopy studies show that dendrites in the PEG-contg. electrolyte have been inhibited, leading to much smaller/smoother surface features than those of the control. The facile prepn. process of the aq. electrolyte combined with low cost and vast performance improvement in batteries of all sizes indicates high upscaling viability.
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    54. 54
      Jian, Q.; Wan, Y.; Lin, Y.; Ni, M.; Wu, M.; Zhao, T. A Highly Reversible Zinc Anode for Rechargeable Aqueous Batteries. ACS Appl. Mater. Interfaces 2021, 13, 52659– 52669,  DOI: 10.1021/acsami.1c15628
      54
      A Highly Reversible Zinc Anode for Rechargeable Aqueous Batteries
      Jian, Qinping; Wan, Yuhan; Lin, Yanke; Ni, Meng; Wu, Maochun; Zhao, Tianshou
      ACS Applied Materials & Interfaces (2021), 13 (44), 52659-52669CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Zinc metal holds a great potential as an anode material for next-generation aq. batteries due to its suitable redox potential, high specific capacity, and low cost. However, the uncontrollable dendrite growth and detrimental side reactions with electrolytes hinder the practical application of this type of electrodes. To tackle the issues, an ultrathin (~ 1μm) sulfonated poly(ether ether ketone) (SPEEK) solid-electrolyte interphase (SEI) is constructed onto the Zn anode surface by a facile spin-coating method. We demonstrate that the polymeric SEI simultaneously blocks the water mols. and anions, uniformizes the ion flux, and facilitates the desolvation process of Zn2+ ions, thus effectively suppressing the side reactions and Zn dendrite formation. As a result, the newly developed Zn@SPEEK anode enables a sym. cell to stably operate over 1000 cycles at 5 mA cm-2 without degrdn. Moreover, with the Zn anode paired with a MnO2 cathode, the full cell exhibits an improved Coulombic efficiency (over 99% at 0.1 A g-1), a superior rate capability (127 mA h g-1 at 2 A g-1), and excellent cycling stability (capacity retention of 70% over 1000 cycles at 1 A g-1). This work provides a facile yet effective strategy to address the crit. challenges in Zn anodes, paving the way for the development of high-performance rechargeable aq. batteries.
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    55. 55
      Shi, W.; Song, Z.; Wang, J.; Li, Q.; An, Q. Phytic Acid Conversion Film Interfacial Engineering for Stabilizing Zinc Metal Anode. Chem. Eng. J. 2022, 446, 137295  DOI: 10.1016/j.cej.2022.137295
      55
      Phytic acid conversion film interfacial engineering for stabilizing zinc metal anode
      Shi, Wenchao; Song, Zhenjun; Wang, Junjun; Li, Qi; An, Qinyou
      Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 446 (Part_4), 137295CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Due to the high safety and low cost, aq. zinc ion batteries (ZIBs) have attracted more and more attention and are expected to become the next generation energy storage system. However, the cycle lifespan of ZIBs is limited due to the issues of zinc (Zn) dendrites and side reactions, which seriously hinders their further development. Herein, a simple interfacial engineering strategy was designed in which a layer of dense phytic acid (PA) conversion film was constructed on the surface of Zn metal (Zn@PA). The film can inhibit the direct contact between Zn metal and electrolyte, reducing side reactions. Moreover, it can effectively regulate the Zn ions deposition behavior to realize the compact Zn deposition owing to its strong adsorption and extremely low barrier migration of Zn ions, thus significantly extending the cycle lifespan of Zn anode. As proof, the assembled Zn@PA sym. cell exhibited a long-cycle lifespan of 3900 h at a c.d. of 1 mA cm-2. In addn., the Zn@PA-MnO2 full cell showed no capacity decay during 500 cycles at a c.d. of 1 A g-1. Most importantly, it can retain a high discharge specific capacity of 110.6 mAh g-1 after 30,000 cycles at a high c.d. of 5 A g-1. The remarkable effects of the strategy show its application prospect in high-rate and long-life ZIBs.
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    56. 56
      Zhu, J.; Deng, W.; Yang, N.; Xu, X.; Huang, C.; Zhou, Y.; Zhang, M.; Yuan, X.; Hu, J.; Li, C.; Li, R. Biomolecular Regulation of Zinc Deposition to Achieve Ultra-Long Life and High-Rate Zn Metal Anodes. Small 2022, 18, 2202509  DOI: 10.1002/smll.202202509
      56
      Biomolecular Regulation of Zinc Deposition to Achieve Ultra-Long Life and High-Rate Zn Metal Anodes
      Zhu, Jinlin; Deng, Wenjun; Yang, Na; Xu, Xianqi; Huang, Chao; Zhou, Yi; Zhang, Man; Yuan, Xinran; Hu, Jun; Li, Chang; Li, Rui
      Small (2022), 18 (29), 2202509CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Aq. zinc-ion batteries (ZIBs) have been extensively studied due to their inherent safety and high energy d. for large-scale energy storage. However, the practical application is significantly limited by the growing Zn dendrites on metallic Zn anode during cycling. Herein, an environmental biomol. electrolyte additive, fibroin (FI), is proposed to guide the homogeneous Zn deposition and stabilize Zn anode. This work demonstrates that the FI mols. with abundant electron-rich groups (NH, OH, and CO) can anchor on Zn anode surface to provide more nucleation sites and suppress the side reactions, and the strong interaction with water mols. can simultaneously regulate the Zn2+ coordination environment facilitating the uniform deposition of Zn. As a consequence, only 0.5 wt% FI additive enables a highly reversible Zn plating/stripping over 4000 h at 1 mA cm-2, indicating a sufficient advance in performance over state-of-the-art Zn anodes. Furthermore, when applied to a full battery (NaVO/Zn), the cell exhibits excellent capacity retention of 98.4% after 1000 cycles as well as high Coulombic efficiency of 99%, whereas the cell only operates for 68 cycles without FI additive. This work offers a non-toxic, low-cost, effective additive strategy to solve dendrites problems and achieve long-life and high-performance rechargeable aq. ZIBs.
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    57. 57
      Su, T.-T.; Wang, K.; Shao, C.-Y.; Le, J.-B.; Ren, W.-F.; Sun, R.-C. Surface Control Behavior toward Crystal Regulation and Anticorrosion Capacity for Zinc Metal Anodes. ACS Appl. Mater. Interfaces 2023, 15, 20040– 20052,  DOI: 10.1021/acsami.2c22477
      57
      Surface Control Behavior toward Crystal Regulation and Anticorrosion Capacity for Zinc Metal Anodes
      Su, Ting-Ting; Wang, Ke; Shao, Chang-You; Le, Jia-Bo; Ren, Wen-Feng; Sun, Run-Cang
      ACS Applied Materials & Interfaces (2023), 15 (16), 20040-20052CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      The com. application of high-safety aq. zinc (Zn) secondary batteries is hindered by the poor cycling life of Zn metal anodes. Here we propose a dendrite growth and hydrogen evolution corrosion reaction mechanism from the binding energy of the deposited crystal plane on the Zn surface and the adsorption energy of H2O mols. on different crystal planes as well as the binding energy of H2O mols. with Zn2+ ions. The biomass-based alkyl polyglucoside (APG) surfactant is adopted as an electrolyte additive of 0.15% to regulate the preferential growth of a parallel Zn(002) plane and enhance the anticorrosion ability of Zn metal anodes. The robust binding and adsorption energies of APG with Zn2+ ions in the aq. electrolyte and the Zn(002) plane on Zn surface generate a synergistic effect to increase the concn. of Zn2+ ions on the APG-adsorbed Zn(002) plane, endowing the continuous growth of the preferential parallel Zn(002) plane and the excellent anticorrosion capacity. Accordingly, the long-term cycle stability of 4000 h can be achieved for Zn anodes with APG additives, which is better than that with pure ZnSO4 electrolyte. With the addn. of APG in the anolyte electrolyte, Zn-I2 full cells display excellent cycling performance (70 mAh g-1 after 20000 cycles) as compared with that without APG additives.
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    58. 58
      Zhu, Y.; Free, M. L.; Woollam, R.; Durnie, W. A Review of Surfactants as Corrosion Inhibitors and Associated Modeling. Prog. Mater. Sci. 2017, 90, 159– 223,  DOI: 10.1016/j.pmatsci.2017.07.006
      58
      A review of surfactants as corrosion inhibitors and associated modeling
      Zhu, Yakun; Free, Michael L.; Woollam, Richard; Durnie, William
      Progress in Materials Science (2017), 90 (), 159-223CODEN: PRMSAQ; ISSN:0079-6425. (Elsevier Ltd.)
      Surfactants have been commonly used as corrosion inhibitors for the protection of metallic materials against corrosion. The amphiphilic nature of surfactant mols. creates an affinity for adsorption at interfaces such as metal/metal oxide-water interface. The adsorption of surfactant on metals and metal oxides creates a barrier that can inhibit corrosion. The properties of surfactant and the interaction of surfactant with metal or metal oxide and the surrounding soln. environments det. the level of adsorption and corrosion inhibition. Understanding and modeling the behavior of surfactants in corrosive environments is crit. to optimal utilization of surfactants as corrosion inhibitors. This review of surfactants as corrosion inhibitors is designed to provide systemic evaluation of various phys. and chem. properties of surfactants, surfactant behaviors in corrosive environments, and their influence in corrosion inhibition, which can be used to improve the effectiveness with which surfactants are used as corrosion inhibitors in a variety of environments. Progress in the development of various predictive models, including semi-empirical models, mechanistic models, and multiphysics models, are reviewed for the evaluation and prediction of surfactant properties and surfactant corrosion inhibition efficiency. Applications of these models to exptl. design and anal., surfactant design and selection, and lifetime prediction are also discussed.
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    59. 59
      Dong, N.; Zhao, X.; Yan, M.; Li, H.; Pan, H. Synergetic Control of Hydrogen Evolution and Ion-Transport Kinetics Enabling Zn Anodes with High-Areal-Capacity. Nano Energy 2022, 104, 107903  DOI: 10.1016/j.nanoen.2022.107903
      59
      Synergetic control of hydrogen evolution and ion-transport kinetics enabling Zn anodes with high-areal-capacity
      Dong, Ning; Zhao, Xuesong; Yan, Mengdie; Li, Hong; Pan, Huilin
      Nano Energy (2022), 104 (Part_A), 107903CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      Intrinsic uneven Zn deposition-dissoln. and hydrogen evolution reaction (HER) induce poor reversibility and limited cycle life of Zn anodes, which thus restrict the practical application of rechargeable aq. Zn batteries. In this work, a synergistic strategy of porous indium (In) coating layer combined with a polyacrylamide (PAM) polymer layer for Zn anodes is proposed to provide large HER overpotential while facilitating fast and homogeneous Zn2+ transport at the electrode-electrolyte interface. The corrosion reaction and Zn dendrite growth are simultaneously prevented at high utilization of Zn anodes. The optimal ZnIn-PAM electrodes demonstrate outstanding cycling stability at ultra-high c.d. and areal capacity (10 mA cm-2, 10 mAh cm-2, Zn utilization: 57%) for over 400 h, and long-term lifespan for over 1700 h at 5 mA cm-2 and 5 mAh cm-2 (Zn utilization: 28.5%) with only ∼50 mV overpotential. Coupled with electrolytic manganese dioxide cathode, the full cell delivers ultra-long lifespan of 10000 cycles with capacity decay rate of 0.006% per cycle at 5 C. This work provides useful perspective for exploring synergetic strategies to address the limited cycling stability of Zn metal-based aq. batteries for practical use.
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    60. 60
      Zhou, W.; Chen, M.; Tian, Q.; Chen, J.; Xu, Z.; Wong, C.-P. Cotton-Derived Cellulose Film as a Dendrite-Inhibiting Separator to Stabilize the Zinc Metal Anode of Aqueous Zinc Ion Batteries. Energy Storage Mater. 2022, 44, 57– 65,  DOI: 10.1016/j.ensm.2021.10.002
      There is no corresponding record for this reference.
    61. 61
      Zhang, Y.; Chen, P.; Li, M.; Li, S.; Yue, Y.; Wang, Y.; Xie, S.; Zhou, W. Highly Reversible, Dendrite-Free and Low-Polarization Zn Metal Anodes Enabled by a Thin SnO2 Layer for Aqueous Zn-Ion Batteries. J. Mater. Chem. A 2023, 11, 14333– 14344,  DOI: 10.1039/D3TA01415K
      61
      Highly reversible, dendrite-free and low-polarization Zn metal anodes enabled by a thin SnO2 layer for aqueous Zn-ion batteries
      Zhang, Yuejuan; Chen, Penghui; Li, Mingming; Li, Shaoqing; Yue, Ying; Wang, Yanchun; Xie, Sishen; Zhou, Weiya
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2023), 11 (26), 14333-14344CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Aq. Zn-ion batteries (AZIBs) are attractive for next-generation renewable and secure energy storage systems due to their high safety and low cost. However, dendrite growth and side reactions of Zn metal anodes severely limit their practical applications. Moreover, polarization is an important but easily overlooked factor hampering the development of AZIBs. Herein, a zincophilic, hydrophilic, and thin (∼100 nm) SnO2 protective layer is reported to remodel the Zn anode/electrolyte interface via a simple spin-coating approach. The SnO2 layer effectively inhibits the growth of the dendrites, which prolongs the lifetime of Zn anodes to 3900 h. It also alleviates the side reactions and endows Zn‖Cu cells with a high Coulombic efficiency of 99.3% over 2000 cycles. Meanwhile, the SnO2 layer presents fast Zn deposition kinetics to ensure reversible Zn anodes at high current/capacity by decreasing electrochem. polarization and concn. polarization. Consequently, SnO2/Zn anodes exhibit a high cumulative capacity of 4.5 A h cm-2 at an ultrahigh current of 30 mA cm-2 with a low overpotential of 90 mV and even 3.2 A h cm-2 at a high capacity of 4 mA h cm-2 and high current of 8 mA cm-2. Prototype SnO2/Zn‖δ-MnO2 full cells also obtain higher capacities and capacity retention (96.9% after 500 cycles at 2C) than bare Zn. This work offers new insights for ensuring the reversibility and durability of Zn anodes with low polarization at high current/capacity and provides a promising way to promote the practical application of AZIBs.
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    62. 62
      Wang, T.; Xi, Q.; Li, Y.; Fu, H.; Hua, Y.; Shankar, E. G.; Kakarla, A. K.; Yu, J. S. Regulating Dendrite-Free Zinc Deposition by Red Phosphorous-Derived Artificial Protective Layer for Zinc Metal Batteries. Adv. Sci. 2022, 9, 2200155  DOI: 10.1002/advs.202200155
      62
      Regulating Dendrite-Free Zinc Deposition by Red Phosphorous-Derived Artificial Protective Layer for Zinc Metal Batteries
      Wang, Tian; Xi, Qiao; Li, Yifan; Fu, Hao; Hua, Yongbin; Shankar, Edugulla Girija; Kakarla, Ashok Kumar; Yu, Jae Su
      Advanced Science (Weinheim, Germany) (2022), 9 (18), 2200155CODEN: ASDCCF; ISSN:2198-3844. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Rational architecture design of the artificial protective layer on the zinc (Zn) anode surface is a promising strategy to achieve uniform Zn deposition and inhibit the uncontrolled growth of Zn dendrites. Herein, a red phosphorous-derived artificial protective layer combined with a conductive N-doped carbon framework is designed to achieve dendrite-free Zn deposition. The Zn-phosphorus (ZnP) solid soln. alloy artificial protective layer is formed during Zn plating. Meanwhile, the dynamic evolution mechanism of the ZnP on the Zn anode is successfully revealed. The concn. gradient of the electrolyte on the electrode surface can be redistributed by this protective layer, thereby achieving a uniform Zn-ion flux. The fabricated Zn sym. battery delivers a dendrite-free plating/stripping for 1100 h at the c.d. of 2.0 mA cm-2. Furthermore, aq. Zn//MnO2 full cell exhibits a reversible capacity of 200 mAh g-1 after 350 cycles at 1.0 A g-1. This study suggests an effective soln. for the suppression of Zn dendrites in Zn metal batteries, which is expected to provide a deep insight into the design of high-performance rechargeable aq. Zn-ion batteries.
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    63. 63
      Wang, M.; Wu, X.; Yang, D.; Zhao, H.; He, L.; Su, J.; Zhang, X.; Yin, X.; Zhao, K.; Wang, Y.; Wei, Y. A Colloidal Aqueous Electrolyte Modulated by Oleic Acid for Durable Zinc Metal Anode. Chem. Eng. J. 2023, 451, 138589  DOI: 10.1016/j.cej.2022.138589
      63
      A colloidal aqueous electrolyte modulated by oleic acid for durable zinc metal anode
      Wang, Meiling; Wu, Xiaoyu; Yang, Di; Zhao, Hainan; He, Li; Su, Jiaran; Zhang, Xu; Yin, Xiuxiu; Zhao, Kangning; Wang, Yizhan; Wei, Yingjin
      Chemical Engineering Journal (Amsterdam, Netherlands) (2023), 451 (Part_1), 138589CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Continuous dendrites growth, as well as corrosion and side reactions of Zn metal anode seriously hinder the development of aq. zinc ion batteries. To address these issues, oleic acid (OA) is dispersed into a 2 M ZnSO4 soln. to form a novel colloidal Zn-ion electrolyte. The non-sol. OA surfactant doesn't coordinate with Zn2+ and the water solvent. Instead, it works as a "temporary electrolyte additive" during initial stage of battery processing. After, the OA additive is bonded to Zn metal forming an OA adsorption layer on the anode surface. This hydrophobic OA adsorption layer can not only regulate Zn deposition with parallel orientation of the Zn (002) plane to the Zn foil substrate leading to a flat Zn metal anode, but also isolate direct contact of water with Zn thus inhibiting the harmful side reactions on the Zn anode. Consequently, this colloidal electrolyte enables highly reversible Zn deposition with Coulombic efficiency of 99.63% and cycle life over 3340 cycles. This strategy of in-situ facet engineering and interface modification of Zn metal anode using colloidal electrolyte presents a new perspective toward design of high-performance aq. zinc ion batteries.
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    64. 64
      Cao, Z.; Zhuang, P.; Zhang, X.; Ye, M.; Shen, J.; Ajayan, P. M. Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc Ion Batteries. Adv. Energy Mater. 2020, 10, 2001599  DOI: 10.1002/aenm.202001599
      64
      Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc Ion Batteries
      Cao, Ziyi; Zhuang, Peiyuan; Zhang, Xiang; Ye, Mingxin; Shen, Jianfeng; Ajayan, Pulickel M.
      Advanced Energy Materials (2020), 10 (30), 2001599CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      A review. Ongoing interest is focused on aq. zinc ion batteries (ZIBs) for mass-prodn. energy storage systems as a result of their affordability, safety, and high energy d. Ensuring the stability of the electrode/electrolyte interface is of particular importance for prolonging the cycling ability to meet the practical requirements of rechargeable batteries. Zinc anodes exhibit poor cycle life and low coulombic efficiency, stemming from the severe dendrite growth, and irreversible byproducts such as H2 and inactive ZnO. Great efforts have recently been devoted to zinc anode protection for designing high-performance ZIBs. However, the intrinsic origins of zinc plating/striping are poorly understood, which greatly delay its potential applications. Rather than focusing on battery metrics, this review delves deeply into the underlying science that triggers the deposition/dissoln. of zinc ions. Furthermore, recent advances in modulating the zinc coordination environment, uniforming interfacial elec. fields, and inducing zinc deposition are highlighted and summarized. Finally, perspectives and suggestions are provided for designing highly stable zinc anodes for the industrialization of the aq. rechargeable ZIBs in the near future.
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    65. 65
      Li, X. H.; Deng, S. D.; Fu, H.; Mu, G. N. Inhibition Action of Tween-80 on the Corrosion of Cold Rolled Steel in Sulfuric Acid. Mater. Corros. 2009, 60, 969– 976,  DOI: 10.1002/maco.200905217
      65
      Inhibition action of Tween-80 on the corrosion of cold rolled steel in sulfuric acid
      Li, X. H.; Deng, S. D.; Fu, H.; Mu, G. N.
      Materials and Corrosion (2009), 60 (12), 969-976CODEN: MTCREQ; ISSN:0947-5117. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The inhibition action of a nonionic surfactant of tween-80 on the corrosion of cold rolled steel (CRS) in sulfuric acid (H2SO4) has been investigated by wt. loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the CRS surface conditions. The results show that tween-80 is a good inhibitor in 1.0 M H2SO4, and its adsorption obeys Langmuir adsorption isotherm. Effects of temp. (20-50 °C) and acid concn. (0.5-7.0 M) on the inhibition action were investigated. Polarization curves show that tween-80 is a mixed-type inhibitor in sulfuric acid, but prominently inhibits the cathodic reaction. The results obtained from wt. loss and potentiodynamic polarization are consistent, and the inhibition action could also be evidenced by AFM images.
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    66. 66
      Shin, S.; Yoon, J.; Kim, E.; Yoon, W.-S.; Shin, H. High Capacity and Reversibility of Oxygen-Vacancy-Controlled MoO3 on Cu in Li-Ion Batteries: Unveiling Storage Mechanism in Binder-Free MoO3–x Anodes. Energy Technol. 2020, 8, 1901502  DOI: 10.1002/ente.201901502
      66
      High Capacity and Reversibility of Oxygen-Vacancy-Controlled MoO3 on Cu in Li-Ion Batteries: Unveiling Storage Mechanism in Binder-Free MoO3-x Anodes
      Shin, Sooeun; Yoon, Jaesang; Kim, Eunsoo; Yoon, Won-Sub; Shin, Hyunjung
      Energy Technology (Weinheim, Germany) (2020), 8 (6), 1901502CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)
      MoO3 has great potential as an electrode for lithium-ion batteries due to its unique layered structure that can host Li+. Despite high theor. capacity (≈1117 mAh g-1), MoO3 is not widely used simply because of poor rate capability due to lower electronic cond. and severe pulverization. The Li-storage mechanism in MoO3 is also still unclear. Herein, oxygen-vacancy-controlled MoO3 is used without any addnl. binders and conductive materials to directly examine the Li-storage mechanism on MoO3-x. Li-storage capacity based on the reversible formation/decompn. of solid-electrolyte interphase (SEI) films and the transformation of MoO3-x to amorphous Li2MoO3 is demonstrated. The surfaces of MoO3-x are conjugated with Cu2O nanoparticles via annealing at 200°C. Cu2O acts as an effective catalyst for the formation of SEI films and the reversible reaction of MoO3-x with Li+ ions. As a result, Cu2OoO3-x exhibits a charge capacity of 1100 mAh g-1 after the second cycle and maintains a high reversible capacity, whereas MoO3-x exhibits a charge capacity of 900 mAh g-1 and fades to 590 mAh g-1 after 100 cycles at 1 A g-1.
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    67. 67
      Wang, S.; Lu, S.; Yang, X.; Liu, X. Pseudocapacitive MoOx Anode Material with Super-High Rate and Ultra-Long Cycle Properties for Aqueous Zinc Ion Batteries. J. Electroanal. Chem. 2021, 882, 115033  DOI: 10.1016/j.jelechem.2021.115033
      67
      Pseudocapacitive MoOx anode material with super-high rate and ultra-long cycle properties for aqueous zinc ion batteries
      Wang, Sai; Lu, Shaowei; Yang, Xu; Liu, Xingmin
      Journal of Electroanalytical Chemistry (2021), 882 (), 115033CODEN: JECHES; ISSN:1873-2569. (Elsevier B.V.)
      Aq. Zn-ion batteries (AZIBs) are widely concerned and considered as promising candidates for grid-scale energy storage systems due to the simple and feasible prepn. process together with the demonstrated electrochem. properties, but it is still a tremendous challenge to develop new-type anode materials which can effectively overcome the Zn dendrites formation and low use efficiency of the typical Zn metal anodes, not to mention the ones with outstanding rate and cycle properties. Herein, for the 1st time, monoclinic MoOx is verified to be a novel and promising pseudocapacitive anode material for aq. Zn-ion batteries and the MoOx shows excellent Zn ion storage abilities-esp. at 10 A g-1, including ideal av. potential of 0.53 V (vs. Zn2+/Zn), high discharge/charge capacities of 82.5/82.0 mAh g-1 and cycling life of 30,000 cycles. Further, Zn ion storage mechanism of the as proposed monoclinic MoOx is also studied and deduced to be: MoOx + yZn2++2ye-.dblharw. ZnyMoOx.
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    68. 68
      Ding, J.; Du, Z.; Gu, L.; Li, B.; Wang, L.; Wang, S.; Gong, Y.; Yang, S. Ultrafast Zn2+ Intercalation and Deintercalation in Vanadium Dioxide. Adv. Mater. 2018, 30, 1800762  DOI: 10.1002/adma.201800762
      There is no corresponding record for this reference.
    69. 69
      Deka Boruah, B.; Mathieson, A.; Park, S. K.; Zhang, X.; Wen, B.; Tan, L.; Boies, A.; De Volder, M. Vanadium Dioxide Cathodes for High-Rate Photo-Rechargeable Zinc-Ion Batteries. Adv. Energy Mater. 2021, 11, 2100115  DOI: 10.1002/aenm.202100115
      69
      Vanadium Dioxide Cathodes for High-Rate Photo-Rechargeable Zinc-Ion Batteries
      Deka Boruah, Buddha; Mathieson, Angus; Park, Sul Ki; Zhang, Xiao; Wen, Bo; Tan, Lifu; Boies, Adam; De Volder, Michael
      Advanced Energy Materials (2021), 11 (13), 2100115CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      Photovoltaics are an important source of renewable energy, but due to the intermittent nature of insolation, solar cells usually need to be connected to rechargeable batteries, electrochem. capacitors or other energy storage devices, which adds to the complexity and cost of these systems. In this work, a cathode design for photo-rechargeable zinc-ion batteries (photo-ZIBs) is reported, that is inherently capable of harvesting sunlight to recharge without the need for external solar cells. The proposed photocathodes, comprising a composite of vanadium dioxide nanorods and reduced graphene oxide, are engineered to provide the necessary charge sepn. and storage for photocharging under illumination. The photo-ZIBs achieve capacities of ≈282 mAh g-1 in the dark and ≈315 mAh -1 under illumination, at 200 mA g-1, demonstrating the use of light not only to charge the devices, but addnl. to enhance their capacity. The photo-ZIBs also demonstrate enhanced high-rate capabilities under illumination, as well as a capacity retention of ≈90% over 1000 cycles. The proposed photo-ZIBs are considered a promising new technol. for addressing energy poverty, due to their high performance and inherent cost-efficiency and safety.
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    70. 70
      Li, G.; Wang, X.; Lv, S.; Wang, J.; Dong, X.; Liu, D. Long-Life and Low-Polarization Zn Metal Anodes Enabled by a Covalent Triazine Framework Coating. Chem. Eng. J. 2022, 450, 138116  DOI: 10.1016/j.cej.2022.138116
      70
      Long-life and low-polarization Zn metal anodes enabled by a covalent triazine framework coating
      Li, Gaopeng; Wang, Xinlu; Lv, Shuhui; Wang, Jinxian; Dong, Xiangting; Liu, Dongtao
      Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 450 (Part_2), 138116CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      The development of aq. zinc-ion batteries is greatly hindered by the intrinsic defects of Zn metal anodes, such as uncontrollable dendrite growth and complicated side reactions. Herein, a covalent triazine framework (CTF), with abundant zinc ion transfer channels and strong chem. stability, is fabricated as a coating layer of zinc anodes to address these problems. The CTF layer not only regulates uniform Zn2+ transport path but also effectively separates zinc anodes from bulk electrolytes, thereby preventing the occurrence of side reactions. Moreover, the triazine ring can serve as zincophilic sites to enhance Zn deposition kinetics. Thus, the CTF-protected Zn anode enables a Zn//Zn sym. cell to achieve a long cycle lifespan of over 7000 h, about 40 times larger than that of bare Zn anodes. This sym. cell also has a low and stable voltage polarization of 36 mV even after 3000 h. Meanwhile, the full cell coupled with calcium-doped V2O5 exhibits capacity retention of 66.7% after 300 cycles at a c.d. of 1 A g-1, while the cell with bare Zn anode could only retain 24.3% of capacity under the same condition. This work provides a promising method to address the anode problems in metal-ion batteries.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c08474.

    • Experimental section; SEM images of synthesized MoO3 and bare Zn electrode; XPS survey spectra of MoO3 and MoO2; voltage profiles of bare Zn and MoO2@Zn symmetric cells at different cycles; cycling performance of bare Zn and MoO2@Zn symmetric cells under high current density, MoO2@Zn symmetric cells with different electrolytes, MoO3@Zn and different MoO2@Zn symmetric cells; characterization of MoO2@Zn electrodes after cycling with different electrolytes (SEM images and XRD results); characterization of different MoO2 (SEM images and XRD, EPR results); contact angles of bare Zn and MoO2@Zn with different electrolytes; optical images of MoO2@Zn soaking in different electrolytes and corresponding XRD patterns and SEM images; EIS spectra at different temperatures, calculated activation energy, Tafel plots, CA curves of different electrodes in different electrolytes; XRD results of bare Cu foils after Zn deposition in different electrolytes and corresponding peak intensity ratio; digital image of transparent cell using for optical in situ microscope observation; structure of Tween 80; characterization of the VO2 cathode (SEM image and XRD result) and corresponding electrochemical performance of Zn∥VO2 and MoO2@Zn∥VO2 full cells in different electrolytes (PDF)

    • Video S1: In situ optical microscope testing of bare Zn electrode in blank ZnSO4 electrolyte (MP4)

    • Video S2: In situ optical microscope testing of MoO2@Zn electrode in blank ZnSO4 electrolyte (MP4)

    • Video S3: In situ optical microscope testing of bare Zn electrode in ZnSO4-containing Tween 80 electrolyte (MP4)

    • Video S4: In situ optical microscope testing of MoO2@Zn electrode in ZnSO4-containing Tween 80 electrolyte (MP4)


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