What Would Battery Manufacturing Look Like on the Moon and Mars?

This article references 117 other publications.

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   ACS Energy Letters (2022), 7 (3), 1040-1042CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)

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   Anand, M.; Crawford, I. A.; Balat-Pichelin, M.; Abanades, S.; van Westrenen, W.; Peraudeau, G.; Jaumann, R.; Seboldt, W.

   Planetary and Space Science (2012), 74 (1), 42-48CODEN: PLSSAE; ISSN:0032-0633. (Elsevier Ltd.)

   A review. In situ resource utilization (ISRU) refers to the in situ generation of consumables for autonomous or human activities from raw materials found on the Moon or other planetary bodies. The use of ISRU on the Moon may provide a means of reducing the cost and risk of human exploration of the Moon and beyond, and an impetus for com. contributions to lunar exploration. Potential products include O2 and H2O for life support, H2 and O2 for fuel and propellant, and other elements and compds. for metallurgic and chem. prodn. processes. If ISRU is to be applied successfully on the Moon, it is important that landing site selection, surface operations and suitable ISRU technologies are identified using knowledge of the availability and distribution of lunar resources and detailed understanding of the workings of the various processes available. Here, we review current knowledge of chem. and mineralogical resources on the Moon which can be used in the development of ISRU as a realistic component of future lunar exploration.

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   Composites Additive Manufacturing for Space Applications: A Review

   Paek, Sung Wook; Balasubramanian, Sivagaminathan; Stupples, David

   Materials (2022), 15 (13), 4709CODEN: MATEG9; ISSN:1996-1944. (MDPI AG)

   The assembly of 3D printed composites has a wide range of applications for ground prepn. of space systems, in-orbit manufg., or even in-situ resource utilization on planetary surfaces. The recent developments in composites additive manufg. (AM) technologies include indoor experimentation on the International Space Station, and technol. demonstrations will follow using satellite platforms on the Low Earth Orbits (LEOs) in the next few years. This review paper surveys AM technologies for varied off-Earth purposes where components or tools made of composite materials become necessary: mech., elec., electrochem. and medical applications. Recommendations are also made on how to utilize AM technologies developed for ground applications, both com.-off-the-shelf (COTS) and lab.-based, to reduce development costs and promote sustainability.

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    Generating and storing power on the moon using in situ resources

    Ellery, Alex

    Proceedings of the Institution of Mechanical Engineers, Part G: Journal of Aerospace Engineering (2022), 236 (6), 1045-1063CODEN: PMGEEP; ISSN:0954-4100. (Sage Publications Ltd.)

    The Moon Village and similar concepts are strongly reliant on in situ resource utilization (ISRU). There is great interest in harvesting solar power using locally leveraged in situ resources as an essential facet of in situ infrastructure. Traditionally, silicon-based photovoltaic cells have been assumed, preferably manufd. in situ using a 3D printing rover, but there are major difficulties with such scenarios. Solar cells require pre-processing of regolith and solar cell manuf. We present an alternative lunar resource leveraged-solar power prodn. system on the Moon which can yield high conversion efficiencies - solar Fresnel lens-thermionic conversion. The thermionic vacuum tube is constructed from lunar-derived materials and NiFe asteroidal ores on the Moon. Given that the majority of energy required for ISRU is thermal, thermionic conversion exploits this energy source directly. Silicates such as anorthite can be treated with acid to yield alumina and silicic acid in soln. from which pure silica can be pptd. Pure silica when heated to high temp. yields fused silica glass which is transparent - fused silica glass may be employed to manuf. Fresnel lenses and/or mirrors. Both silica and alumina may be input to the Metalysis Fray Farthing Chen Cambridge electrolytic process to yield near pure Si and near pure Al, resp.

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    Lithium and halogens in lunar samples

    Dreibus, G.; Spettel, B.; Waenke, H.

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    The composition of Mars

    Yoshizaki, Takashi; McDonough, William F.

    Geochimica et Cosmochimica Acta (2020), 273 (), 137-162CODEN: GCACAK; ISSN:0016-7037. (Elsevier Ltd.)

    Comparing compositional models of the terrestrial planets provides insights into physicochem. processes that produced planet-scale similarities and differences. The widely accepted compositional model for Mars assumes Mn and more refractory elements are in CI chondrite proportions in the planet, including Fe, Mg, and Si, which along with O make up >90% of the mass of Mars. However, recent improvements in our understandings on the compn. of the solar photosphere and meteorites challenge the use of CI chondrite as an analog of Mars. Here we present an alternative model compn. for Mars that avoids such an assumption and is based on data from Martian meteorites and spacecraft observations. Our modeling method was previously applied to predict the Earth's compn. The model establishes the abs. abundances of refractory lithophile elements in the bulk silicate Mars (BSM) at 2.26 times higher than that in CI carbonaceous chondrites. Relative to this chondritic compn., Mars has a systematic depletion in moderately volatile lithophile elements as a function of their condensation temps. Given this finding, we constrain the abundances of siderophile and chalcophile elements in the bulk Mars and its core. The Martian volatility trend is consistent with ≤7 wt% S in its core, which is significantly lower than that assumed in most core models (i.e., >10 wt% S). Furthermore, the occurrence of ringwoodite at the Martian core-mantle boundary might have contributed to the partitioning of O and H into the Martian core.

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    The authors derive the bulk chem. compn., phys. properties, and trace element abundances of Mars from two assumptions: (1) Mars is the parent body for the Shergottite-Nakhlite-Chassignite (SNC) meteorites, and (2) the oxygen isotopic compn. of Mars was detd. by the oxygen isotopic compns. of the different types of nebular material that accreted to form Mars. They use oxygen isotopes to constrain planetary bulk compns. because oxygen is generally the most abundant element in rock, and is either the first or second (after iron) most abundant element in any terrestrial planet, the Moon, other rocky satellites, and the asteroids. The oxygen isotopic compn. of Mars, calcd. from oxygen isotopic analyses of the SNC meteorites, corresponds to the accretion of about 85% H-, 11% CV-, and 4% CI-chondritic material. The bulk compn. of Mars follows from mass balance calcns. using mean compns. for these chondrite groups. It is predicted that silicates (mantle + crust) comprise about 80% of Mars. The compn. of the silicate fraction represents the compn. of the primordial martian mantle prior to crustal formation. The FeO content of the mantle is 17.2%. A metal-sulfide core, contg. about 10.6% S, makes up the remaining 20% of the planet. Our bulk compn. is similar to those from other models. The abundances of siderophile ("metal-loving") and chalcophile ("sulfide-loving") elements in the martian mantle were calcd. from the bulk compn. using (metal-sulfide)/silicate partition coeffs. These results generally agree with predictions of the SNC meteorite model of Wanke and Dreibus for the compn. of Mars. However, we predict higher abundances for the alkalies and halogens than those derived from SNC meteorite models for Mars. The apparent discrepancy indicates that the alkalies and halogens were lost from the martian mantle by hydrothermal leaching and/or vaporization during accretion. Geochem. arguments suggest that vaporization was only a minor loss process for these elements. On the other hand, aq. transport of the alkalis and halogens to the surface is supported by the terrestrial geochem. of these elements and the high K, Rb, Cl, and Br abundances found by the Viking XRF and Phobos gamma ray expts. on the surface of Mars.

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    Recent Advances in Rechargeable Magnesium-Based Batteries for High-Efficiency Energy Storage

    Guo, Ziqi; Zhao, Shuoqing; Li, Tiexin; Su, Dawei; Guo, Shaojun; Wang, Guoxiu

    Advanced Energy Materials (2020), 10 (21), 1903591CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)

    A review. Benefiting from higher volumetric capacity, environmental friendliness and metallic dendrite-free magnesium (Mg) anodes, rechargeable magnesium batteries (RMBs) are of great importance to the development of energy storage technol. beyond lithium-ion batteries (LIBs). However, their practical applications are still limited by the absence of suitable electrode materials, the sluggish kinetics of Mg2+ insertion/extn. and incompatibilities between electrodes and electrolytes. Herein, a systematic and insightful review of recent advances in RMBs, including intercalation-based cathode materials and conversion reaction-based compds. is presented. The relationship between microstructures with their electrochem. performances is comprehensively elucidated. In particular, anode materials are discussed beyond metallic Mg for RMBs. Furthermore, other Mg-based battery systems are also summarized, including Mg-air batteries, Mg-sulfur batteries, and Mg-iodine batteries. This review provides a comprehensive understanding of Mg-based energy storage technol. and could offer new strategies for designing high-performance rechargeable magnesium batteries.

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    Jiang, M.; Fu, C.; Meng, P.; Ren, J.; Wang, J.; Bu, J.; Dong, A.; Zhang, J.; Xiao, W.; Sun, B. Challenges and Strategies of Low-Cost Aluminum Anodes for High-Performance Al-Based Batteries. Adv. Mater. 2022, 34 (2), e2102026,  DOI: 10.1002/adma.202102026

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    Challenges and Strategies of Low-Cost Aluminum Anodes for High-Performance Al-Based Batteries

    Jiang, Min; Fu, Chaopeng; Meng, Pengyu; Ren, Jianming; Wang, Jing; Bu, Junfu; Dong, Anping; Zhang, Jiao; Xiao, Wei; Sun, Baode

    Advanced Materials (Weinheim, Germany) (2022), 34 (2), 2102026CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)

    A review. The ever-growing market of elec. vehicles and the upcoming grid-scale storage systems have stimulated the fast growth of renewable energy storage technologies. Aluminum-based batteries are considered one of the most promising alternatives to complement or possibly replace the current lithium-ion batteries owing to their high specific capacity, good safety, low cost, light wt., and abundant reserves of Al. However, the anode problems in primary and secondary Al batteries, such as, self-corrosion, passive film, and vol. expansion, severely limit the batteries' practical performance, thus hindering their commercialization. Herein, an overview of the currently emerged Al-based batteries is provided, that primarily focus on the recent research progress for Al anodes in both primary and rechargeable systems. The anode reaction mechanisms and problems in various Al-based batteries are discussed, and various strategies to overcome the challenges of Al anodes, including surface oxidn., self-corrosion, vol. expansion, and dendrite growth, are systematically summarized. Finally, future research perspectives toward advanced Al batteries with higher performance and better safety are presented.

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    Pan, K.; Lu, H.; Zhong, F.; Ai, X.; Yang, H.; Cao, Y. Understanding the Electrochemical Compatibility and Reaction Mechanism on Na Metal and Hard Carbon Anodes of PC-Based Electrolytes for Sodium-Ion Batteries. ACS Appl. Mater. Interfaces 2018, 10 (46), 39651– 39660,  DOI: 10.1021/acsami.8b13236

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    34

    Understanding the Electrochemical Compatibility and Reaction Mechanism on Na Metal and Hard Carbon Anodes of PC-Based Electrolytes for Sodium-Ion Batteries

    Pan, Kanghua; Lu, Haiyan; Zhong, Faping; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    ACS Applied Materials & Interfaces (2018), 10 (46), 39651-39660CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)

    Electrolytes as an important part of sodium-ion batteries have a pivotal role for capacity, rate, and durability of electrode materials. On account of the high redn. activity of sodium metal with org. solvents, it is very important to optimize the electrolyte component to realize high stability on Na metal and hard carbon anodes. Herein, chem. and electrochem. stability of propylene carbonate (PC)-based electrolytes on sodium metal and hard carbon anodes is investigated systematically. The results demonstrate that whether using NaClO4 or NaPF6, the PC-based electrolytes are not stable on Na metal, but adding of FEC can immensely enhance the stability of the electrolyte because of the compact solid electrolyte interphase film formed. The electrolytes contg. FEC also exhibit high electrochem. compatibility on hard carbon anodes, showing high reversible capacity and excellent cycling performance. A reaction mechanism based on the Na+ induction effect is proposed by spectrum and electrochem. measurements. This study can provide a new insight to optimize and develop stable PC-based electrolytes and be helpful for understanding the other electrolyte systems.

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    Jin, Y.; Xu, Y.; Le, P. M. L.; Vo, T. D.; Zhou, Q.; Qi, X.; Engelhard, M. H.; Matthews, B. E.; Jia, H.; Nie, Z.; Niu, C.; Wang, C.; Hu, Y.; Pan, H.; Zhang, J.-G. Highly Reversible Sodium Ion Batteries Enabled by Stable Electrolyte-Electrode Interphases. ACS Energy Lett. 2020, 5 (10), 3212– 3220,  DOI: 10.1021/acsenergylett.0c01712

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    35

    Highly Reversible Sodium Ion Batteries Enabled by Stable Electrolyte-Electrode Interphases

    Jin, Yan; Xu, Yaobin; Le, Phung M. L.; Vo, Thanh D.; Zhou, Quan; Qi, Xingguo; Engelhard, Mark H.; Matthews, Bethany E.; Jia, Hao; Nie, Zimin; Niu, Chaojiang; Wang, Chongmin; Hu, Yongsheng; Pan, Huilin; Zhang, Ji-Guang

    ACS Energy Letters (2020), 5 (10), 3212-3220CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)

    The sodium ion battery (NIB) is a promising alternative technol. for energy storage systems because of the abundance and low cost of sodium in the Earth's crust. However, the limited cycle life and safety concerns of NIBs hinder their large-scale applications. Here, we report a nonflammable localized high concn. electrolyte (sodium bis(fluorosulfonyl)imide-triethyl phosphate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (1:1.5:2 in molar ratio)) for highly reversible NIBs. By using a cryo-transmission electron microscope, it was found that an ultrathin (3 nm) and robust interphase layer formed on the cathode surface can block transition metal dissolns. and minimize surface reconstructions of the cathode. The inorg.-rich solid electrolyte interphase formed on the hard carbon (HC) surface minimized undesirable reactions between HC and the electrolyte. These stable interphases enabled high Coulombic efficiency and long-term stable cycling of the HC anode and the NaCu1/9Ni2/9Fe1/3Mn1/3O2 cathode. The insights obtained in this work can be used to further improve the cycling stability and safety of rechargeable batteries.

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36. 36

    Wang, E.; Niu, Y.; Yin, Y.-X.; Guo, Y.-G. Manipulating Electrode/Electrolyte Interphases of Sodium-Ion Batteries: Strategies and Perspectives. ACS Materials Lett. 2021, 3 (1), 18– 41,  DOI: 10.1021/acsmaterialslett.0c00356

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    36

    Manipulating Electrode/Electrolyte Interphases of Sodium-Ion Batteries: Strategies and Perspectives

    Wang, Enhui; Niu, Yubin; Yin, Ya-Xia; Guo, Yu-Guo

    ACS Materials Letters (2021), 3 (1), 18-41CODEN: AMLCEF; ISSN:2639-4979. (American Chemical Society)

    A review. After the past decade's rapid development, the com. demands for sodium ion batteries (SIBs) have been put on the schedule for large-scale energy storage. Even though the electrode-electrolyte interphases play a very important role in detg. the overall battery performance in terms of high energy d. and long-cycling stability, studies regarding their fundamental understanding and regulation strategies are still in their infancy. Herein, we comprehensively review the current research status and the challenging issues of the as-generated SIB interphases from three main aspects. Firstly, a fundamental understanding of the main body interphase layers is introduced through the development of their formation mechanism, their compn./structure, and the dynamic evolution process involved, all of which are highly responsible for the Na+ ion transport behavior to det. the final kinetic diffusion. Then, interphase manipulation via the parental electrolyte is summarized in terms of electrolyte engineering strategies, such as the solvent/salt selection, the concn. effect, and the functional additive screening to build a more stable interphase layer for desirable electrochem. reversibility. Finally, potential effects from the chosen electrodes are discussed to provide necessary assocns. with the interphase formation and evolution. Crit. challenges for building stable Na-based interphase are identified, and in particular, new ways of thinking about the interphase chem. and the electrolyte chem. based on SIBs, are strongly appealing. We believe that this work is likely to attract attention to the rational design of Na-based interphase layers towards high-energy and long-life-span batteries.

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37. 37

    Yan, G.; Mariyappan, S.; Rousse, G.; Jacquet, Q.; Deschamps, M.; David, R.; Mirvaux, B.; Freeland, J. W.; Tarascon, J.-M. Higher Energy and Safer Sodium Ion Batteries via an Electrochemically Made Disordered Na₃V₂(PO₄)₂F₃ Material. Nat. Commun. 2019, 10 (1), 585,  DOI: 10.1038/s41467-019-08359-y

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    37

    Higher energy and safer sodium ion batteries via an electrochemically made disordered Na3V2(PO4)2F3 material

    Yan, Guochun; Mariyappan, Sathiya; Rousse, Gwenaelle; Jacquet, Quentin; Deschamps, Michael; David, Renald; Mirvaux, Boris; Freeland, John William; Tarascon, Jean-Marie

    Nature Communications (2019), 10 (1), 585CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)

    The growing need to store an increasing amt. of renewable energy in a sustainable way has rekindled interest for sodium-ion battery technol., owing to the natural abundance of sodium. Presently, sodium-ion batteries based on Na3V2(PO4)2F3/C are the subject of intense research focused on improving the energy d. by harnessing the third sodium, which has so far been reported to be electrochem. inaccessible. Here, we are able to trigger the activity of the third sodium electrochem. via the formation of a disordered NaxV2(PO4)2F3 phase of tetragonal symmetry (I4/mmm space group). This phase can reversibly uptake 3 sodium ions per formula unit over the 1 to 4.8 V voltage range, with the last one being re-inserted at 1.6 V vs Na+/Na0. We track the sodium-driven structural/charge compensation mechanism assocd. to the new phase and find that it remains disordered on cycling while its av. vanadium oxidn. state varies from 3 to 4.5. Full sodium-ion cells based on this phase as pos. electrode and carbon as neg. electrode show a 10-20% increase in the overall energy d.

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38. 38

    Wang, M.; Huang, X.; Wang, H.; Zhou, T.; Xie, H.; Ren, Y. Synthesis and Electrochemical Performances of Na₃V₂(PO₄)₂F₃/C Composites as Cathode Materials for Sodium Ion Batteries. RSC Adv. 2019, 9 (53), 30628– 30636,  DOI: 10.1039/C9RA05089B

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    38

    Synthesis and electrochemical performances of Na3V2(PO4)2F3/C composites as cathode materials for sodium ion batteries

    Wang, Mingxue; Huang, Xiaobing; Wang, Haiyan; Zhou, Tao; Xie, Huasheng; Ren, Yurong

    RSC Advances (2019), 9 (53), 30628-30636CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)

    Na3V2(PO4)2F3 (NVPF) with NASCION (Na superionic conductor) is recognized as a potential cathode material owing to its high theor. capacity. However, the electronic cond. of NVPF is much lower than its ionic cond., which seriously affects the properties of this material. The carbon layer can be used as the conductive medium to enhance the cond. of NVPF. In this study, we propose a single-step solid-state reaction method based on mech. activation with pitch as the carbon source to synthesize NVPF/C composites. The crystallog. structure and morphol. of all as-prepd. samples were investigated by XRD, Raman spectroscopy, BET measurement, thermal anal., SEM and TEM. Furthermore, the electrochem. performance and kinetic properties were analyzed by CV, galvanostatic charge-discharge and EIS tests. These tests outcomes demonstrated that the NVPF/C-2 composite with a carbon content of 12.14 wt% showed an excellent rate performance and cycle stability. It presented reversible capacities of 103 and 95 mA h g-1 at 0.2 and 10C, resp., and an outstanding retention of 91.9% after 500 cycles at 5C. These excellent properties of the NVPF/C-2 composite are attributed to its high ion diffusion coeff. and small charge transfer impedance.

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39. 39

    Zhu, L.; Wang, H.; Sun, D.; Tang, Y.; Wang, H. A Comprehensive Review on the Fabrication, Modification and Applications of Na₃V₂(PO₄)₂F₃ Cathodes. J. Mater. Chem. A Mater. Energy Sustain. 2020, 8 (41), 21387– 21407,  DOI: 10.1039/D0TA07872G

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    39

    A comprehensive review on the fabrication, modification and applications of Na3V2(PO4)2F3 cathodes

    Zhu, Lin; Wang, Hong; Sun, Dan; Tang, Yougen; Wang, Haiyan

    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (41), 21387-21407CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)

    A review. Na-ion batteries (SIBs) have garnered tremendous interest due to their unique advantages of high safety, abundant Na resources, and low cost. Great research efforts of SIBs have been devoted to the exploitation and in-depth mechanism investigation of high-performance electrode materials. Among the various cathodes, Na3V2(PO4)2F3 (NVPF), a representative member of Na superionic conductor (NASICON) structured compds., has been considered to be a promising candidate because of its superior structural stability, fast ion transport, high operating potential and so on. However, its electrochem. performance and future large-scale applications have been hindered by the relatively low electronic cond. and high cost of NVPF. This review emphasizes the crystal structure and Na storage mechanisms together with synthetic methods of NVPF, and then summarizes various proposed strategies including carbon coating, element doping, size and morphol. design, etc. to meliorate the electrochem. performance of NVPF. Addnl., the applications of the NVPF cathode in other battery systems are included. Finally, our perspectives on the subsequent research and optimization of NVPF are also shared. This review not only is a comprehensive summary of NVPF for the first time but also provides a good ref. for the rational design of high-performance NVPF in the future.

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40. 40

    Zeng, X.; Peng, J.; Guo, Y.; Zhu, H.; Huang, X. Research Progress on Na₃V₂(PO₄)₃ Cathode Material of Sodium Ion Battery. Front. Chem. 2020, 8, 635,  DOI: 10.3389/fchem.2020.00635

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    40

    Research progress on Na3V2(PO4)3 cathode material of sodium ion battery

    Zeng, Xianguang; Peng, Jing; Guo, Yi; Zhu, Huafeng; Huang, Xi

    Frontiers in Chemistry (Lausanne, Switzerland) (2020), 8 (), 635CODEN: FCLSAA; ISSN:2296-2646. (Frontiers Media S.A.)

    A review. Sodium ion batteries (SIBs) are one of the most potential alternative rechargeable batteries because of their low cost, high energy d., high thermal stability, and good structure stability. The cathode materials play a crucial role in the cycling life and safety of SIBs. Among reported cathode candidates, Na3V2(PO4)3 (NVP), a representative electrode material for sodium super ion conductor, has good application prospects due to its good structural stability, high ion cond. and high platform voltage (~ 3.4 V). However, its practical applications are still restricted by comparatively low electronic cond. In this review, recent progresses of Na3V2(PO4)3 are well summarized and discussed, including prepn. and modification methods, electrochem. properties. Meanwhile, the future research and further development of Na3V2(PO4)3 cathode are also discussed.

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41. 41

    Park, S.; Wang, Z.; Deng, Z.; Moog, I.; Canepa, P.; Fauth, F.; Carlier, D.; Croguennec, L.; Masquelier, C.; Chotard, J.-N. Crystal Structure of Na₂V₂(PO₄)₃, an Intriguing Phase Spotted in the Na₃V₂(PO₄)₃–Na₁V₂(PO₄)₃ System. Chem. Mater. 2022, 34 (1), 451– 462,  DOI: 10.1021/acs.chemmater.1c04033

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    41

    Crystal Structure of Na2V2(PO4)3, an Intriguing Phase Spotted in the Na3V2(PO4)3-Na1V2(PO4)3 System

    Park, Sunkyu; Wang, Ziliang; Deng, Zeyu; Moog, Iona; Canepa, Pieremanuele; Fauth, Francois; Carlier, Dany; Croguennec, Laurence; Masquelier, Christian; Chotard, Jean-Noel

    Chemistry of Materials (2022), 34 (1), 451-462CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    The Na superionic conductor (NASICON) Na3V2(PO4)3 is an important pos. electrode material for Na-ion batteries. Here, we investigate the mechanisms of phase transition in NaxV2(PO4)3 (1 ≤ x ≤ 4) upon nonequil. battery cycling. Unlike the widely believed two-phase reaction in a Na3V2(PO4)3-Na1V2(PO4)3 system, we det., for the first time, the structure of a recently reported intermediate Na2V2(PO4)3 phase using operando synchrotron X-ray diffraction. D. functional theory calcns. further support the existence of the Na2V2(PO4)3 phase. We propose two possible crystal structures of Na2V2(PO4)3 analyzed by Rietveld refinement. The two structure models with the space groups P21/c or P2/c for the new intermediate Na2V2(PO4)3 phase show similar unit cell parameters but different at. arrangements, including vanadium charge ordering. As the appearance of the intermediate Na2V2(PO4)3 phase is accompanied by symmetry redn., Na(1) and Na(2) sites split into several positions in Na2V2(PO4)3, in which one of the splitting Na(2) position is found to be a vacancy, whereas the Na(1) positions are almost fully filled. The intermediate Na2V2(PO4)3 phase reduces the lattice mismatch between Na3V2(PO4)3 and Na1V2(PO4)3 phases, facilitating a fast phase transition. This work paves the way for a better understanding of great rate capabilities of Na3V2(PO4)3.

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42. 42

    Liu, S.; Tong, Z.; Zhao, J.; Liu, X.; Wang, J.; Ma, X.; Chi, C.; Yang, Y.; Liu, X.; Li, Y. Rational Selection of Amorphous or Crystalline V₂O₅ Cathode for Sodium-Ion Batteries. Phys. Chem. Chem. Phys. 2016, 18 (36), 25645– 25654,  DOI: 10.1039/C6CP04064K

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    42

    Rational selection of amorphous or crystalline V2O5 cathode for sodium-ion batteries

    Liu, Shikun; Tong, Zhongqiu; Zhao, Jiupeng; Liu, Xusong; wang, Jing; Ma, Xiaoxuan; Chi, Caixia; Yang, Yu; Liu, Xiaoxu; Li, Yao

    Physical Chemistry Chemical Physics (2016), 18 (36), 25645-25654CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

    Vanadium oxide (V2O5), as a potential pos. electrode for sodium ion batteries (SIBs), has attracted considerable attention from researchers. Herein, amorphous and cryst. V2O5 cathodes on a graphite paper without a binder and conductive additives were synthesized via facile anodic electrochem. deposition following different heat treatments. Both the amorphous V2O5 (a-V2O5) cathode and cryst. V2O5 (c-V2O5) cathode show good rate cycling performance and long cycling life. After five rate cycles, the reversible capacities of both the cathodes were almost unchanged at different current densities from 40 to 5120 mA g-1. Long cycling tests with 10 000 cycles were carried out and the two cathodes exhibit excellent cycling stability. The c-V2O5 cathode retains a high specific capacity of 54 mA h g-1 after 10 000 cycles at 2560 mA g-1 and can be charged within 80 s. Interestingly, the a-V2O5 cathode possesses higher reversible capacities than the c-V2O5 cathode at low current densities, whereas it is inversed at high current densities. The c-V2O5 cathode shows faster capacity recovery from 5120 to 40 mA g-1 than the a-V2O5 cathode. When discharged at 80 mA g-1 (long discharge time of 140 min) and charged at 640 mA g-1 (short charge time of 17 min), the a-V2O5 cathode shows a higher discharge capacity than its c-V2O5 counterpart. The different electrochem. performance of a-V2O5 and c-V2O5 cathodes during various electrochem. processes can provide a rational selection of amorphous or cryst. V2O5 cathode materials for SIBs in their practical applications to meet the variable requirements.

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43. 43

    Van Nghia, N.; Long, P. D.; Tan, T. A.; Jafian, S.; Hung, I.-M. Electrochemical Performance of a V₂O₅ Cathode for a Sodium Ion Battery. J. Electron. Mater. 2017, 46 (6), 3689– 3694,  DOI: 10.1007/s11664-017-5298-y

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44. 44

    Berlanga, C.; Monterrubio, I.; Armand, M.; Rojo, T.; Galceran, M.; Casas-Cabanas, M. Cost-Effective Synthesis of Triphylite-NaFePO₄ Cathode: A Zero-Waste Process. ACS Sustainable Chem. Eng. 2020, 8 (2), 725– 730,  DOI: 10.1021/acssuschemeng.9b05736

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    44

    Cost-Effective Synthesis of Triphylite-NaFePO4 Cathode: A Zero-Waste Process

    Berlanga, Carlos; Monterrubio, Iciar; Armand, Michel; Rojo, Teofilo; Galceran, Montserrat; Casas-Cabanas, Montse

    ACS Sustainable Chemistry & Engineering (2020), 8 (2), 725-730CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)

    Triphylite-NaFePO4 attracts considerable attention as a cathode material for Na-ion batteries due to its theor. capacity (154 mAh/g), sharing also the excellent properties of the analogous triphylite-LiFePO4 used in com. Li-ion batteries. Triphylite-NaFePO4 is synthesized from triphylite-LiFePO4 by a low-cost, eco-friendly method, enabling the recovery and subsequent reuse of Li. NaFePO4 was evaluated as a cathode material in half-cells, exhibiting an initial discharge capacity of 132 mAh/g and good capacity retention (115 mAh/g and ∼100% of Coulombic efficiency after 50 cycles; 101 mAh/g and ∼100% of Coulombic efficiency after 200 cycles). This research confirms that the triphylite-NaFePO4 cathode material is an attractive candidate for Na-ion batteries, with potential for future commercialization. A green and low-cost circular process for the scalable synthesis of triphylite-NaFePO4 with excellent electrochem. performance that includes the recovery of Li from the LiFePO4 precursor is discussed.

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45. 45

    Tang, W.; Song, X.; Du, Y.; Peng, C.; Lin, M.; Xi, S.; Tian, B.; Zheng, J.; Wu, Y.; Pan, F.; Loh, K. P. High-Performance NaFePO₄ Formed by Aqueous Ion-Exchange and Its Mechanism for Advanced Sodium Ion Batteries. J. Mater. Chem. A Mater. Energy Sustain. 2016, 4 (13), 4882– 4892,  DOI: 10.1039/C6TA01111J

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    Wongittharom, N.; Lee, T.-C.; Wang, C.-H.; Wang, Y.-C.; Chang, J.-K. Electrochemical Performance of Na/NaFePO₄ Sodium-Ion Batteries with Ionic Liquid Electrolytes. J. Mater. Chem. A Mater. Energy Sustain. 2014, 2 (16), 5655– 5661,  DOI: 10.1039/c3ta15273a

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47. 47

    Singh, P.; Shiva, K.; Celio, H.; Goodenough, J. B. Eldfellite, NaFe(SO₄)₂: An Intercalation Cathode Host for Low-Cost Na-Ion Batteries. Energy Environ. Sci. 2015, 8 (10), 3000– 3005,  DOI: 10.1039/C5EE02274F

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    47

    Eldfellite, NaFe(SO4)2: an intercalation cathode host for low-cost Na-ion batteries

    Singh, Preetam; Shiva, Konda; Celio, Hugo; Goodenough, John B.

    Energy & Environmental Science (2015), 8 (10), 3000-3005CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)

    The mineral eldfellite, NaFe(SO4)2, is characterized as a potential cathode for a Na-ion battery that is fabricated in charged state; its 3 V discharge vs. sodium for reversible Na+ intercalation is shown to have a better capacity, but lower insertion rate than Li+ intercalation. The theor. specific capacity for Na+ insertion is 99 mA h g-1. After 80 cycles at 0.1C vs. a Na anode, the specific capacity was 78 mA h g-1 with a coulomb efficiency approaching 100%.

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48. 48

    Billaud, J.; Clément, R. J.; Armstrong, A. R.; Canales-Vázquez, J.; Rozier, P.; Grey, C. P.; Bruce, P. G. β-NaMnO₂: A High-Performance Cathode for Sodium-Ion Batteries. J. Am. Chem. Soc. 2014, 136 (49), 17243– 17248,  DOI: 10.1021/ja509704t

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    48

    β-NaMnO2: A High-Performance Cathode for Sodium-Ion Batteries

    Billaud, Juliette; Clement, Raphaele J.; Armstrong, A. Robert; Canales-Vazquez, Jesus; Rozier, Patrick; Grey, Clare P.; Bruce, Peter G.

    Journal of the American Chemical Society (2014), 136 (49), 17243-17248CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    There is much interest in Na-ion batteries for grid storage because of the lower projected cost compared with Li-ion. Identifying Earth-abundant, low-cost, and safe materials that can function as intercalation cathodes in Na-ion batteries is an important challenge facing the field. Here such a material, β-NaMnO2, is investigated with a different structure from that of NaMnO2 polymorphs and other compds. studied extensively in the past. It exhibits a high capacity (of ca. 190 mA h g-1 at a rate of C/20), along with a good rate capability (142 mA h g-1 at a rate of 2C) and a good capacity retention (100 mA h g-1after 100 Na extn./insertion cycles at a rate of 2C). Powder XRD, HRTEM, and 23Na NMR studies revealed that this compd. exhibits a complex structure consisting of intergrown regions of α-NaMnO2 and β-NaMnO2 domains. The collapse of the long-range structure at low Na content is expected to compromise the reversibility of the Na extn. and insertion processes occurring upon charge and discharge of the cathode material, resp. Yet stable, reproducible, and reversible Na intercalation is obsd.

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49. 49

    Lee, E.; Brown, D. E.; Alp, E. E.; Ren, Y.; Lu, J.; Woo, J.-J.; Johnson, C. S. New Insights into the Performance Degradation of Fe-Based Layered Oxides in Sodium-Ion Batteries: Instability of Fe³⁺/Fe⁴⁺ Redox in α-NaFeO₂. Chem. Mater. 2015, 27 (19), 6755– 6764,  DOI: 10.1021/acs.chemmater.5b02918

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    49

    New Insights into the Performance Degradation of Fe-Based Layered Oxides in Sodium-Ion Batteries: Instability of Fe3+/Fe4+ Redox in α-NaFeO2

    Lee, Eungje; Brown, Dennis E.; Alp, Esen E.; Ren, Yang; Lu, Jun; Woo, Jung-Je; Johnson, Christopher S.

    Chemistry of Materials (2015), 27 (19), 6755-6764CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    The emergence of sodium-ion batteries (SIBs) employing cathodes based on earth abundant sodium and iron is expected to be ideal for large-scale elec. energy storage systems, for which the cost factor is of primary importance. However, these iron-based layered oxides still show unsatisfactory cycle performance, and the redox of the fleeting Fe3+/Fe4+ couple needs to be better understood. In this study, we examine the quasi-reversibility of the layered α-NaFeO2 cathode in sodium-ion cells. A NaFeO2 powder sample that has the O3-type layered structure was synthesized via a solid-state synthesis method. The changes in Fe oxidn. states and crystallog. structures were examd. during the electrochem. sodium cycling of the NaFeO2 electrodes. Ex situ Mossbauer spectroscopy anal. revealed the chem. instability of Fe4+ in a battery cell environment: more than 20% of Fe4+ species that was generated in the desodiated Na1-xFeO2 electrode was spontaneously reduced back to Fe3+ states during open circuit storage of the charged cell. The in situ synchrotron X-ray diffraction further revealed the nonequil. phase transition behavior of the NaFeO2 cathode. A new layered phase (denoted as O''3) was obsd. in the course of sodium deintercalation, and an asym. structural behavior during cycling was identified. These findings explain the quasi-reversibility of α-NaFeO2 in the sodium cell and provide guidance for the future development of iron-based cathode materials for sodium-ion batteries.

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50. 50

    Zhuang, Y.; Zhao, J.; Zhao, Y.; Zhu, X.; Xia, H. Carbon-Coated Single Crystal O3-NaFeO₂ Nanoflakes Prepared via Topochemical Reaction for Sodium-Ion Batteries. Sustainable Materials and Technologies 2021, 28, e00258  DOI: 10.1016/j.susmat.2021.e00258

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    50

    Carbon-coated single crystal O3-NaFeO2 nanoflakes prepared via topochemical reaction for sodium-ion batteries

    Zhuang, Yuhang; Zhao, Jing; Zhao, Yang; Zhu, Xiaohui; Xia, Hui

    Sustainable Materials and Technologies (2021), 28 (), e00258CODEN: SMTUAV; ISSN:2214-9937. (Elsevier B.V.)

    Layered O3-NaFeO2 with abundant raw material resources is a promising cathode material for sodium-ion batteries. However, the synthesis of O3-NaFeO2 without using Na2O2 as sodium source is greatly difficult with formation of the electrochem. inactive β-NaFeO2. In the present work, the single crystal O3-NaFeO2 nanoflakes have been synthesized via a facile solvothermal route without using Na2O2 as sodium source. Through the solvothermal treatment, the inactive α-Fe2O3 can be converted into active γ-Fe2O3 first and subsequently into the single crystal NaFeO2 nanoflakes via Na+/Fe3+ topochem. ion exchange reaction. A thin layer of carbon is further coated on NaFeO2 nanoflakes to enhance its electrode kinetics and structural stability. The carbon coated NaFeO2 cathode delivers a high reversible specific capacity of 89.6 mAh g-1 at 0.1C and exhibits 87.3% capacity retention after 100 cycles at 0.1C, maintaining the layered O3-structure. By using hard carbon as anode, a carbon coated NaFeO2//hard carbon full cell is successfully constructed, exhibiting good cyclability with 81.9% capacity retention after 100 cycles. The present work provides a novel synthesis strategy for developing O3-NaFeO2-based cathode for sustainable sodium-ion batteries.

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51. 51

    Susanto, D.; Cho, M. K.; Ali, G.; Kim, J.-Y.; Chang, H. J.; Kim, H.-S.; Nam, K.-W.; Chung, K. Y. Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO₂ Cathodes for Sodium Ion Batteries. Chem. Mater. 2019, 31 (10), 3644– 3651,  DOI: 10.1021/acs.chemmater.9b00149

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    51

    Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO2 Cathodes for Sodium Ion Batteries

    Susanto, Dieky; Cho, Min Kyung; Ali, Ghulam; Kim, Ji-Young; Chang, Hye Jung; Kim, Hyung-Seok; Nam, Kyung-Wan; Chung, Kyung Yoon

    Chemistry of Materials (2019), 31 (10), 3644-3651CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    The origin of the irreversible capacity of O3-type NaFeO2 charged to high voltage is investigated by analyzing the oxidn. state of Fe and phase transition of layered NaFeO2 cathodes for sodium-ion batteries during the charging process. In-situ X-ray absorption spectroscopy results revealed that charge compensation does not occur through the Fe3+/Fe4+ redox reaction during sodium extn. as no significant shift to high energy was obsd. in the Fe K-edge. These results were reinforced with ex-situ near-edge X-ray absorption spectroscopy, which suggests that oxygen redox activity is responsible for charge compensation. Formation of Fe3O4 product occurs because of oxygen release at high voltage when more than 0.5 Na is extd. from the structure; this is obsd. by transmission electron microscopy. NaFeO2 irreversibility is due to the formation of Fe3O4 with oxygen release, which inhibits Na insertion into the structure.

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52. 52

    Kim, D. J.; Ponraj, R.; Kannan, A. G.; Lee, H.-W.; Fathi, R.; Ruffo, R.; Mari, C. M.; Kim, D. K. Diffusion Behavior of Sodium Ions in Na_0.44MnO₂ in Aqueous and Non-Aqueous Electrolytes. J. Power Sources 2013, 244, 758– 763,  DOI: 10.1016/j.jpowsour.2013.02.090

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    52

    Diffusion behavior of sodium ions in Na0.44MnO2 in aqueous and non-aqueous electrolytes

    Kim, Dong Jun; Ponraj, Rubha; Kannan, Aravindaraj G.; Lee, Hyun-Wook; Fathi, Reza; Ruffo, Riccardo; Mari, Claudio M.; Kim, Do Kyung

    Journal of Power Sources (2013), 244 (), 758-763CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)

    The slow kinetics of bigger-sized sodium ions in intercalation compds. restricts the practical applications of sodium batteries. In this work, sodium ion intercalation/deintercalation behavior of Na0.44MnO2 (NMO), which is one of the promising cathode materials for sodium batteries, is presented in both aq. and non-aq. electrolyte systems. The NMO samples synthesized using modified Pechini method shows better rate capability in 0.5 M sodium sulfate aq. electrolyte system than the 1 M sodium perchlorate non-aq. system. The difference in the rate performance is extensively investigated using electrochem. impedance spectroscopy (EIS) measurements and the apparent diffusion coeffs. of sodium in NMO are detd. to be in the range of 1.08 × 10-13 to 9.15 × 10-12 cm2 s-1 in aq. system and in the range of 5.75 × 10-16 to 2.14 × 10-14 cm2 s-1 in non-aq. systems. The differences in the evaluated rate capability are mainly attributed to nearly two to three orders of magnitude difference in the apparent diffusion coeff. along with the charge transfer resistance and the resistance from the formed SEI layer.

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53. 53

    He, X.; Wang, J.; Qiu, B.; Paillard, E.; Ma, C.; Cao, X.; Liu, H.; Stan, M. C.; Liu, H.; Gallash, T.; Meng, Y. S.; Li, J. Durable High-Rate Capability Na_0.44MnO₂ Cathode Material for Sodium-Ion Batteries. Nano Energy 2016, 27, 602– 610,  DOI: 10.1016/j.nanoen.2016.07.021

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    53

    Durable high-rate capability Na0.44MnO2 cathode material for sodium-ion batteries

    He, Xin; Wang, Jun; Qiu, Bao; Paillard, Elie; Ma, Chuze; Cao, Xia; Liu, Haodong; Stan, Marian Cristian; Liu, Haidong; Gallash, Tobias; Meng, Y. Shirley; Li, Jie

    Nano Energy (2016), 27 (), 602-610CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)

    Monocryst. orthorhombic Na0.44MnO2 nanoplate as a potential cathode material for sodium-ion batteries has been synthesized by a template-assisted sol-gel method. It exhibits high crystallinity, pure phase and homogeneous size distribution. During the synthesis, acidic and reductive conditions are applied to limit the prodn. of unfavorable Birnessite phase in the precursor, and colloidal polystyrene is included to avoid morphol. collapse during the gel formation and particle elongation in one direction. The decompns. of polystyrene and citric acid during high temp. firing offer a reductive carbothermal condition which can suppress the formation of unidimensional particles, and limit particle growth along the [001] direction. As a consequence, the material delivers 96 mAh g-1 discharge capacity at 10 C (86% of 0.1 C capacity) and maintains 97.8% capacity after 100 cycles at 0.5 C. Such superior rate capability and cycling stability of this material are among the best to date, suggesting its great interest in practical applications.

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54. 54

    Mao, Y.; Chen, Y.; Qin, J.; Shi, C.; Liu, E.; Zhao, N. Capacitance Controlled, Hierarchical Porous 3D Ultra-Thin Carbon Networks Reinforced Prussian Blue for High Performance Na-Ion Battery Cathode. Nano Energy 2019, 58, 192– 201,  DOI: 10.1016/j.nanoen.2019.01.048

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    54

    Capacitance controlled, hierarchical porous 3D ultra-thin carbon networks reinforced prussian blue for high performance Na-ion battery cathode

    Mao, Yuejia; Chen, Yongtao; Qin, Jian; Shi, Chunsheng; Liu, Enzuo; Zhao, Naiqin

    Nano Energy (2019), 58 (), 192-201CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)

    3D ultra-thin carbon networks are ideal skeleton structures for loading active materials as energy storage and conversion devices. In this work, excellent cathode materials for sodium ion batteries were successfully prepd. by homogeneously anchoring NaxKyMnFe(CN)6 (x + y ≤ 2, NaK-MnHCF) on hierarchical porous 3D N-doped ultra-thin carbon networks (3DNC). The compds. present a high reversible capacity, good rate performance, and superior cycling stability. Combined fully exptl. anal. and first-principles calcn., the interfacial synergistic effect between 3DNC and NaK-MnHCF on the sodium storage capacity is revealed, contributing to the extra capacity and elec. cond. Furthermore, considerable content of capacitive-controlled sodium storage of NaK-MnHCF@3DNC conduces to the rate performance. These results reveal an efficient route for the fabrication of other cathode materials for sodium ion batteries as high-performance energy storage devices.

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55. 55

    Wang, H.; Gao, R.; Li, Z.; Sun, L.; Hu, Z.; Liu, X. Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na_0.67Mn_0.5Fe_0.5O₂ as a Sodium Ion Battery Cathode Material. Inorg. Chem. 2018, 57 (9), 5249– 5257,  DOI: 10.1021/acs.inorgchem.8b00284

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    55

    Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material

    Wang, Huibo; Gao, Rui; Li, Zhengyao; Sun, Limei; Hu, Zhongbo; Liu, Xiangfeng

    Inorganic Chemistry (2018), 57 (9), 5249-5257CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)

    P2-type layered oxides based on the elements Fe and Mn have attracted great interest as sodium ion battery (SIB) cathode materials owing to their inexpensive metal constituents and high specific capacity. However, they suffer from rapid capacity fading and complicated phase transformations. Here, we modulate the crystal structure and optimize the electrochem. performances of Na0.67Mn0.5Fe0.5O2 by Al doping for Mn or Fe, resp., and the roles of Al in the enhancement of the rate capability and cycling performance are unraveled. The substitution of Al for Mn or Fe decreases the lattice parameters a and c but enlarges d spacing and lengthens Na-O bonds, which enhances Na+ diffusion and rate capability esp. for Na0.67Mn0.5Fe0.47Al0.03O2. Al doping reduces the thickness of TMO2 and strengthens TM-O/O-O bonding. This enhances the layered structure stability and the capacity retention. Al doping mitigates Mn3+ and Jahn-Teller distortion, mitigating the irreversible phase transition. Al doping also alleviates the lattice vol. variation and the structure strain. This further improves the stability of the layered structure and the cycling performances particularly in the case of Al doping for Fe. The in-depth insights into the roles of Al substitution might be also useful for designing high-performance cathode materials for SIBs through appropriate lattice doping.

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56. 56

    Xu, S.; Wang, Y.; Ben, L.; Lyu, Y.; Song, N.; Yang, Z.; Li, Y.; Mu, L.; Yang, H.-T.; Gu, L.; Hu, Y.-S.; Li, H.; Cheng, Z.-H.; Chen, L.; Huang, X. Fe-Based Tunnel-Type Na_0.61[Mn_0.27Fe_0.34ti_0.39]O₂ designed by a New Strategy as a Cathode Material for Sodium-Ion Batteries. Adv. Energy Mater. 2015, 5 (22), 1501156,  DOI: 10.1002/aenm.201501156

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57. 57

    Park, J.-K.; Park, G.-G.; Kwak, H. H.; Hong, S.-T.; Lee, J.-W. Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na_0.67Fe_0.5Mn_0.5O₂ as a Cathode for Sodium-Ion Batteries. ACS Omega 2018, 3 (1), 361– 368,  DOI: 10.1021/acsomega.7b01481

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    57

    Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na0.67Fe0.5Mn0.5O2 as a Cathode for Sodium-Ion Batteries

    Park, Joon-ki; Park, Geun-gyung; Kwak, Hunho H.; Hong, Seung-Tae; Lee, Jae-won

    ACS Omega (2018), 3 (1), 361-368CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)

    In this study, we developed a doping technol. capable of improving the electrochem. performance, including the rate capability and cycling stability, of P2-type Na0.67Fe0.5Mn0.5O2 as a cathode material for sodium-ion batteries. Our approach involved using titanium as a doping element to partly substitute either Fe or Mn in Na0.67Fe0.5Mn0.5O2. The Ti-substituted Na0.67Fe0.5Mn0.5O2 shows superior electrochem. properties compared to the pristine sample. We investigated the changes in the crystal structure, surface chem., and particle morphol. caused by Ti doping and correlated these changes to the improved performance. The enhanced rate capability and cycling stability were attributed to the enlargement of the NaO2 slab in the crystal structure because of Ti doping. This promoted Na-ion diffusion and prevented the phase transition from the P2 to the OP4/''Z'' structure.

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58. 58

    Olazabal, I.; Goujon, N.; Mantione, D.; Alvarez-Tirado, M.; Jehanno, C.; Mecerreyes, D.; Sardon, H. From Plastic Waste to New Materials for Energy Storage. Polym. Chem. 2022, 13 (29), 4222– 4229,  DOI: 10.1039/D2PY00592A

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    From plastic waste to new materials for energy storage

    Olazabal, Ion; Goujon, Nicolas; Mantione, Daniele; Alvarez-Tirado, Marta; Jehanno, Coralie; Mecerreyes, David; Sardon, Haritz

    Polymer Chemistry (2022), 13 (29), 4222-4229CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

    A review. The use of plastic waste to develop high added value materials, also known as upcycling, is a useful strategy towards the development of more sustainable materials. More specifically, the use of plastic waste as a feedstock for synthesizing new materials for energy storage devices not only provides a route to upgrading plastic waste but also can help in the search for sustainable materials. This perspective describes recent strategies for the use of plastic waste as a sustainable, cheap and abundant feedstock in the prodn. of new materials for electrochem. energy storage devices such as lithium batteries, sodium batteries and supercapacitors. Two main strategies are described, the development of conducting carbons by combustion of plastic waste and the depolymn. of plastics into new chems. and materials. In both cases, catalysis has been key to ensuring high efficiency and performance. Future opportunities and challenges are highlighted and hypotheses are made on how the use of plastic waste could enhance the circularity of current energy storage devices.

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59. 59

    Kumar, U.; Goonetilleke, D.; Gaikwad, V.; Pramudita, J. C.; Joshi, R. K.; Sharma, N.; Sahajwalla, V. Activated Carbon from E-Waste Plastics as a Promising Anode for Sodium-Ion Batteries. ACS Sustainable Chem. Eng. 2019, 7 (12), 10310– 10322,  DOI: 10.1021/acssuschemeng.9b00135

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    59

    Activated Carbon from E-Waste Plastics as a Promising Anode for Sodium-Ion Batteries

    Kumar, Uttam; Goonetilleke, Damian; Gaikwad, Vaibhav; Pramudita, James C.; Joshi, Rakesh K.; Sharma, Neeraj; Sahajwalla, Veena

    ACS Sustainable Chemistry & Engineering (2019), 7 (12), 10310-10322CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)

    There is a pressing need for the introduction of highly efficient and cost-effective energy storage systems to meet worldwide burgeoning energy demand. Key to these systems is the development of sustainable, higher capacity, electrode materials. Carbonaceous materials have demonstrated the most success as neg. electrode materials for alkali-ion batteries, and the development of novel methods to produce these materials more sustainably will enable the prodn. of next-generation alkali-ion batteries with reduced environmental impact. This study demonstrates that activated carbon derived from end-of-life printer plastics can act as high capacity anode materials for sodium-ion batteries. These carbons exhibited superior rate capability and delivered capacities as high as 190 mAh/g at 3 mA/g after 25 cycles. They were able to retain up to 100% of their second discharge capacity after 100 cycles at 20 mA/g. In-depth ex situ anal. of the electrodes, using a combination of techniques such as solid state NMR and X-ray diffraction is also presented to shed light on the sodium storage mechanism, a topic still being vigorously investigated in the scientific community. This work provides an excellent example of repurposing waste for sustainable energy storage applications.

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60. 60

    Fonseca, W. S.; Meng, X.; Deng, D. Trash to Treasure: Transforming Waste Polystyrene Cups into Negative Electrode Materials for Sodium Ion Batteries. ACS Sustainable Chem. Eng. 2015, 3 (9), 2153– 2159,  DOI: 10.1021/acssuschemeng.5b00403

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    60

    Trash to Treasure: Transforming Waste Polystyrene Cups into Negative Electrode Materials for Sodium Ion Batteries

    Fonseca, Weliton Silva; Meng, Xinghua; Deng, Da

    ACS Sustainable Chemistry & Engineering (2015), 3 (9), 2153-2159CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)

    Modern society generates a huge amt. of plastic wastes that are posing potential disasters to our environment and society. For example, waste polystyrene (PS), such as used PS cups and packing materials, is mainly disposed into landfills. It is very challenging to recycle PS economically. PS cannot be carbonized under conventional conditions, because PS is completely decompd. into toxic gases at moderate temp. instead of carbonization. Here, we demonstrated a facile procedure to transform waste PS cups collected from a local coffee shop into disordered carbon in a sealed reactor at moderate temp. but under high pressure. The as-obtained disordered carbon demonstrated interesting electrochem. characteristics for reversible storage of sodium ions. A highly reversible capacity of 116 mAh g-1 could be achieved for at least 80 cycles. Our preliminary results demonstrated that the trash of waste PS cups could be facilely transformed into treasure of promising neg. electrode materials for sodium ion batteries, offering an alternative and sustainable approach to manage the waste PS issue.

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61. 61

    He, H.; Gan, Q.; Wang, H.; Xu, G.-L.; Zhang, X.; Huang, D.; Fu, F.; Tang, Y.; Amine, K.; Shao, M. Structure-Dependent Performance of TiO₂/C as Anode Material for Na-Ion Batteries. Nano Energy 2018, 44, 217– 227,  DOI: 10.1016/j.nanoen.2017.11.077

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    61

    Structure-dependent performance of TiO2/C as anode material for Na-ion batteries

    He, Hanna; Gan, Qingmeng; Wang, Haiyan; Xu, Gui-Liang; Zhang, Xiaoyi; Huang, Dan; Fu, Fang; Tang, Yougen; Amine, Khalil; Shao, Minhua

    Nano Energy (2018), 44 (), 217-227CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)

    The performance of energy storage materials is highly dependent on their nanostructures. Herein, hierarchical rod-in-tube TiO2 with a uniform carbon coating is synthesized as the anode material for sodium-ion batteries by a facile solvothermal method. This unique structure consists of a tunable nanorod core, interstitial hollow spaces, and a functional nanotube shell assembled from two-dimensional nanosheets. By adjusting the types of solvents used and reaction time, the morphologies of TiO2/C composites can be tuned to nanoparticles, microrods, rod-in-tube structures, or microtubes. Among these materials, rod-in-tube TiO2 with a uniform carbon coating shows the highest electronic cond., sp. surface area (336.4 m2 g-1), and porosity, and these factors lead to the best sodium storage capability. Benefiting from the unique structural features and improved electronic/ionic cond., the as-obtained rod-in-tube TiO2/C in coin cell tests exhibits a high discharge capacity of 277.5 and 153.9 mAh g-1 at 50 and 5000 mA g-1, resp., and almost 100% capacity retention over 14,000 cycles at 5000 mA g-1. In operando high-energy X-ray diffraction further confirms the stable crystal structure of the rod-in-tube TiO2/C during Na+ insertion/extn. This work highlights that nanostructure design is an effective strategy to achieve advanced energy storage materials.

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62. 62

    Brugnetti, G.; Fiore, M.; Lorenzi, R.; Paleari, A.; Ferrara, C.; Ruffo, R. FeTiO₃ as Anode Material for Sodium-ion Batteries: From Morphology Control to Decomposition. ChemElectroChem. 2020, 7 (7), 1713– 1722,  DOI: 10.1002/celc.202000150

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    62

    FeTiO3 as Anode Material for Sodium-Ion Batteries: from Morphology Control to Decomposition

    Brugnetti, Gabriele; Fiore, Michele; Lorenzi, Roberto; Paleari, Alberto; Ferrara, Chiara; Ruffo, Riccardo

    ChemElectroChem (2020), 7 (7), 1713-1722CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)

    Ilmenite, general formula FeTiO3, has been proposed as possible conversion anode material for lithium- and sodium-ion batteries, with theor. capacity of 530 mAhg-1. Exptl., the obsd. specific capacity for pristine ilmenite is far away from the theor. value; for this reason, the control of morphol. via alk. hydrothermal treatment has been proposed as possible strategy to improve the electrochem. performance. At the same time FeTiO3 is prone to react with sodium and potassium hydroxide, as already demonstrated by studies on the degrdn. of ilmenite for the extn. of TiO2. In this paper we demonstrate that the alk. treatment does not induce a morphol. modification of the FeTiO3 powders but involved the degrdn. of the precursor material with the formation of different phases. A complete physicochem. and electrochem. characterization is performed with the aim of correlating structural and functional properties of the obtained products.

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63. 63

    Ding, C.; Nohira, T.; Hagiwara, R. High-Capacity FeTiO₃/C Negative Electrode for Sodium-Ion Batteries with Ultralong Cycle Life. J. Power Sources 2018, 388, 19– 24,  DOI: 10.1016/j.jpowsour.2018.03.068

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    63

    High-capacity FeTiO3/C negative electrode for sodium-ion batteries with ultralong cycle life

    Ding, Changsheng; Nohira, Toshiyuki; Hagiwara, Rika

    Journal of Power Sources (2018), 388 (), 19-24CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)

    The development of electrode materials which improve both the energy d. and cycle life is one of the most challenging issues facing the practical application of sodium-ion batteries today. In this work, FeTiO3/C nanoparticles are synthesized as neg. electrode materials for sodium-ion batteries. The electrochem. performance and charge-discharge mechanism of the FeTiO3/C neg. electrode are investigated in an ionic liq. electrolyte at 90°C. The FeTiO3/C neg. electrode delivers a high reversible capacity of 403 mAh g-1 at a current rate of 10 mA g-1, and exhibits high rate capability and excellent cycling stability for up to 2000 cycles. The results indicate that FeTiO3/C is a promising neg. electrode material for sodium-ion batteries.

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64. 64

    Senguttuvan, P.; Rousse, G.; Seznec, V.; Tarascon, J.-M.; Palacín, M. R. Na₂Ti₃O₇: Lowest Voltage Ever Reported Oxide Insertion Electrode for Sodium Ion Batteries. Chem. Mater. 2011, 23 (18), 4109– 4111,  DOI: 10.1021/cm202076g

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    64

    Na2Ti3O7: Lowest Voltage Ever Reported Oxide Insertion Electrode for Sodium Ion Batteries

    Senguttuvan, Premkumar; Rousse, Gwenaelle; Seznec, Vincent; Tarascon, Jean-Marie; Palacin, M. Rosa

    Chemistry of Materials (2011), 23 (18), 4109-4111CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Na2Ti3O7 works as an effective low-voltage insertion sodium compd. because of its ability to reversibly uptake 2 Na ions per formula unit (200 mA-h/g) at an av. potential of 0.3 V. This is the first ever reported oxide to reversibly react with sodium at such a low potential. Several improvements to the present work are immediately apparent and range from electrode optimization to the detn. of the precise sodium insertion mechanism. Nevertheless, we believe that the result reported in this paper provides great opportunities in the development of room-temp. high-performing sodium-ion batteries.

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65. 65

    Xu, J.; Ma, C.; Balasubramanian, M.; Meng, Y. S. Understanding Na₂Ti₃O₇ as an Ultra-Low Voltage Anode Material for a Na-Ion Battery. Chem. Commun. 2014, 50 (83), 12564– 12567,  DOI: 10.1039/C4CC03973D

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    65

    Understanding Na2Ti3O7 as an ultra-low voltage anode material for a Na-ion battery

    Xu, Jing; Ma, Chuze; Balasubramanian, Mahalingam; Meng, Ying Shirley

    Chemical Communications (Cambridge, United Kingdom) (2014), 50 (83), 12564-12567CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)

    An in-depth understanding of Na2Ti3O7 as a Na-ion battery anode is reported. The battery performance is enhanced by carbon coating, due to increased electronic cond. and reduced solid electrolyte interphase formation. Ti4+ redn. upon discharge is demonstrated using in situ XAS. The self-relaxation behavior of the fully intercalated phase is obsd.

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66. 66

    Yu, L.; Liu, J.; Xu, X.; Zhang, L.; Hu, R.; Liu, J.; Ouyang, L.; Yang, L.; Zhu, M. Ilmenite Nanotubes for High Stability and High Rate Sodium-Ion Battery Anodes. ACS Nano 2017, 11 (5), 5120– 5129,  DOI: 10.1021/acsnano.7b02136

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    66

    Ilmenite Nanotubes for High Stability and High Rate Sodium-Ion Battery Anodes

    Yu, Litao; Liu, Jun; Xu, Xijun; Zhang, Liguo; Hu, Renzong; Liu, Jiangwen; Ouyang, Liuzhang; Yang, Lichun; Zhu, Min

    ACS Nano (2017), 11 (5), 5120-5129CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)

    To solve the problem of large vol. change and low electronic cond. of earth-abundant ilmenite used in rechargeable Na-ion batteries (SIBs), an anode of tiny ilmenite FeTiO3 nanoparticle embedded carbon nanotubes (FTO-CNTs) has been successfully proposed. By introducing a TiO2 shell on metal-org. framework (Fe-MOF) nanorods by sol-gel deposition and subsequent solid-state annealing treatment of these core-shell Fe-MOF@TiO2, such well-defined FTO-CNTs are obtained. The achieved FTO-CNT electrode has several distinct advantages including a hollow interior in the hybrid nanostructure, fully encapsulated ultrasmall electroactive units, flexible conductive carbon matrix, and stable solid electrolyte interface (SEI) of FTO in cycles. FTO-CNT electrodes present an excellent cycle stability (358.8 mA h g-1 after 200 cycles at 100 mA g-1) and remarkable rate capability (201.8 mA h g-1 at 5000 mA g-1) with a high Coulombic efficiency of approx. 99%. In addn., combined with the typical Na3V2(PO4)3 cathode to constitute full SIBs, the assembled FT-CNT//Na3V2(PO4)3 batteries are also demonstrated with superior rate capability and a long cycle life.

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    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXntFaqsrw%253D&md5=e4c098c44f6b44897e03edee9888dec1
67. 67

    Jubinville, D.; Esmizadeh, E.; Saikrishnan, S.; Tzoganakis, C.; Mekonnen, T. A Comprehensive Review of Global Production and Recycling Methods of Polyolefin (PO) Based Products and Their Post-Recycling Applications. Sustainable Materials and Technologies 2020, 25, e00188  DOI: 10.1016/j.susmat.2020.e00188

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    A comprehensive review of global production and recycling methods of polyolefin (PO) based products and their post-recycling applications

    Jubinville, Dylan; Esmizadeh, Elnaz; Saikrishnan, Sainiwetha; Tzoganakis, Costas; Mekonnen, Tizazu

    Sustainable Materials and Technologies (2020), 25 (), e00188CODEN: SMTUAV; ISSN:2214-9937. (Elsevier B.V.)

    A review. Presently, environmental problems and regulations have caused awareness to producer liability concerning plastics recycling as they try to meet global demand. Process-induced degrdn. during recycling as well as degrdn. brought on by thermomech. operations (e.g. extrusion, injection molding, etc.) or other processes typically leads to irreversible changes in the physicochem. properties and structure of the material. Thus, it is important to understand the magnitude and mechanisms of property deterioration during the recycling process via either chem., thermomech., reutilization, or incineration methods while, looking into possible utilizations, applications, and solns. for the existing global accumulated polyolefine (PO) waste. This review provides a comprehensive overview of the recent research efforts and industrial trends in PO recycling. Although a wide variety of POs exist in the market, this review focuses on polyethylene (PE) and polypropylene (PP). The ongoing challenges and future potential of plastic recycling are also discussed.

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68. 68

    Wadsworth, J.; Cockell, C. S. Perchlorates on Mars Enhance the Bacteriocidal Effects of UV Light. Sci. Rep. 2017, 7 (1), 4662,  DOI: 10.1038/s41598-017-04910-3

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    Perchlorates on Mars enhance the bacteriocidal effects of UV light

    Wadsworth Jennifer; Cockell Charles S

    Scientific reports (2017), 7 (1), 4662 ISSN:.

    Perchlorates have been identified on the surface of Mars. This has prompted speculation of what their influence would be on habitability. We show that when irradiated with a simulated Martian UV flux, perchlorates become bacteriocidal. At concentrations associated with Martian surface regolith, vegetative cells of Bacillus subtilis in Martian analogue environments lost viability within minutes. Two other components of the Martian surface, iron oxides and hydrogen peroxide, act in synergy with irradiated perchlorates to cause a 10.8-fold increase in cell death when compared to cells exposed to UV radiation after 60 seconds of exposure. These data show that the combined effects of at least three components of the Martian surface, activated by surface photochemistry, render the present-day surface more uninhabitable than previously thought, and demonstrate the low probability of survival of biological contaminants released from robotic and human exploration missions.

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69. 69

    Ojha, L.; Wilhelm, M. B.; Murchie, S. L.; McEwen, A. S.; Wray, J. J.; Hanley, J.; Massé, M.; Chojnacki, M. Spectral Evidence for Hydrated Salts in Recurring Slope Lineae on Mars. Nat. Geosci. 2015, 8 (11), 829– 832,  DOI: 10.1038/ngeo2546

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    Spectral evidence for hydrated salts in recurring slope lineae on Mars

    Ojha, Lujendra; Wilhelm, Mary Beth; Murchie, Scott L.; McEwen, Alfred S.; Wray, James J.; Hanley, Jennifer; Masse, Marion; Chojnacki, Matt

    Nature Geoscience (2015), 8 (11), 829-832CODEN: NGAEBU; ISSN:1752-0894. (Nature Publishing Group)

    Detg. whether liq. water exists on the Martian surface is central to understanding the hydrol. cycle and potential for extant life on Mars. Recurring slope lineae, narrow streaks of low reflectance compared to the surrounding terrain, appear and grow incrementally in the downslope direction during warm seasons when temps. reach about 250-300 K, a pattern consistent with the transient flow of a volatile species. Brine flows (or seeps) have been proposed to explain the formation of recurring slope lineae, yet no direct evidence for either liq. water or hydrated salts has been found. Here we analyze spectral data from the Compact Reconnaissance Imaging Spectrometer for Mars instrument onboard the Mars Reconnaissance Orbiter from four different locations where recurring slope lineae are present. We find evidence for hydrated salts at all four locations in the seasons when recurring slope lineae are most extensive, which suggests that the source of hydration is recurring slope lineae activity. The hydrated salts most consistent with the spectral absorption features we detect are magnesium perchlorate, magnesium chlorate and sodium perchlorate. Our findings strongly support the hypothesis that recurring slope lineae form as a result of contemporary water activity on Mars.

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70. 70

    Wang, Y.; Song, S.; Xu, C.; Hu, N.; Molenda, J.; Lu, L. Development of Solid-State Electrolytes for Sodium-Ion battery–A Short Review. Nano Materials Science 2019, 1 (2), 91– 100,  DOI: 10.1016/j.nanoms.2019.02.007

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71. 71

    Zhang, Z.; Wenzel, S.; Zhu, Y.; Sann, J.; Shen, L.; Yang, J.; Yao, X.; Hu, Y.-S.; Wolverton, C.; Li, H.; Chen, L.; Janek, J. Na₃Zr₂Si₂PO₁₂: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries. ACS Appl. Energy Mater. 2020, 3 (8), 7427– 7437,  DOI: 10.1021/acsaem.0c00820

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    71

    Na3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries

    Zhang, Zhizhen; Wenzel, Sebastian; Zhu, Yizhou; Sann, Joachim; Shen, Lin; Yang, Jing; Yao, Xiayin; Hu, Yong-Sheng; Wolverton, Christopher; Li, Hong; Chen, Liquan; Janek, Jurgen

    ACS Applied Energy Materials (2020), 3 (8), 7427-7437CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)

    Solid electrolytes (SEs) offer great potential as the basis for safer rechargeable batteries with high energy d. Aside from excellent ion cond., the stability of SEs against the highly reactive metal anode is also a prerequisite to achieve good performance in solid-state batteries (SSBs). Yet, most SEs are found to have limited thermodn. stability and are unstable against Li/Na metal. With the combination of AC impedance spectroscopy, first-principles calcns., and in situ XPS, we unequivocally reveal that a NaSICON-structured Na3Zr2Si2PO12 electrolyte forms a kinetically stable interface against sodium metal. Prolonged galvanostatic cycling of sym. Na|Na3Zr2Si2PO12|Na cells shows stable plating/stripping behavior of sodium metal at a c.d. of 0.1 mA cm-2 and an areal capacity of 0.5 mA h cm-2 at room temp. Evaluation of Na3Zr2Si2PO12 as an electrolyte in SSBs further demonstrates its good cycling stability for over 120 cycles with very limited capacity degrdn. This work provides strong evidence that Na3Zr2Si2PO12 is one of the few electrolytes that simultaneously achieve superionic cond. and excellent chem./electrochem. stability, making it a very promising alternative to liq. electrolytes. Our findings open up a fertile avenue of exploration for SSBs based on Na3Zr2Si2PO12 and related SEs.

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    Hayashi, A.; Noi, K.; Sakuda, A.; Tatsumisago, M. Superionic Glass-Ceramic Electrolytes for Room-Temperature Rechargeable Sodium Batteries. Nat. Commun. 2012, 3, 856,  DOI: 10.1038/ncomms1843

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    Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

    Hayashi Akitoshi; Noi Kousuke; Sakuda Atsushi; Tatsumisago Masahiro

    Nature communications (2012), 3 (), 856 ISSN:.

    Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.

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73. 73

    Kim, J.-J.; Yoon, K.; Park, I.; Kang, K. Progress in the Development of Sodium-Ion Solid Electrolytes. Small Methods 2017, 1 (10), 1700219,  DOI: 10.1002/smtd.201700219

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    Marone, M.; Paley, M. S.; Donovan, D. N.; Karr, L. J. Lunar Oxygen Production and Metals Extraction Using Ionic Liquids. Annual Meeting of the Lunar Exploration Analysis Group (LEAG Meeting) , Houston, TX, Nov 16, 2009. https://ntrs.nasa.gov/citations/20100002191.

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    Karr, L. J.; Paley, M. S.; Marone, M. J.; Kaukler, W. F.; Curreri, P. A. Metals and Oxygen Mining from Meteorites, Asteroids and Planets Using Reusable Ionic Liquids. 2012 PISCES Conference, Pioneering Planetary Surface Systems Technologies and Capabilities , Waikoloa, HI, Nov 11, 2012. https://ntrs.nasa.gov/citations/20130001681.

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    Ionic liquids. NASA, May 22, 2019.https://www.nasa.gov/oem/ionicliquids (accessed 2022-12-17).

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    Fox, E. T.; Karr, L. J.; Curreri, P. A.; Thornton, G. S.; Depew, K. E.; Vankeuren, J. M.; Regelman, M.; Marone, M. J.; Donovan, D. N.; Paley, M. S. Ionic Liquid Facilitated Recovery of Metals and Oxygen from Regolith. AIAA Space Forum , Orlando, FL, Sept 17, 2018. https://ntrs.nasa.gov/citations/20180006392.

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    Mohd Noor, S. A.; Howlett, P. C.; MacFarlane, D. R.; Forsyth, M. Properties of Sodium-Based Ionic Liquid Electrolytes for Sodium Secondary Battery Applications. Electrochim. Acta 2013, 114, 766– 771,  DOI: 10.1016/j.electacta.2013.09.115

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    Properties of sodium-based ionic liquid electrolytes for sodium secondary battery applications

    Mohd Noor, Siti Aminah; Howlett, Patrick C.; MacFarlane, Douglas R.; Forsyth, Maria

    Electrochimica Acta (2013), 114 (), 766-771CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)

    The enormous demands on available global lithium resources have raised concerns about the sustainability of the supply of lithium. Sodium secondary batteries have emerged as promising alternatives to lithium batteries. We describe here sodium bis(trifluoromethylsulfonyl) amide (NaNTf2) electrolyte systems based on 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) amide (C4mpyrNTf2) ionic liqs. The electrochem. stability of the system was examd.; a pair of facile cathodic and anodic processes around 0 V vs. Na/Na+ were obsd. in cyclic voltammetry measurements and interpreted as deposition and dissoln. of sodium metal. D., viscosity and cond. of the electrolytes were studied. The ionic cond. of electrolytes reached as high as 8 mS/cm, decreasing slowly as the salt content increased due to increasing of viscosity and d. of the electrolyte. Therefore, sodium electrolytes based on C4mpyrNTf2 appear to be promising for secondary sodium battery applications.

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79. 79

    Kundu, D.; Talaie, E.; Duffort, V.; Nazar, L. F. The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage. Angew. Chem., Int. Ed. Engl. 2015, 54 (11), 3431– 3448,  DOI: 10.1002/anie.201410376

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    The emerging chemistry of sodium ion batteries for electrochemical energy storage

    Kundu Dipan; Talaie Elahe; Duffort Victor; Nazar Linda F

    Angewandte Chemie (International ed. in English) (2015), 54 (11), 3431-48 ISSN:.

    Energy storage technology has received significant attention for portable electronic devices, electric vehicle propulsion, bulk electricity storage at power stations, and load leveling of renewable sources, such as solar energy and wind power. Lithium ion batteries have dominated most of the first two applications. For the last two cases, however, moving beyond lithium batteries to the element that lies below-sodium-is a sensible step that offers sustainability and cost-effectiveness. This requires an evaluation of the science underpinning these devices, including the discovery of new materials, their electrochemistry, and an increased understanding of ion mobility based on computational methods. The Review considers some of the current scientific issues underpinning sodium ion batteries.

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80. 80

    Peters, F. A.; Johnson, P. W. Revised and Updated Cost Estimates for Producing Alumina from Domestic Raw Materials; U.S. Bureau of Mines, 1974.

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    Mariappan, A.; Kumar, V. R. S.; Weddell, S. J.; Muruganandan, V. A.; Jeung, I. Theoretical Studies on Space Debris Recycling and Energy Conversion System in the International Space Station. Eng. Rep. 2021, 3 (5), 12317,  DOI: 10.1002/eng2.12317

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    Capuzzi, S.; Timelli, G. Preparation and Melting of Scrap in Aluminum Recycling: A Review. Metals 2018, 8 (4), 249,  DOI: 10.3390/met8040249

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    Preparation and melting of scrap in aluminum recycling: a review

    Capuzzi, Stefano; Timelli, Giulio

    Metals (Basel, Switzerland) (2018), 8 (4), 249/1-249/24CODEN: MBSEC7; ISSN:2075-4701. (MDPI AG)

    This work provides an overview of the aluminum (Al) recycling process, from the scrap upgrading to the melting process. Innovations and new trends regarding the Al recycling technologies are highlighted. Aluminum recycling offers advantages in terms of environmental and economic benefits. The presence of deleterious impurities in recycled Al alloys is increasing and this is the main drawback if compared to primary alloys. The continuous growth of undesired elements can be mitigated by different technologies, preliminary operations and treatments, and by the optimization of the melting process. Downgrading and diln. are possible solns. to reduce the rate of impurities, but they are not sustainable if the final use of Al alloy continuously increases. The main objectives in the development of the Al recycling are shown and discussed. In particular, the evolution of preliminary treatments of the scrap, as sorting, comminution and de-coating, is reported and a review of the melting technologies is also presented. However, the choice of performing preliminary operations to the melting stage, thus improving the operating conditions during the furnace running, is a trade-off between costs and process efficiency.

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83. 83

    Prater, T.; Werkheiser, M. J.; Ledbetter, F.; Morgan, K. In-Space Manufacturing at NASA Marshall Space Flight Center: A Portfolio of Fabrication and Recycling Technology Development for the International Space Station. 2018 AIAA Space Forum , Orlando, FL, Sept 17, 2018. https://ntrs.nasa.gov/citations/20180006401.

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    Maurel, A.; Haukka, M.; MacDonald, E.; Kivijärvi, L.; Lahtinen, E.; Kim, H.; Armand, M.; Cayla, A.; Jamali, A.; Grugeon, S.; Dupont, L.; Panier, S. Considering Lithium-Ion Battery 3D-Printing via Thermoplastic Material Extrusion and Polymer Powder Bed Fusion. Additive Manufacturing 2021, 37, 101651,  DOI: 10.1016/j.addma.2020.101651

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    Considering lithium-ion battery 3D-printing via thermoplastic material extrusion and polymer powder bed fusion

    Maurel, Alexis; Haukka, Matti; MacDonald, Eric; Kivijarvi, Lauri; Lahtinen, Elmeri; Kim, Hyeonseok; Armand, Michel; Cayla, Aurelie; Jamali, Arash; Grugeon, Sylvie; Dupont, Loic; Panier, Stephane

    Additive Manufacturing (2021), 37 (), 101651CODEN: AMDAD2; ISSN:2214-7810. (Elsevier B.V.)

    In this paper, the ability to 3D print lithium-ion batteries through Pmnbspace thermoplastic material extrusion and polymer powder bed fusion is considered. Focused on the formulation of pos. electrodes composed of polypropylene, LiFePO4 as active material, and conductive additives, advantages and drawbacks of both additive manufg. technologies, are thoroughly discussed from the electrochem., elec., morphol. and mech. perspectives. Based on these preliminary results, strategies to further optimize the electrochem. performances are proposed. Through a comprehensive modeling study, the enhanced electrochem. suitability at high current densities of various complex three-dimensional lithium-ion battery architectures, in comparison with classical two-dimensional planar design, is highlighted. Finally, the direct printing capability of the complete lithium-ion battery by means of multi-materials printing options processes is examd.

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85. 85

    Long, J. W.; Dunn, B.; Rolison, D. R.; White, H. S. Three-Dimensional Battery Architectures. Chem. Rev. 2004, 104 (10), 4463– 4492,  DOI: 10.1021/cr020740l

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    Three-Dimensional Battery Architectures

    Long, Jeffrey W.; Dunn, Bruce; Rolison, Debra R.; White, Henry S.

    Chemical Reviews (Washington, DC, United States) (2004), 104 (10), 4463-4492CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)

    A review. Consumer electronics is a vibrant, worldwide market force, leading to ever-increasing demands for portable power. As the dimensions of devices continue to shrink, the question arises as to how power sources of comparable scale will be fabricated. The 2-D configurations of traditional batteries may not be effective, despite their high energy d. Energy conversion and harvesting may be more suitable for powering microdevices, simply because of the ability to provide on-board power. Three-dimensional batteries offer a different approach and 3-D designs that emphasize power sources with small areal footprints, without compromising power and energy d., are presented. While this approach may not help solve the power needs for cell phones and laptop computers, it will have a significant impact on current and future generations of microdevices. In particular, distributed sensor networks and wireless communication systems are representative areas where 3-D batteries would be welcomed enthusiastically because the power supplies currently in use are many times the size of the device. Some of the design rules for 3-D batteries are proposed with the necessary materials and fabrication strategies. Hierarchical designs based on nanostructured materials, including the deliberate management of void space, have been organized into larger macroscopic structures and the first results are impressive. Most of the necessary components for 3-D batteries are already available and the demonstration of the first operational 3-D batteries is imminent.

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86. 86

    Maurel, A.; Grugeon, S.; Armand, M.; Fleutot, B.; Courty, M.; Prashantha, K.; Davoisne, C.; Tortajada, H.; Panier, S.; Dupont, L. Overview on Lithium-Ion Battery 3D-Printing By Means of Material Extrusion. ECS Trans. 2020, 98 (13), 3– 21,  DOI: 10.1149/09813.0003ecst

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    Overview on lithium-ion battery 3D-printing by means of material extrusion

    Maurel, A.; Grugeon, S.; Armand, M.; Fleutot, B.; Courty, Matthieu; Prashantha, K.; Davoisne, C.; Tortajada, H.; Panier, S.; Dupont, L.

    ECS Transactions (2020), 98 (13), 3-21CODEN: ECSTF8; ISSN:1938-6737. (IOP Publishing Ltd.)

    Among the various additive manufg. processes, material extrusion techniques recently emerged as an encouraging option in order to 3D-print lithium-ion battery components. In this work, an overview of the recent advances and progress on the ink material extrusion, known as liq. deposition modeling (LDM), as well as the thermoplastic material extrusion process, known originally as the trademark Fused Deposition Modeling (FDM), is discussed. Representing a promising route to achieve complete lithium-ion batteries in a single print without the necessity to perform any postprocesses, a particular consideration is devoted to the FDM process. Trends, prospects as well as an exhaustive list of the parameters still requiring further investigations are provided, thus paving the way towards the next generation of FDM 3D-printed lithium-ion batteries.

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87. 87

    Browne, M. P.; Redondo, E.; Pumera, M. 3D Printing for Electrochemical Energy Applications. Chem. Rev. 2020, 120 (5), 2783– 2810,  DOI: 10.1021/acs.chemrev.9b00783

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    3D Printing for Electrochemical Energy Applications

    Browne, Michelle P.; Redondo, Edurne; Pumera, Martin

    Chemical Reviews (Washington, DC, United States) (2020), 120 (5), 2783-2810CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)

    A review. Additive manufg. (also known as three-dimensional (3D) printing) is being extensively utilized in many areas of electrochem. to produce electrodes and devices, as this technique allows for fast prototyping and is relatively low cost. Furthermore, there is a variety of 3D-printing technologies available, which include fused deposition modeling (FDM), inkjet printing, select laser melting (SLM), and stereolithog. (SLA), making additive manufg. a highly desirable technique for electrochem. purposes. In particular, over the last no. of years, a significant amt. of research into using 3D printing to create electrodes/devices for electrochem. energy conversion and storage has emerged. Strides have been made in this area; however, there are still a no. of challenges and drawbacks that need to be overcome in order to 3D print active and stable electrodes/devices for electrochem. energy conversion and storage to rival that of the state-of-the-art. In this review, an overview is given of the reasoning behind using 3D printing for these electrochem. applications. How the electrochem. performance of the electrodes/devices are affected by the various 3D-printing technologies and by manipulating the 3D-printed electrodes by post modification techniques are discussed. Finally, the insights are given into the future perspectives of this exciting field based on the discussion through the review.

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88. 88

    Maurel, A.; Martinez, A. C.; Grugeon, S.; Panier, S.; Dupont, L.; Cortes, P.; Sherrard, C. G.; Small, I.; Sreenivasan, S. T.; Macdonald, E. Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective. IEEE Access 2021, 9, 140654– 140666,  DOI: 10.1109/ACCESS.2021.3119533

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89. 89

    Sun, K.; Wei, T. S.; Ahn, B. Y.; Seo, J. Y.; Dillon, S. J.; Lewis, J. A. 3D Printing of Interdigitated Li-Ion Microbattery Architectures. Adv. Mater. 2013, 25 (33), 4539– 4543,  DOI: 10.1002/adma.201301036

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    3D Printing of Interdigitated Li-Ion Microbattery Architectures

    Sun, Ke; Wei, Teng-Sing; Ahn, Bok Yeop; Seo, Jung Yoon; Dillon, Shen J.; Lewis, Jennifer A.

    Advanced Materials (Weinheim, Germany) (2013), 25 (33), 4539-4543CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)

    We have printed novel three-dimensional (3D) microbatteries composed of high-aspect ratio electrodes in interdigited architectures. Careful design of concd. LiFePO4 and Li4Ti5O12 viscoelastic inks enabled printing of these thin-walled cathode and anode structures, resp. Using this LiFePO4-Li4Ti5O12 chem., we have demonstrated 3D interdigited microbattery architectures with a high areal energy d. of 9.7 J/cm2 at a power d. of 2.7 mW/cm2. These microbatteries may find potential application in autonomously powered microelectronics and biomedical devices.

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90. 90

    Fu, K.; Wang, Y.; Yan, C.; Yao, Y.; Chen, Y.; Dai, J.; Lacey, S.; Wang, Y.; Wan, J.; Li, T.; Wang, Z.; Xu, Y.; Hu, L. Graphene Oxide-Based Electrode Inks for 3D-Printed Lithium-Ion Batteries. Adv. Mater. 2016, 28 (13), 2587,  DOI: 10.1002/adma.201505391

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    90

    Graphene Oxide-Based Electrode Inks for 3D-Printed Lithium-Ion Batteries

    Fu, Kun; Wang, Yibo; Yan, Chaoyi; Yao, Yonggang; Chen, Yanan; Dai, Jiaqi; Lacey, Steven; Wang, Yanbin; Wan, Jiayu; Li, Tian; Wang, Zhengyang; Xu, Yue; Hu, Liangbing

    Advanced Materials (Weinheim, Germany) (2016), 28 (13), 2587-2594CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)

    In this communication, we developed GO-based electrode composite inks and solid-state electrolyte inks to achieve all component 3D-printed lithium-ion batteries. The 3D-printed lithium-ion batteries were successfully created using aq. GO-based inks consisting of highly concd. graphene oxide sheets as well as cathode and anode active materials. Note that using water as a green solvent makes this aq. ink system feasible for processing, drying safety, and low cost. Highly concd. graphene oxide sheets provide the prerequisite viscosity to bind the electrode materials together and enable 3D printing. Lithium iron phosphate (LiFePO4, LFP) and lithium titanium oxide (Li4Ti5O12, LTO) were selected as the cathode and anode materials, resp., for the demonstration purpose. It is anticipated that this process can also be extended to other active materials. To create high mass loading per unit area electrodes in an interdigitated battery configuration,fine filaments were extruded directly from a nozzle and then deposited layer-by-layer using a preprogrammed printing routine. Due to the shear stress induced by the nozzle, the GO flakes are aligned along the extruding direction, which enhances the electrode's elec. cond. In addn., the GO flake's intrinsically porous structure offers a large amt. of surface area to load the LFP or LTO nanoparticles as well as house the electrolyte. Our demonstration of 3D-printed lithium-ion batteries featured graphene oxide as a promising printable material in 3D printing manufg. and printable energy storage applications.

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91. 91

    Wei, T. S.; Ahn, B. Y.; Grotto, J.; Lewis, J. A. 3D Printing of Customized Li-Ion Batteries with Thick Electrodes. Adv. Mater. 2018, 30 (16), e1703027,  DOI: 10.1002/adma.201703027

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    There is no corresponding record for this reference.
92. 92

    Liu, C. Y.; Xu, F.; Cheng, X. X.; Tong, J. D.; Liu, Y. L.; Chen, Z. W.; Lao, C. S.; Ma, J. Comparative Study on the Electrochemical Performance of LiFePO₄ Cathodes Fabricated by Low Temperature 3D Printing, Direct Ink Writing and Conventional Roller Coating Process. Ceram. Int. 2019, 45 (11), 14188– 14197,  DOI: 10.1016/j.ceramint.2019.04.124

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    92

    Comparative study on the electrochemical performance of LiFePO4 cathodes fabricated by low temperature 3D printing, direct ink writing and conventional roller coating process

    Liu, Changyong; Xu, Feng; Cheng, Xingxing; Tong, Junda; Liu, Yanliang; Chen, Zhangwei; Lao, Changshi; Ma, Jun

    Ceramics International (2019), 45 (11), 14188-14197CODEN: CINNDH; ISSN:0272-8842. (Elsevier Ltd.)

    Electrodes for lithium-ion batteries can be fabricated in many ways including conventional roller coating and 3D printing. Roller coating is a standardized process in current lithium-ion battery industry, while 3D printing has been used to fabricate three-dimensional (3D) unconventional electrodes with tailored geometries. Our previous study proposed a low temp. 3D printing process to fabricate highly-porous LiFePO4 (LFP) electrodes. However, there still lack a study on the comparison of electrochem. performance of LFP electrodes fabricated via the three different fabrication processes including low temp. direct writing-based 3D printing (LTDW), room temp. direct ink writing (DIW) and roller coating process. In this study, we fabricated LFP cathodes using these three fabrication processes from LFP inks with different solid contents. By varying the solid content, LFP electrodes with different geometries (including width and thickness), morphologies and porous microstructures were obtained via LTDW and DIW. Mercury porosimetry was performed to examine the differences of the three types of LFP electrodes in porous microstructures. Electrochem. performance including charge/discharge, rate performance, cyclic voltammetry (CV) and electrochem. impedance spectroscopy (EIS) of the three types of electrodes were measured and compared. Results showed that electrode fabrication processes have important effects on the electrochem. performance of LFP electrodes depending on the ink solid content. LTDW-fabricated electrodes had the best performance at high solid content (≥0.467 g/mL) and conventional roller coated electrodes performed better at low solid content (≤0.356 g/mL). Relationships between ink solid content, fabrication process, resulting porous microstructures and electrochem. performance were discussed. Finally, an optimal specific capacity of ∼82 mAh.g-1 @ 10C was achieved at a solid content of 0.467 g/mL by LTDW process.

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93. 93

    Li, J.; Liang, X. H.; Liou, F.; Park, J. Macro-/Micro-Controlled 3D Lithium-Ion Batteries via Additive Manufacturing and Electric Field Processing. Sci. Rep. 2018, 8, 1846  DOI: 10.1038/s41598-018-20329-w

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    93

    Macro-/Micro-Controlled 3D Lithium-Ion Batteries via Additive Manufacturing and Electric Field Processing

    Li Jie; Liou Frank; Park Jonghyun; Liang Xinhua

    Scientific reports (2018), 8 (1), 1846 ISSN:.

    This paper presents a new concept for making battery electrodes that can simultaneously control macro-/micro-structures and help address current energy storage technology gaps and future energy storage requirements. Modern batteries are fabricated in the form of laminated structures that are composed of randomly mixed constituent materials. This randomness in conventional methods can provide a possibility of developing new breakthrough processing techniques to build well-organized structures that can improve battery performance. In the proposed processing, an electric field (EF) controls the microstructures of manganese-based electrodes, while additive manufacturing controls macro-3D structures and the integration of both scales. The synergistic control of micro-/macro-structures is a novel concept in energy material processing that has considerable potential for providing unprecedented control of electrode structures, thereby enhancing performance. Electrochemical tests have shown that these new electrodes exhibit superior performance in their specific capacity, areal capacity, and life cycle.

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94. 94

    Airoldi, L.; Anselmi-Tamburini, U.; Vigani, B.; Rossi, S.; Mustarelli, P.; Quartarone, E. Additive Manufacturing of Aqueous-Processed LiMn₂O₄ Thick Electrodes for High-Energy-Density Lithium-Ion Batteries. Batteries & Supercaps 2020, 3 (10), 1040– 1050,  DOI: 10.1002/batt.202000058

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    94

    Additive Manufacturing of Aqueous-Processed LiMn2O4 Thick Electrodes for High-Energy-Density Lithium-Ion Batteries

    Airoldi, Lorenzo; Anselmi-Tamburini, Umberto; Vigani, Barbara; Rossi, Silvia; Mustarelli, Piercarlo; Quartarone, Eliana

    Batteries & Supercaps (2020), 3 (10), 1040-1050CODEN: BSAUBU; ISSN:2566-6223. (Wiley-VCH Verlag GmbH & Co. KGaA)

    Enhancing electrode areal capacity of lithium-ion batteries will result in cost saving and better electrochem. performances. Additive manufg. (AM) is a very promising soln., which enables to build structurally complex electrodes with well-controlled geometry, shape and thickness. Here we report on 3D-printed cathodes based on LiMn2O4 (LMO) as the active material, which are fabricated by robocasting AM via aq. processing. Such a technol. is: (i) environmentally friendly, since it works well with water and green binders; (ii) fast, due to very short deposition times and rapid drying process because of low amt. of solvent in the printable pastes; (iii) easily scalable. The cathodes are produced by extruding pastes with higher solid loadings (>70 vol%) than those typically reported in literature. The printing efficiency is strongly affected by both the binder and the carbonaceous additive. The best cathode is composed by LMO, Pluronic as the binder, and a mixt. of graphite/carbon black as the electronic conductor, which is crit. for achieving optimal electrochem. performance. The cathode with thickness of 200μm and mass loading of 13 mg cm-2 exhibits good electrochem. areal capacity (2.3 mAh cm-2) and energy d. (>32 J cm-2). Our results may boost the development of greener, lower cost and more efficient new generation of LIBs for applications as household energy storage or even micro-battery technol.

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95. 95

    Cheng, M.; Jiang, Y. Z.; Yao, W. T.; Yuan, Y. F.; Deivanayagam, R.; Foroozan, T.; Huang, Z. N.; Song, B.; Rojaee, R.; Shokuhfar, T.; Pan, Y. Y.; Lu, J.; Shahbazian-Yassar, R. Elevated-Temperature 3D Printing of Hybrid Solid-State Electrolyte for Li-Ion Batteries. Adv. Mater. 2018, 30 (39), e1800615,  DOI: 10.1002/adma.201800615

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    There is no corresponding record for this reference.
96. 96

    Blake, A. J.; Kohlmeyer, R. R.; Hardin, J. O.; Carmona, E. A.; Maruyama, B.; Berrigan, J. D.; Huang, H.; Durstock, M. F. 3D Printable Ceramic-Polymer Electrolytes for Flexible High-Performance Li-Ion Batteries with Enhanced Thermal Stability. Adv. Energy Mater. 2017, 7 (14), e1602920,  DOI: 10.1002/aenm.201602920

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    There is no corresponding record for this reference.
97. 97

    Gambe, Y.; Kobayashi, H.; Iwase, K.; Stauss, S.; Honma, I. A Photo-Curable Gel Electrolyte Ink for 3D-Printable Quasi-Solid-State Lithium-Ion Batteries. Dalton Trans. 2021, 50 (45), 16504– 16508,  DOI: 10.1039/D1DT02918E

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    97

    A photo-curable gel electrolyte ink for 3D-printable quasi-solid-state lithium-ion batteries

    Gambe, Yoshiyuki; Kobayashi, Hiroaki; Iwase, Kazuyuki; Stauss, Sven; Honma, Itaru

    Dalton Transactions (2021), 50 (45), 16504-16508CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)

    3D printing technologies have been adapted to enable the fabrication of lithium-ion batteries (LIBs), allowing flexible designs such as micro-scale 3D shapes. Here, we demonstrate 3D-printable gel electrolytes, printed at room temp. The electrolyte gel solidified by UV irradn. maintains its structural integrity and high lithium-ion cond., enabling fully 3D-printed quasi-solid-state LIBs.

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98. 98

    Maurel, A.; Courty, M.; Fleutot, B.; Tortajada, H.; Prashantha, K.; Armand, M.; Grugeon, S.; Panier, S.; Dupont, L. Highly Loaded Graphite-Polylactic Acid Composite-Based Filaments for Lithium-Ion Battery Three-Dimensional Printing. Chem. Mater. 2018, 30 (21), 7484– 7493,  DOI: 10.1021/acs.chemmater.8b02062

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    98

    Highly Loaded Graphite-Polylactic Acid Composite-Based Filaments for Lithium-Ion Battery Three-Dimensional Printing

    Maurel, Alexis; Courty, Matthieu; Fleutot, Benoit; Tortajada, Hugues; Prashantha, Kalappa; Armand, Michel; Grugeon, Sylvie; Panier, Stephane; Dupont, Loic

    Chemistry of Materials (2018), 30 (21), 7484-7493CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Actual parallel-plate architecture of lithium-ion batteries consists of lithium-ion diffusion in one dimension between the electrodes. To achieve higher performances in terms of specific capacity and power, configurations enabling lithium-ion diffusion in two or three dimensions is considered. With a view to build these complex three-dimensional (3D) battery architectures avoiding the electrodes interpenetration issues, this work is focused on fused deposition modeling (FDM). In this study, the formulation and characterization of a 3D-printable graphite/polylactic acid (PLA) filament, specially designed to be used as neg. electrode in a lithium-ion battery and to feed a conventional com. available FDM 3D printer, is reported. The graphite active material loading in the produced filament is increased as high as possible to enhance the electrochem. performance, while the addn. of various amts. of plasticizers such as propylene carbonate, poly(ethylene glycol) di-Me ether av. Mn ∼ 2000, poly(ethylene glycol) di-Me ether av. Mn ∼ 500, and acetyl tri-Bu citrate is investigated to provide the necessary flexibility to the filament to be printed. Considering the optimized plasticizer compn., an in-depth study is carried out to identify the elec. and electrochem. impact of carbon black and carbon nanofibers as conductive additives.

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99. 99

    Maurel, A.; Grugeon, S.; Fleutot, B.; Courty, M.; Prashantha, K.; Tortajada, H.; Armand, M.; Panier, S.; Dupont, L. Three-Dimensional Printing of a LiFePO₄/Graphite Battery Cell via Fused Deposition Modeling. Sci. Rep. 2019, 9 (1), 18031,  DOI: 10.1038/s41598-019-54518-y

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    99

    Three-Dimensional Printing of a LiFePO4/Graphite Battery Cell via Fused Deposition Modeling

    Maurel, Alexis; Grugeon, Sylvie; Fleutot, Benoit; Courty, Matthieu; Prashantha, Kalappa; Tortajada, Hugues; Armand, Michel; Panier, Stephane; Dupont, Loic

    Scientific Reports (2019), 9 (1), 18031CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)

    Among the 3D-printing technologies, fused deposition modeling (FDM) represents a promising route to enable direct incorporation of the battery within the final 3D object. Here, the prepn. and characterization of lithium iron phosphate/polylactic acid (LFP/PLA) and SiO2/PLA 3D-printable filaments, specifically conceived resp. as pos. electrode and separator in a lithium-ion battery is reported. By means of plasticizer addn., the active material loading within the pos. electrode is raised as high as possible (up to 52 wt.%) while still providing enough flexibility to the filament to be printed. A thorough anal. is performed to det. the thermal, elec. and electrochem. effect of carbon black as conductive additive in the pos. electrode and the electrolyte uptake impact of ceramic additives in the separator. Considering both optimized filaments compn. and using our previously reported graphite/PLA filament for the neg. electrode, assembled and "printed in one-shot" complete LFP/Graphite battery cells are 3D-printed and characterized. Taking advantage of the new design capabilities conferred by 3D-printing, separator patterns and infill d. are discussed with a view to enhance the liq. electrolyte impregnation and avoid short-circuits.

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100. 100

     Maurel, A.; Russo, R.; Grugeon, S.; Panier, S.; Dupont, L. Environmentally Friendly Lithium-Terephthalate/Polylactic Acid Composite Filament Formulation for Lithium-Ion Battery 3D-Printing via Fused Deposition Modeling. ECS Journal of Solid State Science and Technology 2021, 10 (3), 037004  DOI: 10.1149/2162-8777/abedd4

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     100

     Environmentally friendly lithium-terephthalate/polylactic acid composite filament formulation for lithium-ion battery 3dprinting via fused deposition modeling

     Maurel, Alexis; Russo, Z. Roberto; Grugeon, Sylvie; Panier, Stephane; Dupont, Loic

     ECS Journal of Solid State Science and Technology (2021), 10 (3), 037004CODEN: EJSSBG; ISSN:2162-8777. (IOP Publishing Ltd.)

     In this paper, the development of an environmentally-friendly lithium-terephtalate/polylactic acid (Li2TP/PLA) composite filament, for its use, once 3D-printed via Fused Deposition Modeling (FDM), as neg. electrode of a lithium-ion battery is reported. Solvent-free formulation of the 3D-printable filament is achieved through the direct introduction of synthesized Li2TP particles and PLA polymer powder within an extruder. Printability is improved through the incorporation of poly(ethylene glycol) di-Me ether av. Mn∼500 (PEGDME500) as plasticizer, while elec. performances are enhanced through the introduction of carbon black (CB). Thermal, elec., morphol., electrochem. and printability characteristics are discussed thoroughly. By taking advantage of the 3D-printing slicer software capabilities, an innovative route is proposed to improve the liq. electrolyte impregnation within the 3D-printed electrodes.

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101. 101

     Ragones, H.; Menkin, S.; Kamir, Y.; Gladkikh, A.; Mukra, T.; Kosa, G.; Golodnitsky, D. Towards Smart Free Form-Factor 3D Printable Batteries. Sustainable Energy & Fuels 2018, 2 (7), 1542– 1549,  DOI: 10.1039/C8SE00122G

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     101

     Towards smart free form-factor 3D printable batteries

     Ragones, Heftsi; Menkin, Svetlana; Kamir, Yosi; Gladkikh, Alex; Mukra, Tzach; Kosa, Gabor; Golodnitsky, Diana

     Sustainable Energy & Fuels (2018), 2 (7), 1542-1549CODEN: SEFUA7; ISSN:2398-4902. (Royal Society of Chemistry)

     Continuous novelty as the basis for creative advance in rapidly developing different form-factor microelectronic devices requires seamless integrability of batteries. Thus, in the past decade, along with developments in battery materials, the focus has been shifting more and more towards innovative fabrication processes, unconventional configurations, and designs with multi-functional components. We present here, for the first time, a novel concept and feasibility study of a 3D-microbattery printed by fused-filament fabrication (FFF). The reversible electrochem. cycling of 3D printed lithium iron phosphate (LFP) and lithium titanate (LTO) composite polymer electrodes vs. the lithium metal anode has been demonstrated in cells contg. conventional non-aq. and ionic-liq. electrolytes. We believe that by using comprehensively structured interlaced electrode networks it would be possible not only to fabricate free form-factor batteries but also to alleviate the continuous vol. changes occurring during charge and discharge.

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102. 102

     Reyes, C.; Somogyi, R.; Niu, S.; Cruz, M. A.; Yang, F.; Catenacci, M. J.; Rhodes, C. P.; Wiley, B. J. Three-Dimensional Printing of a Complete Lithium Ion Battery with Fused Filament Fabrication. ACS Applied Energy Materials 2018, 1 (10), 5268– 5279,  DOI: 10.1021/acsaem.8b00885

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     102

     Three-Dimensional Printing of a Complete Lithium Ion Battery with Fused Filament Fabrication

     Reyes, Christopher; Somogyi, Rita; Niu, Sibo; Cruz, Mutya A.; Yang, Feichen; Catenacci, Matthew J.; Rhodes, Christopher P.; Wiley, Benjamin J.

     ACS Applied Energy Materials (2018), 1 (10), 5268-5279CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)

     The ability to 3D print lithium ion batteries (LIBs) in an arbitrary geometry would not only allow the battery form factor to be customized to fit a given product design but also facilitate the use of the battery as a structural component. A major hurdle to achieving this goal is the low ionic cond. of the polymers used for 3D printing. This article reports the development of anode, cathode, and separator materials that enable 3D printing of complete lithium ion batteries with low cost and widely available fused filament fabrication (FFF) 3D printers. Poly(lactic acid) (PLA) was infused with a mixt. of Et Me carbonate, propylene carbonate, and LiClO4 to obtain an ionic cond. of 0.085 mS cm-1, a value comparable to that of polymer and hybrid electrolytes. Different elec. conductive (Super P, graphene, multiwall carbon nanotubes) and active (lithium titanate, lithium manganese oxide) materials were blended into PLA to det. the relationships among filler loading, cond., charge storage capacity, and printability. Up to 30 vol % of solids could be mixed into PLA without degrading its printability, and an 80:20 ratio of conductive to active material maximized the charge storage capacity. The highest capacity was obtained with lithium titanate and graphene nanoplatelets in the anode, and lithium manganese oxide and multiwall carbon nanotubes in the cathode. We demonstrate the use of these novel materials in a fully 3D printed coin cell, as well as 3D printed wearable electronic devices with integrated batteries.

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103. 103

     Maurel, A.; Armand, M.; Grugeon, S.; Fleutot, B.; Davoisne, C.; Tortajada, H.; Courty, M.; Panier, S.; Dupont, L. Poly(Ethylene Oxide)–LiTFSI Solid Polymer Electrolyte Filaments for Fused Deposition Modeling Three-Dimensional Printing. J. Electrochem. Soc. 2020, 167 (7), 070536  DOI: 10.1149/1945-7111/ab7c38

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     There is no corresponding record for this reference.
104. 104

     Ragones, H.; Vinegrad, A.; Ardel, G.; Goor, M.; Kamir, Y.; Dorfman, M. M.; Gladkikh, A.; Golodnitsky, D. On the Road to a Multi-Coaxial-Cable Battery: Development of a Novel 3D-Printed Composite Solid Electrolyte. J. Electrochem. Soc. 2020, 167 (1), 070503,  DOI: 10.1149/2.0032007JES

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     104

     On the road to a multi-coaxial-cable battery: development of a novel 3D-printed composite solid electrolyte

     Ragones, Heftsi; Vinegrad, Adi; Ardel, Gilat; Goor, Meital; Kamir, Yossi; Dorfman, Moty Marcos; Gladkikh, Alexander; Golodnitsky, Diana

     Journal of the Electrochemical Society (2020), 167 (7), 070503CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)

     The high areal-energy and power requirements of advanced microelectronic devices favor the choice of a lithium-ion system, since it provides the highest energy d. of available battery technologies suitable for a variety of applications. Several attempts have been made to produce primary and secondary thin-film batteries utilizing printing techniques. These technologies are still at an early stage, and most currently-printed batteries exploit printed electrodes sandwiching self-standing com. polymer membranes, produced by conventional extrusion or papermaking techniques, followed by soaking in non-aq. liq. electrolytes. In this work, a novel flexible-battery design is suggested and the initial results are reported of development and characterization of novel 3D printed all-solid-state electrolytes prepd. by fused-filament fabrication (FFF). The electrolytes are composed of LiTFSI, polyethylene oxide (PEO), which is a known lithium-ion conductor, and polylactic acid (PLA) for enhanced mech. properties and high-temp. durability. The 3D printed electrolytes were characterized by means of ESEM imaging, mass spectroscopy, differential scanning calorimetry (DSC) and electrochem. impedance spectroscopy (EIS). TOFSIMS anal. reveals formation of lithium complexes with both polymers. The flexible all-solid LiTFSI-based electrolyte exhibited bulk ionic cond. of 3 × 10-5 S/cm at 90° and 156 Ω x cm2 resistance of the solid electrolyte interphase (SEI). It is believed that the coordination mechanism of the lithium cation by the oxygen of the PLA chain is similar to that of PEO and local relaxation motions of PLA chain segments could promote Li-ion hopping between oxygens of adjacent CH-O groups. What is meant by this is that PLA not only improves the mech. properties of PEO, but also serves as a Li-ion-conducting medium. These results pave the way for a fully printed solid battery, which enables free-form-factor flexible geometries.

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105. 105

     Ben-Barak, I.; Ragones, H.; Golodnitsky, D. 3D Printable Solid and Quasi-solid Electrolytes for Advanced Batteries. Electrochemical Science Advances 2022,  DOI: 10.1002/elsa.202100167

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     There is no corresponding record for this reference.
106. 106

     Maurel, A.; Kim, H.; Russo, R.; Grugeon, S.; Armand, M.; Panier, S.; Dupont, L. Ag-Coated Cu/Polylactic Acid Composite Filament for Lithium and Sodium-Ion Battery Current Collector Three-Dimensional Printing via Thermoplastic Material Extrusion. Front. Energy Res. 2021, 9 (70), e651041,  DOI: 10.3389/fenrg.2021.651041

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     There is no corresponding record for this reference.
107. 107

     Yee, D. W.; Citrin, M. A.; Taylor, Z. W.; Saccone, M. A.; Tovmasyan, V. L.; Greer, J. R. Hydrogel-Based Additive Manufacturing of Lithium Cobalt Oxide. Adv. Mater. Technol. 2021, 6 (2), e2000791,  DOI: 10.1002/admt.202000791

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     107

     Hydrogel-Based Additive Manufacturing of Lithium Cobalt Oxide

     Yee, Daryl W.; Citrin, Michael A.; Taylor, Zane W.; Saccone, Max A.; Tovmasyan, Victoria L.; Greer, Julia R.

     Advanced Materials Technologies (Weinheim, Germany) (2021), 6 (2), 2000791CODEN: AMTDCM; ISSN:2365-709X. (Wiley-VCH Verlag GmbH & Co. KGaA)

     3D multicomponent metal oxides with complex architectures can enable previously impossible energy storage devices, particularly lithium-ion battery (LIB) electrodes with fully controllable form factors. Existing additive manufg. approaches for fabricating 3D multicomponent metal oxides rely on particle-based or org.-inorg. binders, which are limited in their resoln. and chem. compn., resp. In this work, aq. metal salt solns. are used as metal precursors to circumvent these limitations, and provide a platform for 3D printing multicomponent metal oxides. As a proof-of-concept, architected lithium cobalt oxide (LCO) structures are fabricated by first synthesizing a homogenous lithium and cobalt nitrate aq. photoresin, and then using it with digital light processing printing to obtain lithium and cobalt ion contg. hydrogels. The 3D hydrogels are calcined to obtain micro-porous self-similar LCO architectures with a resoln. of ≈100μm. These free-standing, binder- and conductive additive-free LCO structures are integrated as cathodes into LIBs, and exhibit electrochem. capacity retention of 76% over 100 cycles at C/10. This facile approach to fabricating 3D LCO structures can be extended to other materials by tailoring the identity and stoichiometry of the metal salt solns. used, providing a versatile method for the fabrication of multicomponent metal oxides with complex 3D architectures.

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108. 108

     Zekoll, S.; Marriner-Edwards, C.; Hekselman, A. K. O.; Kasemchainan, J.; Kuss, C.; Armstrong, D. E. J.; Cai, D. Y.; Wallace, R. J.; Richter, F. H.; Thijssen, J. H. J.; Bruce, P. G. Hybrid Electrolytes with 3D Bicontinuous Ordered Ceramic and Polymer Microchannels for All-Solid-State Batteries. Energy Environ. Sci. 2018, 11 (1), 185– 201,  DOI: 10.1039/C7EE02723K

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     108

     Hybrid electrolytes with 3D bicontinuous ordered ceramic and polymer microchannels for all-solid-state batteries

     Zekoll, Stefanie; Marriner-Edwards, Cassian; Hekselman, A. K. Ola; Kasemchainan, Jitti; Kuss, Christian; Armstrong, David E. J.; Cai, Dongyu; Wallace, Robert J.; Richter, Felix H.; Thijssen, Job H. J.; Bruce, Peter G.

     Energy & Environmental Science (2018), 11 (1), 185-201CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)

     Hybrid solid electrolytes, composed of 3D ordered bicontinuous conducting ceramic and insulating polymer microchannels are reported. The ceramic channels provide continuous, uninterrupted pathways, maintaining high ionic cond. between the electrodes, while the polymer channels permit improvement of the mech. properties from that of the ceramic alone, in particular mitigation of the ceramic brittleness. The cond. of a ceramic electrolyte is usually limited by resistance at the grain boundaries, necessitating dense ceramics. The cond. of the 3D ordered hybrid is reduced by only the vol. fraction occupied by the ceramic, demonstrating that the ceramic channels can be sintered to high d. similar to a dense ceramic disk. The hybrid electrolytes are demonstrated using the ceramic lithium ion conductor Li1.4Al0.4Ge1.6(PO4)3 (LAGP). Structured LAGP 3D scaffolds with empty channels were prepd. by neg. replication of a 3D printed polymer template. Filling the empty channels with non-conducting polypropylene (PP) or epoxy polymer (epoxy) creates the structured hybrid electrolytes with 3D bicontinuous ceramic and polymer microchannels. Printed templating permits precise control of the ceramic to polymer ratio and the microarchitecture; as demonstrated by the formation of cubic, gyroidal, diamond and spinodal (bijel) structures. The elec. and mech. properties depend on the microarchitecture, the gyroid filled with epoxy giving the best combination of cond. and mech. properties. An ionic cond. of 1.6 × 10-4 S cm-1 at room temp. was obtained, reduced from the cond. of a sintered LAGP pellet only by the vol. fraction occupied by the ceramic. The mech. properties of the gyroid LAGP-epoxy electrolyte demonstrate up to 28% higher compressive failure strain and up to five times the flexural failure strain of a LAGP pellet before rupture. Notably, this demonstrates that ordered ceramic and polymer hybrid electrolytes can have superior mech. properties without significantly compromising ionic cond., which addresses one of the key challenges for all-solid-state batteries.

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109. 109

     Chen, Q. M.; Xu, R.; He, Z. T.; Zhao, K. J.; Pan, L. Printing 3D Gel Polymer Electrolyte in Lithium-Ion Microbattery Using Stereolithography. J. Electrochem. Soc. 2017, 164 (9), A1852– A1857,  DOI: 10.1149/2.0651709jes

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     109

     Printing 3D Gel Polymer Electrolyte in Lithium-Ion Microbattery Using Stereolithography

     Chen, Qiming; Xu, Rong; He, Zitao; Zhao, Kejie; Pan, Liang

     Journal of the Electrochemical Society (2017), 164 (9), A1852-A1857CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)

     Here we demonstrate the use of projection stereo-micro-lithog. as a low-cost and high-throughput method to fabricate three dimensional (3D) microbattery. An UV-curable Poly(ethylene glycol) (PEG)-base gel polymer electrolyte (GPE) is first created. The GPE is then used as a resin for micro-stereolithog. in order to build a 3D architecture of battery's electrolyte. Active materials, LiFePO4 (LFP) and Li4Ti5O12 (LTO), are mixed with carbon black and the GPE resin, which is then flown into the 3D structure. Aluminum (Al) foil is cut and inserted as a current collector. The GPE is characterized and the microbattery is performed a cycling test. Results show a feasibility of microbattery fabrication using projection micro-stereolithog.

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110. 110

     Martinez, A. C.; Maurel, A.; Aranzola, A. P.; Grugeon, S.; Panier, S.; Dupont, L.; Hernandez-Viezcas, J. A.; Mummareddy, B.; Armstrong, B. L.; Cortes, P.; Sreenivasan, S. T.; MacDonald, E. Additive Manufacturing of LiNi_1/3Mn_1/3Co_1/3O₂ Battery Electrode Material via Vat Photopolymerization Precursor Approach. Sci. Rep. 2022, 12 (1), 19010,  DOI: 10.1038/s41598-022-22444-1

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     110

     Additive manufacturing of LiNi1/3Mn1/3Co1/3O2 battery electrode material via vat photopolymerization precursor approach

     Martinez, Ana C.; Maurel, Alexis; Aranzola, Ana P.; Grugeon, Sylvie; Panier, Stephane; Dupont, Loic; Hernandez-Viezcas, Jose A.; Mummareddy, Bhargavi; Armstrong, Beth L.; Cortes, Pedro; Sreenivasan, Sreeprasad T.; MacDonald, Eric

     Scientific Reports (2022), 12 (1), 19010CODEN: SRCEC3; ISSN:2045-2322. (Nature Portfolio)

     Additive manufg., also called 3D printing, has the potential to enable the development of flexible, wearable and customizable batteries of any shape, maximizing energy storage while also reducing dead-wt. and vol. In this work, for the first time, three-dimensional complex electrode structures of high-energy d. LiNi1/3Mn1/3Co1/3O2 (NMC 111) material are developed by means of a vat photopolymn. (VPP) process combined with an innovative precursor approach. This innovative approach involves the solubilization of metal precursor salts into a UV-photopolymerizable resin, so that detrimental light scattering and increased viscosity are minimized, followed by the in-situ synthesis of NMC 111 during thermal post-processing of the printed item. The absence of solid particles within the initial resin allows the prodn. of smaller printed features that are crucial for 3D battery design. The formulation of the UV-photopolymerizable composite resin and 3D printing of complex structures, followed by an optimization of the thermal post-processing yielding NMC 111 is thoroughly described in this study. Based on these results, this work addresses one of the key aspects for 3D printed batteries via a precursor approach: the need for a compromise between electrochem. and mech. performance in order to obtain fully functional 3D printed electrodes. In addn., it discusses the gaps that limit the multi-material 3D printing of batteries via the VPP process.

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111. 111

     Lahtinen, E.; Kukkonen, E.; Jokivartio, J.; Parkkonen, J.; Virkajarvi, J.; Kivijarvi, L.; Ahlskog, M.; Haukka, M. Preparation of Highly Porous Carbonous Electrodes by Selective Laser Sintering. Acs Applied Energy Materials 2019, 2 (2), 1314– 1318,  DOI: 10.1021/acsaem.8b01881

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     111

     Preparation of Highly Porous Carbonous Electrodes by Selective Laser Sintering

     Lahtinen, Elmeri; Kukkonen, Esa; Jokivartio, Joonas; Parkkonen, Joni; Virkajarvi, Jussi; Kivijarvi, Lauri; Ahlskog, Markus; Haukka, Matti

     ACS Applied Energy Materials (2019), 2 (2), 1314-1318CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)

     Selective laser sintering (SLS) 3-dimensional printing was used to fabricate highly porous carbonous electrodes. The electrodes were prepd. by using a mixt. of fine graphite powder and either polyamide-12, polystyrene, or polyurethane polymer powder as SLS printing material. During the printing process the graphite powder was dispersed uniformly on the supporting polymer matrix. Graphite's concn. in the mixt. was varied between 5 and 40% to find the correlation between the C content and cond. The graphite concn., polymer matrix, and printing conditions all had an impact on the final cond. Due to the SLS printing technique, all the 3-dimensional printed electrodes were highly porous. By using polyurethane as the supporting matrix it was possible to produce flexible electrodes in which the cond. is sensitive to pressure and mech. stress. Phys. properties such as graphite distribution, attachment, and the overall porosity of the printed electrodes were studied using SEM, He ion microscopy (HIM), and x-ray tomog. The combination of chem. design of the printing material and the use of SLS 3-dimensional printing enables fabrication of highly customizable electrodes with desired chem., phys., mech., and flow-through properties.

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112. 112

     Inamdar, A.; Magana, M.; Medina, F.; Grajeda, Y.; Wicker, R. B. Development of an Automated Multiple Material Stereolithography Machine. International Solid Freeform Fabrication Symposium , 2006.  DOI: 10.26153/tsw/7167 .

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     Choi, J. W.; Kim, H. C.; Wicker, R. Multi-Material Stereolithography. J. Mater. Process. Technol. 2011, 211 (3), 318– 328,  DOI: 10.1016/j.jmatprotec.2010.10.003

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     Multi-material stereolithography

     Choi, Jae-Won; Kim, Ho-Chan; Wicker, Ryan

     Journal of Materials Processing Technology (2011), 211 (3), 318-328CODEN: JMPTEF; ISSN:0924-0136. (Elsevier B.V.)

     A multi-material stereolithog. (MMSL) machine was developed by retrofitting components from a com. 3-dimensional Systems 250/50 stereolithog. (SL) machine on a sep. stand-alone system and adapting the components to function with addnl. components required for MMSL operation. The MMSL machine required construction of a new frame and the development of a new rotating vat carousel system, platform assembly, and automatic leveling system. The overall operation of the MMSL system was managed using a custom LabVIEW program, which included controlling a new vat leveling system and new linear and rotational stages, while the com. SL control software (3-dimensional Systems Buildstation 4.0) was retained for controlling the laser scanning process. During MMSL construction, the sweeping process can be inhibited by previously cured layers, and thus, a deep-dip coating process without sweeping was used with low viscosity resins. Low viscosity resins were created by dilg. com. resins, including DSM Somos WaterShed 11120, ProtoTherm 12120, and 14120 White, with propoxylated (2) neopentyl glycol diacrylate (PNGD). Several multi-material complex parts were produced providing compelling evidence that MMSL can produce unique parts that are functional, visually illustrative, and constructed with multi-materials.

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     Choi, J. W.; MacDonald, E.; Wicker, R. Multi-Material Microstereolithography. Int. J. Adv. Manuf. Technol. 2010, 49 (5–8), 543– 551,  DOI: 10.1007/s00170-009-2434-8

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     Khatri, B.; Frey, M.; Raouf-Fahmy, A.; Scharla, M. V.; Hanemann, T. Development of a Multi-Material Stereolithography 3D Printing Device. Micromachines 2020, 11 (5), 532,  DOI: 10.3390/mi11050532

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     Walker, J.; Middendorf, J. R.; Lesko, C. C. C.; Gockel, J. Multi-Material Laser Powder Bed Fusion Additive Manufacturing in 3-Dimensions. Manufacturing Letters 2022, 31, 74– 77,  DOI: 10.1016/j.mfglet.2021.07.011

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     Wei, C.; Li, L. Recent Progress and Scientific Challenges in Multi-Material Additive Manufacturing via Laser-Based Powder Bed Fusion. Virtual Phys. Prototyp. 2021, 16 (3), 347– 371,  DOI: 10.1080/17452759.2021.1928520

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