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Energy, Environmental, and Catalysis Applications

Fabrication of Oxide-Based All-Solid-State Batteries by a Sintering Process Based on Function Sharing of Solid Electrolytes
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  • Miyuki Sakakura
    Miyuki Sakakura
    Department of Materials Design Innovation Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
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  • Kazutaka Mitsuishi
    Kazutaka Mitsuishi
    Research Center for Advanced Measurement and Characterization, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan
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    Orcidhttps://orcid.org/0000-0002-9361-4057
  • Toyoki Okumura
    Toyoki Okumura
    Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan
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    Orcidhttps://orcid.org/0000-0003-0752-0941
  • Norikazu Ishigaki
    Norikazu Ishigaki
    Department of Materials Design Innovation Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
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  • Yasutoshi Iriyama*
    Yasutoshi Iriyama
    Department of Materials Design Innovation Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0001-8639-0844
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2022, 14, 43, 48547–48557
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https://doi.org/10.1021/acsami.2c10853
Published October 3, 2022

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Abstract

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Garnet-type Li7La3Zr2O12 (LLZ) has advantages of stability with Li metal and high Li+ ionic conductivity, achieving 1 × 10–3 S cm–1, but it is prone to react with electrode active materials during the sintering process. LISICON-type Li3.5Ge0.5V0.5O4 (LGVO) has the advantage of less reactivity with the electrode active material during the sintering process, but its ionic conductivity is on the order of 10–5 S cm–1. In this study, these two solid electrolytes are combined as a multilayer solid electrolyte sheet, where 2 μm thick LGVO films are coated on LLZ sheets to utilize the advantages of these two solid electrolytes. These two solid electrolytes adhere well through Ge diffusion without significant interfacial resistance. The LLZ–LGVO multilayer is combined with a LiCoO2 positive electrode and a lithium metal anode through annealing at 700 °C. The resultant all-solid-state battery can undergo repeated charge–discharge reactions for over 100 cycles at 25 or 60 °C. The LGVO coating suppresses the increases in the resistance from the solid electrolyte and interfacial resistance induced by annealing by ca. 1/40. As with sulfide-based all-solid-state batteries, function sharing of solid electrolytes will be a promising method for developing advanced oxide-based all-solid-state batteries through a sintering process.

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Introduction

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Oxide-based all-solid-state batteries (Ox-SSBs) are attracting attention as candidates for next-generation rechargeable batteries that can realize high energy density while maintaining safety and reliability. Thin-film-type Ox-SSBs with a few mA h sizes were commercialized approximately 20 years ago, where positive electrode, solid electrolyte, and negative electrode materials were sequentially piled up by vapor deposition processes such as RF sputtering and vacuum evaporation. (1,2) In recent years, multilayer-type Ox-SSBs have been commercialized by applying multilayer ceramic capacitor technology, where both electrodes and the solid electrolyte are cosintered, (3,4) and some of them obtain capacities over 20 mA h. (4) Because most oxide-based solid electrolytes, especially those with high Li+ conductivity, are hard and fragile crystalline ceramics, such a sintering process is one of the practical ways to develop advanced Ox-SSBs.
A severe problem accompanying the preparation of Ox-SSBs through the sintering process is the side reactions between the electrode and solid electrolyte. These side reactions provide a large interfacial resistance in many cases. (5−7) Among the various oxide-based solid electrolytes, garnet-structured Li7La3Zr2O12 (LLZ) has been examined through experimental and theoretical approaches because of its high ionic conductivity close to 1 × 10–3 S cm–1 at room temperature in addition to its stability against Li metal. (8−11) However, LLZ highly reacts with many electrode active materials during the sintering process. For example, when a LiCoO2 (LCO) cathode is sintered with LLZ at 700 °C, La2CoO4 is formed as a byproduct at the interface, and the interfacial resistance seriously increases. (5)
An effective way to compensate for the disadvantages of a solid electrolyte is to combine the solid electrolyte with another solid electrolyte. Such function sharing of solid electrolytes has been commonly examined in sulfide-based SSBs from the viewpoint of suppressing side reactions in charge–discharge reactions, (12,13) reducing space charge layer formation, (14,15) or extending the potential window of solid electrolytes. (16) In the case of Ox-SSBs, NASICON-type Li1+xAlxTi2–x(PO4)3 (LATP), which is unstable with Li metal, (17,18) is combined with lithium phosphorus oxynitride glass electrolyte (LiPON), which is stable with Li metal by forming a multilayer-mosaic solid electrolyte interphase (SEI), (19) and then, Li plating–stripping reactions are realized on LiPON/LATP multilayers. (20,21) The concept of function sharing of solid electrolytes will be extended to reduce the reactivity of the electrode/solid electrolyte interface during the sintering process, that is, combining LLZ with another solid electrolyte with less reactivity with electrode materials during the sintering process. Several reports apply Li3BO3 (LBO) with a lower melting point of approximately 700 °C (22,23) as the combined solid electrolyte. Ohta et al. fabricated a LCO–LBO composite layer on a sintered Nb-doped LLZ substrate by a screen printing method and then annealed it at 700 °C for 1 h. (22) The composite electrode ca. 10 μm in thickness can undergo repeated stable charge–discharge reactions. The application of LBO also has advantages in realizing a well-adhered electrode-solid electrolyte interface and then developing bulk-type Ox-SSBs using powder electrode materials. (22,23) However, the ionic conductivity of LBO has been reported to be 2 × 10–6 S cm–1 at room temperature. (22) This ionic conductivity is improved to 5 × 10–6 S cm–1 by Li2+xC1–xBxO3, (24−26) but the ionic conductivity is still 2 orders of magnitude smaller than that of LLZ. Replacing LBO with another material with higher ionic conductivity is a better approach to reduce the Ohmic resistance of solid electrolytes. Okumura et al. developed bulk-type Ox-SSBs by spark plasma sintering, combining LISICON-type Li3.5Ge0.5V0.5O4 (LGVO) with LiNi1/3Co1/3Mn1/3O2 (NCM111). (27) LGVO is stable with various LiCoO2-type electrodes, including NCM111, under sintering at 700 °C, and the resultant Ox-SSBs can undergo repeated stable charge–discharge reactions. The ionic conductivity of LGVO is close to 10–4 S cm–1 at room temperature, (27) which is 1 order of magnitude higher ionic conductivity than that of LBO but smaller than that of LLZ. Therefore, placing a thin layer of LGVO as a protective layer against side reactions on LLZ, in addition to reducing the total Ohmic resistance of the resultant function sharing solid electrolyte, will be useful.
In this work, we prepared LGVO-coated LLZ substrates and investigated whether this kind of function sharing solid electrolyte is effective in suppressing the interfacial reactivity under sintering and then providing a low-resistivity interface. Here, a crystalline LGVO thin film with ca. 2 μm thickness was prepared on an LLZ substrate by aerosol deposition (AD), and the LLZ–LGVO multilayer was annealed at different temperatures. Here, AD is a room-temperature ceramic coating technology, and it has been applied to prepare various coating materials, such as Al2O3, ZrO2, LCO, and electrode-solid electrolyte composite layers. (6,28−31) Then, a LCO thin film was prepared on the LGVO side of the LLZ–LGVO multilayer using AD and annealed at 700 °C. Finally, the resultant LLZ–LGVO/LCO was combined with a lithium metal anode, and an Ox-SSB, Li/LLZ/LGVO/LCO, was prepared. We will show that the LLZ–LGVO multilayer provides a well-adhered low-resistivity interface through Ge diffusion by annealing at 700–900 °C. The 2 μm LGVO coatings effectively reduce the resistance from the solid electrolyte and interfacial resistance by ca. 1/40 compared to the noncoated Ox-SSB. An Ox-SSB using the LLZ–LGVO multilayer can undergo repeated stable charge–discharge reactions for over 100 cycles.

Experimental Section

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Preparation of LGVO Powder for AD

LGVO powder for AD was synthesized from Li4GeO4 and Li4VO4 as the starting material. (27) The Li4GeO4 powder was prepared by mixing LiOH–H2O powder (>99.0%, Nakarai Tesuque) and GeO2 powder (>99.99%, Nakarai Tesque) in a stoichiometric molar ratio and then fired at 600 °C for 12 h in O2. Then, the mixture was pressed into pellets at a pressure of 360 MPa and sintered at 700 °C for 12 h in O2. The Li4VO4 powder was prepared by mixing LiOH–H2O powder (>99.0%, Nacalai Tesque) and V2O5 powder (>99.0%, Kanto Chemical) in a stoichiometric molar ratio and then fired at 450 °C for 12 h in O2. Then, the mixture was pressed into pellets at a pressure of 360 MPa and sintered at 550 °C for 12 h in O2. The resultant Li4GeO4 and Li3VO4 powders were mixed in an agate mortar at a molar ratio of 1:1, then formed into pellets at a pressure of 360 MPa and sintered at 700 °C for 12 h in O2 to obtain LGVO pellets. Electrochemical impedance spectroscopy (EIS) measurements were carried out at 25 °C by applying an alternating current (AC) amplitude of 10 mV (500 kHz to 100 mHz) to check the ionic conductivity of pelletized LGVO. The LGVO pellets were ground in a planetary ball mill (P-5, Fritsch) at a rotational speed of 100 rpm for 2 h in an Ar atmosphere. After removing large particles through a 100 μm mesh sieve, starting powders for AD were prepared. Field emission scanning electron microscopy (FE-SEM) (SU8030, Hitachi Ltd.) and X-ray diffraction (XRD) (40 kV, 40 mA, Cu Kα, Rigaku Ltd.) measurements were carried out to investigate the morphology and crystallinity of the powders, respectively.

Preparation of LGVO Films by AD and Characterization

Ta-doped sintered LLZ substrates (Li6.6La3Zr1.6Ta0.4O12, 0.5 mm in thickness, 10 × 10 mm, Toshima) were used as base substrates. These substrates were first polished by SiC sandpaper (#400), and then, surface residual impurities such as Li2CO3 and polishing dust were removed by acid etching (immersion in 1 mol dm–3 HCl dissolved in H2O, washing with H2O, and then drying under vacuum). (32) The acid-etched LLZ substrates were set in a vacuum evacuated AD chamber, and they were fixed to a substrate holder so that the deposition area was a rectangular shape of 8 × 10 mm (deposition area: 0.8 cm2). The starting powder amount for AD was 2 g. The powders were stored in the AD vessel maintained at 150 °C during deposition. The carrier gas of Ar flowed into the vessel at 15 L min–1, and the resultant aerosol was sprayed onto the substrate through a nozzle. During AD, the substrate was moved back and forth without heating. After AD, substrates were transferred into an Ar-filled glovebox, and the surface dust generated during AD was wiped off using a blower and wiping paper. The resultant LLZ–LGVO multilayers were annealed at 700, 900, or 1050 °C for 2 h under an Ar atmosphere. These annealed multilayers are denoted ML-700, ML-900, and ML-1050, respectively, and as-prepared multilayers without annealing are denoted ML-AP. Both surface and cross-section textures were observed by FE-SEM, and element distributions were analyzed by energy-dispersive X-ray spectroscopy (EDX) (X-max, Horiba Ltd.) at an acceleration voltage of 15 kV. Crystallinity variations of the MLs with annealing were evaluated using XRD. The ionic conductivities of both the MLs and the polished LLZ substrate were measured by EIS. The measurement cells were blocking electrode cells, where Au thin films (3 mm in diameter) were deposited on both sides of these substrates by RF sputtering after polishing the LLZ surface with SiC polishing paper (#400). Cross-sectional TEM specimens were prepared using a focused ion beam (JIB-4501, JEOL Ltd). Their structure and elemental compositions were examined using scanning transmission electron microscopy (STEM; JEM-ARM200F, JEOL Ltd.) equipped with EDX.

Fabrication and Electrochemical Measurements of Ox-SSBs

Crystalline LCO thin films (ca. 1 μm in thickness) were deposited on the LGVO side of ML-900 by AD using laboratory-made LCO particles (D50: 2.2 μm). (33) The AD preparation parameters were the same as those for the LGVO film except for the deposition area (6 mm in diameter). The obtained samples were annealed at 700 or 900 °C for 2 h in an Ar atmosphere. The reactivity of the LCO formed on LGVO with annealing was preliminarily investigated by Raman spectroscopy (NRS-5100, Japan Spectroscopy) and STEM equipped with EDX, and an appropriate annealing temperature was determined to be 700 °C. After annealing at 700 °C, a Au current collector film was deposited on the LCO film by RF sputtering in a 7 mm square region. A Li metal anode film was formed on the LLZ side of ML-900 by vacuum evaporation with an area 7 mm in diameter after polishing the LLZ surface with a SiC polishing paper (#400) in an Ar-filled glovebox (dew point < −80 °C). The resultant Ox-SSB (Li/LLZ/LGVO/LCO/Au) was sealed in a coin-type cell (CR2032, Hosen Corporation) and then heated at 165 °C to obtain a well-adhered Li/LLZ interface. Additionally, Ox-SSBs without a LGVO coating layer were prepared without and with annealing at 700 °C in the same manner to clarify the role of the LGVO coating layer.
Charge–discharge measurements of the Ox-SSBs with ML-900 were performed in the constant-current constant-voltage mode at 25 or 60 °C between 3.0 and 4.2 V. The initial 25 cycles were performed at 60 °C, in which the charge current density was fixed at 2.9 μA cm–2 and the discharge current density was varied from 2.9 to 286 μA cm–2. Then, 11 cycles were performed at 25 °C, in which the charge current density was fixed at 2.9 μA cm–2 and the discharge current density was varied from 2.9 to 57 μA cm–2. Finally, the charge current density and operating temperature were fixed at 5 μA cm–2 and 60 °C, respectively, and the charge–discharge reactions were repeated for 75 cycles. The discharge current density was varied from 5 to 500 μA cm–2 in the first 25 cycles and fixed at 50 μA cm–2 in the last 50 cycles. During these charge–discharge reactions, EIS measurements were carried out at 3.0 and 4.0 V after a given charge–discharge reaction by applying an AC amplitude of 10 mV within the frequency range of 200 kHz to 100 mHz. In the case of the Ox-SSBs without LGVO coating, charge–discharge reactions were repeated for 10 cycles at 5 μA cm–2, where the initial 5 cycles were measured at 60 °C and the later 5 cycles were conducted at 25 °C. Additionally, EIS measurements were carried out after the 5th cycle (60 °C) and the 10th cycle (25 °C) at 3.0 and 4.0 V.

Results and Discussion

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Preparation of LLZ–LGVO MLs

Figure 1a shows an FE-SEM image of the synthesized LGVO powder for AD, and the inset shows a magnified image of the powder. The LGVO powder formed as secondary particles less than 10 μm in diameter, consisting of submicron-sized primary particles. Figure 1b shows the XRD pattern of the LGVO powder. The diffraction pattern from the LGVO powder (black spectrum) was in good agreement with the reported pattern (red spectrum (34)), and impurity peaks were not detected (ND), indicating that single-phase LGVO was synthesized. Figure 1c shows the EIS spectrum of a sintered LGVO pellet (density: 72%) measured at 25 °C. Au films were deposited on both sides of the LGVO pellet (Au/LGVO/Au). The inset spectrum is a magnified image of a higher frequency region. The spectrum consists of one semicircular arc to ca. 8000 Ω, followed by a straight line to the real axis in the lower frequency region. Considering that this semicircular arc is assigned to the ion-conduction resistance of LGVO, the ionic conductivity was calculated to be 5 × 10–5 S cm–1 at 25 °C. This value was comparable to reported values. (27,35)

Figure 1

Figure 1. (a) FE-SEM image of LGVO particles for AD. The inset shows a magnified SEM image of a particle. (b) XRD patterns of the LGVO particles (black) and reported reference data (red). (c) Nyquist plots of a Au/LGVO/Au symmetrical cell at 25 °C. The inset displays a magnified image of a higher frequency region. The numbers in these plots indicate data points measured at 10n Hz.

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Figure 2 summarizes surface and cross-sectional FE-SEM images of the MLs (ML-AP, ML-700, ML-900, and ML-1050). Figure 2a–d shows surface SEM images of the MLs. The inset in each surface SEM image is an optical image of each ML, where a LGVO film was formed in an 8 × 10 mm region on a 10 mm square LLZ substrate. The LGVO film in ML-AP (Figure 2a) appears to be composed of fine particles, and this situation was the same in ML-700 (Figure 2b). In contrast, grain growth was visibly observed in ML-900 (Figure 2c) and more clearly in ML-1050 (Figure 2d). Figure 2e–h shows cross-sectional SEM images of the MLs. For each sample, LGVO films ca. 2 μm in thickness uniformly form on the LLZ substrates. Grain growth proceeds with the increase in annealing temperature to over 900 °C, as shown in Figure 2c,d, but the LGVO film does not peel off from the LLZ substrate. The LLZ region of both ML-AP and ML-700 is porous and densified in ML-900 and ML-1050. As mentioned in the experimental section, the LLZ substrates used in these MLs were acid-etched to remove surface impurities. This acid etching provided a porous LLZ region around the substrate, but such a porous region appeared to be densified with sintering over 900 °C. This densification is caused by the sintering of LLZ itself (Figure S1), and Ge diffusion from LGVO, as described below, may also assist it. (36) Figure S2 summarizes the SEM and EDX mapping images of Ge Lα, V Kα, and La Lα for ML-AP (Figure S2a–d), ML-700 (Figure S2e–h), ML-900 (Figure S2i–l), and ML-1050 (Figure S2m–p). The averaged Ge/V ratio (N3) of ML-AP is 0.99, which is almost consistent with the ideal ratio (1.00). In contrast, MLs with annealing over 700 °C exhibit decreased average Ge/V ratio to 0.79–0.90, indicating that LGVO reacts with LLZ with Ge diffusion. This reactive sintering will work as a driving force for generating a well-adhered interface, which will reasonably explain the in-plane growth of LGVO on LLZ with annealing. It has been reported that Ge can be doped into LLZ and occupy Li or La sites depending on the doping amount. (36) The appropriate amount of Ge doping of less than 1 wt % forms a solid solution with a cubic phase in addition to improving the ionic conductivity, while an excess amount of Ge doping of over 1 wt % provides tetragonal-phase LLZ, detected as (024) peak splitting, in addition to the appearance of impurity diffraction peaks. (36) The XRD patterns from both ML-700 and ML-900 do not show such peak splitting or impurity peaks, as shown in Figure 4. Therefore, the amount of Ge diffusion inside LLZ is expected to be in the solid solution range (less than 1 wt %). Both Ge Lα and V Kα signals are observed in most of the areas on the MLs, but some areas are shown as a dark color, where the La Lα signal from the LLZ substrate appears strong. These results indicate that LGVO films are formed almost uniformly on the LLZ substrates on a microscale, but they may not be coated or may be coated in a thinner state on part of the MLs on the macroscale.

Figure 2

Figure 2. (a–d) Surface and (e–f) cross-sectional FE-SEM images of (a,e) ML-AP, (b,f) ML-700, (c,g) ML-900, and (d,h) ML-1050. The insets in (a–d) display optical images of the MLs.

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Figure 3a,b show cross-sectional TEM images of ML-AP and ML-900. The LGVO films in ML-AP are formed by small-sized grains with voids, and the LGVO/LLZ interface remains a disconnected region along the interface. In contrast, the LGVO films in ML-900 are well sintered and densely adhere to LLZ. Figure 3c,d shows the EDX profile measured inside the LLZ of ML-AP and ML-900, and the analyzed values are summarized in each table, where both the mass % and at. % were estimated by the ζ-factor method. (37) EDX analysis could ND Ge in the LLZ region of ML-AP (Figure 3c). In contrast, Ge was detected at 0.09 at. % in ML-900 (Figure 3d) and widely distributed from the interface, although the detected value was in the lower detection limit range and should be considered a reference value. When Ge occupies the Li site, (36) the wide-range distribution of Ge may be explained by Ge diffusion through the Li+ conduction pathway. This wide-range diffusion, not condensed around the interface, is consistent with the reduction in the Ge/V ratio induced by annealing in the EDX measurements. V appears to be present in the LLZ region from the EDX image, but this is because the V Kα signal overlaps with the La Lα and O Kα signals. The amount of V was estimated by the ζ-factor method, (37) but V was ND in either ML-AP or ML-900, suggesting that V will not diffuse toward LLZ.

Figure 3

Figure 3. Cross-sectional TEM images of (a) ML-AP and (b) ML-900. EDX measurements around the LLZ/LGVO interface of (c) ML-AP and (d) ML-900. The EDX signals were from O Kα, V Kα, Ge Kα, Zr Lα, La Lα, and Ta Lα. The tables in Figure 2c,d summarize the mass %, σ, and at. % evaluated in the LLZ region in the red frame.

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Figure 4 shows the XRD patterns of the MLs. The diffraction patterns of the LLZ substrate after polishing by SiC polishing paper (#400) and LGVO powder are also shown as references. ML-AP presents a broad diffraction pattern from the LGVO film in addition to diffraction peaks from the LLZ substrate. The broad diffraction pattern from the LGVO film is attributed to the crystallinity degradation by AD. In the cases of ML-700 and ML-900, the diffraction peaks from the LGVO film appear sharp, indicating that the crystallinity of the LGVO film has recovered. Although Ge diffusion inside LLZ was suggested by EDX analysis, no impurity peaks were detected. The diffused amount of Ge (0.09 at. %) inside LLZ is estimated to be 0.13 wt % GeO2 against the Li7La3Zr2O12 composition, which is in the range of a solid solution of Ge (less than 1 wt %). (36) Additionally, the Ge/V ratio of 0.79–0.90 is within the range of the solid solution of LGVO, (35) and then, a Li3+xGexV1–xO4 (x = 0.48–0.44) film will be formed on LLZ. The diffraction peak intensity from the LGVO film further increases in ML-1050, and the crystallinity of the LGVO film improves; however, diffraction peaks assigned to La2Zr2O7 newly appear at 28.45, 47.44, and 56.19°. (38) La2Zr2O7 will be generated by thermal decomposition of LLZ, probably through lithium loss due to high-temperature annealing at 1050 °C. To summarize these XRD data, ML-AP provides a lower-crystalline LGVO layer, while ML-1050 provides highly crystalline LGVO, but the resistive impurity phase of La2Zr2O12 is generated as a byproduct. In the case of ML-700 and ML-900, LGVO is highly crystalline, and there are no impurity XRD peaks. Thus, both ML-700 and ML-900 are suitable for structural evaluation.

Figure 4

Figure 4. XRD patterns of ML-AP (blue), ML-700 (orange), ML-900 (red), and ML-1050 (purple). Additionally, XRD patterns of the LLZ substrate after polishing with SiC sandpaper (black) and LGVO powder (green) are shown as references. Diffraction peaks marked by * are assigned to La2Zr2O7.

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Figure 5a shows the EIS spectra of the blocking electrode cell of the MLs and the polished LLZ substrate. Because these substrates have slightly different thicknesses due to the polishing treatment of the LLZ substrates, all the data are normalized by the thickness (Ω cm–1). The EIS spectra exhibit characteristic spectra for blocking electrodes and diverge in lower frequency regions. Figure 5b–f show magnified images of higher frequency regions of LLZ and ML-AP, -700, -900, and -1050. One semicircular arc is observed in the high-frequency range except for ML-AP (Figure 5c). The total ionic conductivity (σtotal) of the MLs was calculated from the diameters of the semicircular arcs (Rtotal), and the values are displayed in each spectrum. The LLZ substrate has a σtotal of 7.3 × 10–4 S cm–1. Assuming that the ionic conductivity of the 2 μm thick LGVO films on LLZ is 5 × 10–5 S cm–1 for all samples and that there is no resistance at the LLZ/LGVO interface, the σtotal of the ML is estimated to be 6.9 × 10–4 S cm–1. The σtotal values of ML-700 and ML-900 are 7.0 × 10–4 and 6.8 × 10–4 S cm–1, respectively. These values are almost consistent with the ionic conductivity estimated from the sum of each resistance of LLZ and LGVO, indicating that there is no significant interfacial resistance at LLZ/LGVO. Although the composition of LGVO may change from the initial Li3.5Ge0.5V0.5O4 with the highest ionic conductivity to Li3+xGexV1–xO4 (x = 0.48–0.44) via Ge diffusion, this compositional change will result in only a slight decrease in the ionic conductivity. (27) In the case of ML-1050, σtotal decreases to 3.3 × 10–4 S cm–1, which is attributed to the formation of resistive La2Zr2O7 as a byproduct detected by XRD. Additionally, ML-AP exhibits quite a large semicircular arc out of the scale in Figure 5c, and σtotal is estimated to be 4.6 × 10–5 S cm–1 from Figure 5a. This decreased ionic conductivity is attributed to the degraded crystallinity of the LGVO film with voids, as shown in Figures 2 and 4, in addition to the formation of the disconnected region along the interface (Figure 3). These results indicate that both ML-700 and ML-900 are appropriate in terms of ionic conductivity.

Figure 5

Figure 5. (a) Nyquist plots of ML-AP (blue), ML-700 (orange), ML-900 (red), ML-1050 (purple), and the LLZ substrate (green) measured at 25 °C. Magnified Nyquist plots in a higher frequency region of the (b) LLZ substrate, (c) ML-AP, (d) ML-700, (e) ML-900, and (f) ML-1050. The numbers in each plot indicate data points measured at 10n Hz. The thickness of each substrate is used to normalize all the resistances.

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From these results, both ML-700 and ML-900 are considered appropriate MLs in this study. ML-900 was selected as a model substrate to fabricate Ox-SSBs through a sintering process in the subsequent evaluation.

Electrochemical Properties of the Ox-SSBs Using ML-900

We checked the reactivity of LGVO with LCO under sintering by Raman spectroscopy before fabricating Ox-SSBs using ML-900. Thin films of LCO were formed on LGVO pellets using AD at room temperature, and then, the LCO/LGVO ML was sintered at 700 or 900 °C in Ar. Figure S3a shows a cross-sectional FE-SEM image of a LCO thin film fabricated on a LGVO pellet. A LCO thin film with a thickness of ca. 1 μm was formed on the LGVO pellet. Figure S3b shows Raman spectra of the as-deposited LCO film and the LCO film after annealing at 700 or 900 °C. The as-deposited LCO film exhibits two Raman bands (A1g and Eg) characteristic of layered-structured LCO. (39) These two bands were observed after annealing at 700 °C but disappeared at 900 °C. These results clarify that LGVO-LCO significantly reacts with annealing at less than 900 °C. Figure S4 shows a cross-sectional TEM image and EDX line profile of LCO/LGVO interface annealing at 700 °C. A mutual diffusion layer may be formed around the interface, but its thickness is less than 20 nm. Wide-range mutual diffusion of Co, V, and Ge was ND.
Based on the above results, a thin film of LCO was deposited on the LGVO side of ML-900 using AD and annealed at 700 °C. Then, a lithium metal anode was deposited on the LLZ side of the ML-900/LCO, and Ox-SSBs (Li/ML-900/LCO) were fabricated. Figure S5 shows a cross-sectional SEM image (Figure S5a) and an EDX mapping image (Figure S5b). Both LCO (ca. 1 μm) and LGVO (ca. 2 μm) films formed an ML on an LLZ substrate. Although we could not measure the correct loading amount of the LCO film because the AD conditions in this work slightly etched the substrate, the expected amount was ca. 0.5 mg/cm2 assuming that the LCO thin film has the ideal density of LCO (5.0 g/cm3). The lithium plating amount during the charging process is estimated to be ca. 0.3 μm.
Figure 6 shows the variation in the discharge capacity of an Ox-SSB with repetition of charge–discharge cycles at different current densities. The reaction temperature was swung: 1st–25th cycles at 60 °C, 26th–36th cycles at 25 °C, and 37th–137th cycles at 60 °C. The charge current density was fixed at 2.9 μA cm–2 for the 1st–36th cycles and 5 μA cm–2 after the 37th cycle, and the discharge current density was changed from 2.9 to 500 μA cm–2. The discharge capacity slightly decreased with the cycles, and the discharge capacity after the 137th cycle (I = 50 μA cm–2) maintained 88% of that after the 11th cycle (I = 57 μA cm–2). Additionally, the total interfacial resistance (Rint) measured after the given charge–discharge reactions is plotted in Figure 6, where Rint is the sum of the interfacial resistances at Li/LLZ (DE1-R) and LCO/LGVO (DE2-R), as discussed below. Figure 7a displays the 1st, 6th, 11th, 16th, and 21st charge–discharge curves at 60 °C, where the discharge current density was varied from 2.9 to 286 μA cm–2. The Coulombic efficiency in the initial cycle was 89.7%. Figure 7b displays the charge–discharge curves at the 26th, 31st, and 36th cycles at 25 °C, where the discharge current density was varied from 2.9 to 57 μA cm–2. In these charge–discharge curves, the hexagonal-monoclinic phase transition of LCO was not observed at 4.1–4.2 V in Figure 7a, but it clearly appeared in Figure 7b. This situation agrees with the temperature dependency of the hexagonal-monoclinic phase transition. (40) These results indicate that the LCO film on ML-900 maintains good crystallinity after annealing at 700 °C. Figure 7c,d shows the EIS spectra measured at 3.0 and 4.0 V after the 5th (60 °C) and 25th (25 °C) charge–discharge cycles, respectively. The high-frequency intercept with the real axis does not depend on the potential, and the values are 60 Ω at 60 °C and 230 Ω at 25 °C, which is assigned to the resistance of ML-900 considering the frequency in Figure 5e. In contrast, a new semicircular arc appears at 4.0 V. This semicircular arc is displayed as Rint in Figure 7c,d. Rint is divided into two relaxation processes from the distribution of relaxation times (DRT) analysis (Figure S6), which is the sum of the interfacial resistances at Li/LLZ (DE1) and LGVO/LCO (DE2). (32) EIS spectra recorded at 3.0 and 4.0 V after the given charge–discharge cycles are displayed in Figure S7. Table 1 summarizes the DRT-analyzed resistances of the solid electrolyte (R1), Li/LLZ interface (DE1-R), and LGVO/LCO interface (DE2-R) in addition to other values [relaxation times (DE-T), depression factors (DE-P), and error % for the fitting] of these EIS spectra at 4.0 V. Additionally, the equivalent circuit model is displayed in Table 1. Here, the variations in Rint in Figure 6 are the sum of DE1-R and DE2-R. DE1-R slightly increases from 13.2 Ω (after the 5th cycle) to 19.2 Ω (after the 136th cycle) with cycling, which is attributed to the formation of a partially disconnected Li/LLZ interface region. (32) DE2-R increases ca. two times from 46.9 Ω (after the 5th cycle) to 109 Ω (after the 136th cycle). As shown in Figure 6, the discharge capacity slightly decreases with the cycles. This increased interfacial resistance at LGVO/LCO will contribute to the degradation and rise of Rint with cycling. A plausible mechanism for the increasing DE2-R is the formation of a disconnected LGVO/LCO interface originating from the volume change of LCO at 3.0–4.2 V (ca. 2%) during the charge–discharge reactions. (6,26,27,40) An effective way to reduce this degradation will be to replace LCO with other electrode materials with smaller volume changes, such as LiNi1/3Co1/3Mn1/3O2. (27,31) Focusing on the interfacial resistivity of LGVO/LCO at 25 °C measured after the 15th charge–discharge reaction is interesting. DE2-R was estimated to be 514 Ω; thus, the interfacial resistivity was calculated to be 145 Ω cm2. This is almost the same value as LCO/LLZ (150 Ω cm2) interface-modified by 10 nm Nb metal, (41) where the interfacial resistance sensitively varied with the thickness of the Nb coating layer. This means that a low-resistivity LGVO/LCO interface is formed even after annealing at 700 °C.

Figure 6

Figure 6. Variation in the discharge capacity and total interfacial resistance (Rint) of an Ox-SSB (Li/ML-900/LCO) with the charge–discharge reactions measured at 60 and 25 °C. The charge current density was fixed at 2.9 μA cm–2 in the 1st–36th cycles and 5 μA cm–2 in the 37th–137th cycles, and the discharge current density was varied from 2.9 to 286 μA cm–2 during the 1st–36th cycles and 5–500 μA cm–2 during the 37th–91st cycles and fixed at 50 μA cm–2 during the 92nd–137th cycles. The Rint values were measured at 4.0 V after charge–discharge reactions in the 5th, 25th, 36th, 86th, and 136th cycles.

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Figure 7

Figure 7. Charge–discharge curves of an Ox-SSB (Li/ML-900/LCO) with 700 °C annealing in the (a) 1st, 6th, 11th, 16th, and 21st cycles and (b) 26th, 31st, and 36th cycles, where the charge current density was fixed at 2.9 μA cm–2 and discharge current density was 2.9 μA cm–2 (1st and 26th), 29 μA cm–2 (6th and 31st), 57 μA cm–2 (11th and 36th), 143 μA cm–2 (16th), and 286 μA cm–2 (21st). Nyquist plots at 3.0 and 4.0 V after the (c) 5th cycle and (d) 25th cycle, where Rint denotes the sum of the interfacial resistances at Li/LLZ and LGVO/LCO. Data were measured at 60 °C in (a,c) and at 25 °C in (b,d). The numbers in (c,d) indicate data points measured at 10n Hz.

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Table 1. Variations in EIS Data Analyzed by DRT of an Ox-SSB with ML-900 after the 5th, 36th, 86th, and 136th Charge–Discharge Cycles Shown in Figure 6; R1 (Solid Electrolyte), DE-1 (Li/LLZ Interface), and DE-2 (LCO/LGVO Interface)a
 5th36th86th136th
 valueerror (%)valueerror (%)valueerror (%)valueerror (%)
R1 (Ω)62.13.0 × 10–561.82.9 × 10–564.52.6 × 10–571.62.7 × 10–5
DE1-R (Ω)13.26.9 × 10–413.16.2 × 10–414.84.7 × 10–419.23.4 × 10–4
DE1-T (s)2.82 × 10–63.3 × 10–42.82 × 10–62.8 × 10–42.82 × 10–62.0 × 10–42.82 × 10–61.5 × 10–4
DE1-P0.892.5 × 10–40.902.3 × 10–40.891.9 × 10–40.881.5 × 10–4
DE2-R (Ω)46.91.7 × 10–459.21.2 × 10–476.58.1 × 10–51095.5 × 10–5
DE2-T (s)2.92 × 10–51.9 × 10–43.55 × 10–61.5 × 10–44.75 × 10–51.2 × 10–47.73 × 10–57.5 × 10–5
DE1-P0.784.5 × 10–50.764.0 × 10–50.733.4 × 10–40.7131 × 10–5
a

The equivalent circuit model of the Ox-SSB is shown in the table.

To clarify the role of the LGVO coating layer in ML-900, an all-solid-state battery (Li/LLZ/LCO) without a LGVO coating layer was fabricated by depositing LCO on an acid-treated LLZ substrate by AD and then annealed at 700 °C in the same manner. Figure 8a shows the charge–discharge curves of the 1st–5th cycles at 60 °C. In the 1st cycle, the open-circuit voltage (OCV) was as low as 1.65 V, and a charging capacity of 13 μA h cm–2 was observed under 3.0 V. The Coulombic efficiency over 3.0 V was decreased to 66.6%, with an irreversible capacity of 24 μA h cm–2. In contrast, the discharge capacities after two cycles were almost consistent with those of the SSBs using ML-900 in Figure 7a and delivered 47 μA h cm–2. Here, the hexagonal-monoclinic phase transition of LCO was not observed, as shown in Figure 7a. Figure 8b shows the EIS spectra recorded after the 5th cycle (60 °C) at 3.0 and 4.0 V. The high-frequency intercept with the real axis was potential-independent, and this part was then assigned to the resistance of the solid electrolyte. However, the resistance increased from 60 Ω (Figure 7a) to 2000 Ω (Figure 8a). Additionally, Rint increased from 60 Ω (Figure 7b) to 2500 Ω (Figure 8b). These results indicate that the LGVO coating effectively inhibits the increase in both the solid electrolyte resistance and Rint because of the suppression of side reactions during the sintering process. When charging and discharging reactions were carried out at 25 °C (Figure 8c), the charge–discharge voltage was visibly polarized, and the hexagonal-monoclinic phase transition peaks were not observed, probably because of the inhomogeneous reaction induced by the large interfacial resistance. Additionally, potential-independent high-frequency intercepts were composed of several semicircular arcs; the value increased from 200 to 17000 Ω, and the potential-dependent Rint increased from 650 Ω (Figure 7d) to 25000 Ω (Figure 8d). This increased resistance reasonably explains the large polarization of the charge–discharge curve.

Figure 8

Figure 8. (a) Charge–discharge curves at 60 °C of an Ox-SSB (Li/LLZ/LCO) with 700 °C annealing in the 1st–5th cycles under a fixed charge–discharge current density of 5 μA cm–2. (b) Nyquist plots at 60 °C of a nonannealed Ox-SSB (Li/LLZ) measured at 3.0 V (blue) and 4.0 V (red) after the 5th cycle. (c) Charge–discharge curves at 25 °C of a nonannealed Ox-SSB (Li/LLZ/LCO) in the 6th–10th cycles under a fixed charge–discharge current density of 5 μA cm–2. (d) Nyquist plots at 25 °C of an Ox-SSB (Li/LLZ/LCO) without annealing measured at 3.0 V (blue) and 4.0 V (red) after the 10th cycle. (e) Charge–discharge curves at 60 °C of an Ox-SSB (Li/LLZ/LCO) without annealing in the 1st–5th cycles under a fixed charge–discharge current density of 5 μA cm–2. (f) Nyquist plots at 60 °C of an Ox-SSB (Li/LLZ) without annealing measured at 3.0 V (blue) and 4.0 V (red) after the 5th cycle. (g) Schematic image of the interface properties with LGVO coating and annealing effects.

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The use of acid-etched LLZ provides a porous region around the LLZ surface, as mentioned in Figure 2, which may increase the cell resistance due to worse physical bonding. (32) Thus, we prepared an Ox-SSB (Li/LLZ/LCO) without annealing after depositing LCO thin films by AD on acid-treated LLZ, where the maximum heating temperature was 165 °C to obtain a well-adhered Li/LLZ interface. Figure 8e shows the charge–discharge curves at 60 °C of the resultant SSB (Li/LLZ/LCO) without LGVO or any annealing. The OCV increased to 2.51 V, and the capacity below 3.0 V disappeared. The presence of an additional plateau at approximately 3.6 V may be due to the degraded crystallinity in part of the as-prepared AD LCO film. (6) In the first cycle, an irreversible capacity of 26 μA h cm–2 was observed, and the Coulombic efficiency was 67.5%. The discharge capacity after the second cycle was ca. 50 μA h cm–2, comparable to those of the annealed Ox-SSB without LGVO (Figure 8a) and the Ox-SSB using ML-900. In contrast, the Coulombic efficiency in the first cycle was ca. 90% for the Ox-SSB with ML-900 and decreased to 67–68% in Ox-SSBs without LGVO regardless of annealing. The difference in the irreversible capacity in the first cycle may arise from the anodic instability of LLZ, (16,42) and LGVO may have a superior anodic stability to LLZ. When the oxidation of LLZ occurs during the first charging reaction, the interface will be modified to a stabilized state at the voltage, similar to SEI formation on a graphite anode in a lithium-ion battery. After the stabilization of the interface, the later charging reaction will not entail any irreversible capacity under the same charging voltage. Figure 8f shows the EIS spectra recorded after the fifth cycle (60 °C) at 3.0 and 4.0 V. The potential-independent high-frequency intercept with the real axis and Rint were 50 and 70 Ω, respectively. These values were comparable to those of the Ox-SSB with ML-900 (Figure 7c) but 2 orders of magnitude smaller than those of the sintered Ox-SSB without LGVO coating (Figure 8d). These results clarify that the porosity of the LLZ does not influence the drastic increase in the cell resistance and that annealing of LLZ/LCO induces an increase in the cell resistance. In other words, the 2 μm thick LGVO coating effectively suppresses the side reactions at LLZ/LCO and then inhibits the increase in the resistance induced by sintering.
Figure 8g summarizes the properties of the LLZ/LCO interface with LGVO coating and annealing. The LLZ/LCO interface without annealing has low resistivity. Once LLZ/LCO is annealed, the materials react with each other, and a high-resistivity interface is generated. The LGVO layer reacts with LLZ through Ge diffusion induced by annealing, but LLZ/LGVO has low resistivity. In contrast, LGVO/LCO is a low-reactivity and low-resistivity interface, and LLZ/LGVO/LCO provides a totally low-resistivity interface. These results indicate that one strategy to realize a low-resistivity LLZ/LCO interface by the sintering process is to insert a coating layer such as LGVO at the interface. Another strategy will be to develop the interface at lower temperatures, which may require low-temperature process technology such as AD.

Conclusions

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We applied the concept of function sharing of a solid electrolyte to an oxide-based all-solid-state oxide battery (Ox-SSB) prepared by sintering processes similar to ML ceramic capacitors technology. We prepared an LLZ–LGVO ML solid electrolyte sheet where a 2 μm thick LGVO film was coated on one side of the LLZ substrate by AD. The ML obtained a total ionic conductivity of 6.9 × 10–4 S cm–1 at 25 °C and was stable up to 900 °C. These two solid electrolytes were well-densified through Ge diffusion and did not provide large interfacial resistance. MLs annealed at 900 °C (ML-900) were applied to develop Ox-SSBs (Li/ML-900/LCO) through sintering at 700 °C. The LGVO coating suppressed the increases in the resistance from the solid electrolyte and interfacial resistance induced by annealing by ca. 1/40. Additionally, the LGVO/LCO interfacial resistivity was decreased to as low as 145 Ω cm2 at 25 °C. Here, a 2 μm coating of LGVO is a tunable parameter in the field of ML ceramic capacitors. (43) Because the LLZ sheet has been successfully prepared by the tape casting method, (44) we can expect that the LLZ–LGVO ML will possibly be prepared through ML ceramic capacitors technology. Of course, the application of LGVO as a coating material may be another choice to develop better performance bulk-type Ox-SSBs (27) by reducing the Ohmic resistance in the composite electrode.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.2c10853.

  • EDX analysis of an LLZ–LGVO multilayer, reactivity between LGVO and LCO analyzed by Raman spectroscopy, cross-sectional SEM and EDX images of an LLZ/LGVO/LCO multilayer, DRT analysis of an EIS spectrum of an Ox-SSB (Li/ML-900/LCO), and EIS spectra of an Ox-SSB (Li/ML-900/LCO) (PDF)

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Author Information

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  • Corresponding Author
  • Authors
    • Miyuki Sakakura - Department of Materials Design Innovation Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
    • Kazutaka Mitsuishi - Research Center for Advanced Measurement and Characterization, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan;  Orcidhttps://orcid.org/0000-0002-9361-4057
    • Toyoki Okumura - Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan;  Orcidhttps://orcid.org/0000-0003-0752-0941
    • Norikazu Ishigaki - Department of Materials Design Innovation Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    This work was supported by ALCA-SPRING (JPMJAL1301) and in part by JSPS KAKENHI number JP19H05813 (Grant-in-Aid for Scientific Research on Innovation Areas “Interface IONICS”).

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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We thank Keisuke Shinoda and Tomoyuki Horie for TEM sample preparation at the National Institute for Materials Science (NIMS) Battery Research Platform. A part of this work was supported by the NIMS Electron Microscopy Analysis Station, Nanostructural Characterization Group.

References

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    Sintering processes yield a mutual diffusion region at the electrode/solid electrolyte interface, which is considered as a crucial problem for developing large-sized all-solid-state rechargeable lithium batteries with high power d. This work focuses on the interface between LiNi1/3Co1/3Mn1/3O2 (NMC) and NASICON-structured Li+ conductive glass ceramics solid electrolyte (Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2: LATP sheet (AG-01)), and investigates the effects of sintering temp. on interfacial structure and interfacial resistance at the NMC/LATP sheet. Thin films of NMC were fabricated on the LATP sheets at 700 °C or 900 °C as a model system. We found that the thickness of the mutual diffusion region was almost the same, ca. 30 nm, in these two samples, but the NMC film prepd. at 900 °C had three orders of magnitude larger interfacial resistance than the NMC film prepd. at 700 °C. Around the interface between the NMC film prepd. at 900 °C and the LATP sheet, Co in the NMC accumulates as a reduced valence and lithium-free impurity cryst. phase will be also formed. These two problems must contribute to drastic increasing of interfacial resistance. Formation of de-lithiated NMC around the interface and its thermal instability at higher temp. may be considerable reason to induce these problems.
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    Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781,  DOI: 10.1002/anie.200701144
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    Fast lithium ion conduction in garnet-type Li7La3Zr2O12
    Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
    Angewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
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    Zhu, Y.; He, X.; Mo, Y. First Principles Study on Electrochemical and Chemical Stability of Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries. J. Mater. Chem. A 2016, 4, 3253– 3266,  DOI: 10.1039/c5ta08574h
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    First principles study on electrochemical and chemical stability of solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries
    Zhu, Yizhou; He, Xingfeng; Mo, Yifei
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (9), 3253-3266CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technol. with high energy d. and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries. In this study, we performed first principles calcns. to evaluate the thermodn. of the interfaces between solid electrolyte and electrode materials and to identify the chem. and electrochem. stabilities of these interfaces. Our computation results reveal that many solid electrolyte-electrode interfaces have limited chem. and electrochem. stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochem. performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chem. and electrochem. stability of heterogeneous solid interfaces. The enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.
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  10. 10
    Xu, L.; Li, J.; Deng, W.; Shuai, H.; Li, S.; Xu, Z.; Li, J.; Hou, H.; Peng, H.; Zou, G.; Ji, X. Garnet Solid Electrolyte for Advanced All-Solid-State Li Batteries. Adv. Energy Mater. 2021, 11, 2000648,  DOI: 10.1002/aenm.202000648
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    Garnet Solid Electrolyte for Advanced All-Solid-State Li Batteries
    Xu, Laiqiang; Li, Jiayang; Deng, Wentao; Shuai, Honglei; Li, Shuo; Xu, Zhifeng; Li, Jinhui; Hou, Hongshuai; Peng, Hongjian; Zou, Guoqiang; Ji, Xiaobo
    Advanced Energy Materials (2021), 11 (2), 2000648CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
    A review. High-capacity cathodes and anodes in energy storage area are required for delivering high energy d. due to the ever-increasing demands in the applications of elec. vehicles and power grids, which suffer from significant safety concerns and poor cycling stability at the current stage. All-solid-state lithium batteries (ASSLBs) have been considered to be particularly promising within the new generation of energy storage, owing to the superiority of safety, wide potential window, and long cycling life. As the key component in ASSLBs, individual solid electrolytes that can meet practical application stds. are very rare due to poor performance. To the present day, numerous research efforts have been expended to find applicable solid-state electrolytes and tremendous progress has been achieved, esp. for garnet-type solid electrolytes. Nevertheless, the garnet-type solid electrolyte is still facing some crucial dilemmas. Hence, the issues of garnet electrolytes' ionic cond., the interfaces between electrodes and garnet solid electrolytes, and application of theor. calcn. on garnet electrolytes are focuses in this review. Furthermore, prospective developments and alternative approaches to the issues are presented, with an aim to improve understanding of garnet electrolytes and promote their practical applications in solid-state batteries.
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    Indu, M. S.; Alexander, G. V.; Sreejith, O. V.; Abraham, S. E.; Murugan, R. Lithium Garnet-Cathode Interfacial Chemistry: Inclusive Insights and Outlook Toward Practical Solid-State Lithium Metal Batteries. Mater. Today Energy 2021, 21, 100804,  DOI: 10.1016/j.mtener.2021.100804
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    11
    Lithium garnet-cathode interfacial chemistry: inclusive insights and outlook toward practical solid-state lithium metal batteries
    Indu, M. S.; Alexander, G. V.; Sreejith, O. V.; Abraham, S. E.; Murugan, R.
    Materials Today Energy (2021), 21 (), 100804CODEN: MTEACH; ISSN:2468-6069. (Elsevier Ltd.)
    A review. Solid-state lithium batteries have attained tremendous interest over the past few years as a possible alternative to the present lithium-ion battery because of their improved safety and higher energy d. The key component of a solid-state battery is the solid electrolyte. Among various inorg. solid electrolytes ranging from sulfides to oxides, garnet structured oxide solid electrolytes emerged as a promising candidate due to their high lithium-ion cond. as well as excellent stability with lithium metal and potential electrodes. However, garnet solid electrolyte-based solid-state battery's practical realization is limited by various challenges at the electrode-garnet interface, particularly the significant interface resistance and poor crit. c.d. Although significant developments have been made toward accomplishing an effective anode-garnet interface, the cathode-garnet interface is still challenging, and in-depth anal. with more emphasis on cathode-garnet interfacial chem. is lacking. From this point of view, this review discusses the fundamentals of the cathode-garnet interface in detail and carefully summarizes the issues with various cathode materials and possible strategies to overcome them for the realization of 'anode free' high energy d. lithium metal batteries.
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  12. 12
    Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO2 Electrode and Li2S–P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956,  DOI: 10.1021/cm901819c
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    12
    Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron Microscopy
    Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro
    Chemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
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    Zhang, W.; Richter, F. H.; Culver, S. P.; Leichtweiss, T.; Lozano, J. G.; Dietrich, C.; Bruce, P. G.; Zeier, W. G.; Janek, J. Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2018, 10, 22226– 22236,  DOI: 10.1021/acsami.8b05132
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    13
    Degradation mechanisms at the Li10GeP2S12/LiCoO2 cathode interface in an all-solid-state lithium-ion battery
    Zhang, Wenbo; Richter, Felix H.; Culver, Sean P.; Leichtweiss, Thomas; Lozano, Juan G.; Dietrich, Christian; Bruce, Peter G.; Zeier, Wolfgang G.; Janek, Juergen
    ACS Applied Materials & Interfaces (2018), 10 (26), 22226-22236CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degrdn. mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy d., the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems assocd. with Li-metal anodes. Capacity fading and increased impedances are obsd. during long-term cycling. Postmortem anal. with scanning transmission electron microscopy, electron energy loss spectroscopy, x-ray diffraction, and XPS show that electrochem. driven mech. failure and degrdn. at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochem. more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.
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    Ohta, N.; Takada, K.; Zhang, L.; Ma, R.; Osada, M.; Sasaki, T. Enhancement of the High-Rate Capability of Solid-State Lithium Batteries by Nanoscale Interfacial Modification. Adv. Mater. 2006, 18, 2226– 2229,  DOI: 10.1002/adma.200502604
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    Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification
    Ohta, Narumi; Takada, Kazunori; Zhang, Lianqi; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
    Advanced Materials (Weinheim, Germany) (2006), 18 (17), 2226-2229CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The high-rate capability of solid-state rechargeable Li batteries with sulfide electrolytes improved when the LiCoO2 particles are spray-coated with Li4Ti5O12. The power densities of the solid-state battery with the coated LiCoO2 are comparable to those of com. Li-ion batteries.
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    Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255,  DOI: 10.1021/cm5016959
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    Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery
    Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, Yoshitaka
    Chemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
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    Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693,  DOI: 10.1021/acsami.5b07517
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    Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
    Zhu, Yizhou; He, Xingfeng; Mo, Yifei
    ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
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    Fu, J. Fast Li+ Ion Conduction in Li2O-Al2O3-TiO2-SiO2-P2O2 Glass-Ceramics. J. Am. Ceram. Soc. 1997, 80, 1901– 1903,  DOI: 10.1111/j.1151-2916.1997.tb03070.x
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    Fast Li+ ion conduction in Li2O-Al2O3-TiO2-SiO2-P2O5 glass-ceramics
    Fu, Jie
    Journal of the American Ceramic Society (1997), 80 (7), 1901-1903CODEN: JACTAW; ISSN:0002-7820. (American Ceramic Society)
    Fast lithium ion conducting glass-ceramics have been successfully prepd. from the pseudobinary system 2[Li1+xTi2SixP3-xO12]-AlPO4. The major phase present in the glass-ceramics was LiTi2P3O12 in which Ti4+ ions and P5+ ions were partially replaced by Al3+ ions and Si4+ ions, resp. Increasing x resulted in a considerable enhancement in cond. and, in a wide compn. range, extremely high cond. over 10-3 S/cm was obtained at room temp.
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    Amiki, Y.; Sagane, F.; Yamamoto, K.; Hirayama, T.; Sudoh, M.; Motoyama, M.; Iriyama, Y. Electrochemical Properties of an All-Solid-State Lithium-Ion Battery with an In-Situ Formed electrode Material Grown from a Lithium Conductive Glass Ceramics Sheet. J. Power Sources 2013, 241, 583– 588,  DOI: 10.1016/j.jpowsour.2013.05.006
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    Electrochemical properties of an all-solid-state lithium-ion battery with an in-situ formed electrode material grown from a lithium conductive glass ceramics sheet
    Amiki, Yuichi; Sagane, Fumihiro; Yamamoto, Kazuo; Hirayama, Tsukasa; Sudoh, Masao; Motoyama, Munekazu; Iriyama, Yasutoshi
    Journal of Power Sources (2013), 241 (), 583-588CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    A lithium insertion reaction in a Li+ conductive glass ceramics solid electrolyte (lithium aluminum titanium phosphate: LATP) sheet produces an in-situ formed electrode active material, which operates at 2.35 V vs. Li/Li+ in the vicinity of the LATP-sheet/current-collector interface. Electron energy loss spectroscopy clarifies that titanium in the LATP sheet in the vicinity of the current collector/LATP-sheet interface is preferentially reduced by this lithium insertion reaction. Charge transfer resistance between the in-situ-formed-electrode and the LATP-sheet is less than 100 Ω cm2, which is smaller than that of the common LiPON/LiCoO2 interface. A thin film of LiCoO2 is deposited on one side of the LATP-sheet as a Li+ source for developing the in-situ formed electrode material. Eventually, a Pt/LATP-sheet/LiCoO2/Au multilayer is fabricated. The multilayer structure successfully works as an all-solid-state lithium-ion battery operating at 1.5 V. A redox peak of the battery is obsd. even at 100 mV s-1 in the potential sweep curve. Addnl., charge-discharge reactions are repeated stably even after 25 cycles.
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    Cheng, D.; Wynn, T. A.; Wang, X.; Wang, S.; Zhang, M.; Shimizu, R.; Bai, S.; Nguyen, H.; Fang, C.; Kim, M.-C.; Li, W.; Lu, B.; Kim, S.-J.; Meng, Y. S. Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy. Joule 2020, 4, 2484– 2500,  DOI: 10.1016/j.joule.2020.08.013
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    Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy
    Cheng, Diyi; Wynn, Thomas A.; Wang, Xuefeng; Wang, Shen; Zhang, Minghao; Shimizu, Ryosuke; Bai, Shuang; Nguyen, Han; Fang, Chengcheng; Kim, Min-cheol; Li, Weikang; Lu, Bingyu; Kim, Suk Jun; Meng, Ying Shirley
    Joule (2020), 4 (11), 2484-2500CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
    The solid electrolyte interphase (SEI) is regarded as the most complex but the least understood constituent in secondary batteries using liq. and solid electrolytes. The dearth of such knowledge in all-solid-state battery (ASSB) has hindered a complete understanding of how certain solid-state electrolytes, such as LiPON, manifest exemplary stability against lithium metal. By employing cryogenic electron microscopy (cryo-EM), the interphase between lithium metal and LiPON is successfully preserved and probed, revealing a multilayer-mosaic SEI structure with concn. gradients of nitrogen and phosphorus, materializing as crystallites within an amorphous matrix. This unique SEI nanostructure is less than 80 nm and is stable and free of any org. lithium-contg. species or lithium fluoride components, in contrast to SEIs often found in state-of-the-art org. liq. electrolytes. Our findings reveal insights on the nanostructures and chem. of such SEIs as a key component in lithium metal batteries to stabilize lithium metal anode.
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    West, W. C.; Whitacre, J. F.; Lim, J. R. Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films. J. Power Sources 2004, 126, 134– 138,  DOI: 10.1016/j.jpowsour.2003.08.030
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    Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films
    West, W. C.; Whitacre, J. F.; Lim, J. R.
    Journal of Power Sources (2004), 126 (1-2), 134-138CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)
    Sputter deposition of LiPON films directly onto high Li+ cond. solid electrolyte plates was studied as a means to minimize the reactivity of the plates to metallic Li. The LiPON films effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal. The cond. of the passivated solid electrolyte plates is 1.0 × 10-4 S cm-1, with Arrhenius activation energy of 0.36 eV and an electrochem. stability window of at least 0-5.0 V vs. Li/Li+. The passivated solid electrolyte was capable of supporting electrochem. plating and stripping of Li metal, as demonstrated by EIS and CV measurements. These high chem. stability, high Li+ cond. solid electrolyte plates will be useful for solid-state batteries employing Li anodes.
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    Sagane, F.; Ikeda, K.; Okita, K.; Sano, H.; Sakaebe, H.; Iriyama, Y. Effects of Current Densities on the Lithium Plating Morphology at a Lithium Phosphorus Oxynitride Glass Electrolyte/Copper Thin Film Interface. J. Power Sources 2013, 233, 34– 42,  DOI: 10.1016/j.jpowsour.2013.01.051
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    Effects of current densities on the lithium plating morphology at a lithium phosphorus oxynitride glass electrolyte/copper thin film interface
    Sagane, Fumihiro; Ikeda, Ken-ichi; Okita, Kengo; Sano, Hikaru; Sakaebe, Hikari; Iriyama, Yasutoshi
    Journal of Power Sources (2013), 233 (), 34-42CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Li metal is electrochem.-grown at the Li P oxynitride glass electrolyte (LiPON)/Cu thin film interface. The plated Li morphol. depends on the current densities and larger current densities bring about smaller-sized pptn. of Li with larger coverage ratio by the ppts. Both SEM and in-situ optical microscopy observations reveal that the Li tends to grow at the Li pre-plated place. Large potential drop was obsd. at the initial Li plating process, suggesting that the nucleation process requires large activation energy at the initial Li plating process at the LiPON/Cu interface. The resultant morphol.-controlled in-situ prepd. Li provides stable and low-resistive Li/LiPON interface compared with the vacuum-evapd. Li thin film.
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    Ohta, S.; Komagata, S.; Seki, J.; Saeki, T.; Morishita, S.; Asaoka, T. All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing. J. Power Sources 2013, 238, 53– 56,  DOI: 10.1016/j.jpowsour.2013.02.073
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    All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing
    Ohta, Shingo; Komagata, Shogo; Seki, Juntaro; Saeki, Tohru; Morishita, Shinya; Asaoka, Takahiko
    Journal of Power Sources (2013), 238 (), 53-56CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    An all-solid-state lithium ion battery was constructed with a screen-printing process using Nb doped Li7La3Zr2O12 (LLZONb) as the solid electrolyte and Li3BO3 (LBO) as a solid electrolyte within the cathode layer. LBO is a lithium ion conductor that is chem. stable with the LiCoO2 (LCO) active cathode material and LLZONb. Sufficient interface contact between the cathode layer and the LLZONb solid electrolyte can be easily achieved with sintering LBO into the cathode layer by an annealing process. The resultant battery exhibited good electrochem. performance and a lower interfacial resistance comparable with that of lithium ion batteries with liq. org. electrolytes.
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  23. 23
    Park, K.; Yu, B. C.; Jung, J. W.; Li, Y.; Zhou, W.; Gao, H.; Son, S.; Goodenough, J. B. Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO2 and Garnet-Li7La3Zr2O12. Chem. Mater. 2016, 28, 8051– 8059,  DOI: 10.1021/acs.chemmater.6b03870
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    23
    Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO2 and Garnet-Li7La3Zr2O12
    Park, Kyusung; Yu, Byeong-Chul; Jung, Ji-Won; Li, Yutao; Zhou, Weidong; Gao, Hongcai; Son, Samick; Goodenough, John B.
    Chemistry of Materials (2016), 28 (21), 8051-8059CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Garnet-structured solid electrolytes have been extensively studied for a solid-state lithium rechargeable battery. Previous works have been mostly focused on the materials' development and basic electrochem. properties but not the cathode/electrolyte interface. Understanding the cathode interface is crit. to enhance chem. stability and electrochem. performance of a solid-state battery cell. In this work, we studied thoroughly the cathode/electrolyte interface between LiCoO2 and Li7La3Zr2O12 (LLZO). It was found that the high-temp. process to fuse LiCoO2 and LLZO induced cross-diffusion of elements and formation of the tetragonal LLZO phase at the interface. These degrdns. affected electrochem. performance, esp. the initial Coulombic efficiency and cycle life. In a clean cathode interface without the thermal process, an irreversible electrochem. decompn. at > ∼ 3.0 V vs Li+/Li was identified. The decompn. was able to be avoided by a surface modification of LLZO (e.g., Co-diffused surface layer and/or presence of an interlayer, Li3BO3), and the surface modification was equally important to suppress a reaction during air storage. In a LiCoO2/LLZO interface, it is important to sep. direct contacts between LiCoO2 and pure LLZO.
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  24. 24
    Shannon, R. D.; Taylor, B. E.; English, A. D.; Berzins, T. New Li Solid Electrolytes. Electrochim. Acta 1977, 22, 783– 796,  DOI: 10.1016/0013-4686(77)80035-2
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    24
    New lithium solid electrolytes
    Shannon, R. D.; Taylor, B. E.; English, A. D.; Berzins, T.
    Electrochimica Acta (1977), 22 (7), 783-96CODEN: ELCAAV; ISSN:0013-4686.
    The elec. cond. is reported of Li-based solid electrolytes and discussed in relation to crystal structure and 7Li-NMR line width data. Li4B7O12BrxCl1-x and LiM2P3O12 (M = Zr, Hf) have framework structures whereas the other electrolytes are based on structures with isolated polyhedrons in a network of edge-linked Li polyhedrons. Li0.8Zr1.8Ta0.2P3O12 has the highest room temp. cond. (∼5 × 10-2/Ω/cm). The conductivities of Li3.75Si0.75P0.25O4, Li3.4Si0.7S0.3O4, and Li2.25C0.75B0.25O3 are 10-2/Ω/cm at 300°. These compns. resist attack by molten Li at 200° and some can easily prepd. as dense ceramics.
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  25. 25
    Okumura, T.; Takeuchi, T.; Kobayashi, H. All-solid-state lithium-ion battery using Li2.2C0.8B0.2O3 electrolyte. Solid State Ionics 2016, 288, 248– 252,  DOI: 10.1016/j.ssi.2016.01.045
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    25
    All-solid-state lithium-ion battery using Li2.2C0.8B0.2O3 electrolyte
    Okumura, Toyoki; Takeuchi, Tomonari; Kobayashi, Hironori
    Solid State Ionics (2016), 288 (), 248-252CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    Oxide-based all-solid-state lithium-ion battery is prepd. by a conventional sintering process, thanks to the intrinsic low m.p. of Li2.2C0.8B0.2O3. A well-defined interface between LiCoO2 and Li2.2C0.8B0.2O3 was confirmed without any traces of impurities. Li ion reversibly (de-)intercalated from/into LiCoO2 at initial charge-discharge process when the charge capacity was limited to 120 mAh g- 1. The capacity degrdn. after subsequent cycling was suppressed by further limitation of the charging capacity. However, capacity fade could still be confirmed after 20 cycles albeit the capacity was limited at 60 mAh g- 1. This study suggests large repetitive expansion-contraction of the electrode during cycling as a possible cause of fatigue failure of the electrode/oxide electrolyte interface.
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  26. 26
    Han, F.; Yue, J.; Chen, C.; Zhao, N.; Fan, X.; Ma, Z.; Gao, T.; Wang, F.; Guo, X.; Wang, C. Interphase Engineering enabled All-Ceramic Lithium Battery. Joule 2018, 2, 497– 508,  DOI: 10.1016/j.joule.2018.02.007
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    26
    Interphase Engineering Enabled All-Ceramic Lithium Battery
    Han, Fudong; Yue, Jie; Chen, Cheng; Zhao, Ning; Fan, Xiulin; Ma, Zhaohui; Gao, Tao; Wang, Fei; Guo, Xiangxin; Wang, Chunsheng
    Joule (2018), 2 (3), 497-508CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
    Solid-state batteries (SSBs) can essentially improve battery safety. Garnet-type Li7La3Zr2O12 (LLZO) is considered one of the most promising solid electrolytes for SSBs. However, the performance of LLZO-based SSBs is limited by the large cathode/electrolyte interfacial resistance. High-rate and long-cycling SSBs were achieved only after adding flammable polymer or liq. electrolyte in the cathode at the sacrifice of safety. Here, we show that an all-ceramic cathode/electrolyte with an extremely low interfacial resistance can be realized by thermally soldering LiCoO2 (LCO) and LLZO together with the Li2.3-xC0.7+xB0.3-xO3 solid electrolyte interphase through the reaction between the Li2.3C0.7B0.3O3 solder and the Li2CO3 layers that can be conformally coated on both LLZO and LCO. The all-solid-state Li/LLZO/LCO battery with such an all-ceramic cathode/electrolyte exhibits high cycling stability and high rate performance, constituting a significant step toward the practical applications of SSBs.
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  27. 27
    Okumura, T.; Takeuchi, T.; Kobayashi, H. All-Solid-State Batteries with LiCoO2-Type Electrodes: Realization of an Impurity-Free Interface by Utilizing a Cosinterable Li3.5Ge0.5V0.5O4 Electrolyte. ACS Appl. Energy Mater. 2021, 4, 30– 34,  DOI: 10.1021/acsaem.0c02785
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    27
    All-Solid-State Batteries with LiCoO2-Type Electrodes: Realization of an Impurity-Free Interface by Utilizing a Cosinterable Li3.5Ge0.5V0.5O4 Electrolyte
    Okumura, Toyoki; Takeuchi, Tomonari; Kobayashi, Hironori
    ACS Applied Energy Materials (2021), 4 (1), 30-34CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    An impurity-free interface was achieved in an oxide-based all-solid-state battery (ASSB) after cosintering, which was facilitated by an enhanced thermal stability between the layered rock-salt LiMO2 electrode materials (LiCoO2 or LiNi1/3Mn1/3Co1/3O2 (NMC)) and a lithium superionic conductor (LISICON)-type Li3.5Ge0.5V0.5O4 (LGVO) electrolyte. The ionic cond. of LGVO reached 9.6 x 10-5 S cm-1, which is the highest reported cond. for an LISICON oxide. These characteristics facilitated a good reversible capacity in the NMC electrode in an ASSB fabricated via cosintering. The high interfacial thermal stability between LiMO2 and LISICON is a useful property in the context of oxide-based ASSBs.
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  28. 28
    Akedo, J.; Lebedev, M. Microstructure and Electrical Properties of Lead Zirconate Titanate (Pb(Zr52/Ti48)O3) Thick Films Deposited by Aerosol Deposition Method. Jpn. J. Appl. Phys. 1999, 38, 5397– 5401,  DOI: 10.1143/jjap.38.5397
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    28
    Microstructure and electrical properties of lead zirconate titanate (Pb(Zr52/Ti48)O3) thick films deposited by aerosol deposition method
    Akedo, Jun; Lebedev, Maxim
    Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers (1999), 38 (9B), 5397-5401CODEN: JAPNDE; ISSN:0021-4922. (Japanese Journal of Applied Physics)
    Lead zirconate titanate (PZT) films with a thickness of more than 10 μm were prepd. by the aerosol deposition method and their microstructure and chem. compn. were investigated by transmission electron microscopy (TEM) and energy dispersive X-ray spectra (EDX) anal. A damage layer was obsd. at the interface between PZT and the Si substrate during the deposition. The microstructure of the as-deposited film at room temp. consisted of randomly oriented small crystallites with sizes of less than 40 nm and large crystallites of 100 nm to 300 nm size, which were obsd. in the primary powder. The Pb/Ti/Zr ratio along the film stacking direction and around the grain boundaries was almost the same as that obsd. inside the crystallites and the primary powder with a morphotropic phase boundary compn. of (Pb(Zr0.52Ti0.48)O3). The marked improvement of the elec. properties obsd. in the deposited films after annealing was mainly due to the crystal growth of small crystallites.
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  29. 29
    Fuchita, E.; Tokizaki, E.; Ozawa, E.; Sakka, Y. Formation of Zirconia Films by the Aerosol Gas Deposition Method (By Jetting of Positive Charged Powder). J. Jpn. Soc. Powder Powder Metall. 2011, 58, 463– 472,  DOI: 10.2497/jjspm.58.463
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    Iwasaki, S.; Hamanaka, T.; Yamakawa, T.; West, W. C.; Yamamoto, K.; Motoyama, M.; Hirayama, T.; Iriyama, Y. Preparation of thick-film LiNi1/3Co1/3Mn1/3O2 electrodes by aerosol deposition and its application to all-solid-state batteries. J. Power Sources 2014, 272, 1086– 1090,  DOI: 10.1016/j.jpowsour.2014.09.038
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    30
    Preparation of thick-film LiNi1/3Co1/3Mn1/3O2 electrodes by aerosol deposition and its application to all-solid-state batteries
    Iwasaki, Shinya; Hamanaka, Tadashi; Yamakawa, Tomohiro; West, William C.; Yamamoto, Kazuo; Motoyama, Munekazu; Hirayama, Tsukasa; Iriyama, Yasutoshi
    Journal of Power Sources (2014), 272 (), 1086-1090CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    The authors prepd. thick and dense-cryst. LiNi1/3Co1/3Mn1/3O2 (NMC) composite films at room temp. that can work well as cathodes in all-solid-state battery cells. The thick films were fabricated by aerosol deposition using NMC powder (D50 = 10.61 μm) as a source material. Com.-obtained NMC powder did not form films at all on Si wafer substrates, and cracking of the substrates was obsd. However, a few tens of nanometer coating with amorphous Nb oxide resulted in the deposition of 7 μm-thick cryst. dense composite films. The films were successfully fabricated also on Li+-conductive glass-ceramic sheets with 150 μm in thickness, and all-solid-state batteries were fabricated. The solid-state battery provided a cathode-basis discharge capacity of 152 mA h g-1 (3.0-4.2 V, 0.025 C, 333 K) and repeated charge-discharge cycles for 20 cycles.
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  31. 31
    Kato, T.; Iwasaki, S.; Ishii, Y.; Motoyama, M.; West, W. C.; Yamamoto, Y.; Iriyama, Y. Preparation of thick-film electrode-solid electrolyte composites on Li7La3Zr2O12 and their electrochemical properties. J. Power Sources 2016, 303, 65– 72,  DOI: 10.1016/j.jpowsour.2015.10.101
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    31
    Preparation of thick-film electrode-solid electrolyte composites on Li7La3Zr2O12 and their electrochemical properties
    Kato, Takehisa; Iwasaki, Shinya; Ishii, Yosuke; Motoyama, Munekazu; West, William C.; Yamamoto, Yuta; Iriyama, Yasutoshi
    Journal of Power Sources (2016), 303 (), 65-72CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    The authors prepd. up to 20 μm-thick LiNi1/3Co1/3Mn1/3O2 (NMC)-Li+ conductive glass-ceramic solid electrolyte (LATP: σLi+ ∼ 10-3 S cm-2 at 298 K) composite cathode films on Li7La3Zr2O12 (LLZ) substrates by aerosol deposition (AD) and studied their electrochem. properties as all-solid-state batteries. The resultant NMC/LATP interface in the composite film had a thin mutual diffusion layer (∼5 nm) and a film had a porosity of ∼0.15% in vol. The composite films were well adhered to the LLZ substrates even though the films were prepd. at room temp. All-solid-state batteries, consisting of Li/LLZ/NMC-LATP composite film (20 μm), repeated charge-discharge reactions for 90 cycles at 100° at a 1/10 C rate (capacity retention: 99.97%/cycle). Rate capability of this battery was improved by modifying both the LATP and electron conductive source amt. in the composite film, and a battery with 16 μm-thick composite electrode delivered 60 mA h g-1 at 1 mA cm-2.
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  32. 32
    Motoyama, M.; Tanaka, Y.; Yamamoto, T.; Tsuchimine, N.; Kobayashi, S.; Iriyama, Y. The Active Interface of Ta-Doped Li7La3Zr2O12 for Li Plating/Stripping Revealed by Acid Aqueous Etching. ACS Appl. Energy Mater. 2019, 2, 6720– 6731,  DOI: 10.1021/acsaem.9b01193
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    32
    Active interface of Ta-doped Li7La3Zr2O12 for Li plating/stripping revealed by acid aqueous etching
    Motoyama, Munekazu; Tanaka, Yuki; Yamamoto, Takayuki; Tsuchimine, Nobuo; Kobayashi, Susumu; Iriyama, Yasutoshi
    ACS Applied Energy Materials (2019), 2 (9), 6720-6731CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    All-solid-state lithium batteries incorporating oxide-based solid electrolytes have attracted much attention as a promising battery system for enabling highly reversible Li metal anodes. However, the cycling stability of Li plating/stripping reactions at higher charging/discharging rates on garnet-type solid-state electrolytes must be improved to realize a practical Li metal anode for solid-state batteries. Here, we report that a short acid etching procedure performed in ambient air significantly activates the Ta-doped Li7La3Zr2O12 (LLZT) surface compared to polishing under inert gas atm. such as dry Ar. It has been believed that Li7La3Zr2O12 (LLZ) and related doped LLZ solid electrolyte surfaces need to be mech. polished in dry Ar before the cell fabrication to remove Li2CO3 and LiOH that are present on the surface. However, a commonly used mech. polishing procedure is found to form a thin electrochem. inactive layer on the LLZT surface, whereas a short acid etching procedure (e.g., HCl) removes the inactive layer, and the acid-etched LLZT exhibits excellent cycling stability.
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    Motoyama, M.; Iwasaki, H.; Sakakura, M.; Yamamoto, T.; Iriyama, Y. Synthesis of LiCoO2 particles with tunable sizes by a urea-based-homogeneous-precipitation method. Int. J. Mater. Res. 2020, 111, 347– 355,  DOI: 10.1515/ijmr-2020-1110411
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    Synthesis of LiCoO2 particles with tunable sizes by a urea-based-homogeneous-precipitation method
    Motoyama, Munekazu; Iwasaki, Hiroki; Sakakura, Miyuki; Yamamoto, Takayuki; Iriyama, Yasutoshi
    International Journal of Materials Research (2020), 111 (4), 347-355CODEN: IJMRFV; ISSN:2195-8556. (Carl Hanser Verlag)
    This paper reports the synthesis of monodisperse spherical LiCoO2 particles in a wide range of av. diam. using a urea-based-uniform-pptn. method. The av. diam. of LiCoO2 particles can be varied from 2 to 14 μm with a uniform size distribution. The effective approach to maintain the size uniformity while changing the av. size of LiCoO2 particles is to keep the ratio of [CO(NH2)2] to [CoSO4] at 8 even when the CoSO4 and urea concns. are changed.
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    Abrahams, I.; Bruce, P. G. Defect Clustering in the Superionic Conductor Lithium Germanium Vanadate. Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater. 1991, 47, 696– 701,  DOI: 10.1107/s0108768191004548
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    Kuwano, J.; West, A. R. New Li+ ion conductors in the system, Li4GeO4-Li3VO4. Mater. Res. Bull. 1980, 15, 1661– 1667,  DOI: 10.1016/0025-5408(80)90249-4
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    New lithium(1+) ion conductors in the system, lithium germanate-lithium vanadate (Li4GeO4-Li3VO4)
    Kuwano, J.; West, A. R.
    Materials Research Bulletin (1980), 15 (11), 1661-7CODEN: MRBUAC; ISSN:0025-5408.
    New Li+ ion conducting solid electrolytes were found in the system Li4GeO4-Li3VO4. Of the compns. studied, Li3.6Ge0.6V0.4O4 has the highest cond. with σ ∼4 × 10-5 Ω-1 cm-1 at 18° rising to ∼10-2 at 190°. The activation energy is ∼0.44 eV. These cond. values are among the highest found for Li+ ion conductors; the room temp. value is much higher in LISICON, Li3.5Zn0.25GeO4, or in Li3.4Si0.4P0.6O4 and is comparable to that in LiI/Al2O3 mixts. These solid electrolytes are easy to synthesize, stable and insensitive to atm. attack. They are solid solns. based on γII Li3VO4, a γ tetrahedral structure; high cond. is due to the interstitial Li+ ions which are created during solid soln. formation.
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    Huang, M.; Xu, W.; Shen, Y.; Lin, Y.-H.; Nan, C.-W. X-ray absorption near-edge spectroscopy study on Ge-doped Li7La3Zr2O12: enhanced ionic conductivity and defect chemistry. Electrochim. Acta 2014, 115, 581– 586,  DOI: 10.1016/j.electacta.2013.11.020
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    X-ray absorption near-edge spectroscopy study on Ge-doped Li7La3Zr2O12: enhanced ionic conductivity and defect chemistry
    Huang, Mian; Xu, Wei; Shen, Yang; Lin, Yuan-Hua; Nan, Ce-Wen
    Electrochimica Acta (2014), 115 (), 581-586CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
    Ge-doped Li7La3Zr2O12 (LLZ) was prepd. via the conventional solid-state reaction. The authors' results showed that doping Ge of <1% could stabilize the cubic phase of garnet-type LLZ and also increase its ionic cond. up to 8.28 × 10-4 S/cm at room temp. When the content of Ge dopant is higher, GeO2 impurity phase would appear and there coexists cubic and tetragonal mixed structures, lowering the cond. By combining x-ray absorption near-edge spectroscopy and full multiple-scattering theory, Ge more likely enters into the Li and La crystallog. sites instead of the Zr site, which provides understanding of the micro-structural modulation by Ge dopants and the subsequent enhancement in the ionic cond.
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    Watanabe, M.; Williams, D. B. The quantitative analysis of thin specimens: a review of progress from the Cliff-Lorimer to the new zeta-factor methods. J. Microsc. 2006, 221, 89– 109,  DOI: 10.1111/j.1365-2818.2006.01549.x
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    The quantitative analysis of thin specimens: a review of progress from the Cliff-Lorimer to the new zeta-factor methods
    Watanabe M; Williams D B
    Journal of microscopy (2006), 221 (Pt 2), 89-109 ISSN:0022-2720.
    A new quantitative thin-film X-ray analysis procedure termed the zeta-factor method is proposed. This new zeta-factor method overcomes the two major limitations of the conventional Cliff-Lorimer method for quantification: (1) use of pure-element rather than multielement, thin-specimen standards and (2) built-in X-ray absorption correction with simultaneous thickness determination. Combined with a universal, standard, thin specimen, a series of zeta-factors covering a significant fraction of the periodic table can be estimated. This zeta-factor estimation can also provide information about both the detector efficiency and the microscope-detector interface system. Light-element analysis can also be performed more easily because of the built-in absorption correction. Additionally, the new zeta-factor method has several advantages over the Cliff-Lorimer ratio method because information on the specimen thickness at the individual analysis points is produced simultaneously with compositions, thus permitting concurrent determination of the spatial resolution and the analytical sensitivity. In this work, details of the zeta-factor method and how it improves on the Cliff-Lorimer approach are demonstrated, along with several applications.
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    Rangasamy, E.; Wolfenstine, J.; Sakamoto, J. The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12. Solid State Ionics 2012, 206, 28– 32,  DOI: 10.1016/j.ssi.2011.10.022
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    The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12
    Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey
    Solid State Ionics (2012), 206 (), 28-32CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    The effect of Al and Li concn. on the formation of cubic garnet of nominal compn. Li7La3Zr2O12 was investigated. It was detd. that at least 0.204 mol of Al is required to stabilize the cubic phase. It was obsd. for the cubic phase (stabilized by the addn. of Al) that as Li content was increased from 6 to 7 mol it transformed to a tetragonal phase. Addnl., powders of cubic Li6.24La3Zr2Al0.24O11.98 were hot-pressed at 1000°C and 40 MPa. The hot-pressed material had a relative d. of 98%. The room temp. total ionic cond. of the hot-pressed material was 4.0 × 10-4 S/cm and the electronic cond. was 2 × 10-8 S/cm.
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    Inaba, M.; Iriyama, Y.; Ogumi, Z.; Todzuka, Y.; Tasaka, A. Raman study of layered rock-salt LiCoO2 and its electrochemical lithium deintercalation. J. Raman Spectrosc. 1997, 28, 613– 617,  DOI: 10.1002/(sici)1097-4555(199708)28:8<613::aid-jrs138>3.0.co;2-t
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    Raman study of layered rock-salt LiCoO2 and its electrochemical lithium deintercalation
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This article is cited by 6 publications.

  1. Myeong Jun Joo, Minseong Kim, Sujong Chae, Minseong Ko, Yong Joon Park. Additive-Derived Surface Modification of Cathodes in All-Solid-State Batteries: The Effect of Lithium Difluorophosphate- and Lithium Difluoro(oxalato)borate-Derived Coating Layers. ACS Applied Materials & Interfaces 2023, 15 (51) , 59389-59402. https://doi.org/10.1021/acsami.3c12858
  2. Yuzhou Bai, Wenqin Ma, Wujie Dong, Yingkang Wu, Xue Wang, Fuqiang Huang. In-Situ-Polymerized 1,3-Dioxolane Solid-State Electrolyte with Space-Confined Plasticizers for High-Voltage and Robust Li/LiCoO2 Batteries. ACS Applied Materials & Interfaces 2023, 15 (22) , 26834-26842. https://doi.org/10.1021/acsami.3c04234
  3. Chunxiang Xian, Qiyue Wang, Yang Xia, Feng Cao, Shenghui Shen, Yongqi Zhang, Minghua Chen, Yu Zhong, Jun Zhang, Xinping He, Xinhui Xia, Wenkui Zhang, Jiangping Tu. Solid‐State Electrolytes in Lithium–Sulfur Batteries: Latest Progresses and Prospects. Small 2023, 19 (24) https://doi.org/10.1002/smll.202208164
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  5. Miyuki Sakakura, Yasutoshi Iriyama. Development of oxide-based all-solid-state batteries using aerosol deposition. Journal of Asian Ceramic Societies 2023, 11 (1) , 1-10. https://doi.org/10.1080/21870764.2022.2163080
  6. Yuan Yang, Nai-Fang Hu, Yong-Cheng Jin, Jun Ma, Guang-Lei Cui, , . Research advance of lithium-rich cathode materials in all-solid-state lithium batteries. Acta Physica Sinica 2023, 72 (11) , 118801. https://doi.org/10.7498/aps.72.20230258
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  • Abstract

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    Figure 1

    Figure 1. (a) FE-SEM image of LGVO particles for AD. The inset shows a magnified SEM image of a particle. (b) XRD patterns of the LGVO particles (black) and reported reference data (red). (c) Nyquist plots of a Au/LGVO/Au symmetrical cell at 25 °C. The inset displays a magnified image of a higher frequency region. The numbers in these plots indicate data points measured at 10n Hz.

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    Figure 2

    Figure 2. (a–d) Surface and (e–f) cross-sectional FE-SEM images of (a,e) ML-AP, (b,f) ML-700, (c,g) ML-900, and (d,h) ML-1050. The insets in (a–d) display optical images of the MLs.

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    Figure 3

    Figure 3. Cross-sectional TEM images of (a) ML-AP and (b) ML-900. EDX measurements around the LLZ/LGVO interface of (c) ML-AP and (d) ML-900. The EDX signals were from O Kα, V Kα, Ge Kα, Zr Lα, La Lα, and Ta Lα. The tables in Figure 2c,d summarize the mass %, σ, and at. % evaluated in the LLZ region in the red frame.

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    Figure 4

    Figure 4. XRD patterns of ML-AP (blue), ML-700 (orange), ML-900 (red), and ML-1050 (purple). Additionally, XRD patterns of the LLZ substrate after polishing with SiC sandpaper (black) and LGVO powder (green) are shown as references. Diffraction peaks marked by * are assigned to La2Zr2O7.

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    Figure 5

    Figure 5. (a) Nyquist plots of ML-AP (blue), ML-700 (orange), ML-900 (red), ML-1050 (purple), and the LLZ substrate (green) measured at 25 °C. Magnified Nyquist plots in a higher frequency region of the (b) LLZ substrate, (c) ML-AP, (d) ML-700, (e) ML-900, and (f) ML-1050. The numbers in each plot indicate data points measured at 10n Hz. The thickness of each substrate is used to normalize all the resistances.

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    Figure 6

    Figure 6. Variation in the discharge capacity and total interfacial resistance (Rint) of an Ox-SSB (Li/ML-900/LCO) with the charge–discharge reactions measured at 60 and 25 °C. The charge current density was fixed at 2.9 μA cm–2 in the 1st–36th cycles and 5 μA cm–2 in the 37th–137th cycles, and the discharge current density was varied from 2.9 to 286 μA cm–2 during the 1st–36th cycles and 5–500 μA cm–2 during the 37th–91st cycles and fixed at 50 μA cm–2 during the 92nd–137th cycles. The Rint values were measured at 4.0 V after charge–discharge reactions in the 5th, 25th, 36th, 86th, and 136th cycles.

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    Figure 7

    Figure 7. Charge–discharge curves of an Ox-SSB (Li/ML-900/LCO) with 700 °C annealing in the (a) 1st, 6th, 11th, 16th, and 21st cycles and (b) 26th, 31st, and 36th cycles, where the charge current density was fixed at 2.9 μA cm–2 and discharge current density was 2.9 μA cm–2 (1st and 26th), 29 μA cm–2 (6th and 31st), 57 μA cm–2 (11th and 36th), 143 μA cm–2 (16th), and 286 μA cm–2 (21st). Nyquist plots at 3.0 and 4.0 V after the (c) 5th cycle and (d) 25th cycle, where Rint denotes the sum of the interfacial resistances at Li/LLZ and LGVO/LCO. Data were measured at 60 °C in (a,c) and at 25 °C in (b,d). The numbers in (c,d) indicate data points measured at 10n Hz.

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    Figure 8

    Figure 8. (a) Charge–discharge curves at 60 °C of an Ox-SSB (Li/LLZ/LCO) with 700 °C annealing in the 1st–5th cycles under a fixed charge–discharge current density of 5 μA cm–2. (b) Nyquist plots at 60 °C of a nonannealed Ox-SSB (Li/LLZ) measured at 3.0 V (blue) and 4.0 V (red) after the 5th cycle. (c) Charge–discharge curves at 25 °C of a nonannealed Ox-SSB (Li/LLZ/LCO) in the 6th–10th cycles under a fixed charge–discharge current density of 5 μA cm–2. (d) Nyquist plots at 25 °C of an Ox-SSB (Li/LLZ/LCO) without annealing measured at 3.0 V (blue) and 4.0 V (red) after the 10th cycle. (e) Charge–discharge curves at 60 °C of an Ox-SSB (Li/LLZ/LCO) without annealing in the 1st–5th cycles under a fixed charge–discharge current density of 5 μA cm–2. (f) Nyquist plots at 60 °C of an Ox-SSB (Li/LLZ) without annealing measured at 3.0 V (blue) and 4.0 V (red) after the 5th cycle. (g) Schematic image of the interface properties with LGVO coating and annealing effects.

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  • References

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    7. 7
      Kato, T.; Yoshida, R.; Yamamoto, K.; Hirayama, T.; Motoyama, M.; West, W. C.; Iriyama, Y. Effects of Sintering Temperature on Interfacial Structure and Interfacial Resistance for All-Solid-State Rechargeable Lithium Batteries. J. Power Sources 2016, 325, 584– 590,  DOI: 10.1016/j.jpowsour.2016.06.068
      7
      Effects of sintering temperature on interfacial structure and interfacial resistance for all-solid-state rechargeable lithium batteries
      Kato, Takehisa; Yoshida, Ryuji; Yamamoto, Kazuo; Hirayama, Tsukasa; Motoyama, Munekazu; West, William C.; Iriyama, Yasutoshi
      Journal of Power Sources (2016), 325 (), 584-590CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Sintering processes yield a mutual diffusion region at the electrode/solid electrolyte interface, which is considered as a crucial problem for developing large-sized all-solid-state rechargeable lithium batteries with high power d. This work focuses on the interface between LiNi1/3Co1/3Mn1/3O2 (NMC) and NASICON-structured Li+ conductive glass ceramics solid electrolyte (Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2: LATP sheet (AG-01)), and investigates the effects of sintering temp. on interfacial structure and interfacial resistance at the NMC/LATP sheet. Thin films of NMC were fabricated on the LATP sheets at 700 °C or 900 °C as a model system. We found that the thickness of the mutual diffusion region was almost the same, ca. 30 nm, in these two samples, but the NMC film prepd. at 900 °C had three orders of magnitude larger interfacial resistance than the NMC film prepd. at 700 °C. Around the interface between the NMC film prepd. at 900 °C and the LATP sheet, Co in the NMC accumulates as a reduced valence and lithium-free impurity cryst. phase will be also formed. These two problems must contribute to drastic increasing of interfacial resistance. Formation of de-lithiated NMC around the interface and its thermal instability at higher temp. may be considerable reason to induce these problems.
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    8. 8
      Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781,  DOI: 10.1002/anie.200701144
      8
      Fast lithium ion conduction in garnet-type Li7La3Zr2O12
      Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
      Angewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
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    9. 9
      Zhu, Y.; He, X.; Mo, Y. First Principles Study on Electrochemical and Chemical Stability of Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries. J. Mater. Chem. A 2016, 4, 3253– 3266,  DOI: 10.1039/c5ta08574h
      9
      First principles study on electrochemical and chemical stability of solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries
      Zhu, Yizhou; He, Xingfeng; Mo, Yifei
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (9), 3253-3266CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technol. with high energy d. and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries. In this study, we performed first principles calcns. to evaluate the thermodn. of the interfaces between solid electrolyte and electrode materials and to identify the chem. and electrochem. stabilities of these interfaces. Our computation results reveal that many solid electrolyte-electrode interfaces have limited chem. and electrochem. stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochem. performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chem. and electrochem. stability of heterogeneous solid interfaces. The enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.
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    10. 10
      Xu, L.; Li, J.; Deng, W.; Shuai, H.; Li, S.; Xu, Z.; Li, J.; Hou, H.; Peng, H.; Zou, G.; Ji, X. Garnet Solid Electrolyte for Advanced All-Solid-State Li Batteries. Adv. Energy Mater. 2021, 11, 2000648,  DOI: 10.1002/aenm.202000648
      10
      Garnet Solid Electrolyte for Advanced All-Solid-State Li Batteries
      Xu, Laiqiang; Li, Jiayang; Deng, Wentao; Shuai, Honglei; Li, Shuo; Xu, Zhifeng; Li, Jinhui; Hou, Hongshuai; Peng, Hongjian; Zou, Guoqiang; Ji, Xiaobo
      Advanced Energy Materials (2021), 11 (2), 2000648CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      A review. High-capacity cathodes and anodes in energy storage area are required for delivering high energy d. due to the ever-increasing demands in the applications of elec. vehicles and power grids, which suffer from significant safety concerns and poor cycling stability at the current stage. All-solid-state lithium batteries (ASSLBs) have been considered to be particularly promising within the new generation of energy storage, owing to the superiority of safety, wide potential window, and long cycling life. As the key component in ASSLBs, individual solid electrolytes that can meet practical application stds. are very rare due to poor performance. To the present day, numerous research efforts have been expended to find applicable solid-state electrolytes and tremendous progress has been achieved, esp. for garnet-type solid electrolytes. Nevertheless, the garnet-type solid electrolyte is still facing some crucial dilemmas. Hence, the issues of garnet electrolytes' ionic cond., the interfaces between electrodes and garnet solid electrolytes, and application of theor. calcn. on garnet electrolytes are focuses in this review. Furthermore, prospective developments and alternative approaches to the issues are presented, with an aim to improve understanding of garnet electrolytes and promote their practical applications in solid-state batteries.
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    11. 11
      Indu, M. S.; Alexander, G. V.; Sreejith, O. V.; Abraham, S. E.; Murugan, R. Lithium Garnet-Cathode Interfacial Chemistry: Inclusive Insights and Outlook Toward Practical Solid-State Lithium Metal Batteries. Mater. Today Energy 2021, 21, 100804,  DOI: 10.1016/j.mtener.2021.100804
      11
      Lithium garnet-cathode interfacial chemistry: inclusive insights and outlook toward practical solid-state lithium metal batteries
      Indu, M. S.; Alexander, G. V.; Sreejith, O. V.; Abraham, S. E.; Murugan, R.
      Materials Today Energy (2021), 21 (), 100804CODEN: MTEACH; ISSN:2468-6069. (Elsevier Ltd.)
      A review. Solid-state lithium batteries have attained tremendous interest over the past few years as a possible alternative to the present lithium-ion battery because of their improved safety and higher energy d. The key component of a solid-state battery is the solid electrolyte. Among various inorg. solid electrolytes ranging from sulfides to oxides, garnet structured oxide solid electrolytes emerged as a promising candidate due to their high lithium-ion cond. as well as excellent stability with lithium metal and potential electrodes. However, garnet solid electrolyte-based solid-state battery's practical realization is limited by various challenges at the electrode-garnet interface, particularly the significant interface resistance and poor crit. c.d. Although significant developments have been made toward accomplishing an effective anode-garnet interface, the cathode-garnet interface is still challenging, and in-depth anal. with more emphasis on cathode-garnet interfacial chem. is lacking. From this point of view, this review discusses the fundamentals of the cathode-garnet interface in detail and carefully summarizes the issues with various cathode materials and possible strategies to overcome them for the realization of 'anode free' high energy d. lithium metal batteries.
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    12. 12
      Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO2 Electrode and Li2S–P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956,  DOI: 10.1021/cm901819c
      12
      Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron Microscopy
      Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro
      Chemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
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    13. 13
      Zhang, W.; Richter, F. H.; Culver, S. P.; Leichtweiss, T.; Lozano, J. G.; Dietrich, C.; Bruce, P. G.; Zeier, W. G.; Janek, J. Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2018, 10, 22226– 22236,  DOI: 10.1021/acsami.8b05132
      13
      Degradation mechanisms at the Li10GeP2S12/LiCoO2 cathode interface in an all-solid-state lithium-ion battery
      Zhang, Wenbo; Richter, Felix H.; Culver, Sean P.; Leichtweiss, Thomas; Lozano, Juan G.; Dietrich, Christian; Bruce, Peter G.; Zeier, Wolfgang G.; Janek, Juergen
      ACS Applied Materials & Interfaces (2018), 10 (26), 22226-22236CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degrdn. mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy d., the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems assocd. with Li-metal anodes. Capacity fading and increased impedances are obsd. during long-term cycling. Postmortem anal. with scanning transmission electron microscopy, electron energy loss spectroscopy, x-ray diffraction, and XPS show that electrochem. driven mech. failure and degrdn. at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochem. more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.
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    14. 14
      Ohta, N.; Takada, K.; Zhang, L.; Ma, R.; Osada, M.; Sasaki, T. Enhancement of the High-Rate Capability of Solid-State Lithium Batteries by Nanoscale Interfacial Modification. Adv. Mater. 2006, 18, 2226– 2229,  DOI: 10.1002/adma.200502604
      14
      Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification
      Ohta, Narumi; Takada, Kazunori; Zhang, Lianqi; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
      Advanced Materials (Weinheim, Germany) (2006), 18 (17), 2226-2229CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The high-rate capability of solid-state rechargeable Li batteries with sulfide electrolytes improved when the LiCoO2 particles are spray-coated with Li4Ti5O12. The power densities of the solid-state battery with the coated LiCoO2 are comparable to those of com. Li-ion batteries.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVSlurvK&md5=bf9357ea331c80ee13711c2dc2240b34
    15. 15
      Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255,  DOI: 10.1021/cm5016959
      15
      Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery
      Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, Yoshitaka
      Chemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
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    16. 16
      Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693,  DOI: 10.1021/acsami.5b07517
      16
      Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
      Zhu, Yizhou; He, Xingfeng; Mo, Yifei
      ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
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    17. 17
      Fu, J. Fast Li+ Ion Conduction in Li2O-Al2O3-TiO2-SiO2-P2O2 Glass-Ceramics. J. Am. Ceram. Soc. 1997, 80, 1901– 1903,  DOI: 10.1111/j.1151-2916.1997.tb03070.x
      17
      Fast Li+ ion conduction in Li2O-Al2O3-TiO2-SiO2-P2O5 glass-ceramics
      Fu, Jie
      Journal of the American Ceramic Society (1997), 80 (7), 1901-1903CODEN: JACTAW; ISSN:0002-7820. (American Ceramic Society)
      Fast lithium ion conducting glass-ceramics have been successfully prepd. from the pseudobinary system 2[Li1+xTi2SixP3-xO12]-AlPO4. The major phase present in the glass-ceramics was LiTi2P3O12 in which Ti4+ ions and P5+ ions were partially replaced by Al3+ ions and Si4+ ions, resp. Increasing x resulted in a considerable enhancement in cond. and, in a wide compn. range, extremely high cond. over 10-3 S/cm was obtained at room temp.
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    18. 18
      Amiki, Y.; Sagane, F.; Yamamoto, K.; Hirayama, T.; Sudoh, M.; Motoyama, M.; Iriyama, Y. Electrochemical Properties of an All-Solid-State Lithium-Ion Battery with an In-Situ Formed electrode Material Grown from a Lithium Conductive Glass Ceramics Sheet. J. Power Sources 2013, 241, 583– 588,  DOI: 10.1016/j.jpowsour.2013.05.006
      18
      Electrochemical properties of an all-solid-state lithium-ion battery with an in-situ formed electrode material grown from a lithium conductive glass ceramics sheet
      Amiki, Yuichi; Sagane, Fumihiro; Yamamoto, Kazuo; Hirayama, Tsukasa; Sudoh, Masao; Motoyama, Munekazu; Iriyama, Yasutoshi
      Journal of Power Sources (2013), 241 (), 583-588CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      A lithium insertion reaction in a Li+ conductive glass ceramics solid electrolyte (lithium aluminum titanium phosphate: LATP) sheet produces an in-situ formed electrode active material, which operates at 2.35 V vs. Li/Li+ in the vicinity of the LATP-sheet/current-collector interface. Electron energy loss spectroscopy clarifies that titanium in the LATP sheet in the vicinity of the current collector/LATP-sheet interface is preferentially reduced by this lithium insertion reaction. Charge transfer resistance between the in-situ-formed-electrode and the LATP-sheet is less than 100 Ω cm2, which is smaller than that of the common LiPON/LiCoO2 interface. A thin film of LiCoO2 is deposited on one side of the LATP-sheet as a Li+ source for developing the in-situ formed electrode material. Eventually, a Pt/LATP-sheet/LiCoO2/Au multilayer is fabricated. The multilayer structure successfully works as an all-solid-state lithium-ion battery operating at 1.5 V. A redox peak of the battery is obsd. even at 100 mV s-1 in the potential sweep curve. Addnl., charge-discharge reactions are repeated stably even after 25 cycles.
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    19. 19
      Cheng, D.; Wynn, T. A.; Wang, X.; Wang, S.; Zhang, M.; Shimizu, R.; Bai, S.; Nguyen, H.; Fang, C.; Kim, M.-C.; Li, W.; Lu, B.; Kim, S.-J.; Meng, Y. S. Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy. Joule 2020, 4, 2484– 2500,  DOI: 10.1016/j.joule.2020.08.013
      19
      Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy
      Cheng, Diyi; Wynn, Thomas A.; Wang, Xuefeng; Wang, Shen; Zhang, Minghao; Shimizu, Ryosuke; Bai, Shuang; Nguyen, Han; Fang, Chengcheng; Kim, Min-cheol; Li, Weikang; Lu, Bingyu; Kim, Suk Jun; Meng, Ying Shirley
      Joule (2020), 4 (11), 2484-2500CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      The solid electrolyte interphase (SEI) is regarded as the most complex but the least understood constituent in secondary batteries using liq. and solid electrolytes. The dearth of such knowledge in all-solid-state battery (ASSB) has hindered a complete understanding of how certain solid-state electrolytes, such as LiPON, manifest exemplary stability against lithium metal. By employing cryogenic electron microscopy (cryo-EM), the interphase between lithium metal and LiPON is successfully preserved and probed, revealing a multilayer-mosaic SEI structure with concn. gradients of nitrogen and phosphorus, materializing as crystallites within an amorphous matrix. This unique SEI nanostructure is less than 80 nm and is stable and free of any org. lithium-contg. species or lithium fluoride components, in contrast to SEIs often found in state-of-the-art org. liq. electrolytes. Our findings reveal insights on the nanostructures and chem. of such SEIs as a key component in lithium metal batteries to stabilize lithium metal anode.
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    20. 20
      West, W. C.; Whitacre, J. F.; Lim, J. R. Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films. J. Power Sources 2004, 126, 134– 138,  DOI: 10.1016/j.jpowsour.2003.08.030
      20
      Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films
      West, W. C.; Whitacre, J. F.; Lim, J. R.
      Journal of Power Sources (2004), 126 (1-2), 134-138CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)
      Sputter deposition of LiPON films directly onto high Li+ cond. solid electrolyte plates was studied as a means to minimize the reactivity of the plates to metallic Li. The LiPON films effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal. The cond. of the passivated solid electrolyte plates is 1.0 × 10-4 S cm-1, with Arrhenius activation energy of 0.36 eV and an electrochem. stability window of at least 0-5.0 V vs. Li/Li+. The passivated solid electrolyte was capable of supporting electrochem. plating and stripping of Li metal, as demonstrated by EIS and CV measurements. These high chem. stability, high Li+ cond. solid electrolyte plates will be useful for solid-state batteries employing Li anodes.
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    21. 21
      Sagane, F.; Ikeda, K.; Okita, K.; Sano, H.; Sakaebe, H.; Iriyama, Y. Effects of Current Densities on the Lithium Plating Morphology at a Lithium Phosphorus Oxynitride Glass Electrolyte/Copper Thin Film Interface. J. Power Sources 2013, 233, 34– 42,  DOI: 10.1016/j.jpowsour.2013.01.051
      21
      Effects of current densities on the lithium plating morphology at a lithium phosphorus oxynitride glass electrolyte/copper thin film interface
      Sagane, Fumihiro; Ikeda, Ken-ichi; Okita, Kengo; Sano, Hikaru; Sakaebe, Hikari; Iriyama, Yasutoshi
      Journal of Power Sources (2013), 233 (), 34-42CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Li metal is electrochem.-grown at the Li P oxynitride glass electrolyte (LiPON)/Cu thin film interface. The plated Li morphol. depends on the current densities and larger current densities bring about smaller-sized pptn. of Li with larger coverage ratio by the ppts. Both SEM and in-situ optical microscopy observations reveal that the Li tends to grow at the Li pre-plated place. Large potential drop was obsd. at the initial Li plating process, suggesting that the nucleation process requires large activation energy at the initial Li plating process at the LiPON/Cu interface. The resultant morphol.-controlled in-situ prepd. Li provides stable and low-resistive Li/LiPON interface compared with the vacuum-evapd. Li thin film.
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    22. 22
      Ohta, S.; Komagata, S.; Seki, J.; Saeki, T.; Morishita, S.; Asaoka, T. All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing. J. Power Sources 2013, 238, 53– 56,  DOI: 10.1016/j.jpowsour.2013.02.073
      22
      All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing
      Ohta, Shingo; Komagata, Shogo; Seki, Juntaro; Saeki, Tohru; Morishita, Shinya; Asaoka, Takahiko
      Journal of Power Sources (2013), 238 (), 53-56CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      An all-solid-state lithium ion battery was constructed with a screen-printing process using Nb doped Li7La3Zr2O12 (LLZONb) as the solid electrolyte and Li3BO3 (LBO) as a solid electrolyte within the cathode layer. LBO is a lithium ion conductor that is chem. stable with the LiCoO2 (LCO) active cathode material and LLZONb. Sufficient interface contact between the cathode layer and the LLZONb solid electrolyte can be easily achieved with sintering LBO into the cathode layer by an annealing process. The resultant battery exhibited good electrochem. performance and a lower interfacial resistance comparable with that of lithium ion batteries with liq. org. electrolytes.
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    23. 23
      Park, K.; Yu, B. C.; Jung, J. W.; Li, Y.; Zhou, W.; Gao, H.; Son, S.; Goodenough, J. B. Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO2 and Garnet-Li7La3Zr2O12. Chem. Mater. 2016, 28, 8051– 8059,  DOI: 10.1021/acs.chemmater.6b03870
      23
      Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO2 and Garnet-Li7La3Zr2O12
      Park, Kyusung; Yu, Byeong-Chul; Jung, Ji-Won; Li, Yutao; Zhou, Weidong; Gao, Hongcai; Son, Samick; Goodenough, John B.
      Chemistry of Materials (2016), 28 (21), 8051-8059CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Garnet-structured solid electrolytes have been extensively studied for a solid-state lithium rechargeable battery. Previous works have been mostly focused on the materials' development and basic electrochem. properties but not the cathode/electrolyte interface. Understanding the cathode interface is crit. to enhance chem. stability and electrochem. performance of a solid-state battery cell. In this work, we studied thoroughly the cathode/electrolyte interface between LiCoO2 and Li7La3Zr2O12 (LLZO). It was found that the high-temp. process to fuse LiCoO2 and LLZO induced cross-diffusion of elements and formation of the tetragonal LLZO phase at the interface. These degrdns. affected electrochem. performance, esp. the initial Coulombic efficiency and cycle life. In a clean cathode interface without the thermal process, an irreversible electrochem. decompn. at > ∼ 3.0 V vs Li+/Li was identified. The decompn. was able to be avoided by a surface modification of LLZO (e.g., Co-diffused surface layer and/or presence of an interlayer, Li3BO3), and the surface modification was equally important to suppress a reaction during air storage. In a LiCoO2/LLZO interface, it is important to sep. direct contacts between LiCoO2 and pure LLZO.
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    24. 24
      Shannon, R. D.; Taylor, B. E.; English, A. D.; Berzins, T. New Li Solid Electrolytes. Electrochim. Acta 1977, 22, 783– 796,  DOI: 10.1016/0013-4686(77)80035-2
      24
      New lithium solid electrolytes
      Shannon, R. D.; Taylor, B. E.; English, A. D.; Berzins, T.
      Electrochimica Acta (1977), 22 (7), 783-96CODEN: ELCAAV; ISSN:0013-4686.
      The elec. cond. is reported of Li-based solid electrolytes and discussed in relation to crystal structure and 7Li-NMR line width data. Li4B7O12BrxCl1-x and LiM2P3O12 (M = Zr, Hf) have framework structures whereas the other electrolytes are based on structures with isolated polyhedrons in a network of edge-linked Li polyhedrons. Li0.8Zr1.8Ta0.2P3O12 has the highest room temp. cond. (∼5 × 10-2/Ω/cm). The conductivities of Li3.75Si0.75P0.25O4, Li3.4Si0.7S0.3O4, and Li2.25C0.75B0.25O3 are 10-2/Ω/cm at 300°. These compns. resist attack by molten Li at 200° and some can easily prepd. as dense ceramics.
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    25. 25
      Okumura, T.; Takeuchi, T.; Kobayashi, H. All-solid-state lithium-ion battery using Li2.2C0.8B0.2O3 electrolyte. Solid State Ionics 2016, 288, 248– 252,  DOI: 10.1016/j.ssi.2016.01.045
      25
      All-solid-state lithium-ion battery using Li2.2C0.8B0.2O3 electrolyte
      Okumura, Toyoki; Takeuchi, Tomonari; Kobayashi, Hironori
      Solid State Ionics (2016), 288 (), 248-252CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      Oxide-based all-solid-state lithium-ion battery is prepd. by a conventional sintering process, thanks to the intrinsic low m.p. of Li2.2C0.8B0.2O3. A well-defined interface between LiCoO2 and Li2.2C0.8B0.2O3 was confirmed without any traces of impurities. Li ion reversibly (de-)intercalated from/into LiCoO2 at initial charge-discharge process when the charge capacity was limited to 120 mAh g- 1. The capacity degrdn. after subsequent cycling was suppressed by further limitation of the charging capacity. However, capacity fade could still be confirmed after 20 cycles albeit the capacity was limited at 60 mAh g- 1. This study suggests large repetitive expansion-contraction of the electrode during cycling as a possible cause of fatigue failure of the electrode/oxide electrolyte interface.
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    26. 26
      Han, F.; Yue, J.; Chen, C.; Zhao, N.; Fan, X.; Ma, Z.; Gao, T.; Wang, F.; Guo, X.; Wang, C. Interphase Engineering enabled All-Ceramic Lithium Battery. Joule 2018, 2, 497– 508,  DOI: 10.1016/j.joule.2018.02.007
      26
      Interphase Engineering Enabled All-Ceramic Lithium Battery
      Han, Fudong; Yue, Jie; Chen, Cheng; Zhao, Ning; Fan, Xiulin; Ma, Zhaohui; Gao, Tao; Wang, Fei; Guo, Xiangxin; Wang, Chunsheng
      Joule (2018), 2 (3), 497-508CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      Solid-state batteries (SSBs) can essentially improve battery safety. Garnet-type Li7La3Zr2O12 (LLZO) is considered one of the most promising solid electrolytes for SSBs. However, the performance of LLZO-based SSBs is limited by the large cathode/electrolyte interfacial resistance. High-rate and long-cycling SSBs were achieved only after adding flammable polymer or liq. electrolyte in the cathode at the sacrifice of safety. Here, we show that an all-ceramic cathode/electrolyte with an extremely low interfacial resistance can be realized by thermally soldering LiCoO2 (LCO) and LLZO together with the Li2.3-xC0.7+xB0.3-xO3 solid electrolyte interphase through the reaction between the Li2.3C0.7B0.3O3 solder and the Li2CO3 layers that can be conformally coated on both LLZO and LCO. The all-solid-state Li/LLZO/LCO battery with such an all-ceramic cathode/electrolyte exhibits high cycling stability and high rate performance, constituting a significant step toward the practical applications of SSBs.
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    27. 27
      Okumura, T.; Takeuchi, T.; Kobayashi, H. All-Solid-State Batteries with LiCoO2-Type Electrodes: Realization of an Impurity-Free Interface by Utilizing a Cosinterable Li3.5Ge0.5V0.5O4 Electrolyte. ACS Appl. Energy Mater. 2021, 4, 30– 34,  DOI: 10.1021/acsaem.0c02785
      27
      All-Solid-State Batteries with LiCoO2-Type Electrodes: Realization of an Impurity-Free Interface by Utilizing a Cosinterable Li3.5Ge0.5V0.5O4 Electrolyte
      Okumura, Toyoki; Takeuchi, Tomonari; Kobayashi, Hironori
      ACS Applied Energy Materials (2021), 4 (1), 30-34CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      An impurity-free interface was achieved in an oxide-based all-solid-state battery (ASSB) after cosintering, which was facilitated by an enhanced thermal stability between the layered rock-salt LiMO2 electrode materials (LiCoO2 or LiNi1/3Mn1/3Co1/3O2 (NMC)) and a lithium superionic conductor (LISICON)-type Li3.5Ge0.5V0.5O4 (LGVO) electrolyte. The ionic cond. of LGVO reached 9.6 x 10-5 S cm-1, which is the highest reported cond. for an LISICON oxide. These characteristics facilitated a good reversible capacity in the NMC electrode in an ASSB fabricated via cosintering. The high interfacial thermal stability between LiMO2 and LISICON is a useful property in the context of oxide-based ASSBs.
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    28. 28
      Akedo, J.; Lebedev, M. Microstructure and Electrical Properties of Lead Zirconate Titanate (Pb(Zr52/Ti48)O3) Thick Films Deposited by Aerosol Deposition Method. Jpn. J. Appl. Phys. 1999, 38, 5397– 5401,  DOI: 10.1143/jjap.38.5397
      28
      Microstructure and electrical properties of lead zirconate titanate (Pb(Zr52/Ti48)O3) thick films deposited by aerosol deposition method
      Akedo, Jun; Lebedev, Maxim
      Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers (1999), 38 (9B), 5397-5401CODEN: JAPNDE; ISSN:0021-4922. (Japanese Journal of Applied Physics)
      Lead zirconate titanate (PZT) films with a thickness of more than 10 μm were prepd. by the aerosol deposition method and their microstructure and chem. compn. were investigated by transmission electron microscopy (TEM) and energy dispersive X-ray spectra (EDX) anal. A damage layer was obsd. at the interface between PZT and the Si substrate during the deposition. The microstructure of the as-deposited film at room temp. consisted of randomly oriented small crystallites with sizes of less than 40 nm and large crystallites of 100 nm to 300 nm size, which were obsd. in the primary powder. The Pb/Ti/Zr ratio along the film stacking direction and around the grain boundaries was almost the same as that obsd. inside the crystallites and the primary powder with a morphotropic phase boundary compn. of (Pb(Zr0.52Ti0.48)O3). The marked improvement of the elec. properties obsd. in the deposited films after annealing was mainly due to the crystal growth of small crystallites.
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    29. 29
      Fuchita, E.; Tokizaki, E.; Ozawa, E.; Sakka, Y. Formation of Zirconia Films by the Aerosol Gas Deposition Method (By Jetting of Positive Charged Powder). J. Jpn. Soc. Powder Powder Metall. 2011, 58, 463– 472,  DOI: 10.2497/jjspm.58.463
      There is no corresponding record for this reference.
    30. 30
      Iwasaki, S.; Hamanaka, T.; Yamakawa, T.; West, W. C.; Yamamoto, K.; Motoyama, M.; Hirayama, T.; Iriyama, Y. Preparation of thick-film LiNi1/3Co1/3Mn1/3O2 electrodes by aerosol deposition and its application to all-solid-state batteries. J. Power Sources 2014, 272, 1086– 1090,  DOI: 10.1016/j.jpowsour.2014.09.038
      30
      Preparation of thick-film LiNi1/3Co1/3Mn1/3O2 electrodes by aerosol deposition and its application to all-solid-state batteries
      Iwasaki, Shinya; Hamanaka, Tadashi; Yamakawa, Tomohiro; West, William C.; Yamamoto, Kazuo; Motoyama, Munekazu; Hirayama, Tsukasa; Iriyama, Yasutoshi
      Journal of Power Sources (2014), 272 (), 1086-1090CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The authors prepd. thick and dense-cryst. LiNi1/3Co1/3Mn1/3O2 (NMC) composite films at room temp. that can work well as cathodes in all-solid-state battery cells. The thick films were fabricated by aerosol deposition using NMC powder (D50 = 10.61 μm) as a source material. Com.-obtained NMC powder did not form films at all on Si wafer substrates, and cracking of the substrates was obsd. However, a few tens of nanometer coating with amorphous Nb oxide resulted in the deposition of 7 μm-thick cryst. dense composite films. The films were successfully fabricated also on Li+-conductive glass-ceramic sheets with 150 μm in thickness, and all-solid-state batteries were fabricated. The solid-state battery provided a cathode-basis discharge capacity of 152 mA h g-1 (3.0-4.2 V, 0.025 C, 333 K) and repeated charge-discharge cycles for 20 cycles.
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    31. 31
      Kato, T.; Iwasaki, S.; Ishii, Y.; Motoyama, M.; West, W. C.; Yamamoto, Y.; Iriyama, Y. Preparation of thick-film electrode-solid electrolyte composites on Li7La3Zr2O12 and their electrochemical properties. J. Power Sources 2016, 303, 65– 72,  DOI: 10.1016/j.jpowsour.2015.10.101
      31
      Preparation of thick-film electrode-solid electrolyte composites on Li7La3Zr2O12 and their electrochemical properties
      Kato, Takehisa; Iwasaki, Shinya; Ishii, Yosuke; Motoyama, Munekazu; West, William C.; Yamamoto, Yuta; Iriyama, Yasutoshi
      Journal of Power Sources (2016), 303 (), 65-72CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The authors prepd. up to 20 μm-thick LiNi1/3Co1/3Mn1/3O2 (NMC)-Li+ conductive glass-ceramic solid electrolyte (LATP: σLi+ ∼ 10-3 S cm-2 at 298 K) composite cathode films on Li7La3Zr2O12 (LLZ) substrates by aerosol deposition (AD) and studied their electrochem. properties as all-solid-state batteries. The resultant NMC/LATP interface in the composite film had a thin mutual diffusion layer (∼5 nm) and a film had a porosity of ∼0.15% in vol. The composite films were well adhered to the LLZ substrates even though the films were prepd. at room temp. All-solid-state batteries, consisting of Li/LLZ/NMC-LATP composite film (20 μm), repeated charge-discharge reactions for 90 cycles at 100° at a 1/10 C rate (capacity retention: 99.97%/cycle). Rate capability of this battery was improved by modifying both the LATP and electron conductive source amt. in the composite film, and a battery with 16 μm-thick composite electrode delivered 60 mA h g-1 at 1 mA cm-2.
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    32. 32
      Motoyama, M.; Tanaka, Y.; Yamamoto, T.; Tsuchimine, N.; Kobayashi, S.; Iriyama, Y. The Active Interface of Ta-Doped Li7La3Zr2O12 for Li Plating/Stripping Revealed by Acid Aqueous Etching. ACS Appl. Energy Mater. 2019, 2, 6720– 6731,  DOI: 10.1021/acsaem.9b01193
      32
      Active interface of Ta-doped Li7La3Zr2O12 for Li plating/stripping revealed by acid aqueous etching
      Motoyama, Munekazu; Tanaka, Yuki; Yamamoto, Takayuki; Tsuchimine, Nobuo; Kobayashi, Susumu; Iriyama, Yasutoshi
      ACS Applied Energy Materials (2019), 2 (9), 6720-6731CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      All-solid-state lithium batteries incorporating oxide-based solid electrolytes have attracted much attention as a promising battery system for enabling highly reversible Li metal anodes. However, the cycling stability of Li plating/stripping reactions at higher charging/discharging rates on garnet-type solid-state electrolytes must be improved to realize a practical Li metal anode for solid-state batteries. Here, we report that a short acid etching procedure performed in ambient air significantly activates the Ta-doped Li7La3Zr2O12 (LLZT) surface compared to polishing under inert gas atm. such as dry Ar. It has been believed that Li7La3Zr2O12 (LLZ) and related doped LLZ solid electrolyte surfaces need to be mech. polished in dry Ar before the cell fabrication to remove Li2CO3 and LiOH that are present on the surface. However, a commonly used mech. polishing procedure is found to form a thin electrochem. inactive layer on the LLZT surface, whereas a short acid etching procedure (e.g., HCl) removes the inactive layer, and the acid-etched LLZT exhibits excellent cycling stability.
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    33. 33
      Motoyama, M.; Iwasaki, H.; Sakakura, M.; Yamamoto, T.; Iriyama, Y. Synthesis of LiCoO2 particles with tunable sizes by a urea-based-homogeneous-precipitation method. Int. J. Mater. Res. 2020, 111, 347– 355,  DOI: 10.1515/ijmr-2020-1110411
      33
      Synthesis of LiCoO2 particles with tunable sizes by a urea-based-homogeneous-precipitation method
      Motoyama, Munekazu; Iwasaki, Hiroki; Sakakura, Miyuki; Yamamoto, Takayuki; Iriyama, Yasutoshi
      International Journal of Materials Research (2020), 111 (4), 347-355CODEN: IJMRFV; ISSN:2195-8556. (Carl Hanser Verlag)
      This paper reports the synthesis of monodisperse spherical LiCoO2 particles in a wide range of av. diam. using a urea-based-uniform-pptn. method. The av. diam. of LiCoO2 particles can be varied from 2 to 14 μm with a uniform size distribution. The effective approach to maintain the size uniformity while changing the av. size of LiCoO2 particles is to keep the ratio of [CO(NH2)2] to [CoSO4] at 8 even when the CoSO4 and urea concns. are changed.
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    34. 34
      Abrahams, I.; Bruce, P. G. Defect Clustering in the Superionic Conductor Lithium Germanium Vanadate. Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater. 1991, 47, 696– 701,  DOI: 10.1107/s0108768191004548
      There is no corresponding record for this reference.
    35. 35
      Kuwano, J.; West, A. R. New Li+ ion conductors in the system, Li4GeO4-Li3VO4. Mater. Res. Bull. 1980, 15, 1661– 1667,  DOI: 10.1016/0025-5408(80)90249-4
      35
      New lithium(1+) ion conductors in the system, lithium germanate-lithium vanadate (Li4GeO4-Li3VO4)
      Kuwano, J.; West, A. R.
      Materials Research Bulletin (1980), 15 (11), 1661-7CODEN: MRBUAC; ISSN:0025-5408.
      New Li+ ion conducting solid electrolytes were found in the system Li4GeO4-Li3VO4. Of the compns. studied, Li3.6Ge0.6V0.4O4 has the highest cond. with σ ∼4 × 10-5 Ω-1 cm-1 at 18° rising to ∼10-2 at 190°. The activation energy is ∼0.44 eV. These cond. values are among the highest found for Li+ ion conductors; the room temp. value is much higher in LISICON, Li3.5Zn0.25GeO4, or in Li3.4Si0.4P0.6O4 and is comparable to that in LiI/Al2O3 mixts. These solid electrolytes are easy to synthesize, stable and insensitive to atm. attack. They are solid solns. based on γII Li3VO4, a γ tetrahedral structure; high cond. is due to the interstitial Li+ ions which are created during solid soln. formation.
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    36. 36
      Huang, M.; Xu, W.; Shen, Y.; Lin, Y.-H.; Nan, C.-W. X-ray absorption near-edge spectroscopy study on Ge-doped Li7La3Zr2O12: enhanced ionic conductivity and defect chemistry. Electrochim. Acta 2014, 115, 581– 586,  DOI: 10.1016/j.electacta.2013.11.020
      36
      X-ray absorption near-edge spectroscopy study on Ge-doped Li7La3Zr2O12: enhanced ionic conductivity and defect chemistry
      Huang, Mian; Xu, Wei; Shen, Yang; Lin, Yuan-Hua; Nan, Ce-Wen
      Electrochimica Acta (2014), 115 (), 581-586CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      Ge-doped Li7La3Zr2O12 (LLZ) was prepd. via the conventional solid-state reaction. The authors' results showed that doping Ge of <1% could stabilize the cubic phase of garnet-type LLZ and also increase its ionic cond. up to 8.28 × 10-4 S/cm at room temp. When the content of Ge dopant is higher, GeO2 impurity phase would appear and there coexists cubic and tetragonal mixed structures, lowering the cond. By combining x-ray absorption near-edge spectroscopy and full multiple-scattering theory, Ge more likely enters into the Li and La crystallog. sites instead of the Zr site, which provides understanding of the micro-structural modulation by Ge dopants and the subsequent enhancement in the ionic cond.
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    37. 37
      Watanabe, M.; Williams, D. B. The quantitative analysis of thin specimens: a review of progress from the Cliff-Lorimer to the new zeta-factor methods. J. Microsc. 2006, 221, 89– 109,  DOI: 10.1111/j.1365-2818.2006.01549.x
      37
      The quantitative analysis of thin specimens: a review of progress from the Cliff-Lorimer to the new zeta-factor methods
      Watanabe M; Williams D B
      Journal of microscopy (2006), 221 (Pt 2), 89-109 ISSN:0022-2720.
      A new quantitative thin-film X-ray analysis procedure termed the zeta-factor method is proposed. This new zeta-factor method overcomes the two major limitations of the conventional Cliff-Lorimer method for quantification: (1) use of pure-element rather than multielement, thin-specimen standards and (2) built-in X-ray absorption correction with simultaneous thickness determination. Combined with a universal, standard, thin specimen, a series of zeta-factors covering a significant fraction of the periodic table can be estimated. This zeta-factor estimation can also provide information about both the detector efficiency and the microscope-detector interface system. Light-element analysis can also be performed more easily because of the built-in absorption correction. Additionally, the new zeta-factor method has several advantages over the Cliff-Lorimer ratio method because information on the specimen thickness at the individual analysis points is produced simultaneously with compositions, thus permitting concurrent determination of the spatial resolution and the analytical sensitivity. In this work, details of the zeta-factor method and how it improves on the Cliff-Lorimer approach are demonstrated, along with several applications.
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    38. 38
      Rangasamy, E.; Wolfenstine, J.; Sakamoto, J. The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12. Solid State Ionics 2012, 206, 28– 32,  DOI: 10.1016/j.ssi.2011.10.022
      38
      The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12
      Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey
      Solid State Ionics (2012), 206 (), 28-32CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      The effect of Al and Li concn. on the formation of cubic garnet of nominal compn. Li7La3Zr2O12 was investigated. It was detd. that at least 0.204 mol of Al is required to stabilize the cubic phase. It was obsd. for the cubic phase (stabilized by the addn. of Al) that as Li content was increased from 6 to 7 mol it transformed to a tetragonal phase. Addnl., powders of cubic Li6.24La3Zr2Al0.24O11.98 were hot-pressed at 1000°C and 40 MPa. The hot-pressed material had a relative d. of 98%. The room temp. total ionic cond. of the hot-pressed material was 4.0 × 10-4 S/cm and the electronic cond. was 2 × 10-8 S/cm.
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    39. 39
      Inaba, M.; Iriyama, Y.; Ogumi, Z.; Todzuka, Y.; Tasaka, A. Raman study of layered rock-salt LiCoO2 and its electrochemical lithium deintercalation. J. Raman Spectrosc. 1997, 28, 613– 617,  DOI: 10.1002/(sici)1097-4555(199708)28:8<613::aid-jrs138>3.0.co;2-t
      39
      Raman study of layered rock-salt LiCoO2 and its electrochemical lithium deintercalation
      Inaba, Minoru; Iriyama, Yasutoshi; Ogumi, Zempachi; Todzuka, Yasufumi; Tasaka, Akimasa
      Journal of Raman Spectroscopy (1997), 28 (8), 613-617CODEN: JRSPAF; ISSN:0377-0486. (Wiley)
      Unpolarized and polarized Raman spectra (200-800 cm-1) of LiCoO2 with a layered rock-salt structure were measured. The Raman-active lattice modes of LiCoO2 were assigned by polarized Raman measurements of a c-axis oriented thin film. The variation of the Raman spectra of Li1-xCoO2 powder prepd. by electrochem. Li deintercalation was studied, and the spectral changes were well correlated with the structural changes detd. by x-ray diffraction except that peak splitting by the distortion in the monoclinic phase was not obsd. The obsd. line broadening of the 2nd hexagonal phase and the monoclinic phase indicated that the Li ions remaining in the lattice after deintercalation randomly occupy the available sites on the Li planes in the lattice the layered rock-salt structure.
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    40. 40
      Reimers, J. N.; Dahn, J. R. Electrochemical and In Situ X-Ray Diffraction Studies of Lithium Intercalation in Li x CoO2. J. Electrochem. Soc. 1992, 139, 2091– 2097,  DOI: 10.1149/1.2221184
      40
      Electrochemical and in-situ x-ray diffraction studies of lithium intercalation in lithium cobalt oxide (LixCoO2)
      Reimers, Jan N.; Dahn, J. R.
      Journal of the Electrochemical Society (1992), 139 (8), 2091-7CODEN: JESOAN; ISSN:0013-4651.
      Electrochem. properties of LixCoO2 are studied as Li is deintercalated from LiCoO2. High-precision voltage measurements and in-situ x-ray diffraction indicate a sequence of 3 distinct phase transitions as x varies from 1 to 0.4. Two of the transitions are situated slightly above and below x = 1/2 and are caused by an order/disorder transition of the Li ions. The order/disorder transition was studied as a function of temp., allowing the detn. of an order/disorder phase diagram. In-situ x-ray diffraction measurements facilitate a direct observation of the effects of deintercalation on the host lattice crystal structure. The other phase transition is 1st order (coexisting phases are obsd. for 0.75 ≤ x ≤ 0.93) involving a significant expansion of the c-lattice parameter of the hexagonal unit cell. The authors report the variation of the lattice consts. of LixCoO2 with x and show that the phase transition to the Li ordered phase near x = 1/2 is accompanied by a lattice distortion to a monoclinic unit cell with aMon 4.865(2), bMon 2.806(1), cMon 14.420(4) Å and β 90.77 (3). The authors report an overall phase diagram for 0.4 ≤ x ≤ 1.0 and -10° ≤ T ≤ 60°.
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    41. 41
      Kato, T.; Hamanaka, T.; Yamamoto, K.; Hirayama, T.; Sagane, F.; Motoyama, M.; Iriyama, Y. In-situ Li7La3Zr2O12/LiCoO2 interface modification for advanced all-solid-state battery. J. Power Sources 2014, 260, 292– 298,  DOI: 10.1016/j.jpowsour.2014.02.102
      41
      In-situ Li7La3Zr2O12/LiCoO2 interface modification for advanced all-solid-state battery
      Kato, Takehisa; Hamanaka, Tadashi; Yamamoto, Kazuo; Hirayama, Tsukasa; Sagane, Fumihiro; Motoyama, Munekazu; Iriyama, Yasutoshi
      Journal of Power Sources (2014), 260 (), 292-298CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The inherent high resistance of electrolyte/electrode interface in all-solid-state-Li-secondary batteries (SSLB) poses a significant hurdle for the SSLB development. The interfacial resistivity between Li7La3Zr2O12 (LLZ) and LiCoO2 is decreased by introducing a thin Nb layer (∼10 nm) at this interface. The interface modification approach using a Nb interlayer dramatically improves the discharge capacity and rate capability of a SSLB.
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    42. 42
      Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28, 266– 273,  DOI: 10.1021/acs.chemmater.5b04082
      42
      Interface Stability in Solid-State Batteries
      Richards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, Gerbrand
      Chemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
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    43. 43
      Kishi, H.; Mizuno, Y.; Chazono, H. Base-Metal Electrode-Multilayer Ceramic Capacitors: Past, Present and Future Perspectives. Jpn. J. Appl. Phys. 2003, 42, 1– 15,  DOI: 10.1143/jjap.42.1
      43
      Base-metal electrode-multilayer ceramic capacitors: Past, present and future perspectives
      Kishi, Hiroshi; Mizuno, Youichi; Chazono, Hirokazu
      Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers (2003), 42 (1), 1-15CODEN: JAPNDE ISSN:. (Japan Society of Applied Physics)
      A review. Multilayer ceramic capacitor (MLCC) prodn. and sales figures are the highest among fine-ceramic products developed in the past 30 yr. The total worldwide prodn. and sales reached 550 billion pieces and 6 billion dollars, resp. in 2000. In the course of progress, the development of base-metal electrode (BME) technol. played an important role in expanding the application area. In this review, the recent progress in MLCCs with BME nickel (Ni) electrodes is reviewed from the viewpoint of nonreducible dielec. materials. Using intermediate-ionic-size rare-earth ion (Dy2O3, Ho2O3, Er2O3, Y2O3) doped BaTiO3 (ABO3)-based dielecs., highly reliable Ni-MLCCs with a very thin layer below 2 μm in thickness have been developed. The effect of site occupancy of rare-earth ions in BaTiO3 on the elec. properties and microstructure of nonreducible dielecs. is studied systematically. It appears that intermediate-ionic-size rare-earth ions occupy both A- and B-sites in the BaTiO3 lattice and effectively control the donor/acceptor dopant ratio and microstructural evolution. The relationship between the elec. properties and the microstructure of Ni-MLCCs is also presented.
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    44. 44
      Hitz, G. T.; McOwen, D. W.; Zhang, L.; Ma, Z.; Fu, Z.; Wen, Y.; Gong, Y.; Dai, J.; Hamann, T. R.; Hu, L.; Wachsman, E. D. High-Rate Lithium Cycling in a Scalable Trilayer Li-Garnet-Electrolyte Architecture. Mater. Today 2019, 22, 50– 57,  DOI: 10.1016/j.mattod.2018.04.004
      44
      High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture
      Hitz, Gregory T.; McOwen, Dennis W.; Zhang, Lei; Ma, Zhaohui; Fu, Zhezhen; Wen, Yang; Gong, Yunhui; Dai, Jiaqi; Hamann, Tanner R.; Hu, Liangbing; Wachsman, Eric D.
      Materials Today (Oxford, United Kingdom) (2019), 22 (), 50-57CODEN: MTOUAN; ISSN:1369-7021. (Elsevier Ltd.)
      Solid-state lithium batteries promise to exceed the capabilities of traditional Li-ion batteries in safety and performance. However, a no. of obstacles have stood in the path of solid-state battery development, primarily high resistance and low capacity. In this work, these barriers are overcome through the fabrication of a uniquely microstructured solid electrolyte architecture based on a doped Li7La3Zr2O12 (LLZ) ceramic Li-conductor. Specifically, a porous-dense-porous trilayer structure was fabricated by tape casting, a scalable roll-to-roll manufg. technique. The dense (>99%) center layer can be fabricated as thin as 10μm and blocks dendrites over hundreds of cycles. The microstructured porous layers serve as electrode supports and increase the mech. strength by 9×, making the cells strong enough to handle with ease. Addnl., the porous layers multiply the electrode-electrolyte interfacial surface area by>40× compared to a typical planar interface. Lithium sym. cells based on the trilayer architecture were cycled at room temp. and achieved area-specific resistances (7Ω-cm2) dramatically lower, and current densities dramatically higher (10 mA/cm2), than previously reported literature results. Moreover, to demonstrate scalability a large-format cell was fabricated with lithium metal in one porous layer and a sulfur electrode with conductive carbon and an ionic liq. interface in the other, achieving 1244 mAh/g S utilization and 195 Wh/kg based on total cell mass, showing a promising path to com. viable, intrinsically safe lithium batteries with high specific energy and high energy d.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.2c10853.

    • EDX analysis of an LLZ–LGVO multilayer, reactivity between LGVO and LCO analyzed by Raman spectroscopy, cross-sectional SEM and EDX images of an LLZ/LGVO/LCO multilayer, DRT analysis of an EIS spectrum of an Ox-SSB (Li/ML-900/LCO), and EIS spectra of an Ox-SSB (Li/ML-900/LCO) (PDF)


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