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Li-ion battery is currently considered to be the most proven technology for energy storage systems when it comes to the overall combination of energy, power, cyclability and cost. However, there are continuous expectations for cost reduction in large-scale applications, especially in electric vehicles and grids, alongside growing concerns over safety, availability of natural resources for lithium, and environmental remediation. Therefore, industry and academia have consequently shifted their focus towards 'beyond Li-ion technologies'. In this respect, other non-Li-based alkali-ion/polyvalent-ion batteries, non-Li-based all solid-state batteries, fluoride-ion/ammonium-ion batteries, redox-flow batteries, sand batteries and hydrogen fuel cells etc. are becoming potential cost-effective alternatives. While there has been notable swift advancement across various materials, chemistries, architectures, and applications in this field, a comprehensive overview encompassing high-energy 'beyond Li-ion' technologies, along with considerations of commercial viability, is currently lacking. Therefore, in this review article, a rationalized approach is adopted to identify notable 'post-Li' candidates. Their pros and cons are comprehensively presented by discussing the fundamental principles in terms of material characteristics, relevant chemistries, and architectural developments that make a good high-energy 'beyond Li' storage system. Furthermore, a concise summary outlining the primary challenges of each system is provided, alongside the potential strategies being implemented to mitigate these issues. Additionally, the extent to which these strategies have positively influenced the performance of these 'post-Li' technologies is discussed. [ABSTRACT FROM AUTHOR]

Recent studies have identified an imbalance between the electronic and ionic conductivities as the drivers of inhomogeneous reactions in composite cathodes, which cause the rapid degradation of all‐solid‐state battery (ASSB). To mitigate localized overcharge and utilize isolated active materials, the study proposes the coating of an argyrodite‐type Li6PS5Cl solid electrolyte (SE) with graphene‐like carbon (GLC@LPSCl), a 2D conductive material, to offer a continuous three‐dimensionally connected electron pathway within the composite cathode to facilitate ion mobility and promote homogeneous reactions. Despite reducing the content of the conducting agent, it is observed that the GLC@LPSCl cell exhibits high initial Coulombic efficiency and discharge capacity, reducing the inhomogeneous reactivity after 200 cycles compared with when ordinary conductive agents are deployed. Additionally, the presence of GLC@LPSCI surface suppresses the interfacial reaction between SE–cathode material, thus imparting the cell with excellent capacity retention (≈90%) after 200 cycles. Furthermore, the cell performance improves even after a fourfold increase in the cathode loading amount, demonstrating the criticality of a well‐developed continuous electron pathway to cell performance and highlighting the key role of ensuring a balance between the electron and ion conductivities in the development of high‐energy‐density and high‐power ASSBs. [ABSTRACT FROM AUTHOR]

All‐solid‐state lithium‐sulfur batteries (ASSLSBs) are garnering significant interest due to their high energy density and safety. Nevertheless, the interfacial instability, particularly with sulfide‐based solid electrolytes, poses a formidable challenge to their widespread application. Herein, to adjust the p‐band center of the tetrahedron in Li6PS5Cl is proposed to alleviate undesirable reactions at anode and cathode interfaces via facile Sb/O co‐doping. The incorporation of Sb into Li6PS5Cl forms an SbS4 tetrahedron, resulting in the downward shift of the S‐p band center. This benefits the acquisition of electrons from Li to in situ forming stable LixSbySz interphase at the Li/LPSC‐SbO interface. The Li symmetric cell endows a high stability for over 4000 h. Moreover, the lower p‐band center of the S‐p band also strengthens the interaction of the SbS4 tetrahedron with surrounding Li atoms, impeding charge transfer to S8 and mitigating interfacial side reactions on the sulfur cathode. Additionally, O doping enhances the air stability of the electrolyte. The ASSLSBs with LPSC‐SbO achieve a high specific capacity of 932.6 mAh g−1 at 0.1 C with 83.7% capacity retention over 150 cycles. Furthermore, the practical all‐solid‐state pouch cell demonstrates stable cycling performance and anticipated safety. This work provides insights into constructing stable dual solid–solid interfaces for sulfide‐based room‐temperature high‐performance ASSLSBs. [ABSTRACT FROM AUTHOR]

This study reports that hot pressing a high loading (9.375 mg cm−2; > 5 mAh cm−2) all-solid-state FeS2 composite cathodes at 240 °C and 47 MPa improved initial cycle performance. At 25 °C, a cold-pressed cell delivered negligible capacity whereas a hot-pressed cell delivered 332 mAh g−1 (2.34 mAh cm−2). At 60 °C, a cold-pressed cell delivered 666 mAh g−1 (4.70 mAh cm−2) whereas a hot-pressed cell delivered 782 mAh g−1 (5.52 mAh cm−2). Hot-pressed cathode composites had a 20% porosity whereas cold-pressed cathode composites had a 30% porosity. Increased initial discharge capacity was attributed to better solid–solid interfacial contact between sulfide solid-state electrolyte (SSE) particles and between SSE and FeS2 active material particles. Cell failure occurred upon extended cycling due to the stresses generated by the expansion of lithiated FeS2. FIBSEM cross-sectional imaging of post mortem cathode composites revealed horizontal cracking indicative of electrode delamination due to electrode expansion. [ABSTRACT FROM AUTHOR]

Despite their potential as next-generation energy storage devices, all-solid-state batteries (ASSBs) have not been widely developed because of the low ionic conductivity of solid electrolytes and the high interfacial impedance with electrodes. This study addressed these issues by enhancing the electrochemical properties through composition control. A composite solid electrolyte (CSE) was fabricated using Li6.5Ga0.2La2.95Rb0.05Zr2O12 (Ga–Rb-doped LLZO) and poly(ethylene oxide) (PEO) with various compositions. The results demonstrated high ionic conductivity and electrochemical stability when the weight ratio of Ga–Rb-doped LLZO to PEO was 6:4. These characteristics effectively mitigated Li dendrite formation and ensured excellent interfacial stability. Notably, LiFePO4/CSEs/Li full cells retained 92.3% of their initial capacity after 100 cycles at a 0.3 C rate. This study will promote the research and development of practical ASSBs incorporating LLZO solid electrolytes. [ABSTRACT FROM AUTHOR]

Sulfide‐based all‐solid‐state lithium batteries (ASSLBs) are potential alternatives to conventional lithium‐ion batteries for enhancing energy density and battery safety. However, the industrial sector encounters technical challenges in the fabrication of high‐mass‐loaded composite cathodes to improve the energy densities of ASSLBs. Thus, the selection of an appropriate binder and cathode active material is very important for achieving a good cycling performance of ASSLBs. In this study, wet‐processable poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) (EMG) binder and full‐concentration gradient (FCG) LiNi0.78Co0.10Mn0.12O2 (NCM) cathode active material are employed to fabricate the composite cathode with high active mass loading (21.4 mg cm−2). The EMG binder provided strong binding properties to the cathode constituents and improved the electrical conductivity of the composite cathode. The FCG NCM mitigated the morphology damages caused by volume changes in the cathode active material during cycling. Consequently, the solid‐state lithium battery with the composite cathode employing EMG binder and FCG NCM delivered a high discharge capacity of 196.6 mAh g−1 corresponding to an areal capacity of 4.21 mAh cm−2 and showed good capacity retention of 85.1% after 300 cycles at 0.2 C rate and 30 °C. [ABSTRACT FROM AUTHOR]

This study reports a facile and reliable operando X‐ray photoelectron spectroscopy (XPS) system for the characterization of the chemical state and electronic structure during Li‐plating/stripping in all‐solid‐state batteries (ASSBs). The measurement conditions (including manufacturing an in situ sample holder) and experimental parameters have been optimized through experimentation. The proposed system accurately defines the status of every metal interlayer component during real‐time battery operation (with simultaneous Li+‐ion in/out migration) under a repeating Li‐plating/stripping process. Moreover, it enables elucidation of ambiguous reaction mechanisms depending on the battery performance, such as the interlayer‐material effect on the efficiency and reversibility of the Li‐plating/stripping process, and changes in the oxygen‐containing bonds due to reaction with Li. The significance of the developed system is further validated by the usefulness and reliability of the valence band structure as a criterion for the analysis of lithium‐metal alloy formation and the progress of de‐alloying reactions. [ABSTRACT FROM AUTHOR]

In the ongoing quest to develop lithium‐ion batteries with superior capacity and enhanced safety, the focus has shifted toward all‐solid‐state batteries (SSBs) and nickel‐rich cathode materials. Despite their promise, these technologies face significant interface challenges, notably poor contact and low ion transport efficiency, leading to substantial stability issues. This review aims to provide a comprehensive analysis of both the advantages and the challenges associated with all‐solid‐state batteries. In addition, it discusses the benefits of single‐crystal application in SSBs, in terms of their kinetic performance, mechanical properties, and stability. The review concludes by proposing various strategies to optimize single‐crystal technologies, targeting the development of efficient nickel‐rich single‐crystal materials for use in all‐solid‐state batteries. These approaches offer the potential to address the core challenges currently faced by SSBs and pave the way for the next generation of high‐performance batteries. [ABSTRACT FROM AUTHOR]

The cathode surface of sulfide‐based all‐solid‐state batteries (SBs) is commonly coated with amorphous‐LiNbO3 in order to stabilize charge–discharge reactions. However, high‐voltage charging diminishes the advantages, which is caused by problems with the amorphous‐LiNbO3 coating layer. This study has investigated the degradation of amorphous‐LiNbO3 coating layer directly during the high‐voltage charging of SBs. O2 generation via Li extraction from the amorphous‐LiNbO3 coating layer is observed using electrochemical gas analysis and electrochemical X‐ray photoelectron spectroscopy. This O2 leads to the formation of an oxidative solid electrolyte (SE) around the coating layer and degrades the battery performance. On the other hand, elemental substitution (i.e., amorphous‐LiNbxP1‐xO3) reduces O2 release, leading to stable high‐voltage charge–discharge reactions of SBs. The results have emphasized that the suppression of O2 generation is a key factor in improving the energy density of SBs. [ABSTRACT FROM AUTHOR]

Laser irradiation of β-NaFeO2 shows local melting and crystal growth from the melt pool and sodium ion conductivity. Local melting, densification, and crystal growth were confirmed on the β-NaFeO2 surface through laser irradiation with a wavelength of 1 μm. Scanning electron microscopy and electron backscatter diffraction analysis confirmed anisotropic grain growth and grain boundary shrinkage in the laser- irradiated area. X-ray diffraction results suggested that the laser-irradiated area was in a low crystalline state. In addition, the precipitation of Fe3O4 in laser-irradiated β-NaFeO2 indicates a reduction reaction, suggesting that the laser-irradiated area is heated to 1500℃ or higher. We confirmed that the structure change region could be controlled down to a thickness of about 10 μm by laser irradiation with varying laser power to β-NaFeO2. [ABSTRACT FROM AUTHOR]

Sulfide glass electrolytes with high ionic conductivities and formabilities are key materials for practical use in all‐solid‐state sodium secondary batteries. Both sealing and quenching are considered to be necessary for producing high‐alkali‐content sulfide glass electrolytes. In this study, the glass‐forming ability of sodium thiosilicate glasses is enhanced by adding a small quantity of SiO2. Consequently, high‐sodium‐content oxythiosilicate glass is synthesized without sealing and quenching processes under Ar atmosphere. The prepared Na4SiS4·0.200SiO2 (molar ratio) glass exhibits ionic conductivity of 4.0 × 10−5 S cm−1 at 25 °C, surpassing that of Na4SiS4 glass. The Na4SiS4·0.200SiO2 glass shows high reduction stability to sodium metal. The all‐solid‐state Na metal/Na4SiS4·0.200SiO2 glass/Na2.88Sb0.88W0.12S4/TiS2 cell shows a reversible capacity of 140 mAh g−1 for 5 cycles. The amount of H2S gas generated in Na4SiS4·0.0830SiO2 and Na4SiS4·0.200SiO2 glasses is one‐tenth that of the Na4SiS4 glass, suggesting increased chemical stability to humidity by incorporating oxygen in the structure. High‐sodium‐content oxythiosilicate glass with high ionic conductivity, high chemical stability against humidity, and high reduction stability is successfully prepared under ambient pressure without sealing and quenching processes. [ABSTRACT FROM AUTHOR]

This study focused on achieving high ionic conductivity in Li-La-TiO (LLTO) solid electrolyte. To enhance ionic conductivity, the synthesis reaction was optimized by controlling the composite crystal structure of TiO2 at the B-site of the perovskite (ABO3) structured LLTO, incorporating rutile, brookite, and anatase phases. The solid-phase LLTO, synthesized utilizing the core – shell structured composite-phase TiO2 developed in this study for the first time, successfully transformed its crystal structure to β-LLTO (tetragonal to cubic). This resulted in a significant improvement in ionic conductivity (i.e. 1.11 × 10−4 Scm−1). The study findings confirmed that the composite crystal structure TiO2 used in the solid-phase synthesis of LLTO induced an increase in oxygen vacancies during the synthesis process, thereby reducing the step-free energy required for the final synthesis.

MgH2 and TiH2 have been extensively studied as potential anode materials due to their high theoretical specific capacities of 2036 and 1024 mAh/g, respectively. However, the large volume changes that these compounds undergo during cycling affects their performance and limits practical applications. The present work demonstrates a novel approach to limiting the volume changes of active materials. This effect is based on mechanical support from an intimate interface generated in situ via the reaction between MgH2 and Ti within the electrode prior to lithiation to form Mg and TiH2. The resulting Mg can be transformed back to MgH2 by reaction with LiH during delithiation. In addition, the TiH2 improves the reaction kinetics of MgH2 and enhances electrochemical performance. The intimate interface produced in this manner is found to improve the electrochemical properties of a MgH2-Ti-LiH electrode. An exceptional reversible capacity of 800 mAh/g is observed even after 200 cycles with a high current density of 1 mA/cm2 and a high proportion of active material (90 wt.%) at an operation temperature of 120 °C. This study therefore showcases a new means of improving the performance of electrodes by limiting the volume changes of active materials.

Solid polymer electrolytes (SPEs) are highly promising for realizing high-capacity, low-cost, and safe Li metal batteries. However, the Li dendritic growth and side reactions between Li and SPEs also plague these systems. Herein, a fluorinated lithium salt coating (FC) with organic-inorganic gradient and soft–rigid feature is introduced on Li surface as an artificial protective layer by the in-situ reaction between Li metal and fluorinated carboxylic acid. The FC layer can improve the interface stability and wettability between Li and SPEs, assist the transport of Li ions, and guide Li nucleation, contributing to a dendrite-free Li deposition and long-lifespan Li metal batteries. The symmetric cell with FC-Li anodes exhibits a high areal capacity of 1 mAh cm−2 at 0.5 mA cm−2, and an ultra-long lifespan of 2000 h at a current density of 0.1 mA cm−2. Moreover, the full cell paired with the LiFePO4 cathode exhibits improved cycling stability, remaining 83.7% capacity after 500 cycles at 1 C. When matching with the S cathode, the FC layer can prevent the shuttle effect, contributing to stable and high-capacity Li–S battery. This work provided a promising way for the construction of stable all-solid-state lithium metal batteries with prolonged lifespan.

The all‐solid‐state lithium metal battery is considered the next‐generation energy storage device with the potential to double the energy density of state‐of‐the‐art Li‐ion batteries and eliminate safety hazards. Achieving stable Li plating/stripping without dendrite propagation within the solid electrolyte is crucial for delivering the promised high energy density. In this study, through the comparison of various synthesis routes, a novel cube‐shaped microstructure in the Li5.3PS4.3ClBr0.7 argyrodite electrolyte, synthesized using the high‐speed mechanical milling followed by annealing method (BMAN‐LPSCB) is identified. The uniform microstructure allows for the production of an electrolyte pellet with significantly reduced porosity through cold pressing. The removal of defects has significantly enhanced the electrolyte's ability to inhibit dendrite formation, with a critical current density reaching 3.8 mA cm−2. The lithium symmetric cell with BMAN‐LPSCB electrolyte exhibits stable Li plating/stripping for over 150 h at a high current density and cutoff capacity of 3 mA cm−2 / 3 mAh cm−2. The all‐solid‐state Li/NCM battery utilizing the BMAN‐LPSCB electrolyte also demonstrates excellent durability, with a capacity retention of 96% over 1000 cycles at a 1C rate. This study emphasizes that the microstructure of the sulfide electrolyte is a critical factor influencing mechanically‐driven Li dendrite propagation in all‐solid‐state batteries. [ABSTRACT FROM AUTHOR]

Garnet Li7La3Zr2O12 (LLZO)‐based solid‐state electrolytes (SSEs) hold promise for realizing next‐generation lithium metal batteries with high energy density. However, the high stiffness of high‐temperature sintered LLZO makes it brittle and susceptible to strain during the fabrication of solid‐state batteries. Cold‐pressed LLZO exhibits improved ductility but suffers from insufficient Li+ conductivity. Here, we report cold‐pressed Ta‐doped LLZO (Ta−LZ) particles integrated with ductile Li6PS5Cl (LPSC) via a Li+ conductive Li‐containing Ta−Cl structure. This configuration creates a continuous Li+ conduction network by enhancing the Li+ exchange at the Ta−LZ/LPSC interface. The resulting Ta−LZ/LPSC SSE exhibits Li+ conductivity of 4.42×10−4 S cm−1 and a low activation energy of 0.31 eV. Li symmetric cells with Ta−LZ/LPSC SSE demonstrate excellent Li dendrite suppression ability, with an improved critical current density of 5.0 mA cm−2 and a prolonged cycle life exceeding 600 h at 1 mA cm−2. Our finding provides valuable insights into developing cold‐pressed ceramic powder electrolytes for high‐performance all‐solid‐state batteries. [ABSTRACT FROM AUTHOR]

All‐solid‐state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next‐generation energy storage devices. Among various solid electrolytes, sulfide‐based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high‐voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas‐solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high‐voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs. [ABSTRACT FROM AUTHOR]

The intermittent nature of renewable energy generation can be tackled by integrating them with electrochemical energy storage, which can also close the gap between supply and demand effectively. It has recently been demonstrated that Si3N4‐based negative electrodes are a promising option for lithium‐ion batteries due to their large theoretical capacity and appropriate working potential with extremely low polarization. In the present work, Si3N4 was utilized as anode material in all‐solid‐state lithium‐ion battery with lithium borohydride as a solid electrolyte and Li foil placed as a counter electrode. The electrochemical properties were investigated using galvanostatic charge/discharge profiling whereas the mechanism of lithiation delithiation was investigated in detail using x‐ray diffraction (XRD). The highest capacity of the composite materials was obtained as 1700 mAhg−1 at 0.05 C current rate in the first cycle, which is reduced to 370 in 5 cycles. However, a stability in the capacity was observed in subsequent cycles and a retention of almost 88% could be achieved in 150 cycles. The interfacial resistance before and after the electrochemical cycling was observed as 326 Ω and 13 kΩ, respectively which is also supported by the microstructural investigations where the cracks are observed because of thermochemical reactions. [ABSTRACT FROM AUTHOR]

• The reaction kinetics and electrochemical performance of MgH 2 are improved by addition of TiH 2. • MgH 2 can react with Ti to successfully in situ form an intimate interface that supplies mechanical support. • MgH 2 -Ti-LiH-AB (27:47:16:10 wt%, AB: acetylene black) electrode can deliver a high reversible capacity of 829 mAh/g after 200 cycles even with a high active content of 90 wt%. • After 30 charge-discharge cycles, the in situ formed intimate interface can be preserved and no voids were observed in the MgH 2 -Ti-LiH-AB electrode. MgH 2 and TiH 2 have been extensively studied as potential anode materials due to their high theoretical specific capacities of 2036 and 1024 mAh/g, respectively. However, the large volume changes that these compounds undergo during cycling affects their performance and limits practical applications. The present work demonstrates a novel approach to limiting the volume changes of active materials. This effect is based on mechanical support from an intimate interface generated in situ via the reaction between MgH 2 and Ti within the electrode prior to lithiation to form Mg and TiH 2. The resulting Mg can be transformed back to MgH 2 by reaction with LiH during delithiation. In addition, the TiH 2 improves the reaction kinetics of MgH 2 and enhances electrochemical performance. The intimate interface produced in this manner is found to improve the electrochemical properties of a MgH 2 -Ti-LiH electrode. An exceptional reversible capacity of 800 mAh/g is observed even after 200 cycles with a high current density of 1 mA/cm2 and a high proportion of active material (90 wt.%) at an operation temperature of 120 °C. This study therefore showcases a new means of improving the performance of electrodes by limiting the volume changes of active materials. [Display omitted] [ABSTRACT FROM AUTHOR]

Dendrite growth is one of the main challenges in maintaining the service life of all-solid-state lithium-ion batteries. Mechanical stress has been reported to significantly affect dendrite growth. In this study, to explain the effect of mechanical stress on electrochemical reactions in all-solid-state batteries, a modified phase-field model for dendrite growth is proposed by considering the stress-dependent overpotential. Dendrite growth under different mechanical loadings in an all-solid-state battery is investigated using the proposed model. Consistent with previous experimental results, the current result shows that compressive stress inhibits dendrite growth. Considering the stress concentration at the tips of processing-induced microcracks, the effects of the number and distribution of microcracks on dendrite growth are investigated. The results show that the stress-concentration field induced at the tips of cracks or voids can change the morphology of dendrites and decrease their growth rates. This study provides a new perspective for explaining Li dendrite growth under mechanical stress and offers inspiration for prolonging the service life of all-solid-state batteries based on defect and stress regulation, which may be further realized in experiments by filling solid electrolytes with different types of nanofillers. [ABSTRACT FROM AUTHOR]

Copyright of Journal of the Chinese Society of Rare Earths is the property of Editorial Department of Journal of the Chinese Society of Rare Earths and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

High ionic conductivity is the key point in the development of new solid‐state electrolytes. Herein, a combining strategy of anion (O2−) doping and structure distortion is applied to enhance the Li+ ion conductivity in Li15P4S16Cl3, thus converting the nonionic conductor into fast ionic conductor. Solid‐state 6Li nuclear magnetic resonance analysis shows redistribution of Li+ ions in Li15P4S16Cl3 with O2− doping or local structure distortion via ball milling, indicating energy changes at different lithium sites. As a result, the activation energy is reduced from 0.50 to 0.35 eV for the ball‐milled Li15P4S15.6O0.4Cl3, and the ionic conductivity is enhanced from 10−9 to 10−4 S cm−1. The electrochemical stability of Li15P4S15.6O0.4Cl3 is broadened at the anode side as well. The symmetric cell Li|Li15P4S15.6O0.4Cl3|Li can cycle more than 1000 h with negligible voltage increase. The LiCoO2|Li15P4S15.6O0.4Cl3|Li‐Si all‐solid‐state battery demonstrates an initial capacity of 106 mA h g−1 and retains 92% capacity after 200 cycles at 0.5 C, highlighting excellent rate performance and electrochemical stability. [ABSTRACT FROM AUTHOR]

Inorganic solid‐state electrolytes (SSEs) play a vital role in high‐energy all‐solid‐state batteries (ASSBs). However, the current method of SSE preparation usually involves high‐energy mechanical ball milling and/or a high‐temperature annealing process, which is not suitable for practical application. Here, a facile strategy is developed to realize the scalable synthesis of cost‐effective aluminum‐based oxyhalide SSEs, which involves a self‐propagating method by the exothermic reaction of the raw materials. This strategy enables the synthesis of various aluminum‐based oxyhalide SSEs with tunable components and high ionic conductivities (over 10−3 S cm−1 at 25 °C) for different cations (Li+, Na+, Ag+). It is elucidated that the amorphous matrix, which mainly consists of various oxidized chloroaluminate species that provide numerous sites for smooth ion migration, is actually the key factor for the achieved high conductivities. Benefit from their easy synthesis, low cost, and low weight, the aluminum‐based oxyhalide SSEs synthesized by our approach could further promote practical application of high‐energy‐density ASSBs. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Ceramics / Taoci Xuebao is the property of Journal of Ceramics Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

All-solid-state batteries with a lithium negative electrode and a ceramic electrolyte are key toward high energy density. To ensure a safe, fast, accurate, and cost-effective development of this technology, the experimental methodology must be supported by the numerical modeling approach. This work proposes and describes an electrochemical model of a Li7La3Zr2O12 (LLZO) and Ni-rich NMC-based lithium cell with a deformable lithium negative electrode. Simulations were computed using the finite element method at different operating conditions to demonstrate the scope of the modeling work. Discharge rate tests, deformation tracking, geometric defect investigation, and polarization decomposition are described. Theoretical validation of the mass balance, the stripping rate, the ohmic polarization, and the mesh deformation demonstrated the consistency of the volumetric deformation strategy. We demonstrated in this study a deformable modeling strategy, which was found to be useful for the electrostripping analysis of anodic geometry defects during discharge. Non-uniformity in the lithium stripping rate was found along the anodic interface with defects, and this non-uniformity was accentuated with a higher discharge rate. The cell's discharge potential was decomposed by considering the equilibrium potential and the polarizations of the main components of the cell. This post-processing was found to be useful for the understanding of the cell's behavior. [ABSTRACT FROM AUTHOR]

High ionic conductivity is the key point in the development of new solid‐state electrolytes. Herein, a combining strategy of anion (O2−) doping and structure distortion is applied to enhance the Li+ ion conductivity in Li15P4S16Cl3, thus converting the nonionic conductor into fast ionic conductor. Solid‐state 6Li nuclear magnetic resonance analysis shows redistribution of Li+ ions in Li15P4S16Cl3 with O2− doping or local structure distortion via ball milling, indicating energy changes at different lithium sites. As a result, the activation energy is reduced from 0.50 to 0.35 eV for the ball‐milled Li15P4S15.6O0.4Cl3, and the ionic conductivity is enhanced from 10−9 to 10−4 S cm−1. The electrochemical stability of Li15P4S15.6O0.4Cl3 is broadened at the anode side as well. The symmetric cell Li|Li15P4S15.6O0.4Cl3|Li can cycle more than 1000 h with negligible voltage increase. The LiCoO2|Li15P4S15.6O0.4Cl3|Li‐Si all‐solid‐state battery demonstrates an initial capacity of 106 mA h g−1 and retains 92% capacity after 200 cycles at 0.5 C, highlighting excellent rate performance and electrochemical stability. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries (ASSBs) based on inorganic solid electrolytes fascinate a large body of researchers in terms of overcoming the inferior energy density and safety issues of existing lithium‐ion batteries. To date, the cathode designs in the ASSBs achieve remarkable achievements, adding the urgency of scaling up the battery system toward inorganic solid‐state pouch cell configuration for the application market. Herein, the recent developments of cathode materials and the design considerations for their application in the pouch cell format are reviewed to straighten out the roadmap of ASSBs. Specifically, the intercalation compounds and the conversion materials with conversion chemistries are highlighted and discussed as two potentially valuable material types. This review focuses on the basic electrochemical mechanisms, mechanical contact issues, and sheet‐type structure in inorganic solid‐state pouch cells with corresponding perspectives, thus guiding the future research direction. Finally, the benchmarks for manufacturing inorganic solid‐state pouch cells to meet practical high energy density targets are provided in this review for the development of commercially viable products. [ABSTRACT FROM AUTHOR]

Low ionic conductivity, oxidation potential, and poor lithium stability limit the applications of solid polymer electrolyte (SPE) in advanced energy storage systems. Combining functional inorganic materials and flexible polymers is crucial for achieving high ionic conductivity and exceptional rate performance in all-solid-state batteries (ASSBs). Herein, uniform boron nitride nanosphere (BNSPH) with reactive surface defects was prepared through an improved chemical vapor deposition method with high-temperature ammonia immobilization treatment and was introduced to the poly-(ethylene oxide) (PEO)-based SPE. Homogeneously dispersed nanostructures reduce the polymer's crystallinity, facilitating the movement of polymer chain segments and significantly improving the composite electrolyte's ionic conductivity. The interaction between BNSPH and the PEO chain enhances the structural stability of the composite polymer electrolyte (CPE) under high voltage, and the oxygen vacancies on the BNSPH surface immobilize TFSI–, promoting the transfer of more dissociated Li+ through the PEO chain. In addition, the excellent thermal conductivity enhances the interface stability and effectively avoids the growth of lithium dendrites. The CPE-5% exhibits an ionic conductivity of 3.86 × 10–4 S cm–1 and high voltage stability at 60 °C. Therefore, the assembled Li|CPE-5%|Li cell exhibited stable plating/stripping for 2000 h with a small polarization voltage. Furthermore, Li/LFP batteries incorporating CPE-5% exhibit remarkable rate performance (87.8 mA h g–1 at 2.0 C) and outstanding cycle stability (157.4 mA h g–1 after 150 cycles at 0.5 C and 60 °C). Furthermore, the NCM622/Li assembled with CPE-5% could achieve an excellent lifespan. This study confirms the feasibility of this application and inspire the application of defect-rich BNSPH in SPEs. [ABSTRACT FROM AUTHOR]

Argyrodite sulfide solid electrolytes (SSEs) have been attracting more concentration in ionic conductivity, crystal structure, and mechanical properties. Nevertheless, shortcomings of SSEs like poor air‐vapor stability and interface reactions limit the wider application in batteries. Herein, a double‐element ZnO substitution strategy is applied to enhancing Li5.5PS4.5Br1.5 Argyrodite electrolyte structure stability and property, Li5.5PS4.5Br1.5 electrolyte with a small amount of ZnO substitution to P and S. Li5.5+3xZnxP1‐xOxS4.5‐xBr1.5 solid electrolytes have achieved improved performance, interface composition also has changed, and crystal structure is becoming more stable. Specifically, LPSBr1.5‐4 %ZnO exhibits the most promising comprehensive properties, more expanded lithium pathway and crystal cell size, 2.25 mS cm−1 ionic conductivity at 25 °C, 65 % electronic conductivity decline, and air stability enhancement. Moreover, LPSBr1.5‐4 %ZnO show decent lithium compatibility and dendrite suppression capability, LPSBr1.5‐4 %ZnO can continue cycling for more than 800 h at 0.1 mA cm−2 in Li symmetric cell, and critical current density has reached 1.4 mA cm−2. More importantly, an all‐solid‐state battery (ASSB) with LPSBr1.5‐4 %ZnO electrolyte can cycle with 130 mAh g−1 capacity and more than 120 cycles in LiCoO2|SSE|In‐Li cell. Our work might provide a strategy to promote structure stability and electrochemical durability, and how element substitution affects ionic transport pathway and crystal structure. [ABSTRACT FROM AUTHOR]

Abstract The cathode surface of sulfide‐based all‐solid‐state batteries (SBs) is commonly coated with amorphous‐LiNbO3 in order to stabilize charge–discharge reactions. However, high‐voltage charging diminishes the advantages, which is caused by problems with the amorphous‐LiNbO3 coating layer. This study has investigated the degradation of amorphous‐LiNbO3 coating layer directly during the high‐voltage charging of SBs. O2 generation via Li extraction from the amorphous‐LiNbO3 coating layer is observed using electrochemical gas analysis and electrochemical X‐ray photoelectron spectroscopy. This O2 leads to the formation of an oxidative solid electrolyte (SE) around the coating layer and degrades the battery performance. On the other hand, elemental substitution (i.e., amorphous‐LiNbxP1‐xO3) reduces O2 release, leading to stable high‐voltage charge–discharge reactions of SBs. The results have emphasized that the suppression of O2 generation is a key factor in improving the energy density of SBs.

All-solid-state batteries (ASSBs) with solid electrolytes are expected to be promising energy storage devices. However, the large charge-transfer resistance at the electrode/electrode homo-interface and/or electrode/solid-electrolyte hetero-interface needs to be solved for practical applications. To overcome this problem, it is necessary to understand how the ions are transferred during battery operation. Here, we used operando electron energy-loss spectroscopy (EELS) using a scanning transmission electron microscope (STEM) to directly visualize the Li-ion movement in the cathode materials in bulk-type ASSBs. We show that the ion movement is strongly related to the crystal orientations of the cathode particles, and that Li-ions move even in the open-circuit conditions of the batteries. [ABSTRACT FROM AUTHOR]

All‐solid‐state‐batteries (ASSBs) are considered as promising next‐generation batteries in order to achieve improvements in both energy density and safety. The complex electrochemical processes in ASSBs taking place on different time scales can be probed by means of electrochemical impedance spectroscopy. However, the separation of anode and cathode contributions to the impedance and the understanding of the underlying electrochemical processes in both electrodes is a challenging task. Here, we compare the impedance spectrum of a prototypical full ASSB to those of symmetric cells anode | separator | anode and cathode | separator | cathode. We use Ni‐rich polycrystalline LiNi0.85Co0.10Mn0.05O2 particles as active material inside the composite cathode and an indium‐lithium alloy as anode. Based on the comparison, we show that the charge transfer process inside the cathode is remarkably fast, i. e., even faster than observed for cathodes of batteries with liquid electrolyte. Our results give indication that the differences in the time scales of cathode and anode processes are related to the distinct transport properties of interphases inside the cathode and at the anode | separator interface, respectively. [ABSTRACT FROM AUTHOR]

Solid electrolytes (SEs) play an essential role in the development of all‐solid‐state batteries (ASSBs) due to their exceptional ionic conductivity. However, conventional pelletized SEs with hundreds of micrometers result in highly reduced energy density and suffer from mechanical brittleness, which delay the commercialization of ASSBs. In this study, we present an innovative approach to fabricate SE membranes with perforated Al2O3 nanolayer‐coated polyethylene (PE) separator as a mechanical supporter. Al2O3‐coated separators exhibit better adhesion with LPSCl particles and better thermal stability. As a result, the SE membrane exhibits thickness of 35 μm while maintaining a superior mechanical tensile strength. Furthermore, when the SE membrane is applied to Li||LiNi0.7Co0.15Mn0.15O2 full‐cells, stable cycling performance over 250 cycles, which is comparable to thick LPSCl pellet cell, can be achieved even with higher conductance (>150 mS). Our results highlight the potential of thin and durable SE membranes in contributing to the commercialization of ASSBs. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries have gained considerable attention due to their high safety and energy density. However, solid state electrolytes which contribute to the ionic conductivity component of a composite electrode, are not utilized during the electrode reaction and cannot directly contribute to capacity. This study focuses on decreasing the amount of electrolyte in the electrode by utilizing Ca(BH4)2 as an active electrode material. In this work, the charge‐discharge properties of Ca(BH4)2 as an electrode material were determined for the first time. The lithiation of the Ca(BH4)2 anode creates LiBH4 within the electrode mixture, providing new Li‐ion conduction pathways within the composite electrode in situ. An electrode fabricated only from Ca(BH4)2 and acetylene black (AB) showed an initial capacity of 473 mAh g−1 at 120 °C, which is comparable to the performance obtained from a composite electrode additionally containing electrolyte. Evidently, Ca(BH4)2 is a promising candidate negative electrode for increased energy density all‐solid‐state Li‐ion batteries. [ABSTRACT FROM AUTHOR]

All‐solid‐state rechargeable batteries are regarded as one of the most promising next‐generation energy storage devices, while their cycling stability is still a great challenge due to the nonuniform lithium ion transportation and the loss of active lithium during cycling. Herein, a LiF embedded prelithiated graphite interface layer is designed and inserted between Li6PS5Cl solid electrolyte layer and graphite anode layer. The presence of LiF, C−F bonds and prelithiated graphite in this unique interface layer can facilitate uniform lithium ion migration and compensate the loss of active lithium, thus significantly improving the cyclic performances of both monopolar and bipolar all‐solid‐state lithium ion batteries. After 100 cycles at 0.1 C, the capacity retention increases from 58 % to 78.5 % for the monopolar LiNi0.5Co0.2Mn0.3O2|Li6PS5Cl|LiF@2.5 %Li@G|graphite all‐solid‐state lithium ion battery. Besides, the bipolar all‐solid‐state lithium ion batteries show a high discharge plateau of ~7.6 V with a capacity retention of 60.2 % after 190 cycles at 0.1 C. This work demonstrates the effectiveness of LiF embedded prelithiated graphite interface layer for improving the electrochemical performances of all‐solid‐state lithium ion batteries. [ABSTRACT FROM AUTHOR]

Low-melting-point Ga–xSn eutectic composites and natural silicate mineral powders were used as the electrode and solid-state electrolyte, respectively, in all-solid-state batteries for green energy storage systems. The influences of the Sn content in the Ga–xSn composite electrode on the electrochemical performance of the batteries were evaluated, and liquid composites with a Sn concentration of up to 30 wt.% demonstrated suitability for electrode fabrication through dip coating. Sodium-enriched silicate was synthesized to serve as the solid-state electrolyte membrane because of the abundance of water molecules in its interlayer structure, enabling ion exchange. The battery capacity increased with the Sn content of the Ga–xSn anode. The formation of intermetallic compounds and oxides (CuGa2, Ga2O3, Cu6Sn5, and SnO2) resulted in a high charge–discharge capacity and stability. The Ga–Sn composite electrode for all-solid-state batteries exhibits a satisfiable capacity and stability and shows potential for jet-printed electrode applications. [ABSTRACT FROM AUTHOR]

Mechanical properties of Li10.35Ge1.35P1.65S12(LGPS) solid electrolytes with different grain sizes were investigated via indentation tests. Hand-milled LGPS (HM LGPS, d50:1.32 µm) and wet-milled LGPS (WM LGPS, d50:0.46 µm) powders were uniaxially pressed to obtain pellet samples. The HM LGPS and WM LGPS pellets had a similar bulk density of 1.63 g cm–3. At the initial loading/unloading, the WM LPGS pellet showed a large deformation owing to a decrease in cavities compared with the HM LGPS. In the subsequent cycles, both pellets exhibited elastic deformation behavior in the pressure range up to 20 N. The elastic modulus and relative residual depth of HM LGPS and WM LGPS were 21.7 GPa and 0.41 GPa and 0.75 and 0.71, respectively. This result revealed that WM LGPS is more elastically deformable and less plastically deformable than HM LGPS, which could be associated with the grain boundary strengthening interpreted by the Hall-Petch relation. Based on these mechanical properties, the superior cycle stability at the In-Li electrode/WM LGPS electrolyte interface during charging/discharging was discussed. Controlling the mechanical properties of sulfide solid electrolytes by the grain size is important for suppressing physical degradation in all-solid-state batteries. [ABSTRACT FROM AUTHOR]

We have been conducting research to explore new materials and their use in batteries by pursuing the phenomenon of high ion diffusion in solids. Lithium ion conducting materials have been particularly explored because of their potential application to all-solid-state batteries with high energy density. In addition to an overview of lithium ionic conductors, we will review the material search process for Li10GeP2S12, which exhibits particularly high ionic conductivity. We will also review the research that clarified the formation region of this material, investigated the ionic conduction mechanism, and applied this material to all-solid-state batteries. [ABSTRACT FROM AUTHOR]