All-solid-state lithium metal batteries offer high energy density and enhanced safety, yet mechanical instability at both positive electrode/solid electrolyte and Li metal/solid electrolyte interfaces severely limits cycling stability and rate performance, particularly at a low stacking pressure. Here, we report a facile, industry-compatible strategy to refine polycrystalline Li5.5PS4.5Cl1.5 grains using Al4C3 abrasives. The resulting Al4C3-engineered Li5.5PS4.5Cl1.5 exhibits reduced average particle size and a narrowed size distribution. The refined electrolyte grains enable a high relative density in both anolytes and composite positive electrodes. Beyond particle refinement, Al4C3 in the anolyte stabilizes the Li/electrolyte interface through its high modulus, low electronic conductivity, and favorable interfacial mechanics, enabling a high critical current density/capacity of 3.2 mA cm‒2/3.2 mAh cm-2. Leveraging our designed electrolyte as both anolyte and catholyte, the all-solid-state lithium metal batteries demonstrate stable cycling performance under a low stack pressure of 4 MPa and a positive electrode loading of 1.4 mAh cm-2, sustaining over 1500 cycles at 1.4 mA cm‒2. This study provides a potentially simple and scalable approach to optimize solid electrolyte particles and interfacial mechanics.

All-solid-state batteries (ASSBs) with inorganic solid-state electrolytes (SSEs) hold vast potential for next-generation electric vehicles (EVs) due to their high energy density and enhanced safety. However, their self-discharge behaviour, a critical factor for EVs, has not been adequately investigated so far. Here we reveal that the electronic conductivity of SSEs, typically in the range of 10−8–10−9 S cm−1, contributes to considerable physical self-discharge in ASSBs, particularly when the SSE thickness is on the order of tens of micrometres. To mitigate this physical self-discharge, the electronic conductivity of SSEs needs to be reduced to approximately 10−12 S cm−1. However, none of the prevalent SSEs meets this threshold. Therefore, reducing physical self-discharge in ASSBs will require the development of SSEs with lower electronic conductivity, alongside rational interface and full-cell designs in future research. This study provides critical insights into the self-discharge phenomenon of ASSBs, which may reshape their future design and development. Physical self-discharge critically limits the lifetime of all-solid-state batteries (ASSBs). Wang et al. showed that the non-negligible electronic conductivity of solid-state electrolytes can lead to substantial physical self-discharge in ASSBs.

Inorganic solid electrolytes offer transformative opportunities for next-generation lithium batteries by enabling new chemistries and cell architectures. Among them, sulfide electrolytes are particularly attractive due to their high ionic conductivity and favorable mechanical processability. However, scalable synthesis of sulfide electrolytes with high ionic conductivity remains a significant bottleneck. Here, we report a liquid-phase synthesis platform based on a Li2S-SiS2-P2S5 ternary system, capable of producing electrolytes with high ionic conductivity at kilogram scale. Beyond fast ionic transport kinetics, the electrolytes prepared via this platform function effectively as catholytes for high-loading sulfur electrodes, promoting uniform ion transport and enhanced electrochemical kinetics. Building on this approach, a Li2S-SiS2-P2S5-LiI quaternary system is developed to produce lithium-metal compatible anolytes. As a result, we realize a long-cycling all-solid-state lithium-sulfur battery in which the catholyte, interlayer, and anolyte are all synthesized via liquid-phase methods. This work proposes a scalable route for producing sulfide electrolytes, potentially contributing to the industrial development of all-solid-state batteries. Sulfide electrolytes are promising candidates for solid-state batteries, but their scalable production remains challenging. Here, the authors develop a kilogram-scale liquid-phase synthesis platform for sulfide electrolytes used across all key components in all-solid-state lithium–sulfur batteries.

Supported platinum-group-metal single-atom catalysts (SACs) have garnered widespread attention in heterogeneous catalysis due to their theoretical 100% atomic utilization efficiency. Isolated metal atoms usually exhibit high oxidation states rather than metallic states owing to the coordination with nonmetal atoms in the supports. Despite recent advances in modulating the coordination environments of SACs, achieving metallic state-dominated SACs remains a formidable challenge. Herein, a new configuration of metallic Pt single atoms (Pt0) anchored on the CeO2 support is constructed by introducing a localized Pt-Ce metal-metal coordination at the interface in a molten NaAlCl4 environment. The extensive Pt─Ce bonding and electron transfer from the support to the Pt atoms ensure the metallic nature of isolated Pt atoms. This work opens up a new avenue for constructing metallic single atoms and enriches the SACs chemistry.

All-solid-state lithium-sulfur batteries (ASSLSBs) are emerging as next-generation energy storage systems, offering enhanced energy density, safety, and cost-effectiveness. However, the breakdown of the ion-conducting network within sulfur cathode limits their cycling life and poses challenges to practical application. Here, we design an innovative unitized encapsulation architecture to decouple and rebuild Li-ion transport pathways through interfacial spontaneous anion exchange behavior between Li5.5PS4.5Cl1.5 and Li3YBr6 electrolytes. In this design, the internal Li5.5PS4.5Cl1.5 enables durable intra-particle charge transfer trails, while the external halide Li3YBr6 framework establishes inter-particle Li-ion diffusion highways. This hierarchical ion-conducting mechanism facilitates efficient and durable Li-ion flow. Moreover, the core-shell configuration alleviates localized stress accumulation and catholyte irreversible decomposition during cycling, reinforcing robust ion-conducting pathways and persistent phase contact. The optimized sulfur cathode, S/LPSC@LYB-0.25, exhibits remarkable electrochemical performance, achieving 85% capacity retention over 1000 cycles under high sulfur loading of 8 mg cm-2 and a high current density of 6.7 mA cm-2. Developed pouch cells demonstrate unparalleled cycling stability under low stack pressure, retaining 76.9% capacity after 500 cycles. This work provides a practical and scalable strategy for tailored ion-conducing network architecture, advancing the industrial viability of ASSLSBs.

Halide solid electrolytes (HSEs) have seen rapid progress in the development of all‐solid‐state lithium batteries (ASSLBs), offering favorable lithium‐ion transport properties, broad electrochemical stability, and strong interfacial compatibility with high‐voltage oxide cathodes. However, developing HSEs that simultaneously offer high ionic conductivity and low cost remains a significant challenge. Most high‐conductivity halides rely on expensive metal elements, whereas cost‐effective Zr‐based halides are limited by their relatively low ionic conductivity. In this study, a new composite electrolyte (LA/LZCO) is developed via an interfacial coordination reaction between Zr‐based oxychlorides (LZCO) and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP). The coordination between PO 4 3− groups in LATP and Zr 4+ in LZCO induces local structural disorder, promoting LZCO amorphization. As a result, the ionic conductivity of LA/LZCO composite electrolyte is enhanced by more than twofold compared to LZCO, reaching 2.81 mS cm −1 , among one of the highest reported for Zr‐based halide electrolytes. When integrated into ASSLBs with NCM83125 cathodes, the composite electrolyte enables excellent cycling stability, with 92.4% and 87.5% capacity retention after 1000 cycles at 0.5 and 2 C under 4.25 V. Even at an elevated cut‐off voltage of 4.5 V, 85.1% capacity is retained after 380 cycles, highlighting the promise of this composite strategy for high‐energy, long‐life ASSLBs.

Halide solid-state electrolytes (SSEs) are promising superionic conductors with high oxidative stability and ionic conductivity, making them attractive for all-solid-state lithium-ion batteries. However, most studies have focused on ion-stacking structures, overlooking the role of bond characteristics in ionic transport. Here, we investigate bond dynamics and the superionic transition (SIT) in bromide electrolyte, Li 3 InBr 6 , using synchrotron X-ray techniques and ab initio molecular dynamics (AIMD) simulations. We demonstrate that the SIT in halide SSEs is driven by a thermally induced transition in bonding character (ionic to covalent) rather than a change in crystal phase. AIMD simulations further reveal enhanced Li⁺ diffusion and collective anion motion at elevated temperatures. Expanding our study to Li 3 LnBr 6 (Ln = Gd, Tb, Ho, Tm, and Lu), we confirm the widespread occurrence of SIT in this material class, with Li 3 GdBr 6 exhibiting the highest ionic conductivity (5.2 mS cm −1 at 298 K). More importantly, the ionic-covalent transition is highly tunable through electrolyte modifications, such as cation/anion substitution and synthesis methods. Our findings provide a new perspective on ionic transport, highlighting the critical role of chemical bond characteristics in halide SSEs.

Strong metal-support interaction (SMSI) is a special form of interaction between metal species and supports in heterogeneous catalysts, and manifests as various types of geometric structure changes. These SMSI behaviors serve as effective strategies to precisely regulate the surface and interface structures of supported metals, and hence has stimulated extensive research interest on the construction and regulation of SMSI. While the nature of SMSI has long been regarded as the strong interfacial metallic bonds between the supported metals and the metal cations in supports, it remains elusive why such a universal principle results in diverse structural changes in different material systems. In this perspective, it is explored and summarized the SMSI behaviors across different material systems, aiming to provide a systematic and unified framework for understanding SMSI. It is suggested that the direct reduction of surface energy and the increase of entropy is the thermodynamic driving force of SMSI, and the kinetic factors, i.e. the diffusion rate of metal atoms, determine the specific form of SMSI. This perspective would provide deeper and more systematic insights into SMSI behaviors and is instrumental to the precise regulation of the surface and interface structures of supported metal catalysts.

All-solid-state batteries require advanced cathode designs to realize their potential for high energy density and economic viability1-3. Integrated all-in-one cathodes, which eliminate inactive conductive additives and heterogeneous interfaces, hold promise for substantial energy and stability gains but are hindered by materials lacking sufficient Li+/e- conductivity, mechanical robustness and structural stability4-14. Here we present Li1.3Fe1.2Cl4, a cost-effective halide material that overcomes these challenges. Leveraging reversible Fe2+/Fe3+ redox and rapid Li+/e- transport within its framework, Li1.3Fe1.2Cl4 achieves an electrode energy density of 529.3 Wh kg-1 versus Li+/Li. Critically, Li1.3Fe1.2Cl4 shows unique dynamic properties during cycling, including reversible local Fe migration and a brittle-to-ductile transition that confers self-healing behaviour. This enables exceptional cycling stability, maintaining 90% capacity retention for 3,000 cycles at a rate of 5 C. Integration of Li1.3Fe1.2Cl4 with a nickel-rich layered oxide further increases the energy density to 725.6 Wh kg-1. By harnessing the advantageous dynamic mechanical and diffusion properties of all-in-one halides, this work establishes all-in-one halides as an avenue for energy-dense, durable cathodes in next-generation all-solid-state batteries.

Organic electrode materials offer a versatile, sustainable approach for next-generation lithium-ion batteries but are limited by low working voltages and poor cycling stability. Here we report a solid-solvation-structure design strategy to improve both the voltage and stability of organic electrode materials in all-solid-state batteries. As a proof of concept, we incorporate halide electrolytes as solid solutes and tetrachloro-o-benzoquinone as a solid solvent to form homogeneous solid cathode solutions. Systematic optimization of the inner solvation configuration enables tetrachloro-o-benzoquinone to achieve a high working voltage (3.6 V vs. Li+/Li) at room temperature within an asymmetric solid solvation sheath. Moreover, the equilibrium redox pathway and electrostatically driven self-healing interfaces revealed rapid redox kinetics and stable performance over 7,500 cycles in all-solid-state batteries under low stack pressures. This work demonstrates that organic electrode materials can serve as viable, durable and cost-effective alternatives to transition metal oxides in all-solid-state batteries. Organic electrode materials offer a versatile and sustainable route for lithium-ion batteries, but their application is hindered by low working voltages and poor cycling stability. Now, it has been shown that dissolving halide electrolytes into organic electrodes effectively tunes the working voltage and enhances the electrochemical performance of all-solid-state batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) show great promise for next-generation energy storage systems due to their high energy density, low cost, and enhanced safety features. However, constrained solid-state sulfur conversion severely limits their cycling stability and rate performance, presenting significant obstacles to industrial implementation. Here, a mechanochemical synthesis approach is developed that simultaneously addresses multiscale kinetic limitations of all-solid-state sulfur cathodes across molecular, interfacial, and electrode levels. The in situ generated amorphous lithium iodothiophosphate (LPSI) interlayer, chemically bridged between sulfur active materials and sulfide catholytes, establishes effective and durable Li-ion conduction pathways through reduced diffusion resistance and reinforced interfacial contact. Moreover, the LPSI functions as percolated redox mediators that modulate sulfur redox pathways and electrochemically activate sulfur species, facilitating rapid sulfur redox kinetics. The developed sulfur cathode (S@LPSI/LPSC) demonstrates exceptional electrochemical performance, maintaining 93.8% capacity retention, exceeding 1600 cycles at a high sulfur loading of 6 mg cm-2 and an elevated current density of 5 mA cm-2. Pouch cells incorporating the S@LPSI/LPSC cathode demonstrate gravimetric energy densities exceeding 420 Wh kg-1. This work provides valuable insights into highly reversible all-solid-state sulfur cathodes, significantly advancing the industrialization of ASSLSB technology.

All-solid-state lithium metal batteries (ASSLMBs) with solid-state electrolytes (SSEs) are regarded as nextgeneration energy storage technology due to their superior safety and exceptional energy density. However, soft breakdown-a prevalent failure mechanism in ASSLMBs-has hindered their development. In this study, we introduce Li/SSE/current collector (CC) asymmetric cells as a novel evaluation method to assess the susceptibility of various SSEs to soft breakdown. Our findings reveal that metal-contained SSEs (e.g., LGPS) exhibit a stronger resistance to soft breakdown compared to metal-free SSEs (e.g., LPSC) through phase characterization including ToF-SIMS and XPS. This enhanced stability is attributed to the formation of a metal-containing solid electrolyte interphase (SEI) at the interface. Moreover, the impact of practical cell configuration including current density, stack pressure, cutoff voltage on the occurrence of soft breakdown was also discussed. The insights gained from this work deepen the understanding of the soft breakdown phenomenon in SSEs and provide valuable guidance for the design of advanced solid-state electrolytes.

Halide electrolytes are recognized as highly promising catholytes for all-solid-state lithium batteries (ASSLBs) owing to their wide electrochemical windows, high ionic conductivity, and excellent compatibility with layered oxide cathodes. Despite these advantages, the practical application of halide-based ASSLBs remains constrained by their low areal capacity, which stems from the necessity of high catholyte loadings to establish percolating Li+ conduction pathways within composite cathodes. Here, a self-dispersing halide catholyte engineering is proposed to achieve a high-loading cathode via coordinating chemistry between tetrafluorobenzoquinone (TCBQ) and Li3InCl6. The coordinated TCBQ molecules introduce steric hindrance effects, preventing thermodynamically driven halide particle agglomeration while achieving particle size reduction. Moreover, the dry process in thick cathode preparation further promotes particle rearrangement during thermal calendaring. Consequently, these optimizations reduce the catholyte content from the typical 30-17 wt.%, while maintaining an efficient and robust ion/electron conduction network. The optimized high-Ni layered oxide cathode exhibits exceptional rate capability, delivering 145.8 mAh g-1 at 2C. Moreover, at a high active material loading of 12 mg cm-2, the cathode achieves a remarkable initial areal capacity of 1.845 mAh cm-2, while retaining 1.512 mAh cm-2 after 400 cycles.

Utilizing thin Li anodes is the key to realizing high-energy-density solid-state lithium metal batteries (SSLMBs). However, the practical implementation of thin Li anodes is significantly challenged by the inevitable formation of lithium dendrites, as well as the lithium depletion caused by interfacial side reactions. To address this, we propose a lumped Li-Gr@MgF2 (LGMF) anode comprised of lithiated MgF2-coated graphite, which precisely reconstructs the lean-lithium metal anode through bottom-up integration. Finely optimized electrode units of LiC6-LiMg/LiF possess lithiophilic Li-Mg alloy and high-interface-energy LiF interfacial modification, which regulate the lithium-ion flux and effectively suppress dendrite growth. Assembling electrode units collaboratively establishes the ion-electron percolating network within the LGMF, fully activating the entire anode. The optimized LGMF anodes extend the longevity of carbonate-based quasi-solid-state symmetric cells to 2400 h at 0.2 mA cm-2/0.2 mAh cm-2, even under limited lithium conditions. LiFePO4 full cells utilizing LGMF anodes exhibit steady galvanostatic cycling over 400 cycles, attaining a notable capacity retention of 95.5 % at 0.5 C. Meanwhile, the LGMF||LiNi0.83Co0.12Mn0.05O2 cells demonstrate enhanced rate capability and prolonged electrochemical lifespan. This strategy offers practical insight for lean-lithium metal anode engineering toward highenergy-density SSLMBs.

Traditionally, metal-free interphases were preferred to avoid continuous electrolyte reduction. Recent studies, however, show that some metal-incorporated interphases formed between inorganic solid electrolytes and Li can enhance Li reversibility.

Li intrusion is the primary factor contributing to the undesirable cycling durability and rate capability of all-solid-state lithium metal batteries. However, conventional engineering methodologies for solid electrolytes (SEs) that focus on crystalline scales, such as doping, have limited efficacy in addressing this issue, as they not only involve cumbersome trial-and-error processes but also struggle to simultaneously optimize the multiple macroscopic properties necessary for effectively suppressing Li intrusion. Herein, rather than following the conventional practice of SE engineering, it is concentrated on optimizing SEs at the grain-aggregate level. A highly scalable chemical approach based on a thermodynamic-favored anion exchange reaction is first developed to engineer an amorphous metal compound layer on the surface of argyrodite-type electrolyte grains. Further, a novel localized grain engineering concept is introduced, which combines engineered and pure electrolyte grains to enable aggregates with favorable macroscopic properties for suppressing Li intrusion. The localized grain-engineered electrolyte aggregates greatly enhance Li reversibility and are able to suppress Li intrusion under practical working conditions. Notably, the 20 µm-Li||LiNi0.83Co0.12Mn0.05O2 cell using localized grain-engineered electrolyte aggregates can stably cycle for over 2000 cycles at a high current density of 1.6 mA cm-2.

All solid-state lithium batteries (ASSLBs) overcome the safety concerns associated with traditional lithium-ion batteries and ensure the safe utilization of high-energy-density electrodes, particularly Li metal anodes with ultrahigh specific capacities. However, the practical implementation of ASSLBs is limited by the instability of the interface between the anode and solid-state electrolyte (SSE). To mitigate this, considerable research has been dedicated to achieving enhanced stability at the anode/SSE interface. Among the current strategies for enhancing interface performance, the concept of Li-alloy materials is extensively used and well functionalized in various scenarios, including Li alloys as anodes, Li-alloy interlayers and Li alloys in the anode. Despite the notable achievements of Li-alloy materials in ASSLBs, the functionality, practicality and working mechanism of Li-alloys have not been fully elucidated. This review commences by providing an exhaustive and in-depth examination of the fundamental kinetics, thermodynamics, and mechanics, highlighting Li-alloy materials. Subsequently, through a systematic interconnection of material properties and their practical applications, we undertake a comprehensive analysis of the operative principles governing Li alloys. This analytical approach allows a thorough evaluation of the viability and utility of Li alloys within the context of ASSLBs. Finally, this review concludes by succinctly summarizing the future prospects and inherent potential of Li-alloy materials for further advancing the field of ASSLBs.

Sulfide-based all-solid-state lithium batteries (ASSLBs) featuring Ni-rich layered oxide cathodes are emerging as the leading contenders for the next generation of rechargeable batteries with outstanding safety and energy density characteristics. However, the composites of Ni-rich oxides and sulfide electrolytes continue to grapple with persistent challenges encompassing structural deterioration, adverse interfacial parasitic reactions, and sluggish kinetics within the carbon-free cathodes. Here, a synergistic design to circumvent these issues via the coupling of Zr/F co-doping and conductive cyclized polyacrylonitrile (cPAN) coating to tailor both the bulk and surface chemistry of the Ni-rich layered oxide LiNi0.83Co0.12Mn0.05O2 (NCM83125) cathode is proposed. The cathode subjected to this coordinated modification strategy showcases exceptional performance in sulfide-based ASSLBs. It demonstrates robust cycling performance, with a capacity retention of 95% observed after 300 cycles at a rate of 0.2 C, alongside satisfactory rate performance, achieving a capacity of 109 mAh g-1 at a high rate of 3 C. The coupling of Zr/F co-doping and cPAN coating tailors both the bulk and surface chemistry of the Ni-rich layered oxide LiNi0.83Co0.12Mn0.05O2 cathode, which demonstrates exceptional performance, with a capacity retention of 95% observed after 300 cycles at a rate of 0.2 C, achieving a capacity of 109 mAh g-1 at a high rate of 3 C. image

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. A novel cube-shaped microstructure in the Li5.3PS4.3ClBr0.7 argyrodite electrolyte is identified by synthesizing via high-speed mechanical milling followed by an annealing method (BMAN-LPSCB). The uniform microstructure allows to produce 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. image

Glassy sulfide electrolytes represent ideal materials for all-solid-state lithium metal batteries (ASSLMBs) owing to their grain-boundary-free and soft nature. Nevertheless, current glassy sulfides remain constrained ionic conductivity and unsatisfactory Li compatibility. Herein, we propose a novel design for glassy sulfide electrolytes by incorporating a transfer accelerator (LiI) and an interface modifier (SnO2) into the conventional 75Li2S-25P2S5 glass matrix. The introduction of LiI serves to enhance ion transport, resulting in a commendable ionic conductivity of 1.93 mS cm-1 at room temperature in the optimized glass. Additionally, the presence of the interface modifier induces the formation of Li-Sn alloys and insulates Li2O upon reduction. The Li-Sn alloy with high adsorption energy towards the Li and electronically insulated Li2O components in the interphase ensure the interfacial contact and minimize side reactions. Consequently, symmetric cells utilizing the optimized glassy sulfide electrolyte demonstrate stable operation for over 4500 h at 0.2 mA cm-2 / 0.2 mAh cm-2. The Li || NCM83125 full cell utilizing the glass retains a capacity retention of 81.7 % after 250 cycles at 0.5 C. This study offers valuable insights into the design methodology of glassy sulfide electrolytes for suppressing dendrite growth.