Covalent organic frameworks-based solid-state electrolytes have attracted significant attention in recent years due to their design flexibility, intrinsic porosity, and environmentally friendly characteristics. However, their practical application in batteries remains limited by inadequate ionic conductivity and Li+ transference number, primarily arising from the absence of effective strategies to modulate the pore chemical environment for ion transport. In this study, we introduce a pore-engineering approach by incorporating alternating oxyethylene and perfluoroalkyl chains into the covalent organic frameworks. This sequence-controlled modification simultaneously suppresses anion migration and mitigates lithium-ion aggregation, thereby constructing a continuous and efficient site-to-site Li+ transport pathway. Benefiting from this design, the resulting covalent organic framework exhibits a high Li+ conductivity of 1.06 mS·cm-1 at 25 °C and an Li+ transference number of 0.9. A symmetric Li | |Li cell delivers Li plating/stripping stability over 7500 hours with minimal voltage polarization at 0.2 mA·cm-2 and areal capacity of 0.2 mAh·cm-2. Furthermore, solid-state Li | |LiNi0.8Mn0.1Co0.1O2 battery demonstrates a specific capacity of 180 mAh·g-1 at 1 C (1 C = 200 mA·g-1) and long-term stability at 5 C, retaining 80% capacity after 700 cycles. Here we report pore design strategy and open avenues for the development of high-performance, fast-charging solid-state lithium batteries.

Silicon (Si) has been widely accepted as a promising anode material owing to its high theoretical capacity (3590 mAh g-1) and abundance. Nevertheless, its practical application in next-generation batteries has long been hindered by several inherent challenges, including an unstable solid-electrolyte interphase (SEI), large volume changes, and low electrical conductivity. Herein, a facile and effective chemical route is proposed to construct a functional organic molecule that could constrain the framework and tune the interfacial properties of Si/C electrodes. Superior electrochemical performance with high anode material loading (similar to 8.0 mg cm-2) and high areal capacity (above 3.0 mAh cm-2) is achieved for the Si/C anode in terms of excellent cycling stability. A unique interfacial anchoring mechanism is found that plays a major role in effectively alleviating the huge volume expansion and maintaining the integrity of the Si/C electrode. Moreover, an investigation of the surface chemistry confirms that the constructed molecule can improve the stability of the SEI by promoting the formation of a LiF-rich interphase. Our findings provide deep insights into the design of high-performance Si/C anodes for practical applications in next-generation batteries.

In recent years, oxychloride‐based materials have emerged as a promising solid‐state electrolyte (SSE) candidate owing to its ultrahigh ionic conductivity and decent cathode compatibility. Although the fabrication of SSE coatings for cathode materials has been recognized as a promising strategy, a precise synthesis of oxychloride‐based SSE coating is still not realized due to the lack of appropriate preparation method. As a proof of concept, we propose a superior lithium‐ion conductive aluminum‐based oxychloride (LAOC) coating synthesized by atomic level fabrication strategy with unique self‐limiting reaction mechanism. The LAOC modified lithium cobalt oxide (LCO) cathode exhibits a high capacity retention of 86.4% after 500 cycles at 5 C and significantly improved high‐voltage cycling stability. The outstanding performance is ascribed to the high interfacial ionic conductivity and construction of robust cathode electrolyte interphase. The ionic conductivity of LCO increased from 1.785 × 10 −7 to 2.823 × 10 −6 S cm −1 after LAOC coating. Scanning transmission X‐ray microscopy and transmission electron microscopy reveal that the LAOC coating suppresses interfacial degradation and mitigates the structural collapse of LCO. This study offers great opportunity for the atomic level fabrication of superior ionic conductive oxychloride thin films to realize high performance lithium‐ion batteries.

We report a phosphine 1-azaallyl ligand L2 [2-(diphenylphosphino)-2'-(3,3-dimethyl-1-azaallyl)-1,1'-biphenyl], which enables reversible coordination of Lewis bases through changes in ligand hapticity. In the palladium methyl complex [Pd(CH3)(L2)], L2 adopts a κ1-P;η3-NCC coordination mode. Pyridine binding induces reorganization to a κ2-PN mode, while reversion to the κ1-P;η3-NCC mode facilitates pyridine dissociation. These interconversions were established by 13C{1H} and 1H-31P HMBC NMR spectroscopy, X-ray absorption spectroscopy, and density-functional theory calculations. The results highlight a ligand-controlled mechanism for reversible substrate coordination based on tunable binding modes.

Alloy-based anodes, particularly indium (In) are emerging as promising candidates for achieving long-cycle life in all-solid-state lithium batteries (ASSLBs), due to their dendrite-free characteristics and ability to stabilize the anode interface. However, their practical applications remain hindered by limitations in the failure of In anodes under high current densities and areal capacities, where the incomplete understanding of the underlying failure mechanism limits the optimization strategies. Herein, we employ advanced characterization techniques to systematically investigate the failure mechanisms of In anodes under high current densities and areal capacities. Our findings reveal that alloying and dealloying processes involve an electro-chemo-mechanical coupling failure mechanism and further exacerbate performance degradation. By elucidating these failure mechanisms, our work provides critical insights and rational surface protection strategies by ALD coating with Al2O3 layer for enhancing the interfacial stability and performance of alloy anodes in ASSLBs. The maximum cycling capacity of the Li/In asymmetric cell at 0.5 mA/cm2 was enhanced from 0.2 to 2 mAh/cm(2) (>200 cycles). This work paves the way for the development of durable, high-energy-density batteries.

Halide-based solid-state electrolytes (SSEs), such as Li3InCl6 (LIC), are promising catholytes for all-solid-state batteries (ASSBs) because of their high ionic conductivity and high-voltage stability. However, the aging mechanism between halide SSEs and Ni-rich cathodes (LiNixCoyMn1 -x-yO2, NCM) remain poorly understood. Herein, we investigate the state-of-charge (SoC)-dependent aging behavior of LIC/NCM composite cathodes and reveal a non-monotonic relationship between SoC and capacity retention after aging. Severe capacity loss occurs under both low- and high-SoC conditions, whereas high capacity retention is achieved after aging at a mid-range SoC. Comprehensive structural and chemical analyses uncover a synergistic aging mechanism: reductive decomposition of LIC dominates aging at low SoCs, while structural degradation of NCM accounts for aging at high SoCs. Furthermore, an ultrathin coating layer introduced onto the NCM particle surface via atomic layer deposition effectively suppresses interfacial reactions and enhances electrochemical stability, particularly during low-SoC storage. This work provides mechanistic insights into SoC-dependent interfacial aging in halide-based ASSBs and proposes both SoC management and interface engineering strategy to extend their calendar life.

The energy density of lithium-ion batteries (LIBs) can be improved significantly by elevating the working voltage. Nevertheless, serious issues are generally induced at higher cut-off voltages for LIBs, including structural collapse and oxygen loss on the cathode side. Constructing a stable cathode-electrolyte interface (CEI) is considered as an effective approach to tackle these issues. Previous research has predominantly focused on designing crystallized interfacial structures. This omits the coating materials with other structures that could potentially surpass crystallized counterparts. Herein, the amorphization of the phosphate interface has been designed for high-voltage stable LCO by precisely tailored atomic-level fabrication. The modified LCO cathode exhibits excellent high-voltage rate capability of 142.1 mAh g-1 at 10 C and significantly improved cycling stability with a capacity retention of 83.3% after 200 cycles at 1 C. The outstanding performance attributes to the conformal high-voltage stable interface with favorable Li-ion conducting kinetics at LCO surface. Additionally, synchrotron-based X-ray analysis demonstrates that this amorphous layer helps stabilize lattice oxygen and alleviate the variation in the chemical state and local environment of Co at the deep charging state. This work offers new perspectives and possibilities on interphase engineering toward high-energy and stable LIBs.

Poly(vinylidene fluoride) (PVDF)-based solid polymer electrolytes (SPEs) are regarded as promising candidates for solid-state lithium batteries due to their excellent flexibility and processability. However, their practical applications are hindered by insufficient ion transport and severe interfacial side reactions, which originate from the strong Li+ coordination and intrinsic electrochemical instability of residual solvents such as N,N-dimethylformamide (DMF). To address these DMF-induced issues, we report a dipole-anchoring strategy that immobilizes residual DMF by integrating poly(1,3-dioxolane) (PDOL) into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF)-based SPE matrix. The PDOL-DMF interaction weakens Li+-DMF coordination and reshapes the solvation environment, resulting in an ionic conductivity of 0.62 mS cm⁻1 and an activation energy of 0.21eV. Furthermore, this dipole-dipole interaction enhances the electrochemical stability of DMF toward electrodes through frontier molecular orbital modulation, thereby promoting the formation of inorganic-rich interphases on both lithium anodes and high-voltage cathodes. Consequently, Li||Li symmetric cells deliver ultra-stable cycling over 5000h at 0.1mAcm⁻2, Li||LiFePO4 full cells achieve 2500 cycles at 3C, and Li||LiNi0.8Co0.1Mn0.1O2 cells retain 82.5% capacity after 500 cycles at 1C. This work demonstrates dipole-anchoring of residual solvent as an effective design principle for enhancing ion transport and interfacial stability in polymer-based solid-state lithium batteries.

Organic-inorganic composite solid-state electrolytes (CSSEs) represent a promising class of electrolyte materials for solid-state lithium batteries, as they effectively integrate the processability of polymers with the ionic transport, mechanical, and interfacial properties of inorganic solid-state electrolytes. However, their design usually does not rely on straight-forward filler-addition strategy, because each category of inorganic phases exhibits distinct conductivities, surface chemistries, structural connectivity, and processing compatibility. In this review, we discuss CSSEs based on specific functions and limitations of filler materials. For polymer-oxide systems, of the analysis focuses on local interfacial regulation, continuous ceramic pathways, and multilayer architectures tailored for electrode-specific interfaces. Polymer-sulfide systems are discussed with an emphasis on the preservation of intrinsic ionic conductivity during thin-film formation, which critically depends on binder chemistry, solvent compatibility, film density, and sulfide-sulfide contact. Polymer-halide systems are examined as an emerging direction for high-voltage cathode environments and interfacial stabilization, where growing opportunities emerge to extend their use toward thin, stable, and low-resistance electrolyte films. Finally, this review links filler-specific design with scalable, low-resistance thin films and practical cell integration, while identifying quantitative filler-polymer interfacial relationships, mechanical reliability, low-pressure operation, and dry-room processability as key future directions.

Lithium sulfide (Li2S), a key cathode material for all-solid-state lithium-sulfur (Li-S) batteries, faces challenges such as low electronic and ionic conductivities and limited active material utilization during cycling. In this study, we developed a new cathode featuring nanosized Li2S embedded in an amorphous LiFeS2 matrix (92Li2S@8LiFeS2). Benefiting from the mixed electronic and ionic conductivities of LiFeS2 along with its catalytic effect and the nanosized Li2S that shortens electron and ion transport distances, this 92Li2S@8LiFeS2 cathode exhibits long-term cycling stability with a capacity retention of over 99% after 320 cycles. With an active material content of 48% and a mass loading of 19.1 mg/cm2, the cathode achieves an areal capacity of 13.2 mAh/cm2. This work presents a facile and novel approach to designing Li2S-based cathodes for high-performance, all-solid-state Li-S batteries.

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.

Low-nickel O3-type layered oxides have emerged as cost-effective cathode candidates for sodium-ion batteries (SIBs). However, their practical viability is challenged by rapid capacity decay and insufficient redox activity within safe voltage windows. Here, we report a multi-cationic compositional regulation strategy for Na 0.96 Ni 0.2 Mn 0.32 Fe 0.4 Mg 0.04 Cu 0.04 O 2 (NMFMC), which tunes the energy levels of transition metal (TM) 3d orbitals to enhance two-electron Ni 2+ /Ni 4+ redox activity and facilitate cooperative Fe 3+ oxidation. This approach unlocks a 17% capacity enhancement (2.0–4.0 V) over conventional low-Ni cathodes while maintaining structural integrity. Operando measurements and theoretical calculations demonstrate that the reinforced TM─O bonding upon Mg/Cu co-doping mitigates structural distortion and suppresses multiphase transitions, thereby enabling superior cycling stability. A 2.65 Ah NMFMC||hard carbon pouch cell maintains 80% capacity after 1600 cycles at 1C and preserves 94% capacity when cycled from 0.5C to 4C, demonstrating practical potential for grid-scale storage. By elucidating the interplay between orbital hybridization, redox chemistry, and structural evolution, this work establishes fundamental design principles for high-energy, durable SIB's cathodes while advancing sustainable large-scale energy storage solutions.

All‐solid‐state batteries (ASSBs) are emerging as a next‐generation energy storage technology, offering enhanced safety and energy density compared to conventional lithium‐ion batteries. However, critical challenges related to material design and interfacial stability hinder their practical deployment. Advanced synchrotron X‐ray and neutron‐based techniques have become indispensable for probing the structural, chemical, and morphological evolutions within ASSBs across multiple length scales and under realistic operating conditions. This review provides a comprehensive and critical overview of recent in situ and operando studies of ASSBs enabled by synchrotron and neutron sources. The discussion is organized by the key components and interfaces of ASSBs, highlighting how these techniques elucidate dynamic processes during battery operation. Fundamental principles of the characterization methods are introduced, along with perspectives on future directions. This work aims to guide the rational design of high‐performance ASSBs by showcasing how cutting‐edge characterization advances can address longstanding challenges.

A significant obstacle in the manufacturing and practical application of Ni-rich cathode materials is decreasing the manufacturing cost without sacrificing the cycling stability. Here a high-energy, ultrahigh-Ni, and nearly Co-free cathode with outstanding cycling performance is proposed. This promising cathode is enabled by artificially constructing an "outside-in" interface structure toward LiNi0.94Co0.05Mn0.01O2 (NCM94) cathodes. Combining theoretical prediction and experimental results, it is revealed that high interfacial stability is achieved by a specific surface chemistry with an outside-in structure composed of an inner organic layer and an outer inorganic layer. Benefiting from the protection effect of the robust outside layer and the strain relieve function of the inside layer, the intrinsic challenges of interfacial reactions, transition metal (TM) dissolution, and micro-crack propagation have been mitigated for the Ni-rich cathode. As a result, the "outside-in" strategy enables superior cycling stability with a 92.7% retention after 200 cycles and an excellent rate capability of 149.1 mAh g-1 at 10 C, achieved by adding only 0.5% of the production cost. This study unlocks the possibilities of achieving outstanding performance for ultrahigh Ni cathode by spending minimum cost through the facile surface chemistry method.

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly by addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide-based all-solid-state lithium-organic batteries still face challenges such as high working temperatures, high costs, and low voltages. Here, we design an all-solid-state lithium battery based on a cost-effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li 2 ZrCl 6 . Thanks to the good compatibility between PQ and Li 2 ZrCl 6 , the PQ cathode achieved a high specific capacity of 248 mAh g −1 (96 % of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li + /Li), and a good capacity retention of 95 % after 100 cycles at room temperature (25 °C). Furthermore, the interactions between the high-voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of the PQ cathode in all-solid-state batteries, were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations into the underlying chemistry give insights for the further development of practical all-solid-state lithium-organic batteries.

The interlaboratory comparability and reproducibility of all-solid-state battery cell cycling performance are poorly understood due to the lack of standardized set-ups and assembly parameters. This study quantifies the extent of this variability by providing commercially sourced battery materials-LiNi0.6Mn0.2Co0.2O2 for the positive electrode, Li6PS5Cl as the solid electrolyte and indium for the negative electrode-to 21 research groups. Each group was asked to use their own cell assembly protocol but follow a specific electrochemical protocol. The results show large variability in assembly and electrochemical performance, including differences in processing pressures, pressing durations and In-to-Li ratios. Despite this, an initial open circuit voltage of 2.5 and 2.7 V vs Li+/Li is a good predictor of successful cycling for cells using these electroactive materials. We suggest a set of parameters for reporting all-solid-state battery cycling results and advocate for reporting data in triplicate.

Designing Na-ion solid electrolytes (SEs) of high ionic conductivity and excellent chemical/mechanical compatibility with cathode materials remains challenging for all -solid-state Na-ion batteries (ASSNIBs). In this study, we successfully design and synthesize a novel amorphous NaTaCl6 halide SE with unprecedented ionic conductivity of 4 x 10-3 S cm -1 at room temperature. The exceptional ionic conductivity arises from a unique reconstructed amorphous poly-(TaCl6) octahedra network with weakening Na-Cl interactions through high-energy mechanochemical reactions. Notably, the amorphous NaTaCl6 halide SE exhibits remarkable mechanical deformability, chemical/electrochemical stability, and outstanding electrochemical performance when coupled with the Na3V2(PO4)3 cathode in ASSNIBs, resulting in a remarkable initial Coulombic efficiency of 99.60%, excellent rate performance (85% capacity retention at 2 C), and stable long -cycling profiles (81%/95%/98% capacity retention after 4,000/600/1,500 cycles at 3/1/0.5 C). This discovery of superionic amorphous Na-ion halide SEs opens a promising avenue for advancing high-performance ASSNIBs.

A thin molecular level surface modification layer is constructed for a nickel-rich layered oxide cathode to boost long-term cycling stability.

High-energy Ni-rich layered oxide cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) suffer from detrimental side reactions and interfacial structural instability when coupled with sulfide solid-state electrolytes in all-solid-state lithium-based batteries. To circumvent this issue, here we propose a gradient coating of the NMC811 particles with lithium oxy-thiophosphate (Li3P1+xO4S4x). Via atomic layer deposition of Li3PO4 and subsequent in situ formation of a gradient Li3P1+xO4S4x coating, a precise and conformal covering for NMC811 particles is obtained. The tailored surface structure and chemistry of NMC811 hinder the structural degradation associated with the layered-to-spinel transformation in the grain boundaries and effectively stabilize the cathode|solid electrolyte interface during cycling. Indeed, when tested in combination with an indium metal negative electrode and a Li10GeP2S12 solid electrolyte, the gradient oxy-thiophosphate-coated NCM811-based positive electrode enables the delivery of a specific discharge capacity of 128 mAh/g after almost 250 cycles at 0.178 mA/cm2 and 25 °C.