Halide superionic conductors, distinguished by their remarkable oxidative stability and exceptional mechanical deformability, are emerging as a transformative class of materials poised to revolutionize high-performance, all-solid-state lithium batteries (ASSLBs). However, challenges related to the stability of halide solid-state electrolytes (SSEs) against lithium metal remain unresolved. Designing a halide SSE to address this challenge is crucial for its development. This study proposes an oxy-fluoro-synergistic strategy to synthesize Li2.8ZrCl4.8-O0.8F0.4 (LZC-OF) with Li2O&LiF protective layers on its surface. It exhibits an excellent ionic conductivity of 0.72 mS cm-1 (25 °C) and superior lithium metal stability. The in situ-formed fluoride interfacial layer between LZC-OF and Li results in excellent cycling stability of symmetric Li|LZC-OF|Li cell (600 h @ 0.1 mA cm-2). Meanwhile, the LZC-OF SSE exhibits satisfactory capacity retention (87.4% after 100 cycles at 0.5C) and excellent high-rate performance (105.3 mAh g-1 at 1C) in a full cell. This study presents an innovative design approach to enhance the electrochemical stability of halide SSEs and promotes the application of the Li2ZrCl6-family in high-performance ASSLBs.

All-solid-state lithium batteries (ASSLBs) are promising next-generation energy storage systems due to their superior safety. While low-cost Li2ZrCl6 is a candidate halide solid electrolyte, its ionic conductivity remains modest (0.33 mS cm-1). Herein, we report a highly conductive amorphous halide solid electrolyte (1.64 mS cm-1), synthesized using high-energy Li2CO3 as a precursor to replace conventional Li2O. This approach enhances reaction efficiency and reduces cost. The resulting Li2ZrOCl4 (LZOC) structure facilitates Li+ migration, as confirmed by experimental and theoretical results. ASSLBs incorporating the LZOC electrolyte with a Li-In anode and uncoated LiCoO2 (LCO) cathode demonstrate excellent cycling stability (97% capacity retention after 200 cycles at 1 C) and high-rate capability (over 70 mAh g-1 at 2 C). This work establishes the use of low-cost Li2CO3 as a practical strategy for developing high-performance, cost-effective ASSLBs.

Halide solid-state electrolytes (SSEs) have emerged as promising candidates owing to their excellent chemical oxidation stability, mechanical deformability, and good compatibility with oxide cathode materials. However, studies on the correlation between ionic conductivity and structural characteristics remain limited. Here, we introduce equivalent state halide anions bromide (Br-) into the Li3YbCl6 matrix through mechanical chemistry and heat treatment, and report the dynamic evolution of the crystal structure of Li3YbCl6-xBrx (0 <= x <= 6). The significant change in the anion sublattice framework leads to the transformation of the initial hexagonal close-packed arrangement of Li3YbCl6 (space group: Pnma) to the cubic close-packed arrangement of Li3YbCl6-xBrx (1 <= x <= 6) (space group: C2/m). Ab initio molecular dynamics (AIMD) and nudged elastic band (NEB) simulations investigate that within the highly symmetric monoclinic crystal system, the ion transport path along the c-axis changes from the octahedron-octahedron configuration to the octahedron-tetrahedron-octahedron configuration. This transformation effectively mitigates c-axis blockage caused by Li/Yb co-occupation and significantly enhances lithium-ion transport within the lattice. The results of this work highlight the complex relationship between structure and ionic transport mechanism and provide valuable insights into the ionic conduction mechanism of this class of halide electrolytes.

The advancement of sulfide‐based all‐solid‐state lithium batteries (ASSLBs) is frequently constrained by the low initial Coulombic efficiency and interfacial degradation of graphite anodes, phenomena that predominantly originate from surface impurities of organic origin. In this work, we introduce a facile yet highly effective thermal purification strategy for industrial‐grade graphite (SG‐17), enabling the restoration of its intrinsic electrochemical properties. Multimodal spectroscopic and microscopic characterizations demonstrate that annealing at 500°C under an inert atmosphere effectively eliminates oxygenated surface species while preserving the crystalline architecture of graphite. When deployed in sulfide solid‐state configurations, the purified graphite exhibits a substantially improved initial coulombic efficiency (94.6% vs. 86.3%), enhanced Li+ diffusion coefficients, suppressed charge–transfer resistance, and remarkable cycling stability with 81% capacity retention over 300 cycles. Distribution of relaxation time analyses further elucidates the critical role of surface purification in mitigating interfacial impedance growth and promoting efficient ion transport. These findings not only provide fundamental mechanistic insight into impurity‐driven interfacial phenomena in ASSLBs but also establish a scalable and cost‐effective pathway to advance graphite anodes for next‐generation solid‐state energy storage technologies.

Developing high-voltage all-solid-state batteries is crucial for achieving high-energy-density energy storage systems. However, most traditional solid electrolytes are incompatible with the interfaces of cathode materials under high voltage due to their narrow electrochemical windows. During the cycling process, continuous interfacial side reactions and the surface dissolution of cathode materials occur, leading to a rapid decline in battery performance. Herein, LiNbOCl3.6F0.4, which features high-voltage stability (vs Li+/Li > 4.65V) and a high ionic conductivity of 2.3 mS cm(-1), is successfully synthesized by randomly introducing fluorine into the Cl sites of LiNbOCl4 through a mechanochemical method. The cell assembled with the LiNbOCl3.6F0.4 electrolyte and the nickel-rich layered oxide cathode LiNi0.83Co0.12Mn0.05O2 achieves a high initial discharge specific capacity of 195.6 mAh g(-1) at a cutoff voltage of 4.5 V versus Li+/Li. After 200 cycles at a rate of 0.1 C, the capacity retention rate reaches 84.1%. Through in-situ interfacial impedance analysis and the characterization of cathode lattice changes, the continuous interfacial chemical reactions are suppressed, and a fluoride-rich dynamic self-stabilizing cathode/electrolyte interface is formed during the battery cycling process. This cathode/electrolyte interface can significantly enhance the interfacial stability under high voltage. This unique self-stabilizing interface formation mechanism provides a structural guarantee for the long-term cycling stability of the battery.

Strategies to optimize the cathode/solid electrolyte interphase (CSEI) have been developed to improve the high voltage durability of LiCoO2 (LCO), yet the underlying interfacial mechanism remains unclear. Here, we construct a stable oxyhalide-derived CSEI for all-solid-state batteries (ASSBs) to identify the key interfacial features required for high-voltage operation. At 4.6 volts, commercial LCO coupled with Li6PS5Cl (LPSC) suffers from severe interfacial instability, sluggish Li+ transport, and continuous side reactions. By introducing LiNbOCl4 (LNOC), an in situ formed CSEI rich in Li-Cl/Nb-O/Nb-O-Cl species is established, lowering the interfacial energy barrier to 0.363 electron volts and enhancing interfacial toughness and ionic conductivity. This stabilized interface suppresses lattice oxygen activity, accelerates Li+ transport, and improves the reversibility of O3/H1-3 phase transitions. Consequently, LCO|LNOC|LPSC|Li-In ASSBs deliver 95.8% capacity retention after 500 cycles at ∼1.0 C-rate with an LCO loading of 15.31 milligrams per square centimeter. The pouch cell achieves 90% initial Coulombic efficiency and stable cycling over 50 cycles.

Despite their enhanced safety and energy density, the practical deployment of halide-based all-solid-state lithium batteries (ASSLBs) is limited due to their interfacial instability and parasitic side reactions between lithium metal anodes and solid electrolytes. In this study, we systematically explore the use of lithium phosphorus oxynitride (LiPON) as an interfacial functional layer to mitigate these degradation phenomena in halide-based ASSLBs. LiPON thin films were deposited on lithium metal substrates via magnetron sputtering, resulting in a uniform and amorphous protective layer that effectively stabilizes the interface. Cells modified with LiPON exhibit stable cycling performance for over 2000 h, in stark contrast to unmodified cells, which undergo rapid degradation due to the formation of resistive by-products such as LiCl. Surface analyses by X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and scanning electron microscopy indicate that the LiPON functional layer facilitates the formation of a robust and high-performing solid electrolyte interphase layer enriched in Li3N and Li3P species, while simultaneously suppressing deleterious reactions at the lithium/halide interface. These results highlight the importance of interfacial engineering in halide-based ASSLBs and offer new insights and strategies for the development of future high-performance energy storage systems.

Solid-state lithium batteries (SSLBs) hold promise for next-generation energy storage due to their high safety and energy density. However, challenges such as poor interfacial contact, high interfacial impedance, and lithium dendrite growth limit the practical application of garnet-type Li7La3Zr2O12 (LLZO) and its derivatives (Ta-doped Li7La3Zr2O12, LLZTO). This study investigates the effects of incorporating LiGaO2 (LGO) into LLZTO to enhance grain-boundary bonding, reduce activation energy, and suppress lithium dendrite growth. LiGaO2 powder was synthesized via a solid-state reaction and mixed with LLZTO to form composite ceramics. Structural characterization using XRD and SEM confirmed that LGO stabilizes the cubic garnet structure of LLZTO without forming impurity phases. The LLZTO-1 wt% LGO composition, sintered at 1260 degrees C, exhibited superior performance with a room-temperature ionic conductivity of 0.951 mS cm-1 and a relative density of 96.3%. Electrochemical impedance spectroscopy shows that the interfacial resistance decreases by similar to 50% (from similar to 30 Omega to similar to 15 Omega). The hybrid full cell retains 99.3% capacity after 200 cycles at 0.8C, showcasing practical applicability. These results highlight the effectiveness of LGO-mediated grain boundary engineering in improving the electrochemical performance of LLZTO-based solid electrolytes, paving the way for their large-scale preparation and application in SSLBs.

The addition of LiGaO 2 to Ta-doped Li 7 La 3 Zr 2 O 12 (LLZTO) can effectively enhance the ionic conductivity and electrochemical performance of LLZTO garnet-type solid electrolytes.

Solid polymer electrolytes (SPEs) are considered an extremely competitive technology roadmap for all-solid-state lithium metal batteries (LMBs) that are expected to address the safety issues of liquid electrolytes. However, insufficient ionic conductivity and inadequate mechanical strength constrain their practical applications. In this work, we first explored the oxygen defect effect of V2O5 on the dissociation of lithium salt. Both calculations and experimental measurements reveal that increased oxygen vacancy concentration in V2O5 enhances its ability to dissociate bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Therefore, we applied defect engineering to maximize dissociation ability of V2O5. Furthermore, the interlinked V2O5 nanowires are used to construct fast Li+ conducting percolation network in SPEs to enhance their ionic conductivity and interfacial stability. Benefit from the synergistic effect of defect engineering and percolation network, the SPEs exhibited a high ionic conductivity of 1.05 mS cm(-1) at 60 degrees C, a high lithium-ion transference number of 0.53, and enhanced interfacial stability. The Li+/Li symmetric battery demonstrates a long cycle life of 2000 h at 0.1 mA cm(-2), the Li/LiFePO4 battery retains a capacity of 144.93 mAh g(-1) after 200 cycles at 60 degrees C and 1C. This work synergistically combines defect engineering with percolation network design to tailor polymer electrolytes, offering a transformative strategy for the development of high-performance solid-state polymer electrolytes.

Correction for ‘LiGaO 2 -mediated grain boundary engineering in Ta-doped Li 7 La 3 Zr 2 O 12 solid electrolyte’ by Jie Liu et al. , Mater. Chem. Front. , 2026, 10 , 428–437, https://doi.org/10.1039/D5QM00736D.

All-solid-state lithium batteries (ASSLBs) have attracted significant attention due to their advantages of high energy density, enhanced safety profile, and potential for cost-effective manufacturing. At the same time, a superior anode that matches the ASSLBs is particularly important. In this work, we demonstrated chemically prelithiated MoS2 as an anode material for ASSLBs, which embeds lithium ions into a MoS2 matrix (LixMoS2) in advance to counteract lithium loss during the cycling. By a combination of LixMoS2, Li6PS5Cl (LPSC), and Li-In alloy, an all-solid-state lithium battery with superior long-term cycling and rate capability has been achieved. The cells exhibited a capacity retention rates of 93.4 and 90.8% after 100 cycles at both 0.2 and 1C, alongside a high specific discharge capacity of 480 mAh g(-1) at 1C. Furthermore, when paired with a LiCoO2 (LCO) cathode, the full cell maintained a capacity retention rate of 95% over 300 cycles at 1C, with an average capacity loss of only 0.013 mAh g(-1) per cycle. This work offers a feasible strategy for optimizing anode materials within sulfide-based ASSLBs, providing valuable insights for the development of high-performance ASSLBs for practical applications.

The garnet-type Li7La3Zr2O12 (LLZO) solid electrolyte is regarded as a promising option for all-solid-state batteries owing to its notable features, including high ionic conductivity and wide electrochemical window. Although aluminum-doped LLZO (Al-LLZO) is crucial for achieving LLZO ceramics with high critical current density, the characteristics of its grain and grain boundary structures remain largely elusive. In this work, the electrochemical impedance spectroscopy (EIS) technique, in conjunction with the distribution of relaxation times (DRT) method, was employed to investigate structural alterations in Al-LLZO ceramics modified by La2Zr2O7 (LZO) additives. Additionally, the impact of sintering temperature and electrolyte testing temperature on ceramic structural changes was investigated using the DRT tools. By optimizing experimental conditions such as the concentration of added LZO and the sintering temperature of Al-LLZO, the study was further refined. This enabled us to successfully identify Al-LLZO solid electrolytes exhibiting uniform morphological structures, moderate crystal grain sizes and high density. By adding 6 wt

Solid-state lithium metal batteries (SSLMBs) based on garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZTO) electrolytes have faced significant challenges due to surface Li2CO3 contamination, which leads to increased interfacial resistance and degraded electrochemical performance. Herein, we report a simple and cost-effective interfacial modification strategy via an AlCl3 aqueous solution to address these issues. By using the drop-casting method, this strategy effectively removes the Li2CO3 layers while maintaining the structural integrity of the garnet lattice. During the subsequent lithium melting process, the in situ-formed Li-Al alloy enhances lithiophilicity and Li+ diffusion kinetics, reducing the Li-LLZTO interfacial resistance from 38.80 to 13.23 Omegacm(2). The symmetric cell achieves a critical current density (CCD) of 1.1 mA cm(-2) (compared with 0.3 mA cm(-2) for the untreated cell) and demonstrates stable cycling for over 2000 h at 0.2 mA cm(-2). The full cell paired with LiFePO4 (LFP) cathodes exhibits a discharge capacity of 130.5 mAh g(-1) at 1.0C and retains 93.3% capacity after 100 cycles at 0.1C, with Coulombic efficiencies exceeding 99%. This work provides a feasible strategy for constructing garnet-based solid-state Li metal batteries.

Solid-state electrolytes (SSEs) are the core components for achieving high-performance all-solid-state lithium batteries (ASSLBs), which require high ionic conductivity and good physical contact with the positive electrode. Herein, we report a lithium-poor tantalum oxychloride solid electrolyte (0.5Li(2)Oz-TaCl5), which still possesses an ultra-high ionic conductivity (8.54 x 10(- 3) S cm(-1)) and good compatibility with LiCoO2/LiNi0.83Co0.12Mn0.05O2 (LCO/NCM83) cathodes. The ASSLBs (LCO cathode) with this amorphous electrolyte not only exhibit a high discharge capacity of 155mAh g(-1) at 0.1C, but also demonstrate excellent rate performance (90mAh g(-1), 5C). It should be emphasized that due to the extremely high compaction density (3.28 g cm(-3)) of 0.5Li(2)O-TaCl5, it can maintain stable contact and low interface impedance with the positive electrode interface, thus exhibiting superior cycling stability in the ASSLBs. Furthermore, the capacity retention rate is as high as 97.14 % even after 3000 cycles at 3C. This work inspires the composition design for oxyhalide solid electrolytes containing low Li but delivering high Li+ conductivity.

In recent times, there has been extensive exploration of Schiff base chemistry or dynamic imine chemistry for synthesis of covalent organic frameworks (COFs). Schiff base COFs are found to be very attractive for the applications in photocatalysis due to their dynamic imine chemistry and π-conjugated structures. Their extensive π-delocalization and donor-acceptor (D-A) framework enhances light absorption, charge separation, and electron transport, allowing for band gap tuning from UV to near-infrared absorption. Consequently, numerous investigations have been conducted to examine and comprehend the photocatalytic efficacy of Schiff base COFs. As a contribution, we present a comprehensive overview of recent advancements in research concerning COFs incorporating Schiff base-type linkages imine, hydrazone, azine, and β-ketoenamine or keto-enol linkages in multiple photocatalytic processes, such as organic transformation, hydrogen (H2) production, carbon dioxide (CO2) reduction, and pollution degradation. This review encompasses discussions on the linkage chemistry, concise synthetic methodologies, and the advantages of employing Schiff base COFs as photocatalysts, which represent a forefront area in materials science research. Additionally, the opportunities and challenges in advancing Schiff base COFs for photocatalysis and strategies to enhance their performance, aiming to inspire further research in this field are discussed.

Halide superionic conductors have garnered considerable attention due to their high ionic conductivity, mechanical deformability, and excellent oxidative stability. However, their incompatibility with lithium metal results in a thermodynamically unstable interface that increases interfacial impedance, thereby limiting the performance of halide-based all-solid-state lithium-metal batteries (ASSLBs). In this study, we report the synthesis of a series of iodide-chloride solid electrolytes, Li2ZrCl6-xIx (x = 0-3), designed to enhance the reduction stability of the electrolyte through the high polarizability of I-. The substitution of I- promotes covalent bonding with the central cation, thereby reducing its reduction tendency. The Li/Li2ZrCl4I2/Li symmetric cell exhibits stable cycling for over 6000 h at 0.2 mA cm-2 and withstands high critical current densities up to 6 mA cm-2. Full cells incorporating Li2ZrCl4I2 as the solid electrolyte exhibit enhanced cycling stability and capacity retention. Furthermore, the characterization by XPS and ToF-SIMS revealed the formation of an interfacial passivation layer composed of LiI and LiCl, which effectively stabilized the lithium-metal electrode and inhibited further electrolyte decomposition. These findings highlight the potential of iodide-substituted halide electrolytes in addressing interfacial challenges associated with lithium metal anodes, providing a promising pathway for the practical implementation of high-energy-density ASSLBs.

Lithium-Sulfur battery (LSB) is promising to be one of the next-generation energy storage systems due to its exceptionally high energy density. Various catalysts are designed into the cathode to enhance the conversion efficiency of lithium polysulfides (LiPSs) and improve the comprehensive performance of LSB. Despite considerable attention devoted to discovering novel catalysts, catalyst passivation remains a frequently overlooked issue. This review summarizes recent findings on catalyst passivation mechanisms and coping strategies in LSBs. It also clarifies a common misconception in LSB catalyst design: that stronger catalyst-polysulfide interactions necessarily improve catalytic performance. A stronger interaction between these two components does not necessarily indicate superior catalytic performance and may actually lead to catalyst passivation. The catalyst passivation mechanisms are categorized into two types, based on the strength of the interaction between the catalyst and sulfur/sulfides. The first type involves a strong interaction, leading to physical coverage-induced reversible catalyst passivation. The second type is characterized by an ultra-strong interaction, resulting in chemical reaction-induced irreversible catalyst passivation. The coping strategies to guide the design of optimal catalyst for the cathode of LSB is also summarized. Finally, the future prospects and challenges of catalyst coping strategies in LSB are discussed.

Co-free Li-rich Mn-based cathode materials (LMNO) have gradually become powerful competitors with ultra-high specific discharge capacity and energy density. However, high-rate performance and severe voltage decay restrict the commercial application of LMNO. Herein, LiAl5O8 acts as a templating agent to construct 3D neural-like networks in LMNO, enabling fast ion diffusion and improving rate performance. Proton exchange is predominantly facilitated by the process of LiAl5O8 constructed to generate vacancies for oxygen preservation, while strong Al-O bonds stabilize interfacial lattice oxygen, effectively suppressing voltage decay due to structural evolution. As a result, the designed cathode exhibits a discharge specific capacity of 154.65 mAh g-1 at 5 C and 91.68% capacity retention after 400 cycles (vs . 66.67% of LMNO), effectively suppressing voltage decay with 90.90% voltage retention (vs . 81.08% of LMNO). The constructed neural-like network structure engineering provides an innovative direction for improving the high-rate performance and structural stability of LMNO.