Wen Zhuang, Beibei Yang, Yao Liu, Hongbin Lu, Duan Bin
Aqueous aluminum metal batteries (AAMBs) have recently emerged as promising candidates for next-generation energy storage systems. Their advantages stem from the abundance and low cost of aluminum, the high theoretical capacity derived from its multielectron redox reaction, and the intrinsic safety of aqueous electrolytes that mitigate flammability risks. Despite these merits, Al3+/Al-based aqueous batteries remain in the early stage of development. Their practical implementation is hindered by persistent challenges in achieving stable electrode-electrolyte interfaces and suppressing parasitic reactions. Specifically, aluminum anodes suffer from spontaneous surface passivation, self-corrosion, and hydrogen evolution in aqueous environments, while aqueous electrolytes generally possess narrow electrochemical stability window (ESW) that promote undesired side reactions and degrade electrode performance. This review systematically summarizes recent progress in modulating the anode/electrolyte interface (AEI) to enhance the electrochemical reversibility and stability of AAMBs. Emphasis is placed on anode design, electrolyte optimization, and the construction of artificial interphases. Finally, the main challenges and future research directions are discussed, offering guidance for the rational design of high-performance AAMBs.
{"title":"Research Progress of Anode/Electrolyte Interface Modulation for Aqueous Aluminum Metal Batteries","authors":"Wen Zhuang, Beibei Yang, Yao Liu, Hongbin Lu, Duan Bin","doi":"10.1039/d5ta09734g","DOIUrl":"https://doi.org/10.1039/d5ta09734g","url":null,"abstract":"Aqueous aluminum metal batteries (AAMBs) have recently emerged as promising candidates for next-generation energy storage systems. Their advantages stem from the abundance and low cost of aluminum, the high theoretical capacity derived from its multielectron redox reaction, and the intrinsic safety of aqueous electrolytes that mitigate flammability risks. Despite these merits, Al3+/Al-based aqueous batteries remain in the early stage of development. Their practical implementation is hindered by persistent challenges in achieving stable electrode-electrolyte interfaces and suppressing parasitic reactions. Specifically, aluminum anodes suffer from spontaneous surface passivation, self-corrosion, and hydrogen evolution in aqueous environments, while aqueous electrolytes generally possess narrow electrochemical stability window (ESW) that promote undesired side reactions and degrade electrode performance. This review systematically summarizes recent progress in modulating the anode/electrolyte interface (AEI) to enhance the electrochemical reversibility and stability of AAMBs. Emphasis is placed on anode design, electrolyte optimization, and the construction of artificial interphases. Finally, the main challenges and future research directions are discussed, offering guidance for the rational design of high-performance AAMBs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"289 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anh Le Mong, Jong Chan Shin, Minjae Lee, Dukjoon Kim
The creation of a highly efficient lithium-ion-conductive solid and/or quasi-solid electrolyte with effective polysulfide (PS) suppression is essential for stable lithium–sulfur (Li–S) batteries. This study presents a self-assembled quasi-solid electrolyte formed by co-grafting zwitterion (ZW) and poly(ethylene glycol) (PEG) segments onto a durable poly(arylene ether sulfone) (PAES) backbone, denoted as PAES-co-(ZW/PEG)2. Within the robust PAES framework, Li-ion conductive (ZW/PEG) domains are generated through phase separation assisted by an ionic liquid and ethylene carbonate, ensuring both excellent ionic conductivity and mechanical integrity. The ZW segments effectively restrict PS migration and promote selective Li-ion transport via electrostatic interactions between delocalized anionic sites and Li-ions. The PAES-co-(ZW/PEG)2 membrane exhibits a high Li+ transference number (0.752), superior ionic conductivity (1.58 mS cm−1), and favorable mechanical strength (Young's modulus: 15 MPa; tensile strength: 1.8 MPa). Furthermore, it provides remarkable PS-blocking performance (∼3.418 × 10−5 cm2 s−1) and excellent oxidative stability (5.28 V). Li–S cells employing this electrolyte demonstrate stable cycling over 350 cycles with 93% capacity retention and outstanding rate capability up to 5 C, indicating strong potential for advanced Li–S battery systems.
{"title":"Engineering of Li+-selective quasi-solid electrolytes via zwitterion and poly(ethylene glycol) co-grafting on poly(arylene ether sulfone) for high-performance lithium–sulfur batteries","authors":"Anh Le Mong, Jong Chan Shin, Minjae Lee, Dukjoon Kim","doi":"10.1039/d5ta08701e","DOIUrl":"https://doi.org/10.1039/d5ta08701e","url":null,"abstract":"The creation of a highly efficient lithium-ion-conductive solid and/or quasi-solid electrolyte with effective polysulfide (PS) suppression is essential for stable lithium–sulfur (Li–S) batteries. This study presents a self-assembled quasi-solid electrolyte formed by co-grafting zwitterion (ZW) and poly(ethylene glycol) (PEG) segments onto a durable poly(arylene ether sulfone) (PAES) backbone, denoted as PAES-<em>co</em>-(ZW/PEG)<small><sub>2</sub></small>. Within the robust PAES framework, Li-ion conductive (ZW/PEG) domains are generated through phase separation assisted by an ionic liquid and ethylene carbonate, ensuring both excellent ionic conductivity and mechanical integrity. The ZW segments effectively restrict PS migration and promote selective Li-ion transport <em>via</em> electrostatic interactions between delocalized anionic sites and Li-ions. The PAES-<em>co</em>-(ZW/PEG)<small><sub>2</sub></small> membrane exhibits a high Li<small><sup>+</sup></small> transference number (0.752), superior ionic conductivity (1.58 mS cm<small><sup>−1</sup></small>), and favorable mechanical strength (Young's modulus: 15 MPa; tensile strength: 1.8 MPa). Furthermore, it provides remarkable PS-blocking performance (∼3.418 × 10<small><sup>−5</sup></small> cm<small><sup>2</sup></small> s<small><sup>−1</sup></small>) and excellent oxidative stability (5.28 V). Li–S cells employing this electrolyte demonstrate stable cycling over 350 cycles with 93% capacity retention and outstanding rate capability up to 5 C, indicating strong potential for advanced Li–S battery systems.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"90 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jingnan Zheng, Jinglei Si, Anyi Feng, Hanxiao Liu, Shijie Zhang, Jian-Guo Wang
Electrochemical synthesis of germane (GeH4) from GeO2 represents a safe and sustainable alternative to conventional thermal methods that suffer from high production costs and excessive byproducts. However, the eight proton-electron transfer steps involve multiple intermediates and competing side reactions, rendering the reaction mechanism highly complex. Herein, a comprehensive reaction network encompassing dissociative and associative mechanisms (D-T, D-H, A-T, and A-H) was systematically established and analysed. Descriptor screening based on density functional theory (DFT) identified *Ge and *GeH adsorption free energies, Gad(Ge) and Gad(GeH), as robust dual descriptors through strong linear scaling relationships with key intermediates. Thermodynamic mapping revealed that non-hydrolysis associative pathways, particularly the A-T mechanism, are most favorable within a moderate adsorption window. Copper (Cu) emerged as the optimal catalyst, balancing hydrogen activation and Ge-H bond formation with a low theoretical limiting potential (0.71 V).Experimental validation confirmed that Cu exhibits superior activity and selectivity compared to Bi and Ni, consistent with descriptor-based predictions. Kinetic analysis on the Cu(111) surface further determined *Ge → *GeH hydrogenation as the rate-determining step in the less favorable pathway, with a free-energy barrier of 0.95 eV, directly linking the dual descriptors to kinetic constraints. This integrated framework provides mechanistic insights and descriptor-driven guidance for the rational design of selective GeH4 electrocatalysts, and establishing a generalizable paradigm for the sustainable electrochemical synthesis of electronic specialty gases.
{"title":"Electrochemical Germane (GeH4) Synthesis via Dual-Descriptor Screening and Integrated Theoretical-Experimental Validation","authors":"Jingnan Zheng, Jinglei Si, Anyi Feng, Hanxiao Liu, Shijie Zhang, Jian-Guo Wang","doi":"10.1039/d5ta10287a","DOIUrl":"https://doi.org/10.1039/d5ta10287a","url":null,"abstract":"Electrochemical synthesis of germane (GeH<small><sub>4</sub></small>) from GeO<small><sub>2</sub></small> represents a safe and sustainable alternative to conventional thermal methods that suffer from high production costs and excessive byproducts. However, the eight proton-electron transfer steps involve multiple intermediates and competing side reactions, rendering the reaction mechanism highly complex. Herein, a comprehensive reaction network encompassing dissociative and associative mechanisms (D-T, D-H, A-T, and A-H) was systematically established and analysed. Descriptor screening based on density functional theory (DFT) identified *Ge and *GeH adsorption free energies, G<small><sub>ad</sub></small>(Ge) and G<small><sub>ad</sub></small>(GeH), as robust dual descriptors through strong linear scaling relationships with key intermediates. Thermodynamic mapping revealed that non-hydrolysis associative pathways, particularly the A-T mechanism, are most favorable within a moderate adsorption window. Copper (Cu) emerged as the optimal catalyst, balancing hydrogen activation and Ge-H bond formation with a low theoretical limiting potential (0.71 V).Experimental validation confirmed that Cu exhibits superior activity and selectivity compared to Bi and Ni, consistent with descriptor-based predictions. Kinetic analysis on the Cu(111) surface further determined *Ge → *GeH hydrogenation as the rate-determining step in the less favorable pathway, with a free-energy barrier of 0.95 eV, directly linking the dual descriptors to kinetic constraints. This integrated framework provides mechanistic insights and descriptor-driven guidance for the rational design of selective GeH<small><sub>4</sub></small> electrocatalysts, and establishing a generalizable paradigm for the sustainable electrochemical synthesis of electronic specialty gases.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"8 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101878","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chan Hwi Kim, Yu Bin Choi, Doo Seok Kwon, JinHa Shim, Jin Ho Bang
The rational design of β-Ni(OH)2 precursors is paramount for realizing the full potential of stoichiometric LiNiO2 (LNO) cathodes. This study demonstrates that strategically engineering the precursor's crystallographic architecture governs the synthesis kinetics, structural integrity, and ultimate electrochemical performance of LNO. By solely manipulating reactant injection intervals during co-precipitation, we modulated the preferential growth of the (001) crystal plane to create distinct β-Ni(OH)2 microstructures. The intentional restriction of (001) plane growth yielded a precursor with a high specific surface area, which significantly lowered the activation energy for lithiation. This kinetic advantage promoted a more complete and uniform phase transformation, resulting in a final LNO cathode with larger crystallites, lower lattice strain, and superior mechanical integrity. Conversely, the dense precursor derived from promoted (001) plane growth imposed a kinetic barrier, leading to incomplete reaction, residual inactive phases, and high internal strain. These profound structural differences translated directly into electrochemical performance. The LNO derived from the engineered precursor delivered higher capacity, superior rate capability, and better cycling stability, whereas its counterpart suffered from severe particle fragmentation and rapid degradation. This work establishes a direct, causal pathway from precursor-level crystallographic engineering to structurally robust, high-performance LNO cathodes.
{"title":"Modulating (001) plane growth in β-Ni(OH)2 precursors: a pathway to controlling lithiation kinetics and enhancing the structural integrity of LiNiO2","authors":"Chan Hwi Kim, Yu Bin Choi, Doo Seok Kwon, JinHa Shim, Jin Ho Bang","doi":"10.1039/d5ta09144f","DOIUrl":"https://doi.org/10.1039/d5ta09144f","url":null,"abstract":"The rational design of β-Ni(OH)<small><sub>2</sub></small> precursors is paramount for realizing the full potential of stoichiometric LiNiO<small><sub>2</sub></small> (LNO) cathodes. This study demonstrates that strategically engineering the precursor's crystallographic architecture governs the synthesis kinetics, structural integrity, and ultimate electrochemical performance of LNO. By solely manipulating reactant injection intervals during co-precipitation, we modulated the preferential growth of the (001) crystal plane to create distinct β-Ni(OH)<small><sub>2</sub></small> microstructures. The intentional restriction of (001) plane growth yielded a precursor with a high specific surface area, which significantly lowered the activation energy for lithiation. This kinetic advantage promoted a more complete and uniform phase transformation, resulting in a final LNO cathode with larger crystallites, lower lattice strain, and superior mechanical integrity. Conversely, the dense precursor derived from promoted (001) plane growth imposed a kinetic barrier, leading to incomplete reaction, residual inactive phases, and high internal strain. These profound structural differences translated directly into electrochemical performance. The LNO derived from the engineered precursor delivered higher capacity, superior rate capability, and better cycling stability, whereas its counterpart suffered from severe particle fragmentation and rapid degradation. This work establishes a direct, causal pathway from precursor-level crystallographic engineering to structurally robust, high-performance LNO cathodes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"17 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ming Liang, Chen Liu, Siwu Li, Ziling Jiang, Lin Li, Ziyu Lu, Qiyue Luo, Miao Deng, Chuang Yu
The Cl-rich argyrodite, Li5.5PS4.5Cl1.5 , has emerged as a promising solid electrolyte candidate due to its high ionic conductivity and good Li metal compatibility. However, its practical application is significantly limited by poor air stability. In this work, we systematically investigate two oxygen doping strategies (Li2O vs P2O5 substitution) to enhance the moisture resistance of while Li5.5PS4.5Cl1.5 maintaining its advantageous ionic transport properties. Our results reveal distinct effects of different doping sources: the Li2O-doped electrolyte achieves superior room-temperature ionic conductivity (3.58 mS cm -1 ), while P2O5 -doped sample demonstrates remarkable air stability with well-preserved structural integrity and conductivity after air exposure. Through combined DFT calculations and experimental characterizations (XRD, SEM), we elucidate that P2O5 -doping induces larger cell parameters and stronger structural robustness against moisture attack.Whenimplemented in all-solid-state batteries using ZrO2 -coated LiNi0.9Mn0.05Co0.05O2 cathodes and Li-In anodes, the exposed P2O5 -doped electrolytes exhibited higher discharge capacity and promising interface compatibility, further confirming its better air stability. Further investigation using a bilayer electrolyte configuration with Li3.25InCl5.75O0.25 confirms the excellent compatibility of P2O5 -LPSC, which achieves a high initial discharge capacity of 230.7 mAh g-1 and maintains 87.1% capacity retention after 200 cycles. Electrochemical impedance spectroscopy revealed that P2O5 -LPSC forms more favorable interfaces with halide electrolytes, contributing to its outstanding cycling stability. This work provides fundamental insights into designing air-stable, high-performance solid electrolytes through rational doping strategies.
富cl银柱石Li5.5PS4.5Cl1.5因其高离子电导率和良好的锂金属相容性而成为一种有前途的固体电解质候选材料。然而，它的实际应用受到空气稳定性差的严重限制。在这项工作中，我们系统地研究了两种氧掺杂策略（Li2O和P2O5取代），以提高Li5.5PS4.5Cl1.5的抗湿性，同时保持其有利的离子传输性能。我们的研究结果揭示了不同掺杂来源的不同影响：li2o掺杂的电解质具有优异的室温离子电导率（3.58 mS cm -1），而P2O5掺杂的样品具有出色的空气稳定性，在空气暴露后具有良好的结构完整性和电导率。通过DFT计算和实验表征（XRD， SEM），我们阐明了P2O5掺杂使电池参数更大，结构抗水分侵蚀的鲁棒性更强。在采用ZrO2包覆LiNi0.9Mn0.05Co0.05O2阴极和Li-In阳极的全固态电池中，暴露的P2O5掺杂电解质表现出更高的放电容量和良好的界面兼容性，进一步证实了其良好的空气稳定性。采用Li3.25InCl5.75O0.25双层电解质结构进一步研究，证实了P2O5 -LPSC具有良好的相容性，其初始放电容量达到230.7 mAh g-1，在200次循环后保持87.1%的容量保持率。电化学阻抗谱分析表明，P2O5 -LPSC与卤化物电解质形成了更有利的界面，具有良好的循环稳定性。这项工作为通过合理的掺杂策略设计空气稳定、高性能的固体电解质提供了基本的见解。
{"title":"Comparative Study of Oxygen Source Doping Effects on the Multidimensional Stability of Li5.5PS4.5Cl1.5 Solid Electrolytes","authors":"Ming Liang, Chen Liu, Siwu Li, Ziling Jiang, Lin Li, Ziyu Lu, Qiyue Luo, Miao Deng, Chuang Yu","doi":"10.1039/d5ta08492j","DOIUrl":"https://doi.org/10.1039/d5ta08492j","url":null,"abstract":"The Cl-rich argyrodite, Li5.5PS4.5Cl1.5 , has emerged as a promising solid electrolyte candidate due to its high ionic conductivity and good Li metal compatibility. However, its practical application is significantly limited by poor air stability. In this work, we systematically investigate two oxygen doping strategies (Li2O vs P2O5 substitution) to enhance the moisture resistance of while Li5.5PS4.5Cl1.5 maintaining its advantageous ionic transport properties. Our results reveal distinct effects of different doping sources: the Li2O-doped electrolyte achieves superior room-temperature ionic conductivity (3.58 mS cm -1 ), while P2O5 -doped sample demonstrates remarkable air stability with well-preserved structural integrity and conductivity after air exposure. Through combined DFT calculations and experimental characterizations (XRD, SEM), we elucidate that P2O5 -doping induces larger cell parameters and stronger structural robustness against moisture attack.Whenimplemented in all-solid-state batteries using ZrO2 -coated LiNi0.9Mn0.05Co0.05O2 cathodes and Li-In anodes, the exposed P2O5 -doped electrolytes exhibited higher discharge capacity and promising interface compatibility, further confirming its better air stability. Further investigation using a bilayer electrolyte configuration with Li3.25InCl5.75O0.25 confirms the excellent compatibility of P2O5 -LPSC, which achieves a high initial discharge capacity of 230.7 mAh g-1 and maintains 87.1% capacity retention after 200 cycles. Electrochemical impedance spectroscopy revealed that P2O5 -LPSC forms more favorable interfaces with halide electrolytes, contributing to its outstanding cycling stability. This work provides fundamental insights into designing air-stable, high-performance solid electrolytes through rational doping strategies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"40 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Steffen Weinmann, Marina Reis, Michael Warnke, Lucie Quincke, Alena Gruendl, Jennifer L. M. Rupp, Kun Joong Kim
Developing scalable processing routes for oxide-based solid-state batteries remains a central challenge, particularly in maintaining lithium stoichiometry and interfacial stability during high-temperature sintering. In this work, we develop alternative lithium compensation strategies for the fabrication of fully dense, secondary-phase-free composite cathodes beyond gas-phase lithiation, using LiCoO2–Li7La3Zr2O12 as a model system. Specifically, two solid-phase approaches were explored: the addition of lithium precursors and the use of an overlithiated garnet catholyte. Both methods effectively suppressed the formation of LaCoO3-type interphases and yielded highly dense microstructures after sintering at 1050 °C, achieving performance comparable to gas-phase lithium compensation. These results, first verified on pellet samples, were successfully translated into flat, 100 µm-thick free-standing membranes via a tape casting process, demonstrating versatility and scalability. The membranes reduce the area-specific resistance to 4.5 Ω cm2 while maintaining high electrochemical activity and delivering a discharge capacity of up to 1.49 mAh cm−2 at 0.25 mA cm−2. These advances establish a scalable route toward industrially relevant, all-ceramic composite cathodes for garnet-based solid-state batteries.
开发可扩展的氧化基固态电池工艺路线仍然是一个核心挑战，特别是在高温烧结过程中保持锂的化学计量和界面稳定性。在这项工作中，我们以LiCoO2-Li7La3Zr2O12为模型体系，开发了替代锂补偿策略，用于制造除气相锂化之外的全致密、无二次相的复合阴极。具体来说，研究人员探索了两种固相方法：添加锂前体和使用过锂化石榴石阴极电解质。两种方法都有效抑制了lacoo3型界面相的形成，并在1050℃烧结后产生了高密度的微观结构，实现了与气相锂补偿相当的性能。这些结果首先在颗粒样品上得到验证，并通过胶带铸造工艺成功转化为100微米厚的扁平独立膜，证明了其通用性和可扩展性。该膜将面积比电阻降低至4.5 Ω cm2，同时保持高电化学活性，并在0.25 mA cm - 2时提供高达1.49 mAh cm - 2的放电容量。这些进展为工业相关的、用于石榴石基固态电池的全陶瓷复合阴极建立了一条可扩展的路线。
{"title":"Scalable fabrication of all-ceramic composite cathodes via controlled lithium compensation for Li-garnet batteries","authors":"Steffen Weinmann, Marina Reis, Michael Warnke, Lucie Quincke, Alena Gruendl, Jennifer L. M. Rupp, Kun Joong Kim","doi":"10.1039/d5ta09479h","DOIUrl":"https://doi.org/10.1039/d5ta09479h","url":null,"abstract":"Developing scalable processing routes for oxide-based solid-state batteries remains a central challenge, particularly in maintaining lithium stoichiometry and interfacial stability during high-temperature sintering. In this work, we develop alternative lithium compensation strategies for the fabrication of fully dense, secondary-phase-free composite cathodes beyond gas-phase lithiation, using LiCoO<small><sub>2</sub></small>–Li<small><sub>7</sub></small>La<small><sub>3</sub></small>Zr<small><sub>2</sub></small>O<small><sub>12</sub></small> as a model system. Specifically, two solid-phase approaches were explored: the addition of lithium precursors and the use of an overlithiated garnet catholyte. Both methods effectively suppressed the formation of LaCoO<small><sub>3</sub></small>-type interphases and yielded highly dense microstructures after sintering at 1050 °C, achieving performance comparable to gas-phase lithium compensation. These results, first verified on pellet samples, were successfully translated into flat, 100 µm-thick free-standing membranes <em>via</em> a tape casting process, demonstrating versatility and scalability. The membranes reduce the area-specific resistance to 4.5 Ω cm<small><sup>2</sup></small> while maintaining high electrochemical activity and delivering a discharge capacity of up to 1.49 mAh cm<small><sup>−2</sup></small> at 0.25 mA cm<small><sup>−2</sup></small>. These advances establish a scalable route toward industrially relevant, all-ceramic composite cathodes for garnet-based solid-state batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"44 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yingbing Zou, Xinyuan Zheng, Xueyan Yang, Huixian Ye, Cheng Liu, Wen-Tong Chen, Hongzhou Li
Epoxy resin (EP) is intrinsically flammable and generates dense smoke and toxic gases during combustion, which severely restricts its application in fire-sensitive environments. In this work, an in situ interfacial assembly strategy was developed to construct a P-MXene@COF hybrid, where covalent organic framework (COF) layers were grown on amino-functionalized MXene nanosheets and subsequently integrated with phosphorus species. At a low loading of 3 wt%, the EP/P-MXene@COF composite maintained satisfactory mechanical performance while achieving remarkable fire safety. The limiting oxygen index (LOI) reached 27.2%, and cone calorimetry revealed substantial reductions in combustion intensity, with the peak heat release rate and total heat release decreased by 43.4% and 22.2%, respectively. Moreover, smoke and toxic gas emissions were effectively suppressed, as reflected by a 22.6% reduction in peak smoke production rate and a 44.8% decrease in CO 2 release rate. Char residue analyses confirmed the formation of a compact, highly graphitized phosphorus-rich protective barrier, while TG-FTIR demonstrated significant inhibition of volatile evolution. These results indicate that the synergy of gas-phase radical quenching, inert-gas dilution, and condensed-phase catalytic charring endows EP/P-MXene@COF with superior flame retardancy and smoke suppression. This study provides new insights into the scalable design of multifunctional flame-retardant fillers for epoxy composites.
{"title":"In situ interfacial assembly of P-MXene@COF hybrids for flame-retardant and smoke-suppressive epoxy resin","authors":"Yingbing Zou, Xinyuan Zheng, Xueyan Yang, Huixian Ye, Cheng Liu, Wen-Tong Chen, Hongzhou Li","doi":"10.1039/d5ta08312e","DOIUrl":"https://doi.org/10.1039/d5ta08312e","url":null,"abstract":"Epoxy resin (EP) is intrinsically flammable and generates dense smoke and toxic gases during combustion, which severely restricts its application in fire-sensitive environments. In this work, an in situ interfacial assembly strategy was developed to construct a P-MXene@COF hybrid, where covalent organic framework (COF) layers were grown on amino-functionalized MXene nanosheets and subsequently integrated with phosphorus species. At a low loading of 3 wt%, the EP/P-MXene@COF composite maintained satisfactory mechanical performance while achieving remarkable fire safety. The limiting oxygen index (LOI) reached 27.2%, and cone calorimetry revealed substantial reductions in combustion intensity, with the peak heat release rate and total heat release decreased by 43.4% and 22.2%, respectively. Moreover, smoke and toxic gas emissions were effectively suppressed, as reflected by a 22.6% reduction in peak smoke production rate and a 44.8% decrease in CO 2 release rate. Char residue analyses confirmed the formation of a compact, highly graphitized phosphorus-rich protective barrier, while TG-FTIR demonstrated significant inhibition of volatile evolution. These results indicate that the synergy of gas-phase radical quenching, inert-gas dilution, and condensed-phase catalytic charring endows EP/P-MXene@COF with superior flame retardancy and smoke suppression. This study provides new insights into the scalable design of multifunctional flame-retardant fillers for epoxy composites.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"275 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chai Hua, Yan Guo, Jun Nan, Yongfa Zhu, Qixin Zhou
Organic semiconductor photocatalysts provide a promising platform for solar hydrogen evolution by integrating light harvesting, exciton dynamics, and interfacial catalysis. However, in most organic semiconductors, slow proton transport through hydrophobic domains decouples photogenerated electrons from proton-coupled electron transfer and limits activity. Here we encapsulate perylenetetracarboxylic acid dianhydride (PTCDA) into a hydrogen-bonded organic framework (HOF) of H4TBAPy linkers to build proton-conductive nanochannels around photoactive π-stacks. The hydrogen-bond network supports proton diffusion along confined pathways, increasing proton conductivity from 0.7 to 9.6 mS cm-1, while the π–π stacked heterojunction generates an internal electric field that enhances interfacial charge separation. As a result, the PTCDA-in-HOF composite achieves a hydrogen evolution rate of 709.05 mmol g-1 h-1 with an apparent quantum efficiency of 29.4% at 450 nm and robust cycling stability. By coupling proton-transport engineering with organic semiconductor design, this work clarifies the role of local proton availability in organic photocatalysts and guides optimization of solar hydrogen fuel production.
有机半导体光催化剂集光收集、激子动力学和界面催化为太阳能析氢提供了一个很有前景的平台。然而，在大多数有机半导体中，通过疏水域的质子慢输运会使光生电子与质子耦合电子转移分离，从而限制了活性。本研究将苝四羧酸二酐（PTCDA）包封在h4tbby连接体的氢键有机框架（HOF）中，在光活性π堆叠周围构建质子导电纳米通道。氢键网络支持质子沿限定路径扩散，将质子电导率从0.7 mS cm-1提高到9.6 mS cm-1，而π -π堆叠异质结产生的内部电场增强了界面电荷分离。结果表明，PTCDA-in-HOF复合材料在450 nm处的析氢速率为709.05 mmol g-1 h-1，表观量子效率为29.4%，循环稳定性良好。通过耦合质子输运工程与有机半导体设计，本工作阐明了局部质子可用性在有机光催化剂中的作用，并指导太阳能氢燃料生产的优化。
{"title":"Proton-conducting hydrogen-bonded nanochannels encapsulating perylene-based photocatalysts for solar hydrogen evolution","authors":"Chai Hua, Yan Guo, Jun Nan, Yongfa Zhu, Qixin Zhou","doi":"10.1039/d5ta10040b","DOIUrl":"https://doi.org/10.1039/d5ta10040b","url":null,"abstract":"Organic semiconductor photocatalysts provide a promising platform for solar hydrogen evolution by integrating light harvesting, exciton dynamics, and interfacial catalysis. However, in most organic semiconductors, slow proton transport through hydrophobic domains decouples photogenerated electrons from proton-coupled electron transfer and limits activity. Here we encapsulate perylenetetracarboxylic acid dianhydride (PTCDA) into a hydrogen-bonded organic framework (HOF) of H4TBAPy linkers to build proton-conductive nanochannels around photoactive π-stacks. The hydrogen-bond network supports proton diffusion along confined pathways, increasing proton conductivity from 0.7 to 9.6 mS cm-1, while the π–π stacked heterojunction generates an internal electric field that enhances interfacial charge separation. As a result, the PTCDA-in-HOF composite achieves a hydrogen evolution rate of 709.05 mmol g-1 h-1 with an apparent quantum efficiency of 29.4% at 450 nm and robust cycling stability. By coupling proton-transport engineering with organic semiconductor design, this work clarifies the role of local proton availability in organic photocatalysts and guides optimization of solar hydrogen fuel production.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"61 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yu Zhang, Jiawei Liu, Xiujie Yu, Jiayao Wen, Wei He, Xinyu Yue, Lei Ye, Yabin Zhang
Achieving stable dispersion of liquid metal within hydrogels remains a key challenge for developing durable multifunctional sensors. Here, we report a green and facile one-pot synthesis of high-performance eutectic gallium-indium (EGaIn)reinforced hydrogels via a dual-level stabilization and interfacial reinforcement strategy. This strategy employs the synergistic effect of plant-derived tannic acid (TA) and guar gum (GG) to homogeneously disperse EGaIn droplets, followed by their spontaneous polymerization and cross-linking without any external initiators. The resulting hydrogel integrates remarkable stretchability (1770%), high toughness (3.75 mJ•m⁻³), strong adhesion to diverse substrates, and exceptional anti-swelling capacity (swelling ratio of 4.1%). It also maintains high electrical conductivity (11.2 mS•cm⁻¹), enabling real-time and accurate monitoring of human motions. Furthermore, the hydrogel exhibits efficient photothermal conversion, demonstrating great potential for infrared camouflage applications. This work provides a universal and sustainable platform for fabricating integrated soft materials for next-generation wearable electronics and adaptive interfaces.
{"title":"A plant-stabilized and self-initiated liquid metal hydrogel for high-performance multifunctional sensing and infrared camouflage","authors":"Yu Zhang, Jiawei Liu, Xiujie Yu, Jiayao Wen, Wei He, Xinyu Yue, Lei Ye, Yabin Zhang","doi":"10.1039/d5ta10002j","DOIUrl":"https://doi.org/10.1039/d5ta10002j","url":null,"abstract":"Achieving stable dispersion of liquid metal within hydrogels remains a key challenge for developing durable multifunctional sensors. Here, we report a green and facile one-pot synthesis of high-performance eutectic gallium-indium (EGaIn)reinforced hydrogels via a dual-level stabilization and interfacial reinforcement strategy. This strategy employs the synergistic effect of plant-derived tannic acid (TA) and guar gum (GG) to homogeneously disperse EGaIn droplets, followed by their spontaneous polymerization and cross-linking without any external initiators. The resulting hydrogel integrates remarkable stretchability (1770%), high toughness (3.75 mJ•m⁻³), strong adhesion to diverse substrates, and exceptional anti-swelling capacity (swelling ratio of 4.1%). It also maintains high electrical conductivity (11.2 mS•cm⁻¹), enabling real-time and accurate monitoring of human motions. Furthermore, the hydrogel exhibits efficient photothermal conversion, demonstrating great potential for infrared camouflage applications. This work provides a universal and sustainable platform for fabricating integrated soft materials for next-generation wearable electronics and adaptive interfaces.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"67 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seungil Lee, Pedro Oliveira, Mehdi Shamekhi, Raaja Rajeshwari Manickam, Woo Young Kim, Jong Hyun Lim, Ayse Turak
Zinc-based rechargeable batteries are a promising low-cost alternative for grid-scale energy storage, but their lifetimes are limited by dendritic growth and side reactions at the metal anode. Here, we demonstrate a simple solution-based strategy to stabilize Zn anodes using a periodically sparse array of gold nanoparticles (Au NPs) deposited by reverse micelle templating. Unlike dense coatings or randomly aggregated particles, isolated Au NPs act as uniformly distributed nucleation sites that homogenize local charge fields, enhance ion transport, and suppress dendrite formation while preserving the active Zn surface. The process, achieved by gold-halide-loaded block copolymer micelles followed by plasma etching, provides precise nanoparticle size control and reproducible submonolayer coverage. Electrochemical testing shows reduced nucleation barriers, improved charge transfer kinetics, and markedly enhanced cycling stability, with symmetric cells exceeding 4000 hours of operation and delivering up to 50-fold lifetime improvements compared to bare Zn. Full-cell tests with V2O5 cathodes further confirm the improved efficiency and stability of Au NP-modified anodes. This work highlights nanoparticle decoration as a cost-effective and scalable interface engineering strategy for achieving long-life Zn batteries without compromising active surface area.
{"title":"Sparse Au nanoparticle arrays modulate Zn nucleation pathways and ion transport: a mechanistic approach to dendrite-free aqueous battery cycling","authors":"Seungil Lee, Pedro Oliveira, Mehdi Shamekhi, Raaja Rajeshwari Manickam, Woo Young Kim, Jong Hyun Lim, Ayse Turak","doi":"10.1039/d5ta08137h","DOIUrl":"https://doi.org/10.1039/d5ta08137h","url":null,"abstract":"Zinc-based rechargeable batteries are a promising low-cost alternative for grid-scale energy storage, but their lifetimes are limited by dendritic growth and side reactions at the metal anode. Here, we demonstrate a simple solution-based strategy to stabilize Zn anodes using a periodically sparse array of gold nanoparticles (Au NPs) deposited by reverse micelle templating. Unlike dense coatings or randomly aggregated particles, isolated Au NPs act as uniformly distributed nucleation sites that homogenize local charge fields, enhance ion transport, and suppress dendrite formation while preserving the active Zn surface. The process, achieved by gold-halide-loaded block copolymer micelles followed by plasma etching, provides precise nanoparticle size control and reproducible submonolayer coverage. Electrochemical testing shows reduced nucleation barriers, improved charge transfer kinetics, and markedly enhanced cycling stability, with symmetric cells exceeding 4000 hours of operation and delivering up to 50-fold lifetime improvements compared to bare Zn. Full-cell tests with V<small><sub>2</sub></small>O<small><sub>5</sub></small> cathodes further confirm the improved efficiency and stability of Au NP-modified anodes. This work highlights nanoparticle decoration as a cost-effective and scalable interface engineering strategy for achieving long-life Zn batteries without compromising active surface area.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"16 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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