Ruthenium (Ru) is a promising electrocatalyst for hydrogen and chlor-alkali co-production, but suffers from poor water adsorption and hydrogen desorption. To enhance its hydrogen evolution reaction (HER) performance, this study employs density functional theory (DFT) to explore how non-metallic supports (B, C, N) modulate the electronic structure of Ru via metal-support interactions (MSIs). Results reveal B4C as the optimal support, with 1.56 electrons transferred from Ru13 to B4C, shifting the Ru d-band center closer to the Fermi level and synergistically optimizing the adsorption of HER intermediates. The synthesized N-doped carbon-coated Ru/B4C catalyst (Ru/B4C@NC) exhibits outstanding alkaline HER activity, achieving overpotentials of only 5 mV at 10 mA cm−2 and 361 mV at 1 A cm−2, along with stability over 500 h. Under chlor-alkali conditions, Ru/B4C@NC also maintains high HER activity with overpotentials of 5 and 99 mV at 10 and 500 mA cm−2 and long-term stability for 300 h. A hybrid electrolysis cell with Ru/B4C@NC (−) //RuO2/IrO2-coated Ti mesh (+) achieves a record low voltage of 2.33 V at 10 mA cm−2 with long-term stability for 100 h. This work provides valuable insights for designing advanced Ru-based catalysts for integrated hydrogen and chlor-alkali production.
钌（Ru）是一种很有前途的氢氯碱联产电催化剂，但其吸水性和解吸氢性能较差。为了提高Ru的析氢反应（HER）性能，本研究采用密度泛函理论（DFT）探讨了非金属载体（B， C， N）如何通过金属-载体相互作用（msi）调节Ru的电子结构。结果表明，B4C是最佳载体，有1.56个电子从Ru13转移到B4C，使Ru带中心更接近费米能级，协同优化了HER中间体的吸附。合成的n掺杂碳包覆Ru/B4C催化剂（Ru/B4C@NC）表现出出色的碱性HER活性，在10 mA cm−2时过电位仅为5 mV，在1 A cm−2时过电位仅为361 mV，并且在500 h内稳定。Ru/B4C@NC还保持了高HER活性，在10和500 mA cm - 2下的过电位为5和99 mV，长期稳定性为300小时。Ru/B4C@NC(−)//RuO2/ iro2涂层Ti网（+）的混合电解池在10 mA cm - 2下达到了创纪录的2.33 V的低电压，长期稳定性为100小时。这项工作为设计先进的Ru基催化剂提供了宝贵的见解。
{"title":"Boron Carbide Supported Ultra-Small Ruthenium Nanoparticles with High-Performance for Hydrogen and Chlor-Alkali Co-Production","authors":"Abdulwahab Salah, Hong-Da Ren, Feiyang Yu, Nabilah Al-Ansi, Zhongling Lang, Yangguang Li, Yonghui Wang, Huaqiao Tan","doi":"10.1002/aenm.202506175","DOIUrl":"https://doi.org/10.1002/aenm.202506175","url":null,"abstract":"Ruthenium (Ru) is a promising electrocatalyst for hydrogen and chlor-alkali co-production, but suffers from poor water adsorption and hydrogen desorption. To enhance its hydrogen evolution reaction (HER) performance, this study employs density functional theory (DFT) to explore how non-metallic supports (B, C, N) modulate the electronic structure of Ru via metal-support interactions (MSIs). Results reveal B<sub>4</sub>C as the optimal support, with 1.56 electrons transferred from Ru<sub>13</sub> to B<sub>4</sub>C, shifting the Ru d-band center closer to the Fermi level and synergistically optimizing the adsorption of HER intermediates. The synthesized N-doped carbon-coated Ru/B<sub>4</sub>C catalyst (Ru/B<sub>4</sub>C@NC) exhibits outstanding alkaline HER activity, achieving overpotentials of only 5 mV at 10 mA cm<sup>−2</sup> and 361 mV at 1 A cm<sup>−2</sup>, along with stability over 500 h. Under chlor-alkali conditions, Ru/B<sub>4</sub>C@NC also maintains high HER activity with overpotentials of 5 and 99 mV at 10 and 500 mA cm<sup>−2</sup> and long-term stability for 300 h. A hybrid electrolysis cell with Ru/B<sub>4</sub>C@NC (−) //RuO<sub>2</sub>/IrO<sub>2</sub>-coated Ti mesh (+) achieves a record low voltage of 2.33 V at 10 mA cm<sup>−2</sup> with long-term stability for 100 h. This work provides valuable insights for designing advanced Ru-based catalysts for integrated hydrogen and chlor-alkali production.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"90 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of wide-temperature gel polymer electrolytes (GPEs) represents a promising strategy for enhancing the extreme environment tolerance of lithium-metal batteries (LMBs), which requires simultaneously optimizing Li+ transport kinetics at low temperatures and maintaining the thermal and mechanical stability. This work addresses the intrinsic limitations of conventional GPEs by employing a molecular engineering strategy that achieves molecular-scale hybridization of organic and inorganic units. Specifically, a fluorinated hybrid gel polymer electrolyte (FHPE) is fabricated through the in situ crosslinking polymerization of trifluoroethyl acrylate (TFEA) and acryloxypropyl polyhedral oligomeric silsesquioxane (Acry-POSS) within 2,2-difluoroethyl acetate (DFEA). The FHPE displays high Li+ conductivity (3.54 × 10−4 S cm−1 at −30°C), broad electrochemical stability window (>4.7 V), and remarkable mechanical strength (58.7 MPa). Moreover, the FHPE promotes the formation of LiF-rich interphases on the LiCoO2 cathode and lithium metal anode, thereby effectively mitigating dendrite growth and interfacial side reactions. Consequently, FHPE-based Li/Li coin cells stably cycle for 1500 h at 0.3 mA cm−2 and −30°C, while Li/LiCoO2 coin cells exhibit 86.7% capacity retention after 200 cycles at −30°C and 77.9% after 400 cycles at 60°C. Furthermore, Li/FHPE/LiCoO2 pouch cells exhibit stable operation during nail penetration tests, thereby confirming their exceptional safety.
宽温度凝胶聚合物电解质（gpe）的开发是提高锂金属电池（lmb）极端环境耐受性的一种有前景的策略，这需要同时优化Li+在低温下的传输动力学，并保持热稳定性和机械稳定性。这项工作通过采用分子工程策略实现有机和无机单元的分子尺度杂交，解决了传统gpe的内在局限性。具体而言，通过在2,2-二氟乙酸乙酯（DFEA）中原位交联聚合三氟丙烯酸乙酯（TFEA）和丙烯氧丙基多面体低聚硅氧烷（acy - poss）制备了氟化杂化凝胶聚合物电解质（FHPE）。FHPE具有较高的Li+电导率（- 30°C时为3.54 × 10−4 S cm−1）、较宽的电化学稳定窗口（>4.7 V）和显著的机械强度（58.7 MPa）。此外，FHPE促进了LiCoO2阴极和锂金属阳极上富liff界面相的形成，从而有效地减缓了枝晶生长和界面副反应。因此，基于fhpe的Li/Li硬币电池在0.3 mA cm - 2和- 30°C下稳定循环1500 h，而Li/LiCoO2硬币电池在- 30°C下循环200次后容量保持率为86.7%，在60°C下循环400次后容量保持率为77.9%。此外，Li/FHPE/LiCoO2袋状电池在指甲穿透测试中表现出稳定的运行，从而证实了它们卓越的安全性。
{"title":"Molecular Engineering of Fluorinated Hybrid Gel Polymer Electrolytes Enables Ultra-Wide-Temperature Operation of High-Voltage Lithium Metal Batteries","authors":"Zhenxiang Zhu, Xianbin Wu, Hong Xu, Dayao Zhang, Zhen Geng, Cunman Zhang, Stefano Passerini, Mingzhe Xue","doi":"10.1002/aenm.202506074","DOIUrl":"https://doi.org/10.1002/aenm.202506074","url":null,"abstract":"The development of wide-temperature gel polymer electrolytes (GPEs) represents a promising strategy for enhancing the extreme environment tolerance of lithium-metal batteries (LMBs), which requires simultaneously optimizing Li<sup>+</sup> transport kinetics at low temperatures and maintaining the thermal and mechanical stability. This work addresses the intrinsic limitations of conventional GPEs by employing a molecular engineering strategy that achieves molecular-scale hybridization of organic and inorganic units. Specifically, a fluorinated hybrid gel polymer electrolyte (FHPE) is fabricated through the in situ crosslinking polymerization of trifluoroethyl acrylate (TFEA) and acryloxypropyl polyhedral oligomeric silsesquioxane (Acry-POSS) within 2,2-difluoroethyl acetate (DFEA). The FHPE displays high Li<sup>+</sup> conductivity (3.54 × 10<sup>−4</sup> S cm<sup>−1</sup> at −30°C), broad electrochemical stability window (>4.7 V), and remarkable mechanical strength (58.7 MPa). Moreover, the FHPE promotes the formation of LiF-rich interphases on the LiCoO<sub>2</sub> cathode and lithium metal anode, thereby effectively mitigating dendrite growth and interfacial side reactions. Consequently, FHPE-based Li/Li coin cells stably cycle for 1500 h at 0.3 mA cm<sup>−2</sup> and −30°C, while Li/LiCoO<sub>2</sub> coin cells exhibit 86.7% capacity retention after 200 cycles at −30°C and 77.9% after 400 cycles at 60°C. Furthermore, Li/FHPE/LiCoO<sub>2</sub> pouch cells exhibit stable operation during nail penetration tests, thereby confirming their exceptional safety.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"58 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sreelakshmi Anil Kumar, Dhanush Shanbhag, Ove Korjus, Prashanth Sivakumar, Laurence Croguennec, Christian Masquelier, Jean-Noël Chotard, Emmanuelle Suard
All-Solid-State Batteries (ASSBs) are promising emerging devices for meeting high-energy demands and an in-depth understanding of the reaction mechanisms occuring during their operation will help in their design for better performance. In this context, neutrons, with their high penetration depth and sensitivity to light elements such as lithium, provide a powerful tool for investigating the structural mechanisms occurring in bulk ASSBs, while the electrochemical operation of large batteries (required for neutron diffraction) remains a challenge. In this study, we demonstrate the reversible electrochemical Li+ extraction/insertion within a 2.5 mm thick ASSB system comprising 140 mg of LiNi0.6Mn0.2Co0.2O2 (NMC622) as the positive electrode material (238 mWh energy density), Li5.4PS4.4BrCl0.6 (LPSClBr) as the solid electrolyte and Li0.5In as the negative electrode. Thanks to the use of the newly-designed ILLBAT#5 electrochemical cell, we were able to perform operando neutron powder diffraction (NPD) of the system, which coupled with ex situ diffraction, allowed us to gain valuable insights into the structural evolution of NMC622 within the ASSB as well as to probe the structural stability of the Argyrodite solid electrolyte throughout the initial cycle. Herein, we report on the formation and the co-existence of H1-H2 phases in NMC622, attributed to system inhomogeneity.
{"title":"Investigation of the Lithium Extraction Mechanism from LiNi0.6Mn0.2Co0.2O2 by Using Operando Neutron Diffraction in an All-Solid-State Battery","authors":"Sreelakshmi Anil Kumar, Dhanush Shanbhag, Ove Korjus, Prashanth Sivakumar, Laurence Croguennec, Christian Masquelier, Jean-Noël Chotard, Emmanuelle Suard","doi":"10.1002/aenm.202506600","DOIUrl":"https://doi.org/10.1002/aenm.202506600","url":null,"abstract":"All-Solid-State Batteries (ASSBs) are promising emerging devices for meeting high-energy demands and an in-depth understanding of the reaction mechanisms occuring during their operation will help in their design for better performance. In this context, neutrons, with their high penetration depth and sensitivity to light elements such as lithium, provide a powerful tool for investigating the structural mechanisms occurring in bulk ASSBs, while the electrochemical operation of large batteries (required for neutron diffraction) remains a challenge. In this study, we demonstrate the reversible electrochemical Li<sup>+</sup> extraction/insertion within a 2.5 mm thick ASSB system comprising 140 mg of LiNi<sub>0.6</sub>Mn<sub>0.2</sub>Co<sub>0.2</sub>O<sub>2</sub> (NMC622) as the positive electrode material (238 mWh energy density), Li<sub>5.4</sub>PS<sub>4.4</sub>BrCl<sub>0.6</sub> (LPSClBr) as the solid electrolyte and Li<sub>0.5</sub>In as the negative electrode. Thanks to the use of the newly-designed ILLBAT#5 electrochemical cell, we were able to perform <i>operando</i> neutron powder diffraction (NPD) of the system, which coupled with ex situ diffraction, allowed us to gain valuable insights into the structural evolution of NMC622 within the ASSB as well as to probe the structural stability of the Argyrodite solid electrolyte throughout the initial cycle. Herein, we report on the formation and the co-existence of H1-H2 phases in NMC622, attributed to system inhomogeneity.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"235 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical CO2 reduction reaction (CO2RR) in proton exchange membrane electrolyzers offers a pathway to close the carbon cycle and produce sustainable fuels and chemicals at industrial-scale current densities. Acidic operation enables compact reactor architectures and superior single-pass carbon utilization, yet faces persistent challenges including parasitic hydrogen evolution, catalyst corrosion and deactivation, along with constrained local CO2 transport. This review highlights recent progress in interfacial microenvironmental engineering that reconcile acidic operation with selective and durable CO2 conversion. We organize strategies across four critical interfaces: (1) the gas diffusion layer-catalyst layer interface, where engineered hydrophobicity and pore structure promote CO2 delivery while maintaining a stable three-phase boundary; (2) the catalyst-electrolyte electric double layer interface, where control over interfacial fields, pH gradients, and adsorbate binding energetics suppresses the hydrogen evolution reaction while promoting CO2RR selectivity; (3) at the catalyst layer-membrane interface, where optimized ionomer distribution and tailored proton conductivity balance local proton availability, mitigating catalyst degradation; and (4) the integrated membrane-electrode assembly, where harmonized ion transport, CO2 flux, and electron conduction stabilizes the microenvironment for long-term durability. By consolidating mechanistic insights and practical design principles, this review provides a roadmap for rational interfacial engineering to realize efficient, durable, and scalable acidic CO2 electroreduction in PEM electrolyzers.
{"title":"Interfacial Microenvironmental Engineering for Acidic CO2 Electroreduction in Proton Exchange Membrane Electrolyzers","authors":"Shengjie Bai, Xufei Gu, Jianxin Dong, Jirui Yang, Wenyu Zheng, Cong Guo, Ya Liu, TingTing Kong, Shaohua Shen","doi":"10.1002/aenm.202506790","DOIUrl":"https://doi.org/10.1002/aenm.202506790","url":null,"abstract":"Electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) in proton exchange membrane electrolyzers offers a pathway to close the carbon cycle and produce sustainable fuels and chemicals at industrial-scale current densities. Acidic operation enables compact reactor architectures and superior single-pass carbon utilization, yet faces persistent challenges including parasitic hydrogen evolution, catalyst corrosion and deactivation, along with constrained local CO<sub>2</sub> transport. This review highlights recent progress in interfacial microenvironmental engineering that reconcile acidic operation with selective and durable CO<sub>2</sub> conversion. We organize strategies across four critical interfaces: (1) the gas diffusion layer-catalyst layer interface, where engineered hydrophobicity and pore structure promote CO<sub>2</sub> delivery while maintaining a stable three-phase boundary; (2) the catalyst-electrolyte electric double layer interface, where control over interfacial fields, pH gradients, and adsorbate binding energetics suppresses the hydrogen evolution reaction while promoting CO<sub>2</sub>RR selectivity; (3) at the catalyst layer-membrane interface, where optimized ionomer distribution and tailored proton conductivity balance local proton availability, mitigating catalyst degradation; and (4) the integrated membrane-electrode assembly, where harmonized ion transport, CO<sub>2</sub> flux, and electron conduction stabilizes the microenvironment for long-term durability. By consolidating mechanistic insights and practical design principles, this review provides a roadmap for rational interfacial engineering to realize efficient, durable, and scalable acidic CO<sub>2</sub> electroreduction in PEM electrolyzers.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"87 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal halide perovskite indoor photovoltaics (IPVs) are the top contenders in terms of efficiency among emerging IPV technologies. The state-of-the-art perovskite IPVs have already achieved reported efficiencies above 44%, indicating their significant potential. However, only a small percentage of reports discuss stability measurements, with approximately 7% adopting the International Summit on Organic PV Stability (ISOS) protocol for stability evaluation. A standard for the stability assessment of emerging thin film IPVs still lags. This research area remains largely unexplored, yet it is essential to the commercialization of IPV technologies. This review focuses on perovskite-based IPVs, with an emphasis on device stability. It provides discussions of the origins of degradation in perovskite materials and their corresponding IPV devices. This is followed by an overview of various structure–property–stability strategies, including compositional, interface, and device design engineering for perovskite materials to improve their performance. Finally, the review outlines some existing stability test protocols that could apply to perovskite IPVs, including addressing mitigation issues, such as encapsulation, draws the attention of researchers in the field, and calls for the development of standardized stability test protocols for perovskite IPVs and for understanding how these tests correlate with actual indoor lifespans to enable the commercialization of perovskite IPVs.
{"title":"Stability of Perovskite Indoor Photovoltaics: A Focused Review and a Call for Standardized Stability Reporting","authors":"Ivy Mawusi Asuo, Arezo Mahdavi Varposhti, Cyril Chu Fubin Kumachang, Gopal Krishnamurthy Grandhi, Vincenzo Pecunia, Thomas Meredith Brown, Paola Vivo, Nutifafa Yao Doumon","doi":"10.1002/aenm.202506091","DOIUrl":"https://doi.org/10.1002/aenm.202506091","url":null,"abstract":"Metal halide perovskite indoor photovoltaics (IPVs) are the top contenders in terms of efficiency among emerging IPV technologies. The state-of-the-art perovskite IPVs have already achieved reported efficiencies above 44%, indicating their significant potential. However, only a small percentage of reports discuss stability measurements, with approximately 7% adopting the International Summit on Organic PV Stability (ISOS) protocol for stability evaluation. A standard for the stability assessment of emerging thin film IPVs still lags. This research area remains largely unexplored, yet it is essential to the commercialization of IPV technologies. This review focuses on perovskite-based IPVs, with an emphasis on device stability. It provides discussions of the origins of degradation in perovskite materials and their corresponding IPV devices. This is followed by an overview of various structure–property–stability strategies, including compositional, interface, and device design engineering for perovskite materials to improve their performance. Finally, the review outlines some existing stability test protocols that could apply to perovskite IPVs, including addressing mitigation issues, such as encapsulation, draws the attention of researchers in the field, and calls for the development of standardized stability test protocols for perovskite IPVs and for understanding how these tests correlate with actual indoor lifespans to enable the commercialization of perovskite IPVs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"21 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bowen Wang, Yang Yang, Qianhe Xu, Xubin Wang, Lihao Tang, Xueyan Cui, Hongyue Cui, Han Tang, Hong Li, Yong-Sheng Hu, Yaxiang Lu
All-solid-state batteries (ASSBs) are widely regarded as promising nextgeneration energy storage systems due to their high energy density and enhanced safety. Na-based ASSBs, in particular, offer compelling advantages through the use of earth-abundant and low-cost materials. However, a critical knowledge gap remains regarding the thermal stability of sodium solid electrolytes (SEs)—especially their reactivity with electrode materials—hindering reliable safety assessment. Herein, we present a systematic comparison of the thermal behavior of six representative sodium SEs: Na3Zr2Si2PO12, Na3PS4, NaAlCl4, Na2ZrCl6, NaAlCl2.5O0.75, and PEO. While inorganic SEs demonstrate good intrinsic thermal stability, most exhibit significant exothermic reactions with cathode or anode materials upon heating, releasing considerable heat that could trigger thermal runaway. Notably, chloride-based SEs show markedly different reactivities—NaAlCl4 reacts violently with Na15Sn4, whereas Na2ZrCl6 remains remarkably stable, highlighting the crucial role of reaction kinetics and melting point in modulating thermal stability. The findings reveal that electrode–electrolyte compatibility under thermal stress—not just the stability of the SE alone—is a decisive factor for ASSB safety. Our work underscores the critical role of electrode-electrolyte thermal stability, offering new insights into the safety design of all-solid-state batteries.
{"title":"Thermal Stability Assessment of Sodium Solid Electrolytes","authors":"Bowen Wang, Yang Yang, Qianhe Xu, Xubin Wang, Lihao Tang, Xueyan Cui, Hongyue Cui, Han Tang, Hong Li, Yong-Sheng Hu, Yaxiang Lu","doi":"10.1002/aenm.202506749","DOIUrl":"https://doi.org/10.1002/aenm.202506749","url":null,"abstract":"All-solid-state batteries (ASSBs) are widely regarded as promising nextgeneration energy storage systems due to their high energy density and enhanced safety. Na-based ASSBs, in particular, offer compelling advantages through the use of earth-abundant and low-cost materials. However, a critical knowledge gap remains regarding the thermal stability of sodium solid electrolytes (SEs)—especially their reactivity with electrode materials—hindering reliable safety assessment. Herein, we present a systematic comparison of the thermal behavior of six representative sodium SEs: Na<sub>3</sub>Zr<sub>2</sub>Si<sub>2</sub>PO<sub>12</sub>, Na<sub>3</sub>PS<sub>4</sub>, NaAlCl<sub>4</sub>, Na<sub>2</sub>ZrCl<sub>6</sub>, NaAlCl<sub>2.5</sub>O<sub>0.75,</sub> and PEO. While inorganic SEs demonstrate good intrinsic thermal stability, most exhibit significant exothermic reactions with cathode or anode materials upon heating, releasing considerable heat that could trigger thermal runaway. Notably, chloride-based SEs show markedly different reactivities—NaAlCl<sub>4</sub> reacts violently with Na<sub>15</sub>Sn<sub>4</sub>, whereas Na<sub>2</sub>ZrCl<sub>6</sub> remains remarkably stable, highlighting the crucial role of reaction kinetics and melting point in modulating thermal stability. The findings reveal that electrode–electrolyte compatibility under thermal stress—not just the stability of the SE alone—is a decisive factor for ASSB safety. Our work underscores the critical role of electrode-electrolyte thermal stability, offering new insights into the safety design of all-solid-state batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"58 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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/cm2 (>200 cycles). This work paves the way for the development of durable, high-energy-density batteries.
{"title":"Unraveling Failure Mechanism of Indium Anodes in all-Solid-State Batteries","authors":"Haoqi Ren, Xiaoting Lin, Jiamin Fu, Yipeng Sun, Xiaozhang Yao, Yingjie Gao, Bolin Fu, Weihan Li, Changhong Wang, Xueliang Sun","doi":"10.1002/aenm.202504932","DOIUrl":"https://doi.org/10.1002/aenm.202504932","url":null,"abstract":"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 Al<sub>2</sub>O<sub>3</sub> 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/cm<sup>2</sup> was enhanced from 0.2 to 2 mAh/cm<sup>2</sup> (>200 cycles). This work paves the way for the development of durable, high-energy-density batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"32 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianfeng Yao, Long Pang, Yuwei Su, Limin Guo, Erkang Wang, Zhangquan Peng, Zhiwei Zhao
Redox mediators (RMs) emerge as critical enablers for unlocking the energy potentials of aprotic Li-CO2 batteries through solution-mediated CO2 reduction reaction (CO2RR). However, the structural effect of RMs on CO2RR pathways and catalytic efficiency remains insufficiently understood. Herein, through a comparative investigation of model quinone (Q)-based RMs using in situ spectroscopic techniques coupled with theoretical calculations, it is revealed that reduced Q species chemically bind with CO2 to form metastable Lin(Q-xCO2) adducts (n, x = 1 or 2), which subsequently dissociate into LiCO2 intermediates and further generate Li2CO3 and CO as discharge product while regenerating LinQ (n = 0 or 1) for sustained redox cycling. The dissociation of Lin(Q-xCO2) adducts constitutes the rate-determining step under non-polarization conditions. The introduction of electron-withdrawing groups (EWGs) into the Q moiety can enhance discharge potentials, but creates a kinetic trade-off: increased dissociation kinetics of Lin(Q-xCO2) adducts and suppressed adduct formation due to diminished CO2 binding affinity for reduced Q species. Strategic electronic modulation via optimized EWG substitution balances this CO2 affinity and adducts dissociation equilibrium, achieving simultaneous improvements in discharge potential and capacity. Our work provides fundamental guidelines for the rational design of advanced RMs in next-generation Li-CO2 batteries.
氧化还原介质（RMs）是通过溶液介导的CO2还原反应（CO2RR）释放非质子锂-CO2电池能量潜力的关键促成因素。然而，RMs对CO2RR途径和催化效率的结构影响尚不清楚。本文利用原位光谱技术结合理论计算对模型醌(Q)基RMs进行了对比研究，发现还原后的Q与CO2化学结合形成亚稳的Lin（Q- xco2）加合物（n, x = 1或2），这些加合物随后解离成LiCO2中间体，并进一步生成Li2CO3和CO作为排放产物，同时再生LinQ （n = 0或1）进行持续的氧化还原循环。在非极化条件下，Lin（Q-xCO2）加合物的离解是速率决定步骤。在Q部分引入吸电子基团（ewg）可以增强放电电位，但会产生动力学上的权衡：由于CO2对还原Q的结合亲和力降低，增加了Lin（Q- xco2）加合物的解离动力学和抑制了加合物的形成。通过优化的EWG替代，战略性电子调制平衡了这种CO2亲和力和加合物解离平衡，同时实现了放电电位和容量的改善。我们的工作为下一代锂-二氧化碳电池的先进RMs的合理设计提供了基本指导。
{"title":"Deciphering Molecular Structural Effect on Redox-Mediated CO2 Reduction Reaction Mechanisms for Aprotic Li-CO2 Batteries","authors":"Tianfeng Yao, Long Pang, Yuwei Su, Limin Guo, Erkang Wang, Zhangquan Peng, Zhiwei Zhao","doi":"10.1002/aenm.202506608","DOIUrl":"https://doi.org/10.1002/aenm.202506608","url":null,"abstract":"Redox mediators (RMs) emerge as critical enablers for unlocking the energy potentials of aprotic Li-CO<sub>2</sub> batteries through solution-mediated CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). However, the structural effect of RMs on CO<sub>2</sub>RR pathways and catalytic efficiency remains insufficiently understood. Herein, through a comparative investigation of model quinone (Q)-based RMs using in situ spectroscopic techniques coupled with theoretical calculations, it is revealed that reduced Q species chemically bind with CO<sub>2</sub> to form metastable Li<sub>n</sub>(Q-xCO<sub>2</sub>) adducts (n, x = 1 or 2), which subsequently dissociate into LiCO<sub>2</sub> intermediates and further generate Li<sub>2</sub>CO<sub>3</sub> and CO as discharge product while regenerating Li<sub>n</sub>Q (n = 0 or 1) for sustained redox cycling. The dissociation of Li<sub>n</sub>(Q-xCO<sub>2</sub>) adducts constitutes the rate-determining step under non-polarization conditions. The introduction of electron-withdrawing groups (EWGs) into the Q moiety can enhance discharge potentials, but creates a kinetic trade-off: increased dissociation kinetics of Li<sub>n</sub>(Q-xCO<sub>2</sub>) adducts and suppressed adduct formation due to diminished CO<sub>2</sub> binding affinity for reduced Q species. Strategic electronic modulation via optimized EWG substitution balances this CO<sub>2</sub> affinity and adducts dissociation equilibrium, achieving simultaneous improvements in discharge potential and capacity. Our work provides fundamental guidelines for the rational design of advanced RMs in next-generation Li-CO<sub>2</sub> batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"19 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photocatalytic CO2 methanation is fundamentally constrained by two intertwined bottlenecks: inefficient proton generation from H2O dissociation and the premature desorption of the critical *CO intermediate. Here, we design metal cation vacancy clusters-O− motifs for accelerating H2O dissociation and boosting *CO protonation, while supported metal sites for CO2 activation over metal-anchored metal oxide nanosheets. As a prototype, we fabricate Au/TiO2-VTi nanosheets, where synchrotron-radiation X-ray absorption fine structure and electron paramagnetic resonance spectroscopy confirm VTi-O− and coordination-unsaturated Au sites. Density-functional-theory calculations reveal the creation of VTi-O− sites drive the step of *CO protonation toward *CHO from an endothermic process (0.09 eV) to an exothermic one (−0.29 eV), and concurrently the energy for H2O dissociation into protons is lowered by a factor of two (1.31 eV → 0.65 eV). In situ Fourier-transform infrared spectroscopy directly captures a distinct *CO intermediate, confirming its stabilization on the photocatalyst surface and thereby promoting the protonation step toward *CHO. Consequently, the Au/TiO2-VTi nanosheets show a superior CH4 formation rate of 156.5 µmol g−1 h−1 with near-100% selectivity. Briefly, this work offers key insights into CO2 methanation bottlenecks and proposes a catalyst design blueprint to advance CO2 valorization.
{"title":"Selective CO2-to-CH4 Photoreduction Enabled by Au/TiO2-VTi Nanosheets via Boosting H2O Dissociation and CO Protonation","authors":"Kai Zheng, Bangwang Li, Youbin Zheng, Xiulai Zhang, Runhua Chen, Shengyue Zhang, Siying Liu, Juncheng Zhu, Jianyi Liu, Wenxiu Liu, Jun Hu, Chengyuan Liu, Fanfei Sun, Zhongqin Dai, Yongfu Sun, Yi Xie","doi":"10.1002/aenm.202506793","DOIUrl":"https://doi.org/10.1002/aenm.202506793","url":null,"abstract":"Photocatalytic CO<sub>2</sub> methanation is fundamentally constrained by two intertwined bottlenecks: inefficient proton generation from H<sub>2</sub>O dissociation and the premature desorption of the critical <sup>*</sup>CO intermediate. Here, we design metal cation vacancy clusters-O<sup>−</sup> motifs for accelerating H<sub>2</sub>O dissociation and boosting <sup>*</sup>CO protonation, while supported metal sites for CO<sub>2</sub> activation over metal-anchored metal oxide nanosheets. As a prototype, we fabricate Au/TiO<sub>2</sub>-<i>V</i><sub>Ti</sub> nanosheets, where synchrotron-radiation X-ray absorption fine structure and electron paramagnetic resonance spectroscopy confirm <i>V</i><sub>Ti</sub>-O<sup>−</sup> and coordination-unsaturated Au sites. Density-functional-theory calculations reveal the creation of <i>V</i><sub>Ti</sub>-O<sup>−</sup> sites drive the step of <sup>*</sup>CO protonation toward <sup>*</sup>CHO from an endothermic process (0.09 eV) to an exothermic one (−0.29 eV), and concurrently the energy for H<sub>2</sub>O dissociation into protons is lowered by a factor of two (1.31 eV → 0.65 eV). In situ Fourier-transform infrared spectroscopy directly captures a distinct <sup>*</sup>CO intermediate, confirming its stabilization on the photocatalyst surface and thereby promoting the protonation step toward <sup>*</sup>CHO. Consequently, the Au/TiO<sub>2</sub>-<i>V</i><sub>Ti</sub> nanosheets show a superior CH<sub>4</sub> formation rate of 156.5 µmol g<sup>−1</sup> h<sup>−1</sup> with near-100% selectivity. Briefly, this work offers key insights into CO<sub>2</sub> methanation bottlenecks and proposes a catalyst design blueprint to advance CO<sub>2</sub> valorization.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"96 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal-organic frameworks (MOFs) are rising stars for Li-ion batteries (LIBs) electrodes. However, low conductivity of MOFs easily caused polarization and poor active site utilization. Here, an innovative electronic inversion layer (EIL) was proposed to guide the composite and interface design of MIL-53(Fe) with Ti3C2Tx, prompting a remarkable increase in the electrical conductivity of MIL-53(Fe) from 4.94 × 10−2 µS/cm to 46.65 mS/cm (30 MPa). This enhancement is attributed to the EIL activated by Ti3C2Tx effectively shift the primary charge carriers from holes to high-mobility electrons. Simultaneously, the localized EIL promoted the formation of a p–n junction and establishes a hole concentration gradient in MIL-53(Fe)@Ti3C2Tx, thereby accelerating lithium-ion diffusion kinetics. Consequently, the MIL-53(Fe)@Ti3C2Tx delivered a superior capacity of 450.3 mAh/g at 1 A/g, and the possible retention of 94% capacity after 1000 cycles, exceeding those of the MIL-53(Fe) and Ti3C2Tx. This investigation into MXene-activated EIL presents an innovative strategy and mechanism of universal significance for addressing the inherent conductivity challenges acted by a series of electrode materials, especially MOFs and COFs.
金属有机骨架（mof）是锂离子电池（LIBs）电极领域的新星。然而，mof的电导率低，容易引起极化，活性位点利用率差。本文提出了一个创新的电子反转层（EIL）来指导MIL-53（Fe）与Ti3C2Tx的复合和界面设计，使MIL-53（Fe）的电导率从4.94 × 10−2µS/cm显著提高到46.65 mS/cm （30 MPa）。这种增强归因于Ti3C2Tx激活的EIL有效地将初级载流子从空穴转移到高迁移率电子。同时，局域化的EIL促进了MIL-53(Fe)@Ti3C2Tx中p-n结的形成，并建立了空穴浓度梯度，从而加速了锂离子的扩散动力学。因此，MIL-53(Fe)@Ti3C2Tx在1 a /g时提供了450.3 mAh/g的优越容量，并且在1000次循环后可能保持94%的容量，超过了MIL-53（Fe）和Ti3C2Tx。这项对mxene活化的EIL的研究为解决一系列电极材料，特别是mof和COFs所带来的固有导电性挑战提供了一种具有普遍意义的创新策略和机制。
{"title":"Unlocking Superior Conductivity in MOF Electrodes via a MXene-Activated Electronic Inversion Layer","authors":"Zhiyuan Zhang, Jiequn Liu, Luzhi Liu, Xueling Hu, Huijue Luo, Yan Su, Jishu Zeng, Zejun Jiang, Yanfang Wang, Fangping Wang, Zongkang Sun, Zhuokui Zhong, Shibao Tang, Zhengfang Tang, Xiangbing Cai, Shengkui Zhong, Renheng Wang","doi":"10.1002/aenm.70713","DOIUrl":"https://doi.org/10.1002/aenm.70713","url":null,"abstract":"Metal-organic frameworks (MOFs) are rising stars for Li-ion batteries (LIBs) electrodes. However, low conductivity of MOFs easily caused polarization and poor active site utilization. Here, an innovative electronic inversion layer (EIL) was proposed to guide the composite and interface design of MIL-53(Fe) with Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>, prompting a remarkable increase in the electrical conductivity of MIL-53(Fe) from 4.94 × 10<sup>−2</sup> µS/cm to 46.65 mS/cm (30 MPa). This enhancement is attributed to the EIL activated by Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> effectively shift the primary charge carriers from holes to high-mobility electrons. Simultaneously, the localized EIL promoted the formation of a p–n junction and establishes a hole concentration gradient in MIL-53(Fe)@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>, thereby accelerating lithium-ion diffusion kinetics. Consequently, the MIL-53(Fe)@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> delivered a superior capacity of 450.3 mAh/g at 1 A/g, and the possible retention of 94% capacity after 1000 cycles, exceeding those of the MIL-53(Fe) and Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>. This investigation into MXene-activated EIL presents an innovative strategy and mechanism of universal significance for addressing the inherent conductivity challenges acted by a series of electrode materials, especially MOFs and COFs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"98 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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