The decomposition of sulfide-based electrolytes (SEs), notably Li3PS4 (LPS), at the electrode interface during battery cycling significantly hinders their practical application in all-solid-state batteries (ASSBs). However, the underlying mechanism through which chemical bonding modification enhances the electrochemical stability of SEs without compromising other properties remains unclear. Herein, we investigate the effect of introducing highly electronegative elements Q (Q ═ N, O, F) into LPS to strengthen chemical bonds and optimize lithium-ion (Li+) migration pathways in LPSQ electrolytes. Our results reveal that N and O facilitate the formation of PS3Q polyanions, whereas F tends to exist as LiF. All LPSQ systems exhibit an extended electrochemical stability window than pristine LPS, substantially enhancing their compatibility with high-voltage LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes. The strengthened chemical bonding environment further proves beneficial for both electronic and ionic conductivities, leading to superior performance in Li|LPSQ|Li symmetric batteries. Furthermore, by achieving an optimal balance between electronic and ionic conductivity, LPSN enables stable long-term cycling for over 300 cycles at 1C in LiIn||NCM811 full battery, while maintaining high Coulombic efficiency and minimal interfacial degradation. These findings provide guidelines for dopant selection in SE design and offer perspectives on SE engineering aimed at enhancing the high-voltage stability of ASSBs.
{"title":"Highly Electronegative Anions Doping Effects in Sulfide-Based Electrolytes: Toward High-Voltage All-Solid-State Batteries","authors":"Yujun Li, Wei Hao, Xinyang Yue, Tinghu Liu, Tong Duan, Jiangkai Kong, Siyuan Shen, Junjian Zhao, Xiaoya He, Yakun Liu, Zheng Liang, Song Du","doi":"10.1002/aenm.70855","DOIUrl":"https://doi.org/10.1002/aenm.70855","url":null,"abstract":"The decomposition of sulfide-based electrolytes (SEs), notably Li<sub>3</sub>PS<sub>4</sub> (LPS), at the electrode interface during battery cycling significantly hinders their practical application in all-solid-state batteries (ASSBs). However, the underlying mechanism through which chemical bonding modification enhances the electrochemical stability of SEs without compromising other properties remains unclear. Herein, we investigate the effect of introducing highly electronegative elements Q (Q ═ N, O, F) into LPS to strengthen chemical bonds and optimize lithium-ion (Li<sup>+</sup>) migration pathways in LPSQ electrolytes. Our results reveal that N and O facilitate the formation of PS<sub>3</sub>Q polyanions, whereas F tends to exist as LiF. All LPSQ systems exhibit an extended electrochemical stability window than pristine LPS, substantially enhancing their compatibility with high-voltage LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NCM811) cathodes. The strengthened chemical bonding environment further proves beneficial for both electronic and ionic conductivities, leading to superior performance in Li|LPSQ|Li symmetric batteries. Furthermore, by achieving an optimal balance between electronic and ionic conductivity, LPSN enables stable long-term cycling for over 300 cycles at 1C in LiIn||NCM811 full battery, while maintaining high Coulombic efficiency and minimal interfacial degradation. These findings provide guidelines for dopant selection in SE design and offer perspectives on SE engineering aimed at enhancing the high-voltage stability of ASSBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"14 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506965","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}
Layered high-Ni (Ni ≥ 0.9) cathodes are being developed to endure high-voltage operations above 4.5 V for unlocking unprecedented energy density, but they still suffer from exacerbated chemomechanical and electrochemical degradation primarily due to excessive lattice strain, oxygen loss, and phase distortion during prolonged cycling. Herein, we design a high-Ni, Co-free cathode, which features an entropy-assisted core–shell layered/spinel dual-phase, coupled with a Ni-valence gradient framework, via a multi-component complex doping involved co-precipitation strategy. The coherent structural ordering from surface spinel phase to bulk layered phase, driven by the Ni-enriched core/Mn-enriched shell arrangement, and the entropy-assistance and valence-gradient layout, hugely prevents mechanical degradation, surface side-reactions, and oxygen loss, delivering a pseudo strain-free cathode. Thanks to these appealing merits, the cathode breaks through current voltage limitations while maintaining an optimal balance between capacity and sustainability, enabling the stable high-voltage operation up to 4.9 V. Moreover, an exceptional cyclability under strenuous conditions is achieved in practical Ah-level pouch-type cells employing graphite and metallic Li anodes, operating at ultrahigh voltages of 4.65 and 4.8 V, respectively. Besides, the oxygen loss-triggered phase transitions upon heating are markedly delayed. More significantly, our contribution here propels the tremendous advancement of high-Ni, Co-free cathodes to the commercializable levels.
{"title":"Dual-Phase Engineering Coupled With Valence Gradient and Entropy Assistance Unlocking 4.9 V-Tolerant Co-Free High-Ni Cathodes","authors":"Longwei Liang, Yahui Chen, Jiahui Ye, Qingyun Zhang, Hongqiang Xi, Youfeng Tian, Linrui Hou, Changzhou Yuan","doi":"10.1002/aenm.70868","DOIUrl":"https://doi.org/10.1002/aenm.70868","url":null,"abstract":"Layered high-Ni (Ni ≥ 0.9) cathodes are being developed to endure high-voltage operations above 4.5 V for unlocking unprecedented energy density, but they still suffer from exacerbated chemomechanical and electrochemical degradation primarily due to excessive lattice strain, oxygen loss, and phase distortion during prolonged cycling. Herein, we design a high-Ni, Co-free cathode, which features an entropy-assisted core–shell layered/spinel dual-phase, coupled with a Ni-valence gradient framework, via a multi-component complex doping involved co-precipitation strategy. The coherent structural ordering from surface spinel phase to bulk layered phase, driven by the Ni-enriched core/Mn-enriched shell arrangement, and the entropy-assistance and valence-gradient layout, hugely prevents mechanical degradation, surface side-reactions, and oxygen loss, delivering a pseudo strain-free cathode. Thanks to these appealing merits, the cathode breaks through current voltage limitations while maintaining an optimal balance between capacity and sustainability, enabling the stable high-voltage operation up to 4.9 V. Moreover, an exceptional cyclability under strenuous conditions is achieved in practical Ah-level pouch-type cells employing graphite and metallic Li anodes, operating at ultrahigh voltages of 4.65 and 4.8 V, respectively. Besides, the oxygen loss-triggered phase transitions upon heating are markedly delayed. More significantly, our contribution here propels the tremendous advancement of high-Ni, Co-free cathodes to the commercializable levels.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"60 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507081","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}
Ahui Zhu, Ersha Fan, Xiaodong Zhang, Renjie Chen, Li Li
High-value recycling of retired lithium-ion battery materials is pivotal for the circular economy. The nickel-rich strategy, with its merits in boosting energy density, stands out as a key approach for upcycling spent LiNi0.54Co0.16Mn0.3O2 (SNCM). However, the inherent structural defects of SNCM and the heterogeneous reactions among precursors during regeneration jointly induce irreversible phase transformations, preventing the formation of an ideally ordered layered structure. Therefore, we developed a targeted bidirectional anchoring strategy involving pre-anchoring Al species on both SNCM and Ni(OH)2 surfaces. This method reduces the energy barrier for lithiation in the surface-disordered structures of SNCM and suppresses the structural degradation of nickel-rich intermediate phases, thereby addressing the root cause of structural disorder during upcycling. The upcycled cathode material exhibits a stable layered structure and a distinctive nickel concentration gradient from the surface toward the bulk. It delivers outstanding electrochemical performance, including a reversible capacity of 186.84 mAh g−1 at 0.2C and retaining 90.17% of its initial capacity after 200 cycles at 1C, outperforming current commercial materials. Furthermore, this study provides essential insights into solid-state regeneration and establishes a pathway toward the high-value recycling of degraded lithium-ion batteries, demonstrating great potential for practical application.
退役锂离子电池材料的高价值回收是循环经济的关键。富镍策略具有提高能量密度的优点，是升级回收废LiNi0.54Co0.16Mn0.3O2 （SNCM）的关键方法。然而，SNCM固有的结构缺陷和再生过程中前驱体之间的非均相反应共同诱导了不可逆的相变，阻碍了理想有序层状结构的形成。因此，我们开发了一种有针对性的双向锚定策略，包括在SNCM和Ni(OH)2表面预锚定Al物质。该方法降低了SNCM表面无序结构中的锂化能垒，抑制了富镍中间相的结构降解，从而解决了升级回收过程中结构无序的根本原因。升级后的正极材料具有稳定的层状结构和从表面到本体的独特的镍浓度梯度。它具有出色的电化学性能，包括在0.2C时的可逆容量为186.84 mAh g - 1，在1C下循环200次后保持其初始容量的90.17%，优于目前的商用材料。此外，该研究为固态再生提供了重要的见解，并为降解锂离子电池的高价值回收开辟了一条途径，显示了巨大的实际应用潜力。
{"title":"Bidirectional Lattice Anchoring Enhances Composition Reconfiguration of Spent Lithium-Ion Cathodes","authors":"Ahui Zhu, Ersha Fan, Xiaodong Zhang, Renjie Chen, Li Li","doi":"10.1002/aenm.70869","DOIUrl":"https://doi.org/10.1002/aenm.70869","url":null,"abstract":"High-value recycling of retired lithium-ion battery materials is pivotal for the circular economy. The nickel-rich strategy, with its merits in boosting energy density, stands out as a key approach for upcycling spent LiNi<sub>0.54</sub>Co<sub>0.16</sub>Mn<sub>0.3</sub>O<sub>2</sub> (SNCM). However, the inherent structural defects of SNCM and the heterogeneous reactions among precursors during regeneration jointly induce irreversible phase transformations, preventing the formation of an ideally ordered layered structure. Therefore, we developed a targeted bidirectional anchoring strategy involving pre-anchoring Al species on both SNCM and Ni(OH)<sub>2</sub> surfaces. This method reduces the energy barrier for lithiation in the surface-disordered structures of SNCM and suppresses the structural degradation of nickel-rich intermediate phases, thereby addressing the root cause of structural disorder during upcycling. The upcycled cathode material exhibits a stable layered structure and a distinctive nickel concentration gradient from the surface toward the bulk. It delivers outstanding electrochemical performance, including a reversible capacity of 186.84 mAh g<sup>−1</sup> at 0.2C and retaining 90.17% of its initial capacity after 200 cycles at 1C, outperforming current commercial materials. Furthermore, this study provides essential insights into solid-state regeneration and establishes a pathway toward the high-value recycling of degraded lithium-ion batteries, demonstrating great potential for practical application.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"15 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507083","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 strong metal-support interactions (SMSI) between supported clusters and substrate can drive the local structure reconstructions, which stabilize the supported clusters to avoid migration and aggregation. Such reconstruction and stabilization mechanism are crucial to construct the atomically dispersed catalysts (ADCs), but they are too complex to simulate in most catalyst theoretical studies for a relative long time. Herein, an accurate machine learning potential (MLP) is employed into Monte Carlo simulation on the MnN (1 ≤ N ≤ 7) clusters supported on MoS2 layer. The adsorption, reconstruction and thermodynamic and kinetical stabilization of Mn clusters on perfect and defective MoS2 are compared studied. The results indicate that the S vacancies can effectively anchor Mn clusters and are feasible to control the dual-atom catalysts (DACs) on the MoS2 surface. Besides, Comparative analysis reveals that the Mn2@MoS2-S2V exhibits superior NH3-SCR catalytic activity. The complete reaction process of Mn2@MoS2-S2V following the “Fast-SCR” mechanism and the NO2 reduction pathway is the dominant route, with a rate-determining barrier of 1.03 eV. This work provides a pioneer way to disclose the very complex reconstruction of supported clusters with SMSI in simulation, which is indeed helpful to design real atomic structure of ADCs.
{"title":"The Reconstruction Mechanism and NH3-SCR Kinetics of Mn Clusters on MoS2 by Ab Initio Data Driven Machine Learning Simulations","authors":"Ziyi Wang, Luneng Zhao, Yuan Chang, Chunqiang Zhuang, Hongsheng Liu, Jiaxu Liu, Tao Liu, Junfeng Gao","doi":"10.1002/aenm.70851","DOIUrl":"https://doi.org/10.1002/aenm.70851","url":null,"abstract":"The strong metal-support interactions (SMSI) between supported clusters and substrate can drive the local structure reconstructions, which stabilize the supported clusters to avoid migration and aggregation. Such reconstruction and stabilization mechanism are crucial to construct the atomically dispersed catalysts (ADCs), but they are too complex to simulate in most catalyst theoretical studies for a relative long time. Herein, an accurate machine learning potential (MLP) is employed into Monte Carlo simulation on the Mn<i><sub>N</sub></i> (1 ≤ <i>N</i> ≤ 7) clusters supported on MoS<sub>2</sub> layer. The adsorption, reconstruction and thermodynamic and kinetical stabilization of Mn clusters on perfect and defective MoS<sub>2</sub> are compared studied. The results indicate that the S vacancies can effectively anchor Mn clusters and are feasible to control the dual-atom catalysts (DACs) on the MoS<sub>2</sub> surface. Besides, Comparative analysis reveals that the Mn<sub>2</sub>@MoS<sub>2</sub>-S<sub>2</sub>V exhibits superior NH<sub>3</sub>-SCR catalytic activity. The complete reaction process of Mn<sub>2</sub>@MoS<sub>2</sub>-S<sub>2</sub>V following the “Fast-SCR” mechanism and the NO<sub>2</sub> reduction pathway is the dominant route, with a rate-determining barrier of 1.03 eV. This work provides a pioneer way to disclose the very complex reconstruction of supported clusters with SMSI in simulation, which is indeed helpful to design real atomic structure of ADCs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"476 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507084","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}
Sodium metal batteries (SMB) and anode-free sodium metal batteries (AFSMB) are considered as a key candidate for next-generation energy storage technologies due to their advantages, such as high energy density and cost. However, their practical implementation remains fundamentally challenged by the complex interplay of thermodynamic instability and kinetic limitations at the Na anode interface. Moving beyond conventional, isolated approaches to dendrite suppression, this review presents a holistic design philosophy that integrates electrolyte engineering, interfacial control, and structural architecture. We critically dissect the electro-chemo-mechanical interplay governing sodium deposition, from the molecular level solvation structures in liquid and solid electrolytes to the nanoscale properties of the SEI and the three dimensional of current collectors. A dedicated analysis of external field regulation further reveals the profound impact of thermal and pressure management on plating homogeneity. By synthesizing these cross-cutting strategies, we construct a coherent framework that links fundamental mechanisms to practical cell design. Finally, we pinpoint persistent scientific gaps and outline emerging paradigms, including advanced in-situ diagnostics and AI-guided materials discovery, to illuminate the path toward intrinsically safe and commercially viable sodium metal batteries.
{"title":"Toward Safe and Efficient Energy Storage: Progress and Challenges of Dendrite-Free Sodium Metal Batteries","authors":"Wenbo Hou, Hui Peng, Yawen Ren, Huanhuan Wang, Kanjun Sun, Guofu Ma, Imran Shakir, Yuxi Xu","doi":"10.1002/aenm.70866","DOIUrl":"https://doi.org/10.1002/aenm.70866","url":null,"abstract":"Sodium metal batteries (SMB) and anode-free sodium metal batteries (AFSMB) are considered as a key candidate for next-generation energy storage technologies due to their advantages, such as high energy density and cost. However, their practical implementation remains fundamentally challenged by the complex interplay of thermodynamic instability and kinetic limitations at the Na anode interface. Moving beyond conventional, isolated approaches to dendrite suppression, this review presents a holistic design philosophy that integrates electrolyte engineering, interfacial control, and structural architecture. We critically dissect the electro-chemo-mechanical interplay governing sodium deposition, from the molecular level solvation structures in liquid and solid electrolytes to the nanoscale properties of the SEI and the three dimensional of current collectors. A dedicated analysis of external field regulation further reveals the profound impact of thermal and pressure management on plating homogeneity. By synthesizing these cross-cutting strategies, we construct a coherent framework that links fundamental mechanisms to practical cell design. Finally, we pinpoint persistent scientific gaps and outline emerging paradigms, including advanced in-situ diagnostics and AI-guided materials discovery, to illuminate the path toward intrinsically safe and commercially viable sodium metal batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"14 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507082","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}
Xinyue Wang, Lirong Zhang, Jun Wang, Chi Zhang, Di Wang, Fengfeng Han, Qi Jin, Lu Li, Xinzhi Ma, Keya Zhou, Xitian Zhang, Ying Xie, Lili Wu
The integration of solar energy into rechargeable battery systems represents a pivotal advancement in sustainable energy technology. Herein, we develop a photo-assisted lithium–sulfur battery (PALSB) that synergistically enables light energy harvesting, conversion, and electrochemical energy storage. Its multifunctional photocathode consists of 2D polycrystalline La0.65Sr0.35Co0.20Ni0.19Fe0.24Cr0.18Cu0.19O3 high-entropy oxide (LSCO-HEO) nanosheets with grain boundaries. Owing to the distinct surface work functions of its crystal facets, a spontaneously formed built-in electric field at the binary facet junction effectively suppresses the recombination of photogenerated carriers, thereby substantially enhancing photo‑chemical‑electrical energy conversion efficiency. Moreover, optimal band alignment between LSCO-HEOs and polysulfides enables direct participation of photoexcited electrons and holes in sulfur reduction and oxidation, respectively. Light-induced electron redistribution in LSCO-HEOs generates more dynamic and complementary highly active catalytic sites that effectively inhibit polysulfide shuttling, lower Li2S nucleation barriers, and enhance sulfur redox reaction kinetics. As a result, the PALSB achieves an ultra-high photoelectric energy conversion efficiency of 12.98% and exhibits exceptional cycling stability over 1000 cycles at 8.0 C, with a minimal capacity decay of only 0.025% per cycle. This work introduces a breakthrough strategy for direct solar-to-chemical energy conversion within batteries, opening avenues for high-efficiency photoelectrochemical energy storage.
{"title":"Photo-Assisted Li–S Batteries With 2D High-Entropy Oxide Nanosheets: Coupling Built-In Electric Field for Ultra-High Photoelectric Energy Conversion","authors":"Xinyue Wang, Lirong Zhang, Jun Wang, Chi Zhang, Di Wang, Fengfeng Han, Qi Jin, Lu Li, Xinzhi Ma, Keya Zhou, Xitian Zhang, Ying Xie, Lili Wu","doi":"10.1002/aenm.202505635","DOIUrl":"https://doi.org/10.1002/aenm.202505635","url":null,"abstract":"The integration of solar energy into rechargeable battery systems represents a pivotal advancement in sustainable energy technology. Herein, we develop a photo-assisted lithium–sulfur battery (PALSB) that synergistically enables light energy harvesting, conversion, and electrochemical energy storage. Its multifunctional photocathode consists of 2D polycrystalline La<sub>0.65</sub>Sr<sub>0.35</sub>Co<sub>0.20</sub>Ni<sub>0.19</sub>Fe<sub>0.24</sub>Cr<sub>0.18</sub>Cu<sub>0.19</sub>O<sub>3</sub> high-entropy oxide (LSCO-HEO) nanosheets with grain boundaries. Owing to the distinct surface work functions of its crystal facets, a spontaneously formed built-in electric field at the binary facet junction effectively suppresses the recombination of photogenerated carriers, thereby substantially enhancing photo‑chemical‑electrical energy conversion efficiency. Moreover, optimal band alignment between LSCO-HEOs and polysulfides enables direct participation of photoexcited electrons and holes in sulfur reduction and oxidation, respectively. Light-induced electron redistribution in LSCO-HEOs generates more dynamic and complementary highly active catalytic sites that effectively inhibit polysulfide shuttling, lower Li<sub>2</sub>S nucleation barriers, and enhance sulfur redox reaction kinetics. As a result, the PALSB achieves an ultra-high photoelectric energy conversion efficiency of 12.98% and exhibits exceptional cycling stability over 1000 cycles at 8.0 C, with a minimal capacity decay of only 0.025% per cycle. This work introduces a breakthrough strategy for direct solar-to-chemical energy conversion within batteries, opening avenues for high-efficiency photoelectrochemical energy storage.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"18 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496585","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}
Converting CO2 into value-added fuels using a Ni-based core–shell catalyst is beneficial for addressing the carbon deposition-induced deactivation of Ni. However, designing highly active shells is critical. In this study, nickel titanate-coated metallic Ni nanoparticles (Ni@NiTiO3) are synthesized via laser-induced nonequilibrium reaction. The obtained Ni@NiTiO3 as a photothermal catalyst for converting CO2 to CH4 achieves a high CH4 yield of 1.48 mol gcat−1 h−1 and CH4 selectivity of 94.3% under the light intensity of 2.52 W cm−2. The outstanding catalytic performance is ascribed to the presence of the Ni-O-Ti structure with dual active sites in the shell of Ni@NiTiO3. Specifically, Ni2+ species in the Ni-O-Ti structure enhance CO2 adsorption and activation, while Ti species stabilize high-valent Ni species to maintain activity. Meanwhile, the metallic Ni core reduces the energy barrier for H2 dissociation on the shell surface, thus facilitating the subsequent CO2 hydrogenation. In a flow reactor (weight hourly space velocity of 200 000 mL gcat−1 h−1), Ni@NiTiO3 achieves 77.1% CO2 conversion and maintains long-term stability for 100 h, which can also be efficiently driven under sunny conditions. This work demonstrates the design concept of core–shell catalyst with a highly active shell prepared via laser-induced nonequilibrium reactions for efficient photothermal catalytic CO2 hydrogenation reactions.
利用镍基核壳催化剂将二氧化碳转化为增值燃料有利于解决镍的碳沉积失活问题。然而，设计高活性外壳是至关重要的。本研究通过激光诱导非平衡反应合成了钛酸镍包覆金属镍纳米粒子（Ni@NiTiO3）。所得Ni@NiTiO3光热催化剂在光强为2.52 W cm−2的条件下，CH4产率为1.48 mol gcat−1 h−1，CH4选择性为94.3%。优异的催化性能归功于Ni@NiTiO3壳层中具有双活性位点的Ni-O-Ti结构。具体来说，Ni- o -Ti结构中的Ni2+组分增强了CO2的吸附和活化，而Ti组分稳定了高价Ni组分以保持活性。同时，金属镍核降低了壳表面H2解离的能垒，有利于后续的CO2加氢。在流动反应器（重量小时空速为200000 mL gcat−1 h−1）中，Ni@NiTiO3的CO2转化率达到77.1%，并保持100 h的长期稳定性，在阳光条件下也可以高效驱动。本研究证明了采用激光诱导非平衡反应制备高活性壳层的核壳催化剂的设计理念，用于高效光热催化CO2加氢反应。
{"title":"Dual Active Sites of Ni-O-Ti on NiTiO3 Coated Ni for Efficient and Robust Photothermal CO2 Methanation","authors":"Chengxin Liu, Hui Kong, Minghui Liu, Xingzhi Wang, Lili Zhao, Hong Liu, Xiaoyan Liu, Shengping Wang, Weijia Zhou","doi":"10.1002/aenm.70870","DOIUrl":"https://doi.org/10.1002/aenm.70870","url":null,"abstract":"Converting CO<sub>2</sub> into value-added fuels using a Ni-based core–shell catalyst is beneficial for addressing the carbon deposition-induced deactivation of Ni. However, designing highly active shells is critical. In this study, nickel titanate-coated metallic Ni nanoparticles (Ni@NiTiO<sub>3</sub>) are synthesized via laser-induced nonequilibrium reaction. The obtained Ni@NiTiO<sub>3</sub> as a photothermal catalyst for converting CO<sub>2</sub> to CH<sub>4</sub> achieves a high CH<sub>4</sub> yield of 1.48 mol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> and CH<sub>4</sub> selectivity of 94.3% under the light intensity of 2.52 W cm<sup>−2</sup>. The outstanding catalytic performance is ascribed to the presence of the Ni-O-Ti structure with dual active sites in the shell of Ni@NiTiO<sub>3</sub>. Specifically, Ni<sup>2+</sup> species in the Ni-O-Ti structure enhance CO<sub>2</sub> adsorption and activation, while Ti species stabilize high-valent Ni species to maintain activity. Meanwhile, the metallic Ni core reduces the energy barrier for H<sub>2</sub> dissociation on the shell surface, thus facilitating the subsequent CO<sub>2</sub> hydrogenation. In a flow reactor (weight hourly space velocity of 200 000 mL g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>), Ni@NiTiO<sub>3</sub> achieves 77.1% CO<sub>2</sub> conversion and maintains long-term stability for 100 h, which can also be efficiently driven under sunny conditions. This work demonstrates the design concept of core–shell catalyst with a highly active shell prepared via laser-induced nonequilibrium reactions for efficient photothermal catalytic CO<sub>2</sub> hydrogenation reactions.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"52 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496584","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}
Di Wang, Mingfan Li, Jun Mei, Juan Bai, Qianqian Yao, Yahui Wang, Shixue Dou
With the rapid development of renewable energy, electrocatalysis has assumed a central role in the conversion and storage of sustainable energy. Rare-earth (RE) elements, characterized by their unique 4f electronic configurations, reversible multivalent states, and highly tunable physicochemical properties, offer a fundamentally distinct pathway for achieving precise control over catalyst electronic structures, interfacial chemistry, and reaction pathways. This review presents a comprehensive and mechanistic perspective on the distinctive, multi-faceted roles of RE elements in advanced electrocatalysis. By systematically analyzing their intrinsic properties, the review elucidates the quantum-chemical origins of their advantages in electronic structure modulation, stabilization of high-energy intermediates, and enhancement of interfacial charge transport. Building upon these foundations, some major catalyst design strategies, encompassing atomic doping, defect engineering, nanostructuring, and interface construction, are critically summarized. Then, recent progress of RE-based catalysts in various electrocatalytic reactions, including oxygen and hydrogen evolution, and carbon dioxide and nitrogen reduction reactions, are thoroughly reviewed to establish structure-activity correlations. Finally, the review outlines future prospects and emerging frontiers in RE-mediated catalysis, such as multi-electron reaction pathway regulation and the construction of adaptive interfaces. This work aims to provide a fundamental understanding and strategic guidance for the rational design of efficient electrocatalysts enabled by RE elements.
{"title":"Beyond Doping: Rare-Earth Mediated Strategies for Rational Design of Multifunctional Electrocatalysts","authors":"Di Wang, Mingfan Li, Jun Mei, Juan Bai, Qianqian Yao, Yahui Wang, Shixue Dou","doi":"10.1002/aenm.70863","DOIUrl":"https://doi.org/10.1002/aenm.70863","url":null,"abstract":"With the rapid development of renewable energy, electrocatalysis has assumed a central role in the conversion and storage of sustainable energy. Rare-earth (RE) elements, characterized by their unique <i>4f</i> electronic configurations, reversible multivalent states, and highly tunable physicochemical properties, offer a fundamentally distinct pathway for achieving precise control over catalyst electronic structures, interfacial chemistry, and reaction pathways. This review presents a comprehensive and mechanistic perspective on the distinctive, multi-faceted roles of RE elements in advanced electrocatalysis. By systematically analyzing their intrinsic properties, the review elucidates the quantum-chemical origins of their advantages in electronic structure modulation, stabilization of high-energy intermediates, and enhancement of interfacial charge transport. Building upon these foundations, some major catalyst design strategies, encompassing atomic doping, defect engineering, nanostructuring, and interface construction, are critically summarized. Then, recent progress of RE-based catalysts in various electrocatalytic reactions, including oxygen and hydrogen evolution, and carbon dioxide and nitrogen reduction reactions, are thoroughly reviewed to establish structure-activity correlations. Finally, the review outlines future prospects and emerging frontiers in RE-mediated catalysis, such as multi-electron reaction pathway regulation and the construction of adaptive interfaces. This work aims to provide a fundamental understanding and strategic guidance for the rational design of efficient electrocatalysts enabled by RE elements.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"1 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496591","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}
Ananta R. Fareza, Hank Garg, Luis Miguel Azofra, Darcy Simondson, Tam D. Nguyen, Mohamed R. Rizk, Khang N. Dinh, Rosalie K. Hocking, Douglas R. MacFarlane, Hoang-Long Du, Alexandr N. Simonov
Direct seawater electrolysis overcomes one major hurdle in sustainable hydrogen production, viz. the requirement to use high-purity water, which is currently a scarce resource for ∼80% of the global population. On the other hand, the natural composition of seawater makes it unsuitable for direct use in conventional electrolyzer systems, primarily due to the occurrence of the chlorine evolution reaction (CER) at the anode, instead of the desired oxygen evolution reaction (OER), and the build-up of insulating Mg2+/Ca2+ hydroxides at the cathode. Herein, we present an electrolyzer fed with artificial seawater with no added electrolyte and enabling selective splitting of H2O, rather than H2 generation coupled to the CER. This selectivity was provided by the anodes derived from a cobalt iron boride material, which was predicted to favor the OER rather than the CER by the density functional theory calculations. The compact design of the electrode-separator assembly suppressed the cathodic Mg/Ca(OH)2 precipitation. Robust operation of the electrolyzer over one week was demonstrated at 100 mA cm−2 with a cell voltage of ca. –2.6 V at 80 ± 1°C. These operating conditions were selected based on a preliminary techno-economic analysis as a realistic benchmark for cost-competitive hydrogen production.
直接海水电解克服了可持续制氢的一个主要障碍，即使用高纯度水的要求，目前全球80%的人口使用高纯度水是稀缺资源。另一方面，海水的天然成分使其不适合直接用于传统的电解槽系统，主要原因是在阳极发生氯析出反应（CER），而不是期望的氧析出反应（OER），以及在阴极形成绝缘的Mg2+/Ca2+氢氧化物。在这里，我们提出了一个不添加电解质的人工海水的电解槽，可以选择性地分裂H2O，而不是与CER耦合产生H2。这种选择性是由钴铁硼化材料制备的阳极提供的，通过密度泛函理论计算预测其有利于OER而不是CER。紧凑的电极-分离器组件设计抑制了阴极Mg/Ca(OH)2的析出。电解槽在100 mA cm−2下，在80±1°C下，电池电压约为-2.6 V，稳健运行超过一周。这些操作条件的选择是基于初步的技术经济分析，作为具有成本竞争力的氢气生产的现实基准。
{"title":"Selective Electrolysis of Water Under Artificial Seawater Conditions Using Transition Metal Borate Anodes","authors":"Ananta R. Fareza, Hank Garg, Luis Miguel Azofra, Darcy Simondson, Tam D. Nguyen, Mohamed R. Rizk, Khang N. Dinh, Rosalie K. Hocking, Douglas R. MacFarlane, Hoang-Long Du, Alexandr N. Simonov","doi":"10.1002/aenm.202506788","DOIUrl":"https://doi.org/10.1002/aenm.202506788","url":null,"abstract":"Direct seawater electrolysis overcomes one major hurdle in sustainable hydrogen production, viz. the requirement to use high-purity water, which is currently a scarce resource for ∼80% of the global population. On the other hand, the natural composition of seawater makes it unsuitable for direct use in conventional electrolyzer systems, primarily due to the occurrence of the chlorine evolution reaction (CER) at the anode, instead of the desired oxygen evolution reaction (OER), and the build-up of insulating Mg<sup>2+</sup>/Ca<sup>2+</sup> hydroxides at the cathode. Herein, we present an electrolyzer fed with artificial seawater with no added electrolyte and enabling selective splitting of H<sub>2</sub>O, rather than H<sub>2</sub> generation coupled to the CER. This selectivity was provided by the anodes derived from a cobalt iron boride material, which was predicted to favor the OER rather than the CER by the density functional theory calculations. The compact design of the electrode-separator assembly suppressed the cathodic Mg/Ca(OH)<sub>2</sub> precipitation. Robust operation of the electrolyzer over one week was demonstrated at 100 mA cm<sup>−2</sup> with a cell voltage of ca. –2.6 V at 80 ± 1°C. These operating conditions were selected based on a preliminary techno-economic analysis as a realistic benchmark for cost-competitive hydrogen production.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"177 2 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496592","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 highly efficient and stable electrocatalysts for the oxygen evolution reaction (OER) is crucial for advancing proton exchange membrane water electrolysis (PEMWE) for sustainable hydrogen production. Recently, Iridium centers on transition metal oxides (TMOs) have emerged as promising alternatives to conventional noble metal oxides, demonstrating superior activity, stability, and cost-effectiveness. This review systematically summarizes these advancements by elucidating the intrinsic mechanisms and dynamic evolution patterns of Ir active centers under acidic OER conditions, discussing core strategies for enhancing catalytic performance, and attention is mainly directed to the industrial application requirements by evaluating breakthrough solutions for key technical challenges, including long-term stability under high-current-density operation and Ir dissolution suppression. Finally, from the perspective of rational design, the review outlines current challenges and prospects for oxide-supported Ir catalysts, emphasizing the urgent need for advanced operando characterization techniques and scalable fabrication processes. By integrating fundamental research with practical applications, this review aims to provide theoretical guidance and technical references for developing next-generation OER catalysts suitable for large-scale PEMWE implementation.
{"title":"Challenges and Opportunities for the Emerging Iridium Center on Transition Metal Oxide for PEM Water Electrolysis","authors":"Bingjie Zhang, Fulin Yang, Anantharaj Sengeni, Ligang Feng","doi":"10.1002/aenm.70852","DOIUrl":"https://doi.org/10.1002/aenm.70852","url":null,"abstract":"The development of highly efficient and stable electrocatalysts for the oxygen evolution reaction (OER) is crucial for advancing proton exchange membrane water electrolysis (PEMWE) for sustainable hydrogen production. Recently, Iridium centers on transition metal oxides (TMOs) have emerged as promising alternatives to conventional noble metal oxides, demonstrating superior activity, stability, and cost-effectiveness. This review systematically summarizes these advancements by elucidating the intrinsic mechanisms and dynamic evolution patterns of Ir active centers under acidic OER conditions, discussing core strategies for enhancing catalytic performance, and attention is mainly directed to the industrial application requirements by evaluating breakthrough solutions for key technical challenges, including long-term stability under high-current-density operation and Ir dissolution suppression. Finally, from the perspective of rational design, the review outlines current challenges and prospects for oxide-supported Ir catalysts, emphasizing the urgent need for advanced operando characterization techniques and scalable fabrication processes. By integrating fundamental research with practical applications, this review aims to provide theoretical guidance and technical references for developing next-generation OER catalysts suitable for large-scale PEMWE implementation.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"81 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496588","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：