Single‐crystal (SC) cathodes have rapidly emerged as a transformative architecture in next‐generation lithium‐ion batteries, offering superior structural stability and extended cycle life by eliminating intergranular boundaries. Yet a critical question remains—can single‐crystal particles truly match the fast‐charging performance of polycrystalline (PC) cathodes which continue to dominate commercial batteries due to their high tap density and ease of synthesis? The answer has remained elusive because the quantitative roles of grains, grain boundaries, and cracks in Li + transport are not fully understood. Here, a unified quantitative framework is established that links apparent diffusivity and exchange current density to crack‐generated interfaces under near‐surface diffusion conditions. Applied to compositionally identical SC‐ and PC‐NMC811 and integrated with ab initio calculations, machine‐learning molecular dynamics, and finite‐element fracture modeling, this framework reveals identical intrinsic lattice and interfacial kinetics prior to cracking. The apparent kinetic advantage of PC arises from electrolyte infiltration into intergranular cracks that both create new electrochemically active interfaces and shorten diffusion pathways. Particle size–rate modeling, validated experimentally, further demonstrates that downsized SC particles can achieve PC‐like fast‐charging performance while retaining mechanical integrity. These findings quantitatively resolve the long‐standing SC–PC rate paradox and provide mechanistic guidance for designing durable, high‐rate cathodes.
{"title":"Quantifying Lattice–Crack–Electrochemical Transport Coupling for Durable, Fast‐Charging Battery Cathodes","authors":"Chen‐Hao Tu, Chi‐En Tseng, Wei‐Cheng Lai, Chao‐Hsiang Hsu, Jing‐Sen Yang, Yu‐Cheng Zheng, Huy Hoang Dang, Ping‐Chun Tsai","doi":"10.1002/aenm.202506427","DOIUrl":"https://doi.org/10.1002/aenm.202506427","url":null,"abstract":"Single‐crystal (SC) cathodes have rapidly emerged as a transformative architecture in next‐generation lithium‐ion batteries, offering superior structural stability and extended cycle life by eliminating intergranular boundaries. Yet a critical question remains—can single‐crystal particles truly match the fast‐charging performance of polycrystalline (PC) cathodes which continue to dominate commercial batteries due to their high tap density and ease of synthesis? The answer has remained elusive because the quantitative roles of grains, grain boundaries, and cracks in Li <jats:sup>+</jats:sup> transport are not fully understood. Here, a unified quantitative framework is established that links apparent diffusivity and exchange current density to crack‐generated interfaces under near‐surface diffusion conditions. Applied to compositionally identical SC‐ and PC‐NMC811 and integrated with ab initio calculations, machine‐learning molecular dynamics, and finite‐element fracture modeling, this framework reveals identical intrinsic lattice and interfacial kinetics prior to cracking. The apparent kinetic advantage of PC arises from electrolyte infiltration into intergranular cracks that both create new electrochemically active interfaces and shorten diffusion pathways. Particle size–rate modeling, validated experimentally, further demonstrates that downsized SC particles can achieve PC‐like fast‐charging performance while retaining mechanical integrity. These findings quantitatively resolve the long‐standing SC–PC rate paradox and provide mechanistic guidance for designing durable, high‐rate cathodes.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"3 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089602","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}
High‐voltage nickel‐rich layered oxide cathodes have attracted much attention due to their high capacity and elevated voltage plateau. However, the intrinsic Ni 3 d ‐O 2 p orbital overlapping promotes lattice oxygen release during the Ni valence transition, thereby accelerating structural degradation and interfacial parasitic reactions. Herein, we found that the position‐isomer slurry additive lithium 2‐thiopheneboron (2LTB) suppresses Ni‐O orbital overlap by enhancing the coordination of its Li, B, O, and S atoms with Ni and O in the cathode lattice, thereby stabilizing lattice oxygen at both the initial and deep discharge states. Electroactive 2LTB can form a thin and robust cathode electrolyte interface (CEI) that enhances Li + diffusion dynamics while alleviating transition metal dissolution, irreversible phase transformation, gas evolution and electrolyte invasion under high voltage. Consequently, LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li cells with 1.5 wt.% 2LTB addition exhibits exceptional cycling performances, retaining 82.92% capacity retention after 450 cycles at 1 C and 76.09% after 800 cycles at 5 C under 4.5 V. A 1000‐mAh LiNi 0.8 Co 0.1 Mn 0.1 O 2 ‐2LTB||graphite pouch cell maintains 81.34% capacity retention after 700 cycles. Our findings establish a versatile framework for leveraging lithiation reagents to regulate orbital interactions, providing both mechanistic insights and practical guidance for the development of high‐voltage lithium‐ion batteries.
高压富镍层状氧化物阴极由于其高容量和高电压平台而受到广泛关注。然而，在Ni价跃迁过程中，Ni 3 d‐O 2 p轨道重叠促进了晶格氧的释放，从而加速了结构降解和界面寄生反应。本研究发现，位置异构体浆料添加剂锂- 2 -噻苯硼（2LTB）通过增强阴极晶格中Li、B、O和S原子与Ni和O的配位来抑制Ni - O轨道重叠，从而稳定了初始和深度放电状态下的晶格氧。电活性2LTB可以形成薄而坚固的阴极电解质界面（CEI），增强Li +扩散动力学，同时减轻高压下过渡金属溶解、不可逆相变、气体析出和电解质侵入。因此，添加1.5 wt.% 2LTB的LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||锂电池表现出优异的循环性能，在1℃下循环450次后容量保持率为82.92%，在4.5 V下5℃下循环800次后容量保持率为76.09%。1000 mAh的LiNi 0.8 Co 0.1 Mn 0.1 O 2‐2LTB||石墨袋电池在700次循环后保持81.34%的容量保持率。我们的研究结果为利用锂化试剂调节轨道相互作用建立了一个通用的框架，为高压锂离子电池的发展提供了机理见解和实践指导。
{"title":"Regulating Ni 3 d ‐O 2 p Orbital Interaction with Position‐Isomer Organic Lithiation Additive for High‐Voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cathode","authors":"Xinyu Zhang, Xianshu Wang, Yuanpeng Cao, Chao Zhao, Wenhui Tu, Yun Zhao, Peng Dong, Yingjie Zhang, Zhongyuan Luo, Ding Wang, Baohua Li, Zhenyu Guo, Maria‐Magdalena Titirici, Jianguo Duan","doi":"10.1002/aenm.202506157","DOIUrl":"https://doi.org/10.1002/aenm.202506157","url":null,"abstract":"High‐voltage nickel‐rich layered oxide cathodes have attracted much attention due to their high capacity and elevated voltage plateau. However, the intrinsic Ni 3 <jats:italic>d</jats:italic> ‐O 2 <jats:italic>p</jats:italic> orbital overlapping promotes lattice oxygen release during the Ni valence transition, thereby accelerating structural degradation and interfacial parasitic reactions. Herein, we found that the position‐isomer slurry additive lithium 2‐thiopheneboron (2LTB) suppresses Ni‐O orbital overlap by enhancing the coordination of its Li, B, O, and S atoms with Ni and O in the cathode lattice, thereby stabilizing lattice oxygen at both the initial and deep discharge states. Electroactive 2LTB can form a thin and robust cathode electrolyte interface (CEI) that enhances Li <jats:sup>+</jats:sup> diffusion dynamics while alleviating transition metal dissolution, irreversible phase transformation, gas evolution and electrolyte invasion under high voltage. Consequently, LiNi <jats:sub>0.8</jats:sub> Co <jats:sub>0.1</jats:sub> Mn <jats:sub>0.1</jats:sub> O <jats:sub>2</jats:sub> ||Li cells with 1.5 wt.% 2LTB addition exhibits exceptional cycling performances, retaining 82.92% capacity retention after 450 cycles at 1 C and 76.09% after 800 cycles at 5 C under 4.5 V. A 1000‐mAh LiNi <jats:sub>0.8</jats:sub> Co <jats:sub>0.1</jats:sub> Mn <jats:sub>0.1</jats:sub> O <jats:sub>2</jats:sub> ‐2LTB||graphite pouch cell maintains 81.34% capacity retention after 700 cycles. Our findings establish a versatile framework for leveraging lithiation reagents to regulate orbital interactions, providing both mechanistic insights and practical guidance for the development of high‐voltage lithium‐ion batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"58 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089764","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}
Changhee Lee, Zachary T. Gossage, Shinichi Kumakura, Shinichi Komaba
Although Na‐ and K‐ion batteries are emerging as cost‐effective and sustainable alternatives to Li‐ion batteries (LIBs) for large‐scale energy storage, their distinct physicochemical characteristics present unique challenges in achieving long‐term stability and high electrochemical performance. Among the various performance‐limiting factors, the electrode–electrolyte interphase, including the solid‐electrolyte interphase (SEI) and the cathode–electrolyte interphase (CEI), plays a crucial, yet still insufficiently understood, role in determining battery performances. From this perspective, this review offers critical insights into the interphase characteristics, with a special focus on not only clarifying the comparative characteristics of interphases across alkali‐ion battery systems, but also addressing several key issues often overlooked or misunderstood even in LIB research, including: (i) the dynamic and metastable nature of SEI and CEI, (ii) the limitations of fluorine‐rich CEI, (iii) the critical role of binders for interphase optimization, (iv) the overgeneralization of CEI functionality and formation mechanisms, and (v) the impact of interphase stability and passivation on self‐discharge. In doing so, this review emphasizes the pivotal role of interphase design in electrochemical performance, attempts to redefine the so‐called ideal interphases, and highlights the need for a clear and accurate understanding of the fundamental nature and functionalities of the interphases, beyond the conventional definitions, in alkali metal‐ion battery systems.
{"title":"Comparative Insights and Overlooked Factors of Interphase Chemistry in Alkali Metal‐Ion Batteries","authors":"Changhee Lee, Zachary T. Gossage, Shinichi Kumakura, Shinichi Komaba","doi":"10.1002/aenm.202506154","DOIUrl":"https://doi.org/10.1002/aenm.202506154","url":null,"abstract":"Although Na‐ and K‐ion batteries are emerging as cost‐effective and sustainable alternatives to Li‐ion batteries (LIBs) for large‐scale energy storage, their distinct physicochemical characteristics present unique challenges in achieving long‐term stability and high electrochemical performance. Among the various performance‐limiting factors, the electrode–electrolyte interphase, including the solid‐electrolyte interphase (SEI) and the cathode–electrolyte interphase (CEI), plays a crucial, yet still insufficiently understood, role in determining battery performances. From this perspective, this review offers critical insights into the interphase characteristics, with a special focus on not only clarifying the comparative characteristics of interphases across alkali‐ion battery systems, but also addressing several key issues often overlooked or misunderstood even in LIB research, including: (i) the dynamic and metastable nature of SEI and CEI, (ii) the limitations of fluorine‐rich CEI, (iii) the critical role of binders for interphase optimization, (iv) the overgeneralization of CEI functionality and formation mechanisms, and (v) the impact of interphase stability and passivation on self‐discharge. In doing so, this review emphasizes the pivotal role of interphase design in electrochemical performance, attempts to redefine the so‐called ideal interphases, and highlights the need for a clear and accurate understanding of the fundamental nature and functionalities of the interphases, beyond the conventional definitions, in alkali metal‐ion battery systems.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"43 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089601","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}
Yalan Zhang, Guiming Fu, Zheng Liang, Sanwan Liu, Nam‐Gyu Park
The remarkable rise of metal halide perovskite photovoltaics and optoelectronics has revealed semiconductive polarity as a central yet insufficiently understood determinant of device performance and stability. The soft ionic‐covalent lattice of halide perovskites hosts highly mobile ions and low‐formation‐energy defects that spontaneously self‐dope and dynamically shift the Fermi level. This unique defect‐lattice interplay profoundly affects band alignment, quasi‐Fermi‐level splitting, interfacial recombination, and ultimately the attainable open‐circuit voltage. In this review, we establish a hierarchical framework for polarity regulation spanning bulk defect thermodynamics, compositional tuning, additive coordination chemistry, and interfacial electronic design. We first elucidate how lattice geometry, orbital hybridization, and intrinsic defect equilibria dictate bulk carrier density and Fermi‐level position. We then discuss how targeted A/B/X‐site substitution, alloying strategies, and stoichiometric control modulate defect landscapes and stabilize desired electronic character. Based on these principles, we highlight how interfacial polarity engineering, including charge‐transfer interlayers and selective‐contact design, enables continuity of quasi‐Fermi levels and minimizes nonradiative losses at both p ‐ and n ‐type contacts. These insights unify defect physics and interfacial electrostatics, guiding polarity‐balanced, defect‐regulated perovskite optoelectronics, and highlighting opportunities in electrostatic modulation, heterovalent doping, surface reconstruction, and polarity engineering for perovskite solar cells.
{"title":"Semiconductive Polarity Control in Halide Perovskites through Defect Chemistry and Interface Engineering","authors":"Yalan Zhang, Guiming Fu, Zheng Liang, Sanwan Liu, Nam‐Gyu Park","doi":"10.1002/aenm.70691","DOIUrl":"https://doi.org/10.1002/aenm.70691","url":null,"abstract":"The remarkable rise of metal halide perovskite photovoltaics and optoelectronics has revealed semiconductive polarity as a central yet insufficiently understood determinant of device performance and stability. The soft ionic‐covalent lattice of halide perovskites hosts highly mobile ions and low‐formation‐energy defects that spontaneously self‐dope and dynamically shift the Fermi level. This unique defect‐lattice interplay profoundly affects band alignment, quasi‐Fermi‐level splitting, interfacial recombination, and ultimately the attainable open‐circuit voltage. In this review, we establish a hierarchical framework for polarity regulation spanning bulk defect thermodynamics, compositional tuning, additive coordination chemistry, and interfacial electronic design. We first elucidate how lattice geometry, orbital hybridization, and intrinsic defect equilibria dictate bulk carrier density and Fermi‐level position. We then discuss how targeted A/B/X‐site substitution, alloying strategies, and stoichiometric control modulate defect landscapes and stabilize desired electronic character. Based on these principles, we highlight how interfacial polarity engineering, including charge‐transfer interlayers and selective‐contact design, enables continuity of quasi‐Fermi levels and minimizes nonradiative losses at both <jats:italic>p</jats:italic> ‐ and <jats:italic>n</jats:italic> ‐type contacts. These insights unify defect physics and interfacial electrostatics, guiding polarity‐balanced, defect‐regulated perovskite optoelectronics, and highlighting opportunities in electrostatic modulation, heterovalent doping, surface reconstruction, and polarity engineering for perovskite solar cells.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"260 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089596","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 growing demand for lithium‐ion batteries has intensified the need for sustainable recycling methods, particularly for high‐nickel cathode materials, which suffer from structural instability during upcycling. This study introduces a high‐entropy doping strategy to stabilize upcycled Ni‐rich cathodes (HE‐NCM811) by incorporating multiple dopants to maximize configurational entropy. Advanced characterization techniques, including in situ XRD, XANES, and cross‐sectional TEM, reveal that high‐entropy doping significantly suppresses irreversible lattice variations along the c‐axis, mitigates microcracking, and maintains stable coordination environments for (Ni, Co, Mn)─O and (Ni, Co, Mn)─Ni bonds during cycling. The optimized HE‐NCM811 cathode exhibits exceptional electrochemical performance, with an ultra‐low capacity decay rate of 0.032% per cycle at 5 C over 1000 cycles. The enhanced stability is attributed to reduced polarization, improved electronic conductivity, and minimized anisotropic lattice strain. These findings demonstrate that high‐entropy doping not only addresses the structural degradation challenges in upcycled Ni‐rich cathodes but also provides a universal approach for designing next‐generation high‐performance cathode materials, including NCM, NCA, and NMA systems. This work not only provides a sustainable solution for spent battery upcycling but also opens avenues for designing zero‐cobalt, high‐performance cathodes. Scaling this technology requires optimizing dopant recovery from spent batteries to close the material loop.
{"title":"High‐Entropy Doping Strategy for Ultra‐Stable Upcycling of Spent High‐Nickel Cathodes","authors":"Jiahui Zhou, Jiehui Hu, Zhen Shang, Zhiyuan Zeng, Xia Zhou, Xiangming He, Shengming Xu","doi":"10.1002/aenm.202505196","DOIUrl":"https://doi.org/10.1002/aenm.202505196","url":null,"abstract":"The growing demand for lithium‐ion batteries has intensified the need for sustainable recycling methods, particularly for high‐nickel cathode materials, which suffer from structural instability during upcycling. This study introduces a high‐entropy doping strategy to stabilize upcycled Ni‐rich cathodes (HE‐NCM811) by incorporating multiple dopants to maximize configurational entropy. Advanced characterization techniques, including in situ XRD, XANES, and cross‐sectional TEM, reveal that high‐entropy doping significantly suppresses irreversible lattice variations along the c‐axis, mitigates microcracking, and maintains stable coordination environments for (Ni, Co, Mn)─O and (Ni, Co, Mn)─Ni bonds during cycling. The optimized HE‐NCM811 cathode exhibits exceptional electrochemical performance, with an ultra‐low capacity decay rate of 0.032% per cycle at 5 C over 1000 cycles. The enhanced stability is attributed to reduced polarization, improved electronic conductivity, and minimized anisotropic lattice strain. These findings demonstrate that high‐entropy doping not only addresses the structural degradation challenges in upcycled Ni‐rich cathodes but also provides a universal approach for designing next‐generation high‐performance cathode materials, including NCM, NCA, and NMA systems. This work not only provides a sustainable solution for spent battery upcycling but also opens avenues for designing zero‐cobalt, high‐performance cathodes. Scaling this technology requires optimizing dopant recovery from spent batteries to close the material loop.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"31 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089603","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}
Liqiang Liu, Jingxiang Xu, Wending Zuo, Jinda Lin, Walid A. Daoud, Tao Jiang, Zhong Lin Wang, Xiya Yang
The escalating global energy crisis and carbon neutrality imperative underscore the critical need for efficient ocean wave energy harvesting. Triboelectric nanogenerators (TENGs), as a transformative technology, can harness low‐frequency, multidirectional wave energy and overcome the limitations of traditional electromagnetic generators, thus attracting widespread attention. This review systematically analyzes high‐output marine TENGs, focusing on material engineering for charge/resilience, structural optimization for wave adaptation, charge regulation and power management for stable output, hybridization strategies for broadband harvesting, and existing challenges in deployment in marine environments. By addressing these five dimensions, this review offers a concise yet comprehensive overview of strategies driving the development of high‐performance marine TENG systems. Furthermore, it provides a forward‐looking perspective, outlining a research trajectory across material‐, device‐, and system‐level innovations aimed at bridging fundamental mechanisms with full‐scale ocean deployment. Key future directions include deciphering atomic‐scale charge dynamics under extreme marine conditions, developing Artificial Intelligence‐guided designs for hybrid and robust devices, and implementing intelligent, sustainable ocean networks for the blue economy. This work establishes that TENGs offer unparalleled advantages for sustainable marine autonomy, powering distributed sensor networks and blue economy infrastructure, while mapping out pathways to overcome scalability, deep‐sea deployment, and commercialization challenges.
{"title":"High‐Performance Triboelectric Nanogenerators for Marine Science: From Material Design, Intelligent Structures to System Integration","authors":"Liqiang Liu, Jingxiang Xu, Wending Zuo, Jinda Lin, Walid A. Daoud, Tao Jiang, Zhong Lin Wang, Xiya Yang","doi":"10.1002/aenm.202506057","DOIUrl":"https://doi.org/10.1002/aenm.202506057","url":null,"abstract":"The escalating global energy crisis and carbon neutrality imperative underscore the critical need for efficient ocean wave energy harvesting. Triboelectric nanogenerators (TENGs), as a transformative technology, can harness low‐frequency, multidirectional wave energy and overcome the limitations of traditional electromagnetic generators, thus attracting widespread attention. This review systematically analyzes high‐output marine TENGs, focusing on material engineering for charge/resilience, structural optimization for wave adaptation, charge regulation and power management for stable output, hybridization strategies for broadband harvesting, and existing challenges in deployment in marine environments. By addressing these five dimensions, this review offers a concise yet comprehensive overview of strategies driving the development of high‐performance marine TENG systems. Furthermore, it provides a forward‐looking perspective, outlining a research trajectory across material‐, device‐, and system‐level innovations aimed at bridging fundamental mechanisms with full‐scale ocean deployment. Key future directions include deciphering atomic‐scale charge dynamics under extreme marine conditions, developing Artificial Intelligence‐guided designs for hybrid and robust devices, and implementing intelligent, sustainable ocean networks for the blue economy. This work establishes that TENGs offer unparalleled advantages for sustainable marine autonomy, powering distributed sensor networks and blue economy infrastructure, while mapping out pathways to overcome scalability, deep‐sea deployment, and commercialization challenges.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"32 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089604","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}
Peng Wang, Hailong Xie, Yike Liu, Zhengyuan Bai, Na Li, Shu Hong, Chuancong Zhou, Lutong Shan, Zaowen Zhao, Xiaodong Shi
Gel polymer electrolytes (GPEs) show great promise for lithium metal batteries (LMBs), yet achieving a durable Li anode remains challenging due to the instability of the solid electrolyte interphase (SEI) layer. Regulating the Li + solvation structure is a critical approach to construct an effective SEI layer on the Li anode. In this work, a nanofiber membrane with polyethylenimine‐iodine (PEI‐I)/PAN complex core and polyacrylonitrile/polyvinylidene fluoride‐co‐hexafluoropropylene (PAN/PVDF‐HFP) polymer sheath (P‐I/P@P/P) is elaborately designed and prepared via the electrospinning method. The synergistic effect between the three‐dimensional matrix and the slowly released PEI‐I additive not only suppresses the combustion property of traditional GPEs, but also promotes the lithium‐ion desolvation and the generation of inorganic SEI layer on Li anode. As demonstrated, the optimized P‐I/P@P/P GPE delivers a high Li + transference number of 0.88, high ionic conductivity of 2.34 mS cm −1 , and heterogeneous SEI composition of Li 3 N/Li 2 CO 3 /LiF. The corresponding Li||Li cell achieves stable voltage polarization for 1000 h at 5 mA cm −2 , and the Li||Cu cell displays a high Coulombic efficiency of 97.84%. Satisfyingly, the targeted Li||LiFePO 4 battery exhibits an impressive capacity retention ratio of 97% after 3000 cycles. These findings offer a design paradigm for functional GPEs to drive the implementation of high‐energy‐density LMBs in practical scenarios.
凝胶聚合物电解质（gpe）在锂金属电池（lmb）中显示出巨大的前景，但由于固体电解质界面层（SEI）的不稳定性，实现耐用的锂阳极仍然具有挑战性。调节Li +溶剂化结构是在Li阳极上构建有效SEI层的关键途径。本文采用静电纺丝法，精心设计并制备了一种聚乙烯亚胺碘（PEI‐I）/PAN配合物芯和聚丙烯腈/聚偏氟乙烯- co -六氟丙烯（PAN/PVDF‐HFP）聚合物鞘（P‐I/P@P/P）的纳米纤维膜。三维基体与缓释的PEI - I添加剂之间的协同作用不仅抑制了传统gpe的燃烧性能，而且促进了锂离子的脱溶和Li阳极上无机SEI层的生成。结果表明，优化后的P‐I/P@P/P GPE具有0.88的高Li +转移数，2.34 mS cm−1的高离子电导率，以及Li 3n /Li 2co 3 /LiF的非均相SEI组成。相应的Li||锂电池在5 mA cm−2下可实现1000 h的稳定电压极化，Li||铜电池的库仑效率高达97.84%。令人满意的是，经过3000次循环后，Li|| lifepo4电池的容量保持率达到了令人印象深刻的97%。这些发现为功能性gpe提供了一个设计范例，以推动高能量密度lmb在实际场景中的实现。
{"title":"Halogen‐Induced Anion‐Rich Solvation Structure Enables High Li + Transference Number of Gel Polymer Electrolyte for Durable Lithium Metal Batteries","authors":"Peng Wang, Hailong Xie, Yike Liu, Zhengyuan Bai, Na Li, Shu Hong, Chuancong Zhou, Lutong Shan, Zaowen Zhao, Xiaodong Shi","doi":"10.1002/aenm.202506710","DOIUrl":"https://doi.org/10.1002/aenm.202506710","url":null,"abstract":"Gel polymer electrolytes (GPEs) show great promise for lithium metal batteries (LMBs), yet achieving a durable Li anode remains challenging due to the instability of the solid electrolyte interphase (SEI) layer. Regulating the Li <jats:sup>+</jats:sup> solvation structure is a critical approach to construct an effective SEI layer on the Li anode. In this work, a nanofiber membrane with polyethylenimine‐iodine (PEI‐I)/PAN complex core and polyacrylonitrile/polyvinylidene fluoride‐co‐hexafluoropropylene (PAN/PVDF‐HFP) polymer sheath (P‐I/P@P/P) is elaborately designed and prepared via the electrospinning method. The synergistic effect between the three‐dimensional matrix and the slowly released PEI‐I additive not only suppresses the combustion property of traditional GPEs, but also promotes the lithium‐ion desolvation and the generation of inorganic SEI layer on Li anode. As demonstrated, the optimized P‐I/P@P/P GPE delivers a high Li <jats:sup>+</jats:sup> transference number of 0.88, high ionic conductivity of 2.34 mS cm <jats:sup>−1</jats:sup> , and heterogeneous SEI composition of Li <jats:sub>3</jats:sub> N/Li <jats:sub>2</jats:sub> CO <jats:sub>3</jats:sub> /LiF. The corresponding Li||Li cell achieves stable voltage polarization for 1000 h at 5 mA cm <jats:sup>−2</jats:sup> , and the Li||Cu cell displays a high Coulombic efficiency of 97.84%. Satisfyingly, the targeted Li||LiFePO <jats:sub>4</jats:sub> battery exhibits an impressive capacity retention ratio of 97% after 3000 cycles. These findings offer a design paradigm for functional GPEs to drive the implementation of high‐energy‐density LMBs in practical scenarios.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"114 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089635","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}
Kyunghee Chae, Jonghoon Park, Shanmugasundaram Kamalakannan, Yunho Ahn, Jeonghyeon Kim, Dong‐Il Won, JaeHong Park, Hyung Chul Ham, Filipe Marques Mota, Hoi Ri Moon, Dong Ha Kim
Lithium–oxygen (Li–O 2 ) batteries offer a high theoretical energy density (~3600 Wh kg −1 ) but remain hindered by large recharge (RC) overpotentials, low efficiency, and limited cycle life. Integrating solar energy through localized surface plasmon resonance (LSPR) provides a sustainable route to overcome these challenges. Here, gold nanoparticles (Au NPs) were embedded into a UiO‐66‐NH 2 metal–organic framework via a one‐step “ship‐in‐a‐bottle” method without capping agents, yielding Au@UiO‐66‐NH 2 with high structural integrity, enhanced visible‐light absorption, and improved charge transport. Under illumination, the plasmon‐governed Li–O 2 battery exhibited striking morphological changes in discharge (DC) products, forming thin and film‐like lithium peroxide (Li 2 O 2 ) that decomposed more readily during RC. In Situ Fourier transform infrared spectroscopy confirmed LSPR‐driven selective Li 2 O 2 formation with suppressed lithium carbonate and carboxylate side‐products. UV‐vis, band alignment, and time‐resolved photoluminescence studies revealed efficient electron transfer from UiO‐66‐NH 2 to adjacent Au sites. Density functional theory further showed that electron‐rich Au@UiO‐66‐NH 2 interfaces lower energy barriers for both oxygen reduction and evolution reactions. The system delivered a low overpotential of 1.05 V in the first DC‐RC cycle and stable performance for over 600 h under light irradiation, with minimal Au loading (3.04 wt%). This work establishes a new benchmark for efficient, durable, and solar‐integrated Li–O 2 energy storage.
{"title":"In Situ Mechanistic Study of Plasmon‐Governed Reaction Pathways in Li−O 2 Batteries With a Au@MOF Cathode","authors":"Kyunghee Chae, Jonghoon Park, Shanmugasundaram Kamalakannan, Yunho Ahn, Jeonghyeon Kim, Dong‐Il Won, JaeHong Park, Hyung Chul Ham, Filipe Marques Mota, Hoi Ri Moon, Dong Ha Kim","doi":"10.1002/aenm.202505822","DOIUrl":"https://doi.org/10.1002/aenm.202505822","url":null,"abstract":"Lithium–oxygen (Li–O <jats:sub>2</jats:sub> ) batteries offer a high theoretical energy density (~3600 Wh kg <jats:sup>−1</jats:sup> ) but remain hindered by large recharge (RC) overpotentials, low efficiency, and limited cycle life. Integrating solar energy through localized surface plasmon resonance (LSPR) provides a sustainable route to overcome these challenges. Here, gold nanoparticles (Au NPs) were embedded into a UiO‐66‐NH <jats:sub>2</jats:sub> metal–organic framework via a one‐step “ship‐in‐a‐bottle” method without capping agents, yielding Au@UiO‐66‐NH <jats:sub>2</jats:sub> with high structural integrity, enhanced visible‐light absorption, and improved charge transport. Under illumination, the plasmon‐governed Li–O <jats:sub>2</jats:sub> battery exhibited striking morphological changes in discharge (DC) products, forming thin and film‐like lithium peroxide (Li <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> ) that decomposed more readily during RC. In Situ Fourier transform infrared spectroscopy confirmed LSPR‐driven selective Li <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> formation with suppressed lithium carbonate and carboxylate side‐products. UV‐vis, band alignment, and time‐resolved photoluminescence studies revealed efficient electron transfer from UiO‐66‐NH <jats:sub>2</jats:sub> to adjacent Au sites. Density functional theory further showed that electron‐rich Au@UiO‐66‐NH <jats:sub>2</jats:sub> interfaces lower energy barriers for both oxygen reduction and evolution reactions. The system delivered a low overpotential of 1.05 V in the first DC‐RC cycle and stable performance for over 600 h under light irradiation, with minimal Au loading (3.04 wt%). This work establishes a new benchmark for efficient, durable, and solar‐integrated Li–O <jats:sub>2</jats:sub> energy storage.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"60 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089767","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 sluggish charge transfer and weak surface‐site reactivity critically limit CO 2 photoreduction efficiency. While the crystal structure dictates bulk charge separation, the surface atomic configuration governs reaction kinetics and thermodynamics. Thus, concurrent optimization of both domains is essential. In this work, we present a concise strategy for the selective conversion of CO 2 to CO using polar Bi 4 O 5 Br 2 nanosheets modified with Cu atoms to induce bulk polarization enhancement and symbiotic electronic structure regulation (SESR). The SESR effect establishes a dynamic coupling between internal polarization and surface electronic states. Cu incorporation into the asymmetric Bi 4 O 5 Br 2 layered framework enhances intrinsic polarization through polar‐unit stacking, thereby extending carrier lifetime by 48.6‐fold and facilitating efficient charge separation and migration. Meanwhile, the strengthened polarization modulates the surface electronic configuration of Cu sites, promoting CO 2 adsorption and activation, as supported by experimental characterization and theoretical simulation under polarized conditions. Without any sacrificial agents or sensitizers, Cu‐Bi 4 O 5 Br 2 achieves a remarkable CO 2 ‐to‐CO rate of 45.34 µmol g −1 h −1 with high selectivity in pure water. This work elucidates the cooperative interplay between polarization fields and surface electronic regulation, providing a generalizable paradigm for manipulating charge dynamics and catalytic‐site chemistry toward efficient solar‐driven CO 2 conversion.
{"title":"Cu Sites Induced Polarization Enhancement and Symbiotic Electronic Structure Regulation to Facilitate CO 2 Photoreduction","authors":"Yutang Yu, Zijian Zhu, Pengwei Jia, Fang Chen, Hongwei Huang","doi":"10.1002/aenm.202506247","DOIUrl":"https://doi.org/10.1002/aenm.202506247","url":null,"abstract":"The sluggish charge transfer and weak surface‐site reactivity critically limit CO <jats:sub>2</jats:sub> photoreduction efficiency. While the crystal structure dictates bulk charge separation, the surface atomic configuration governs reaction kinetics and thermodynamics. Thus, concurrent optimization of both domains is essential. In this work, we present a concise strategy for the selective conversion of CO <jats:sub>2</jats:sub> to CO using polar Bi <jats:sub>4</jats:sub> O <jats:sub>5</jats:sub> Br <jats:sub>2</jats:sub> nanosheets modified with Cu atoms to induce bulk polarization enhancement and symbiotic electronic structure regulation (SESR). The SESR effect establishes a dynamic coupling between internal polarization and surface electronic states. Cu incorporation into the asymmetric Bi <jats:sub>4</jats:sub> O <jats:sub>5</jats:sub> Br <jats:sub>2</jats:sub> layered framework enhances intrinsic polarization through polar‐unit stacking, thereby extending carrier lifetime by 48.6‐fold and facilitating efficient charge separation and migration. Meanwhile, the strengthened polarization modulates the surface electronic configuration of Cu sites, promoting CO <jats:sub>2</jats:sub> adsorption and activation, as supported by experimental characterization and theoretical simulation under polarized conditions. Without any sacrificial agents or sensitizers, Cu‐Bi <jats:sub>4</jats:sub> O <jats:sub>5</jats:sub> Br <jats:sub>2</jats:sub> achieves a remarkable CO <jats:sub>2</jats:sub> ‐to‐CO rate of 45.34 µmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> with high selectivity in pure water. This work elucidates the cooperative interplay between polarization fields and surface electronic regulation, providing a generalizable paradigm for manipulating charge dynamics and catalytic‐site chemistry toward efficient solar‐driven CO <jats:sub>2</jats:sub> conversion.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"76 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071451","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}
Jiawen Zhang, Suli Chen, Yixing Shen, Junhong Guo, Kun He, Sicheng Lu, Zi-Feng Ma, Tianxi Liu
In-situ polymerized polyether electrolytes are highly promising for solid-state sodium metal batteries (SMBs) owing to their high ionic conductivity and favorable interfacial contact. However, their practical application is limited by poor thermal stability, low Na+ transference number, and unstable Na/electrolyte interface, leading to rapid degradation and safety risks. Herein, we demonstrate a molecularly engineered, anion-anchoring crosslinked polyether electrolyte (AICPE) fabricated by in-situ polymerization of 1,3-dioxolane with epoxy-functionalized halloysite nanotubes (e-HNTs). The e-HNTs function as a dual-surface ion-regulator: the inner-surface Al–OH groups act as Lewis acid sites for anion-trapping, while the outer siloxane surface weakens Na+-polymer interactions through competitive coordination. This synergy between the crosslinked network and bidirectional ion-regulation endows the AICPE with a high ionic conductivity of 2.17 mS cm−1, an elevated Na+ transference number of 0.72, significantly improved thermal stability, and superior interfacial compatibility. Consequently, Na/Na symmetric cells achieve ultra-stable cycling over 3600 h at 0.1 mA cm−2 without dendrite penetration. Importantly, the solid-state SMBs exhibit remarkable rate capability and outstanding long-term durability, with 87.5% capacity retention after 1200 cycles at an ultra-high rate of 10 C. Practical pouch cells further confirm exceptional thermal safety, highlighting the practical potential of this design for high-performance, safe, and fast-charging SMBs.
原位聚合聚醚电解质具有高离子电导率和良好的界面接触特性，在固态钠金属电池中具有广阔的应用前景。然而，它们的实际应用受到热稳定性差、Na+转移数低、Na/电解质界面不稳定等因素的限制，导致它们的快速降解和安全风险。在此，我们展示了一种分子工程的阴离子锚定交联聚醚电解质（AICPE），该电解质是通过原位聚合1,3-二氧代烷和环氧官能化高岭土纳米管（e-HNTs）制备的。e-HNTs具有双表面离子调节剂的功能：内表面Al-OH基团作为阴离子捕获的路易斯酸位点，而外硅氧烷表面通过竞争配位削弱Na+-聚合物的相互作用。这种交联网络和双向离子调节之间的协同作用使AICPE具有2.17 mS cm−1的高离子电导率，0.72的Na+转移数，显著改善的热稳定性和优越的界面相容性。因此，Na/Na对称电池在0.1 mA cm - 2下实现了超过3600小时的超稳定循环，没有树突穿透。重要的是，固态smb表现出卓越的倍率能力和出色的长期耐用性，在超高10℃下进行1200次循环后，容量保持率为87.5%。实用的袋状电池进一步证实了卓越的热安全性，突出了该设计在高性能、安全和快速充电的smb方面的实用潜力。
{"title":"A Molecularly Engineered Crosslinked Polyether Electrolyte with Anion-Trapping Nano-Networks for Fast-Charging and Safe Sodium Metal Batteries","authors":"Jiawen Zhang, Suli Chen, Yixing Shen, Junhong Guo, Kun He, Sicheng Lu, Zi-Feng Ma, Tianxi Liu","doi":"10.1002/aenm.202506070","DOIUrl":"https://doi.org/10.1002/aenm.202506070","url":null,"abstract":"In-situ polymerized polyether electrolytes are highly promising for solid-state sodium metal batteries (SMBs) owing to their high ionic conductivity and favorable interfacial contact. However, their practical application is limited by poor thermal stability, low Na<sup>+</sup> transference number, and unstable Na/electrolyte interface, leading to rapid degradation and safety risks. Herein, we demonstrate a molecularly engineered, anion-anchoring crosslinked polyether electrolyte (AICPE) fabricated by in-situ polymerization of 1,3-dioxolane with epoxy-functionalized halloysite nanotubes (e-HNTs). The e-HNTs function as a dual-surface ion-regulator: the inner-surface Al–OH groups act as Lewis acid sites for anion-trapping, while the outer siloxane surface weakens Na<sup>+</sup>-polymer interactions through competitive coordination. This synergy between the crosslinked network and bidirectional ion-regulation endows the AICPE with a high ionic conductivity of 2.17 mS cm<sup>−</sup><sup>1</sup>, an elevated Na<sup>+</sup> transference number of 0.72, significantly improved thermal stability, and superior interfacial compatibility. Consequently, Na/Na symmetric cells achieve ultra-stable cycling over 3600 h at 0.1 mA cm<sup>−</sup><sup>2</sup> without dendrite penetration. Importantly, the solid-state SMBs exhibit remarkable rate capability and outstanding long-term durability, with 87.5% capacity retention after 1200 cycles at an ultra-high rate of 10 C. Practical pouch cells further confirm exceptional thermal safety, highlighting the practical potential of this design for high-performance, safe, and fast-charging SMBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"17 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089599","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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