Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104817
Eric Winter , Eric Ricardo Carreon Ruiz , Łukasz Kondracki , Mohammed Srout , Jongmin Lee , Pierre Boillat , Thomas J. Schmidt , Sigita Trabesinger
Rechargeable lithium (Li) metal batteries, which use Li metal as the negative-electrode, promise energy densities that are two times higher than those achievable with conventional Li-ion batteries. However, the practical application of Li-metal batteries is currently constrained, and where the central challenge is dendritic Li growth, leading to cell failure. To overcome these limitations, electrolytes compatible with Li metal are required, where various electrolyte formulations have been proposed, but a mechanistic understanding of their effects to the kinetics and dynamics of Li deposition remains incomplete. Here, we introduce operando neutron imaging as a versatile modality for observing electrolyte-dependent Li-deposit nucleation, Li-metal plating and stripping behaviour with high temporal and spatial resolution. We tested three different carbonate electrolytes with varying concentrations of fluoroethylene carbonate (FEC) and found that low levels of the FEC additive contribute to better Li cycling reversibility, while higher concentrations lead to adverse effects, revealing an unexpected and critical limitation of FEC-additive application for improving Li-metal cycling. Our imaging methodology can be a starting point for much broader operando studies of the plating and stripping behaviour of Li metal in any electrolyte, potentially making it a key tool for future electrolyte developments.
{"title":"Towards understanding electrolyte-dependant dynamics and kinetics of lithium deposition and stripping by operando neutron imaging","authors":"Eric Winter , Eric Ricardo Carreon Ruiz , Łukasz Kondracki , Mohammed Srout , Jongmin Lee , Pierre Boillat , Thomas J. Schmidt , Sigita Trabesinger","doi":"10.1016/j.ensm.2025.104817","DOIUrl":"10.1016/j.ensm.2025.104817","url":null,"abstract":"<div><div>Rechargeable lithium (Li) metal batteries, which use Li metal as the negative-electrode, promise energy densities that are two times higher than those achievable with conventional Li-ion batteries. However, the practical application of Li-metal batteries is currently constrained, and where the central challenge is dendritic Li growth, leading to cell failure. To overcome these limitations, electrolytes compatible with Li metal are required, where various electrolyte formulations have been proposed, but a mechanistic understanding of their effects to the kinetics and dynamics of Li deposition remains incomplete. Here, we introduce <em>operando</em> neutron imaging as a versatile modality for observing electrolyte-dependent Li-deposit nucleation, Li-metal plating and stripping behaviour with high temporal and spatial resolution. We tested three different carbonate electrolytes with varying concentrations of fluoroethylene carbonate (FEC) and found that low levels of the FEC additive contribute to better Li cycling reversibility, while higher concentrations lead to adverse effects, revealing an unexpected and critical limitation of FEC-additive application for improving Li-metal cycling. Our imaging methodology can be a starting point for much broader <em>operando</em> studies of the plating and stripping behaviour of Li metal in any electrolyte, potentially making it a key tool for future electrolyte developments.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104817"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785916","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104827
Huijie Tian , Erlei Zhang , Wanbao Wu , Yu Wang , Qing Li , Hao Wu , Kai Lu , Jialin Wang , Yunyun Lei , Jiaheng Zhang , Qunhui Yuan
Deep eutectic electrolytes (DEEs) endow lithium metal batteries (LMBs) with enhanced safety via their intrinsic non-flammability and thermal stability; however, they are highly viscous with inferior interfacial stability. Herein, inspired by the intermolecular hydrogen bonding network in low-viscosity “H2O”, we construct a novel DEE through the synergistic coordination of succinonitrile (SN), dimethylsulfone (MSM), and lithium difluoro(oxalate)borate (LiDFOB). The extensive hydrogen bond network between the S = O groups of MSM and α-hydrogens of SN simultaneously improves the Li metal compatibility and salt dissociation, resulting in a low viscosity (18.73 mPa s) and high ionic conductivity (3.14 mS cm−1) comparable to commercial carbonate electrolytes. Crucially, anion-dominated solvation structures induced by the salt concentration promote the formation of a B/F/S-enriched solid-electrolyte interphase (SEI) with an organic-rich outer layer and inorganic-dense inner layer. This gradient SEI alleviates mechanical stresses, homogenizes Li+ flux, and suppresses dendrite growth. Consequently, the LiCoO2||Li cell retains 87.4% capacity after 1000 cycles at 5C (3.0–4.5 V), and the LiCoO2||graphite pouch cell maintains 90.3% after 2500 cycles, validating its practical viability. The intrinsic safety of the electrolyte and its compatibility with high-voltage cathodes underscore the significant possibilities for next-generation, high-energy-density LMBs.
深共晶电解质通过其固有的不可燃性和热稳定性，增强了锂金属电池（lmb）的安全性；然而，它们是高粘性的，界面稳定性较差。在此，受低粘度“H2O”分子间氢键网络的启发，我们通过丁二腈（SN）、二甲砜（MSM）和二氟（草酸）硼酸锂（LiDFOB）的协同配合构建了一种新型DEE。MSM的S = O基团和SN的α-氢之间广泛的氢键网络同时改善了锂金属的相容性和盐的解离，从而使MSM具有与商业碳酸盐电解质相当的低粘度（18.73 mPa S）和高离子电导率（3.14 mS cm−1）。关键是，盐浓度诱导的阴离子主导的溶剂化结构促进了B/F/ s富集的固体电解质间相（SEI）的形成，其外层富含有机物，内层无机密集。这种梯度SEI减轻了机械应力，使Li+通量均匀化，抑制了枝晶的生长。因此，LiCoO2||锂电池在5C （3.0-4.5 V）下循环1000次后保持87.4%的容量，LiCoO2||石墨袋电池在2500次循环后保持90.3%的容量，验证了其实际可行性。电解质的固有安全性及其与高压阴极的兼容性强调了下一代高能量密度lmb的重大可能性。
{"title":"Hydrogen-bond regulated solvent networks for fast-charging high-voltage lithium metal batteries","authors":"Huijie Tian , Erlei Zhang , Wanbao Wu , Yu Wang , Qing Li , Hao Wu , Kai Lu , Jialin Wang , Yunyun Lei , Jiaheng Zhang , Qunhui Yuan","doi":"10.1016/j.ensm.2025.104827","DOIUrl":"10.1016/j.ensm.2025.104827","url":null,"abstract":"<div><div>Deep eutectic electrolytes (DEEs) endow lithium metal batteries (LMBs) with enhanced safety via their intrinsic non-flammability and thermal stability; however, they are highly viscous with inferior interfacial stability. Herein, inspired by the intermolecular hydrogen bonding network in low-viscosity “H<sub>2</sub>O”, we construct a novel DEE through the synergistic coordination of succinonitrile (SN), dimethylsulfone (MSM), and lithium difluoro(oxalate)borate (LiDFOB). The extensive hydrogen bond network between the <em>S</em> = <em>O</em> groups of MSM and α-hydrogens of SN simultaneously improves the Li metal compatibility and salt dissociation, resulting in a low viscosity (18.73 mPa s) and high ionic conductivity (3.14 mS cm<sup>−1</sup>) comparable to commercial carbonate electrolytes. Crucially, anion-dominated solvation structures induced by the salt concentration promote the formation of a B/F/S-enriched solid-electrolyte interphase (SEI) with an organic-rich outer layer and inorganic-dense inner layer. This gradient SEI alleviates mechanical stresses, homogenizes Li<sup>+</sup> flux, and suppresses dendrite growth. Consequently, the LiCoO<sub>2</sub>||Li cell retains 87.4% capacity after 1000 cycles at 5C (3.0–4.5 V), and the LiCoO<sub>2</sub>||graphite pouch cell maintains 90.3% after 2500 cycles, validating its practical viability. The intrinsic safety of the electrolyte and its compatibility with high-voltage cathodes underscore the significant possibilities for next-generation, high-energy-density LMBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104827"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785909","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104860
Yinda Li , Zilong Wang , Yuxuan Wu , Jian Xie , Aijun Zhou , Jicheng Jiang , Yufeng Yin , Liguang Wang , Weixiang Chen , Fang Chen , Yifan Zhao , Chunyang Wu , Bo Xu , Yang Nie , Xiongwen Xu , Jian Tu , Jinlong Zheng , Yunhao Lu
O3-type layered oxide cathodes, recognized as one of the highest energy-density materials for sodium-ion batteries, have attracted extensive research interests. While NiMn-based materials are renowned for their high capacity, their stability is obviously compromised at high voltages. Since high voltage inevitably activates anionic redox that triggers irreversible structural degradation, balancing oxygen-derived capacity with fundamental lattice stabilization remains challenging. In this study, we report a bonding-strain decoupling strategy in O3-NaLi0.08Ni0.42Mn0.47Sn0.03O2 to address this critical issue. The results reveal that the introduction of Sn4+ contributes to a more stable phase structure under high-voltage conditions. Specifically, the Sn-modified material exhibits prolonged retention of the P phase, while suppressing the formation of the O3’ and OP2 phases, thereby enhancing structural stability during cycling. First-principles calculations demonstrate that Li⁺-mediated O 2p-band uplifting enables reversible oxygen redox, whereas Sn-induced bandgap widening suppresses lattice oxygen loss. The cathode delivers superior electrochemical performance: 80.2 % capacity retention after 400 cycles at 5 C (2.0–4.1 V) and a high capacity of 130.3 mAh g⁻¹ at 5 C (2.0–4.2 V). Extending to d¹⁰ elements, we establish the p-band offset descriptor: energy offset between p-band centers of multivalent p-region dopants and O 2p orbitals (MPD-p bc - O-2p bc), validating Sb/Al/Ga dopants while excluding Ge/In. This discovery may offer theoretical insights and guidance for the design of high-voltage layered cathodes for sodium-ion batteries.
o3型层状氧化物阴极作为钠离子电池中能量密度最高的材料之一，引起了广泛的研究兴趣。虽然nimn基材料以其高容量而闻名，但它们在高压下的稳定性明显受到损害。由于高压不可避免地激活阴离子氧化还原，从而引发不可逆的结构降解，因此平衡氧衍生容量与基本晶格稳定仍然是一个挑战。在本研究中，我们报告了在o3 - nali0.08 ni0.42 mn0.47 sn0.030 o2中键合-应变解耦策略来解决这一关键问题。结果表明，Sn4+的引入有助于在高压条件下获得更稳定的相结构。具体来说，sn修饰的材料表现出P相的长时间保留，同时抑制了O3′和OP2相的形成，从而增强了循环过程中的结构稳定性。第一性原理计算表明，Li +介导的o2 - 2p带抬升实现了可逆氧氧化还原，而sn诱导的带隙加宽抑制了晶格氧损失。该阴极具有优异的电化学性能：在5℃（2.0-4.1 V）下循环400次后，容量保持率为80.2%，在5℃（2.0-4.2 V）下的高容量为130.3 mAh g⁻¹。扩展到d¹⁰元素，我们建立了p波段偏移描述符：多价p区掺杂剂的p波段中心与O 2p轨道（MPD-p bc - O-2p bc）之间的能量偏移，验证了Sb/Al/Ga掺杂剂，同时排除了Ge/In。这一发现可能为钠离子电池高压层状阴极的设计提供理论见解和指导。
{"title":"Tuning metal-O bonding to unlock high-voltage stability in sodium-ion layered cathodes","authors":"Yinda Li , Zilong Wang , Yuxuan Wu , Jian Xie , Aijun Zhou , Jicheng Jiang , Yufeng Yin , Liguang Wang , Weixiang Chen , Fang Chen , Yifan Zhao , Chunyang Wu , Bo Xu , Yang Nie , Xiongwen Xu , Jian Tu , Jinlong Zheng , Yunhao Lu","doi":"10.1016/j.ensm.2025.104860","DOIUrl":"10.1016/j.ensm.2025.104860","url":null,"abstract":"<div><div>O3-type layered oxide cathodes, recognized as one of the highest energy-density materials for sodium-ion batteries, have attracted extensive research interests. While NiMn-based materials are renowned for their high capacity, their stability is obviously compromised at high voltages. Since high voltage inevitably activates anionic redox that triggers irreversible structural degradation, balancing oxygen-derived capacity with fundamental lattice stabilization remains challenging. In this study, we report a bonding-strain decoupling strategy in O3-NaLi<sub>0.08</sub>Ni<sub>0.42</sub>Mn<sub>0.47</sub>Sn<sub>0.03</sub>O<sub>2</sub> to address this critical issue. The results reveal that the introduction of Sn<sup>4+</sup> contributes to a more stable phase structure under high-voltage conditions. Specifically, the Sn-modified material exhibits prolonged retention of the P phase, while suppressing the formation of the O3’ and OP2 phases, thereby enhancing structural stability during cycling. First-principles calculations demonstrate that Li⁺-mediated O 2p-band uplifting enables reversible oxygen redox, whereas Sn-induced bandgap widening suppresses lattice oxygen loss. The cathode delivers superior electrochemical performance: 80.2 % capacity retention after 400 cycles at 5 C (2.0–4.1 V) and a high capacity of 130.3 mAh g⁻¹ at 5 C (2.0–4.2 V). Extending to d¹⁰ elements, we establish the p-band offset descriptor: energy offset between p-band centers of multivalent p-region dopants and O 2p orbitals (MPD-p bc - O-2p bc), validating Sb/Al/Ga dopants while excluding Ge/In. This discovery may offer theoretical insights and guidance for the design of high-voltage layered cathodes for sodium-ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104860"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920779","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2026.104875
Baoyin Chen , Zhenjiang He , Yunjiao Li , Zhenya Sui , Guangsheng Huo , Yi Cheng
Manganese recovery remains neglected in spent lithium-ion battery (LIB) recycling systems, due to its comparatively low market value relative to lithium, nickel, and cobalt, compounded by prohibitive operational expenditure in extraction processes. This oversight leads to resource wastage and potential environmental harm. With the steady advancement of LIB technology, the demand for manganese is projected to rise annually, while the available high-grade manganese ore is continuously decreasing. Consequently, the recycling of manganese from LIBs presents significant market potential and strategic advantages. This paper provides a comprehensive review of the current technologies and research status concerning the recovery and utilization of manganese resources from spent LIB cathode materials. Two primary approaches to manganese recovery exist: direct and indirect. At present, indirect recovery dominates commercial recycling practices. This review focuses on the recovery of manganese and outlines the three key stages of closed-loop manganese recycling: extraction of manganese from spent lithium-ion batteries, separation and purification of manganese from the leachate, and regeneration and reuse of manganese-based products. First, various extraction techniques for recovering manganese from spent LIB cathode materials are introduced, along with the chemical forms in which manganese exists during these processes. The efficiency of manganese leaching through methods such as acid leaching, alkali leaching, deep eutectic solvent leaching, bioleaching, electrochemical leaching, reductive roasting, and sulfation roasting is summarized. Subsequently, based on the properties and characteristics of coexisting impurities, different strategies for removing these impurities from the manganese-rich leachate are discussed to achieve effective separation and purification of manganese. Finally, the regeneration of manganese compounds after purification is examined, together with strategies for the direct regeneration of manganese-containing cathode materials. This paper offers a systematic overview of current technologies and research progress in the manganese recovery chain from spent lithium-ion batteries, providing valuable insights and a novel perspective for future research in this field.
{"title":"Manganese: An overlooked yet inevitable element in spent battery recycling processes","authors":"Baoyin Chen , Zhenjiang He , Yunjiao Li , Zhenya Sui , Guangsheng Huo , Yi Cheng","doi":"10.1016/j.ensm.2026.104875","DOIUrl":"10.1016/j.ensm.2026.104875","url":null,"abstract":"<div><div>Manganese recovery remains neglected in spent lithium-ion battery (LIB) recycling systems, due to its comparatively low market value relative to lithium, nickel, and cobalt, compounded by prohibitive operational expenditure in extraction processes. This oversight leads to resource wastage and potential environmental harm. With the steady advancement of LIB technology, the demand for manganese is projected to rise annually, while the available high-grade manganese ore is continuously decreasing. Consequently, the recycling of manganese from LIBs presents significant market potential and strategic advantages. This paper provides a comprehensive review of the current technologies and research status concerning the recovery and utilization of manganese resources from spent LIB cathode materials. Two primary approaches to manganese recovery exist: direct and indirect. At present, indirect recovery dominates commercial recycling practices. This review focuses on the recovery of manganese and outlines the three key stages of closed-loop manganese recycling: extraction of manganese from spent lithium-ion batteries, separation and purification of manganese from the leachate, and regeneration and reuse of manganese-based products. First, various extraction techniques for recovering manganese from spent LIB cathode materials are introduced, along with the chemical forms in which manganese exists during these processes. The efficiency of manganese leaching through methods such as acid leaching, alkali leaching, deep eutectic solvent leaching, bioleaching, electrochemical leaching, reductive roasting, and sulfation roasting is summarized. Subsequently, based on the properties and characteristics of coexisting impurities, different strategies for removing these impurities from the manganese-rich leachate are discussed to achieve effective separation and purification of manganese. Finally, the regeneration of manganese compounds after purification is examined, together with strategies for the direct regeneration of manganese-containing cathode materials. This paper offers a systematic overview of current technologies and research progress in the manganese recovery chain from spent lithium-ion batteries, providing valuable insights and a novel perspective for future research in this field.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104875"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895143","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104857
Yuanjia Wang , Yang Wang , Yuanye Wutian , Guang Feng , Junwen Peng , Tao Chen
Amid the global transition toward clean and sustainable energy systems, the development of cost-effective and resource-abundant energy storage technologies has become increasingly critical. Sodium-ion batteries have emerged as a highly promising candidate due to their material availability and competitive performance. Nevertheless, the practical application of layered oxide cathode materials in these batteries is hindered by mechanical stress accumulation during cycling, which leads to structural degradation, capacity fade, and ultimately battery failure. This review systematically summarizes recent advances in stress engineering strategies aimed at mitigating these challenges. It begins by elucidating the fundamental mechanisms of stress generation associated with sodium ion intercalation and deintercalation processes. The article then provides a comprehensive analysis of various innovative approaches designed to manage stress, including microstructural optimization, surface and interface engineering, and composite material design. Furthermore, it discusses the correlation between atomic-scale lattice strain and macroscopic electrochemical behavior, offering deep insights into failure mechanisms. By integrating theoretical understanding with experimental progress, this review aims to provide valuable guidance for the rational design of durable and high-performance cathode materials, thereby supporting the broader effort to develop reliable sodium-based energy storage systems.
{"title":"Stress-induced challenges in sodium-ion battery layered oxide cathodes: Damage mechanisms and mitigation approaches","authors":"Yuanjia Wang , Yang Wang , Yuanye Wutian , Guang Feng , Junwen Peng , Tao Chen","doi":"10.1016/j.ensm.2025.104857","DOIUrl":"10.1016/j.ensm.2025.104857","url":null,"abstract":"<div><div>Amid the global transition toward clean and sustainable energy systems, the development of cost-effective and resource-abundant energy storage technologies has become increasingly critical. Sodium-ion batteries have emerged as a highly promising candidate due to their material availability and competitive performance. Nevertheless, the practical application of layered oxide cathode materials in these batteries is hindered by mechanical stress accumulation during cycling, which leads to structural degradation, capacity fade, and ultimately battery failure. This review systematically summarizes recent advances in stress engineering strategies aimed at mitigating these challenges. It begins by elucidating the fundamental mechanisms of stress generation associated with sodium ion intercalation and deintercalation processes. The article then provides a comprehensive analysis of various innovative approaches designed to manage stress, including microstructural optimization, surface and interface engineering, and composite material design. Furthermore, it discusses the correlation between atomic-scale lattice strain and macroscopic electrochemical behavior, offering deep insights into failure mechanisms. By integrating theoretical understanding with experimental progress, this review aims to provide valuable guidance for the rational design of durable and high-performance cathode materials, thereby supporting the broader effort to develop reliable sodium-based energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104857"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895326","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}
Molten salt aluminum batteries (MSABs) are promising for next-generation grid-scale energy storage owing to the high capacity and cost-effectiveness. However, the dendrite formation induces safety risks and rapid performance degradation, particularly under high-rate and high-loading conditions. Here, we present a simple and efficient strategy to in-situ construct an aluminum-gallium (Al-Ga) alloy anode by introducing GaCl3 to the chloroaluminate melt electrolyte. The GaCl3 spontaneously reacts with Al at the electrolyte/anode interface through a displacement reaction, yielding metallic Ga that subsequently interdiffuses with Al to form a homogeneous Al-Ga alloy anode, owed to its liquid nature at the temperature of operation. The Al-Ga alloy anode reduces nucleation barriers, homogenizes the interfacial electric field and enhances interfacial charge transport, thereby enabling uniform aluminum deposition and stable dendrite-less cycling. As a result, the in-situ gallium alloying strategy enables symmetric cells to cycle stably for over 1,100 h at 5.0 mA cm-2. The aluminum-sulfur cell using Al-Ga alloy anode maintains 5000 cycles with a capacity decay of only 0.0012% per cycle at 5.83 mA cm-2. Our work highlights the advantage of in-situ alloying strategy with rationally designed alloying elements for a simple, low-cost and scalable approach for practical deployment.
熔盐铝电池（MSABs）因其高容量和高成本效益而成为下一代电网规模储能的理想材料。然而，枝晶的形成会带来安全风险和性能的快速退化，特别是在高速率和高载荷条件下。在这里，我们提出了一种简单有效的策略，通过在氯铝酸盐熔体电解质中引入GaCl3来原位构建铝镓（Al-Ga）合金阳极。在电解液/阳极界面处，GaCl3通过位移反应与Al自发反应，产生金属Ga，随后与Al相互扩散，形成均匀的Al-Ga合金阳极，这是由于其在工作温度下的液态性质。Al-Ga合金阳极减少了成核障碍，使界面电场均匀化，增强了界面电荷输运，从而实现了均匀的铝沉积和稳定的无枝晶循环。因此，原位镓合金化策略使对称电池在5.0 mA cm-2下稳定循环超过1100小时。使用Al-Ga合金阳极的铝硫电池在5.83 mA cm-2下保持5000次循环，每次循环的容量衰减仅为0.0012%。我们的工作突出了原位合金化策略的优势，合理设计合金元素，为实际部署提供了简单，低成本和可扩展的方法。
{"title":"Dendrite-less Aluminum Anodes Enabled with In-situ Gallium Alloying for Molten Salt Aluminum Batteries","authors":"Yongfeng Jia, Zhitong Xiao, Lujun Zhu, Kaier Shen, Mengxue He, Jiashen Meng, Yue Ma, Chenxi Zheng, Quanquan Pang","doi":"10.1016/j.ensm.2026.104869","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.104869","url":null,"abstract":"Molten salt aluminum batteries (MSABs) are promising for next-generation grid-scale energy storage owing to the high capacity and cost-effectiveness. However, the dendrite formation induces safety risks and rapid performance degradation, particularly under high-rate and high-loading conditions. Here, we present a simple and efficient strategy to <em>in-situ</em> construct an aluminum-gallium (Al-Ga) alloy anode by introducing GaCl<sub>3</sub> to the chloroaluminate melt electrolyte. The GaCl<sub>3</sub> spontaneously reacts with Al at the electrolyte/anode interface through a displacement reaction, yielding metallic Ga that subsequently interdiffuses with Al to form a homogeneous Al-Ga alloy anode, owed to its liquid nature at the temperature of operation. The Al-Ga alloy anode reduces nucleation barriers, homogenizes the interfacial electric field and enhances interfacial charge transport, thereby enabling uniform aluminum deposition and stable dendrite-less cycling. As a result, the <em>in-situ</em> gallium alloying strategy enables symmetric cells to cycle stably for over 1,100 h at 5.0 mA cm<sup>-2</sup>. The aluminum-sulfur cell using Al-Ga alloy anode maintains 5000 cycles with a capacity decay of only 0.0012% per cycle at 5.83 mA cm<sup>-2</sup>. Our work highlights the advantage of <em>in-situ</em> alloying strategy with rationally designed alloying elements for a simple, low-cost and scalable approach for practical deployment.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"18 1","pages":"104869"},"PeriodicalIF":20.4,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895300","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104828
Joao Cunha , Ihsan Çaha , Francis Leonard Deepak , Paulo J. Ferreira
Lithium-ion batteries have emerged as the most common energy storage technology. Yet, the characterization and optimization of battery electrode’s morphology is still an underdeveloped route for improving their performance. Particularly, the electrode’s porous microstructural arrangement defines electron and ion transport, as well as electrochemical processes which ultimately determine the battery performance. In this respect, three-dimensional (3D) Focused Ion Beam - Scanning Electron Microscope (FIB-SEM) tomography allows to reconstruct the electrode internal 3D morphology down to ∼10 nm resolution. However, low contrast between electrode constituents, especially the carbon-binder and pores, hinders reliable 3D electrode volume reconstruction. To overcome this issue, we demonstrate contrast-enhanced FIB-SEM tomography of porous battery electrodes via in-situ pore filling at µm depths with platinum, using Gas-Injection System (GIS) electron-induced deposition. This contrast enhancement strategy improved the confidence for pore identification and derived volume fractions, opening the door to precise 3D characterization of battery electrodes, towards their optimization.
{"title":"3D tomography of porous battery electrodes with in-situ contrast enhancement","authors":"Joao Cunha , Ihsan Çaha , Francis Leonard Deepak , Paulo J. Ferreira","doi":"10.1016/j.ensm.2025.104828","DOIUrl":"10.1016/j.ensm.2025.104828","url":null,"abstract":"<div><div>Lithium-ion batteries have emerged as the most common energy storage technology. Yet, the characterization and optimization of battery electrode’s morphology is still an underdeveloped route for improving their performance. Particularly, the electrode’s porous microstructural arrangement defines electron and ion transport, as well as electrochemical processes which ultimately determine the battery performance. In this respect, three-dimensional (3D) Focused Ion Beam - Scanning Electron Microscope (FIB-SEM) tomography allows to reconstruct the electrode internal 3D morphology down to ∼10 nm resolution. However, low contrast between electrode constituents, especially the carbon-binder and pores, hinders reliable 3D electrode volume reconstruction. To overcome this issue, we demonstrate contrast-enhanced FIB-SEM tomography of porous battery electrodes via in-situ pore filling at µm depths with platinum, using Gas-Injection System (GIS) electron-induced deposition. This contrast enhancement strategy improved the confidence for pore identification and derived volume fractions, opening the door to precise 3D characterization of battery electrodes, towards their optimization.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104828"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796167","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}
Pub Date : 2026-01-01DOI: 10.1016/j.ensm.2025.104851
Jiangbo Yang , Yan Zhang , Wangzixi Zhang, Jirui Shao, Yiyang Mao, Wei Zhao, Geping Yin, Shuaifeng Lou
TiNb2O7 holds high safety in fast-charging lithium-ion batteries, but suffers from the sluggish electron/ion kinetics and high desolvation energy barrier, especially at low-temperature conditions. Herein, a lanthanide-regulated TiNb2O7 is constructed by optimizing local electronic delocalization to enhance low-temperature dynamics and Li-storage performance. In-depth DFT analysis reveals that the charge modulation of f-orbital can promote electron transfer from Li-EC to the O atoms, allowing for Li+ with a pronounced adsorption tendency to improve desolvation ability. In addition, the delocalization engineering shortens the band gap and decreases the migration barrier, which in turn increases electron diffusion ability, suppresses charge relaxation effects, and boosts low-temperature Li+ transport behavior. In view of this, La0.01-TNO-based cells deliver enhanced specific capacity and stable low-temperature cycle life with 95.24% retention rate after 650 cycles at 3C and −30 °C. Surprisingly, a 6 Ah-level La0.01-TNO||NCM pouch cell still achieves impressive cyclic stability with slight capacity degradation for 2000 cycles and excellent rate performance of 4.59 Ah at 5C and −30 °C, holding great promise for fast-charging and low-temperature applications. Such work opens new avenues for manipulating local electronic structure to achieve fast-charging applications at low-temperature environments.
{"title":"4f-orbital-induced electron delocalization of TiNb2O7 enables low temperature fast-charging Ah-level pouch cell","authors":"Jiangbo Yang , Yan Zhang , Wangzixi Zhang, Jirui Shao, Yiyang Mao, Wei Zhao, Geping Yin, Shuaifeng Lou","doi":"10.1016/j.ensm.2025.104851","DOIUrl":"10.1016/j.ensm.2025.104851","url":null,"abstract":"<div><div>TiNb<sub>2</sub>O<sub>7</sub> holds high safety in fast-charging lithium-ion batteries, but suffers from the sluggish electron/ion kinetics and high desolvation energy barrier, especially at low-temperature conditions. Herein, a lanthanide-regulated TiNb<sub>2</sub>O<sub>7</sub> is constructed by optimizing local electronic delocalization to enhance low-temperature dynamics and Li-storage performance. In-depth DFT analysis reveals that the charge modulation of <em>f</em>-orbital can promote electron transfer from Li-EC to the O atoms, allowing for Li<sup>+</sup> with a pronounced adsorption tendency to improve desolvation ability. In addition, the delocalization engineering shortens the band gap and decreases the migration barrier, which in turn increases electron diffusion ability, suppresses charge relaxation effects, and boosts low-temperature Li<sup>+</sup> transport behavior. In view of this, La<sub>0.01</sub>-TNO-based cells deliver enhanced specific capacity and stable low-temperature cycle life with 95.24% retention rate after 650 cycles at 3C and −30 °C. Surprisingly, a 6 Ah-level La<sub>0.01</sub>-TNO||NCM pouch cell still achieves impressive cyclic stability with slight capacity degradation for 2000 cycles and excellent rate performance of 4.59 Ah at 5C and −30 °C, holding great promise for fast-charging and low-temperature applications. Such work opens new avenues for manipulating local electronic structure to achieve fast-charging applications at low-temperature environments.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104851"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880570","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}
Solid-state batteries represent a pivotal direction for next-generation energy storage due to their superior safety and high energy density. Among various solid electrolytes, poly(ethylene oxide) (PEO)-based composite electrolytes stand out as promising candidates for commercialization, offering excellent interfacial compatibility, processability, and cost-effectiveness. However, their practical application is impeded by intrinsic challenges such as low room-temperature ionic conductivity, limited electrochemical stability, and interfacial degradation. Addressing these issues requires a fundamental understanding of ion transport and interfacial reactions from coupled thermodynamic and kinetic perspectives, which is essential for the rational design of high-performance solid electrolytes. This review systematically examined recent advances and strategic developments in PEO-based composite solid electrolytes through a theoretical lens integrating thermodynamics and kinetics. We critically analyze key scientific issues, including multicomponent interactions, ion transport mechanisms, and electrode-electrolyte interfacial stability. Furthermore, we elaborate on synergistic strategies for enhancing ionic conductivity, mechanical robustness, and electrochemical stability via functional filler design, PEO molecular modification, and multidimensional electrolyte architecture engineering. A “structure–thermo/kinetics–performance” correlation framework is established to provide profound theoretical insights for interpreting existing studies and guiding the design of next-generation solid electrolytes. We also highlight the crucial role of dynamic electrochemical analysis and advanced in-situ characterization techniques in elucidating interfacial evolution mechanisms. Moreover, this review discusses challenges and countermeasures for operation under extreme conditions and explores emerging paradigms such as machine learning-assisted inverse design of electrolytes. Finally, we highlight the transition from empirical exploration to rational design and lifecycle-aware sustainable development, offering perspectives on future pathways toward high-performance all-solid-state batteries.
{"title":"Decoupling and reconstructing multiscale ion transport in PEO-based composite electrolytes via thermodynamics, kinetics, and rational design","authors":"Jiamin Li, Linhui Chang, Jie Liu, Qiangchao Sun, Xionggang Lu, Hongwei Cheng","doi":"10.1016/j.ensm.2026.104887","DOIUrl":"10.1016/j.ensm.2026.104887","url":null,"abstract":"<div><div>Solid-state batteries represent a pivotal direction for next-generation energy storage due to their superior safety and high energy density. Among various solid electrolytes, poly(ethylene oxide) (PEO)-based composite electrolytes stand out as promising candidates for commercialization, offering excellent interfacial compatibility, processability, and cost-effectiveness. However, their practical application is impeded by intrinsic challenges such as low room-temperature ionic conductivity, limited electrochemical stability, and interfacial degradation. Addressing these issues requires a fundamental understanding of ion transport and interfacial reactions from coupled thermodynamic and kinetic perspectives, which is essential for the rational design of high-performance solid electrolytes. This review systematically examined recent advances and strategic developments in PEO-based composite solid electrolytes through a theoretical lens integrating thermodynamics and kinetics. We critically analyze key scientific issues, including multicomponent interactions, ion transport mechanisms, and electrode-electrolyte interfacial stability. Furthermore, we elaborate on synergistic strategies for enhancing ionic conductivity, mechanical robustness, and electrochemical stability via functional filler design, PEO molecular modification, and multidimensional electrolyte architecture engineering. A “structure–thermo/kinetics–performance” correlation framework is established to provide profound theoretical insights for interpreting existing studies and guiding the design of next-generation solid electrolytes. We also highlight the crucial role of dynamic electrochemical analysis and advanced in-situ characterization techniques in elucidating interfacial evolution mechanisms. Moreover, this review discusses challenges and countermeasures for operation under extreme conditions and explores emerging paradigms such as machine learning-assisted inverse design of electrolytes. Finally, we highlight the transition from empirical exploration to rational design and lifecycle-aware sustainable development, offering perspectives on future pathways toward high-performance all-solid-state batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104887"},"PeriodicalIF":20.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920538","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号