Pub Date : 2026-01-23DOI: 10.1016/j.ensm.2026.104920
Haoran Wei , Hongbin Wang , Lijia Liu , Chufang Chen , Tao Huang , Yang Gu , Hao Guo , Peirou Wang , Shenghua Ye , Xuming Yang , Lianfeng Zou , Jianhong Liu , Biwei Xiao , Qianling Zhang , Jiangtao Hu
Hybrid cathode designed with Ni-rich layered LiNi0.83Mn0.05Co0.12O2 (NMC) single crystals and olivine LiMn0.6Fe0.4PO4 (LMFP) nanoparticles under a controlled ratio was proposed. In contrast to pristine NMC, the optimal hybrid cathode afforded much better performance in rate capability and cycle stability even at high temperatures, which can be attributed to the ion-electron synergistic effect bringing about robust structure and Cathode Electrolyte Interface (CEI) interfaces for NMC single crystals along with free-flowing charge transfer networks for the entire electrode. More interestingly, a unique cathode self-charge (CSC) behavior for an intercrystallite ionic transport between LMFP and NMC was found, where partial Li+ ions transferred preferentially from LMFP to nearby NMC rather than to distant Li metal anode at the end of charge and discharge stages. The CSC behavior can enable a better capacity utilization and dynamic characteristic for LMFP nanoparticles, and also contribute a lot to the enhanced electrochemical/structural stability of NMC single crystals.
{"title":"Ion-electron synergistic effect and cathode self-charge behavior of hybrid cathode","authors":"Haoran Wei , Hongbin Wang , Lijia Liu , Chufang Chen , Tao Huang , Yang Gu , Hao Guo , Peirou Wang , Shenghua Ye , Xuming Yang , Lianfeng Zou , Jianhong Liu , Biwei Xiao , Qianling Zhang , Jiangtao Hu","doi":"10.1016/j.ensm.2026.104920","DOIUrl":"10.1016/j.ensm.2026.104920","url":null,"abstract":"<div><div>Hybrid cathode designed with Ni-rich layered LiNi<sub>0.83</sub>Mn<sub>0.05</sub>Co<sub>0.12</sub>O<sub>2</sub> (NMC) single crystals and olivine LiMn<sub>0.6</sub>Fe<sub>0.4</sub>PO<sub>4</sub> (LMFP) nanoparticles under a controlled ratio was proposed. In contrast to pristine NMC, the optimal hybrid cathode afforded much better performance in rate capability and cycle stability even at high temperatures, which can be attributed to the ion-electron synergistic effect bringing about robust structure and Cathode Electrolyte Interface (CEI) interfaces for NMC single crystals along with free-flowing charge transfer networks for the entire electrode. More interestingly, a unique cathode self-charge (CSC) behavior for an intercrystallite ionic transport between LMFP and NMC was found, where partial Li<sup>+</sup> ions transferred preferentially from LMFP to nearby NMC rather than to distant Li metal anode at the end of charge and discharge stages. The CSC behavior can enable a better capacity utilization and dynamic characteristic for LMFP nanoparticles, and also contribute a lot to the enhanced electrochemical/structural stability of NMC single crystals.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"86 ","pages":"Article 104920"},"PeriodicalIF":20.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034212","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}
Electrolyte additives are essential for enhancing the interfacial stability of Na metal anodes by facilitating the construction of robust solid electrolyte interphases (SEI). However, competition for decomposition between additives and solvents hampers the preferential reduction of additives and diminishes their effectiveness. Herein, we propose an interfacial interaction-driven strategy to selectively regulate the decomposition behavior and maximize the utility of fluoroethylene carbonate (FEC) for constructing a robust NaF-rich SEI for stable sodium-metal batteries (SMBs). An in-situ formed Na3Bi alloy on the Na anode surface exhibits stronger adsorption affinity toward FEC compared to carbonate solvents, leading to FEC enrichment within the electric double layer at the anode surface. Benefiting from the enhanced interfacial interaction, the Na3Bi alloy facilitates preferential reductive decomposition of FEC and maximizes FEC utilization, resulting in a dense, gradient-structured NaF-rich SEI. Furthermore, the sodiophilic Na3Bi alloy effectively homogenizes Na nucleation and enables non-dendritic Na deposition. Importantly, the Na3Bi alloy maintains structural and chemical stability during prolonged cycling, ensuring sustained interfacial regulation. As a result, the modified Na anodes deliver excellent cycling stability in Na||Na symmetric cells. Moreover, the Na||Na3V2(PO4)3 (NVP) cells achieve an ultra-long lifespan exceeding 10,000 cycles at 5 C. The Na||NVP cells with high-loading NVP cathodes (10 mg cm-2) can still stably cycle for over 200 cycles at 1 C. This work reveals the critical role of interfacial engineering in modulating additive decomposition and offers a scalable pathway to enhance the stability of SMBs.
{"title":"Enhanced anode-electrolyte interfacial interaction boosting NaF-rich SEI for stable sodium-metal batteries","authors":"Hui Jiang , Jia Zhu , Minsong Huang , Chuying Ouyang , Zhang-Hui Lu","doi":"10.1016/j.ensm.2026.104919","DOIUrl":"10.1016/j.ensm.2026.104919","url":null,"abstract":"<div><div>Electrolyte additives are essential for enhancing the interfacial stability of Na metal anodes by facilitating the construction of robust solid electrolyte interphases (SEI). However, competition for decomposition between additives and solvents hampers the preferential reduction of additives and diminishes their effectiveness. Herein, we propose an interfacial interaction-driven strategy to selectively regulate the decomposition behavior and maximize the utility of fluoroethylene carbonate (FEC) for constructing a robust NaF-rich SEI for stable sodium-metal batteries (SMBs). An in-situ formed Na<sub>3</sub>Bi alloy on the Na anode surface exhibits stronger adsorption affinity toward FEC compared to carbonate solvents, leading to FEC enrichment within the electric double layer at the anode surface. Benefiting from the enhanced interfacial interaction, the Na<sub>3</sub>Bi alloy facilitates preferential reductive decomposition of FEC and maximizes FEC utilization, resulting in a dense, gradient-structured NaF-rich SEI. Furthermore, the sodiophilic Na<sub>3</sub>Bi alloy effectively homogenizes Na nucleation and enables non-dendritic Na deposition. Importantly, the Na<sub>3</sub>Bi alloy maintains structural and chemical stability during prolonged cycling, ensuring sustained interfacial regulation. As a result, the modified Na anodes deliver excellent cycling stability in Na||Na symmetric cells. Moreover, the Na||Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) cells achieve an ultra-long lifespan exceeding 10,000 cycles at 5 C. The Na||NVP cells with high-loading NVP cathodes (10 mg cm<sup>-2</sup>) can still stably cycle for over 200 cycles at 1 C. This work reveals the critical role of interfacial engineering in modulating additive decomposition and offers a scalable pathway to enhance the stability of SMBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"86 ","pages":"Article 104919"},"PeriodicalIF":20.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033830","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 : 2026-01-20DOI: 10.1016/j.ensm.2026.104917
Shijie Song , Shaowei Wang , Haiping Zhang , Yujing Zhang , Minghua Yang , Xiangdong Zhu , Jie Sun
Sodium-ion batteries (SIBs) are regarded as a promising complement to lithium-ion batteries (LIBs) in future energy-storage systems due to their resource abundance and intrinsic safety. Among various cathodes, sodium iron sulfate has garnered significant attention owing to its compelling combination of the advantages, including high operating voltage, excellent rate performance, long lifespan, high safety, and good adaptability between high and low temperatures. However, the application of sodium iron sulfate is limited by notable challenges such as low electronic conductivity, hygroscopic behavior, and the presence of impurity phases. This review comprehensively summarizes the recent advances in sodium iron sulfate and discusses modification strategies for enhancing electrochemical performance through synthesis process optimization and material design. Combining the strategies of high-voltage sodium-ion battery electrolytes, design principles tailored for NFS cathode materials are proposed. Additionally, a techno-economic evaluation and future prospects of sodium iron sulfate are provided to stimulate further progress in its application for SIBs.
{"title":"Rational design and prospective application of low-cost sodium iron sulfate cathodes for energy-storage sodium-ion battery","authors":"Shijie Song , Shaowei Wang , Haiping Zhang , Yujing Zhang , Minghua Yang , Xiangdong Zhu , Jie Sun","doi":"10.1016/j.ensm.2026.104917","DOIUrl":"10.1016/j.ensm.2026.104917","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) are regarded as a promising complement to lithium-ion batteries (LIBs) in future energy-storage systems due to their resource abundance and intrinsic safety. Among various cathodes, sodium iron sulfate has garnered significant attention owing to its compelling combination of the advantages, including high operating voltage, excellent rate performance, long lifespan, high safety, and good adaptability between high and low temperatures. However, the application of sodium iron sulfate is limited by notable challenges such as low electronic conductivity, hygroscopic behavior, and the presence of impurity phases. This review comprehensively summarizes the recent advances in sodium iron sulfate and discusses modification strategies for enhancing electrochemical performance through synthesis process optimization and material design. Combining the strategies of high-voltage sodium-ion battery electrolytes, design principles tailored for NFS cathode materials are proposed. Additionally, a techno-economic evaluation and future prospects of sodium iron sulfate are provided to stimulate further progress in its application for SIBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"86 ","pages":"Article 104917"},"PeriodicalIF":20.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014751","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 : 2026-01-20DOI: 10.1016/j.ensm.2026.104918
HeXiang Zhang , PeiYi Pan , AnChun Tang , RuiKai Li , BangJun Zhao , ChengYi Hou , ChuBin Wan , XianHe Meng , HuiJun Zhang , XiaoYu Hu , YuTing Wang , MiaoFeng Huang , Xin Ju , Yuan Wu
Na superionic conductor (NASICON)-type cathode materials have attracted considerable attention owing to their robust framework and excellent sodium-ion conductivity. However, these materials still suffer from intrinsic issues such as voltage hysteresis, capacity fading, and Jahn-Teller distortions, which critically hinder their practical applicability. Herein, a rare earth element Ce-doped Na3Mn0.95Ce0.05Ti(PO4)3 (NMCTP) cathode material with reduced intrinsic anti-site defects is designed through local electronic modulation, resulting in suppressed voltage hysteresis and enhanced sodium-ion diffusion. Ce doping, through its highly localized 4f electronic structure, leads to a contraction of the neighboring Mn-O bonds even when the Mn valence state decreases. The strong ionic character of Ce and the suppression of Mn Jahn-Teller distortion collaboratively induce local bonding reconstruction, thereby strengthening the stability of the MnO6 octahedra. Enabled by the Ce-induced electronic structure modulation, NMCTP delivers a high specific capacity of 171.4 mA h g−1 at 0.1C and enhanced cycling stability, with capacity retention improved from ∼50.3 % to ∼73.8 % after 500 cycles at 2 C. This work provides an efficient strategy for suppressing voltage hysteresis and Jahn-Teller distortion through local lattice optimization and electronic structure modulation, advancing the practical application of NASICON-type materials in next-generation energy storage systems.
钠离子超导体（NASICON）型正极材料因其坚固的结构和优异的钠离子导电性而受到广泛关注。然而，这些材料仍然存在固有的问题，如电压滞后、容量衰落和Jahn-Teller畸变，这些问题严重阻碍了它们的实际应用。本文通过局部电子调制，设计了一种稀土元素ce掺杂Na3Mn0.95Ce0.05Ti(PO4)3 （NMCTP）正极材料，减少了本征反位缺陷，从而抑制了电压滞后，增强了钠离子扩散。Ce掺杂通过其高度局域化的4f电子结构，导致相邻的Mn- o键收缩，即使Mn价态降低。Ce的强离子特性和Mn的jhn - teller畸变抑制共同诱导了局部键重建，从而增强了MnO6八面体的稳定性。通过ce诱导的电子结构调制，NMCTP在0.1C时提供了171.4 mA h g−1的高比容量，并增强了循环稳定性，在2 c下循环500次后，容量保持率从~ 50.3%提高到~ 73.8%。这项工作提供了一种有效的策略，通过局部晶格优化和电子结构调制来抑制电压滞后和Jahn-Teller扭曲。推进nasicon型材料在下一代储能系统中的实际应用。
{"title":"Ce-induced optimization of local lattice and electronic structure suppresses voltage hysteresis in Mn-based NASICON cathodes","authors":"HeXiang Zhang , PeiYi Pan , AnChun Tang , RuiKai Li , BangJun Zhao , ChengYi Hou , ChuBin Wan , XianHe Meng , HuiJun Zhang , XiaoYu Hu , YuTing Wang , MiaoFeng Huang , Xin Ju , Yuan Wu","doi":"10.1016/j.ensm.2026.104918","DOIUrl":"10.1016/j.ensm.2026.104918","url":null,"abstract":"<div><div>Na superionic conductor (NASICON)-type cathode materials have attracted considerable attention owing to their robust framework and excellent sodium-ion conductivity. However, these materials still suffer from intrinsic issues such as voltage hysteresis, capacity fading, and Jahn-Teller distortions, which critically hinder their practical applicability. Herein, a rare earth element Ce-doped Na<sub>3</sub>Mn<sub>0.95</sub>Ce<sub>0.05</sub>Ti(PO<sub>4</sub>)<sub>3</sub> (NMCTP) cathode material with reduced intrinsic anti-site defects is designed through local electronic modulation, resulting in suppressed voltage hysteresis and enhanced sodium-ion diffusion. Ce doping, through its highly localized 4f electronic structure, leads to a contraction of the neighboring Mn-O bonds even when the Mn valence state decreases. The strong ionic character of Ce and the suppression of Mn Jahn-Teller distortion collaboratively induce local bonding reconstruction, thereby strengthening the stability of the MnO<sub>6</sub> octahedra. Enabled by the Ce-induced electronic structure modulation, NMCTP delivers a high specific capacity of 171.4 mA h g<sup>−1</sup> at 0.1C and enhanced cycling stability, with capacity retention improved from ∼50.3 % to ∼73.8 % after 500 cycles at 2 C. This work provides an efficient strategy for suppressing voltage hysteresis and Jahn-Teller distortion through local lattice optimization and electronic structure modulation, advancing the practical application of NASICON-type materials in next-generation energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"86 ","pages":"Article 104918"},"PeriodicalIF":20.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005696","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 : 2026-01-19DOI: 10.1016/j.ensm.2026.104914
Xinyu Luo , Haoyu Wang , Mingjun Cen , Tiantian Fang , Shuya Zhang , Rui Yan , Wenchao Peng , Yang Li , Qicheng Zhang , Xiaobin Fan
Rechargeable aqueous zinc-manganese batteries (AZMBs) have received widespread attention as next-generation large-scale energy storage devices. However, there is still some controversy regarding the energy storage mechanism of the cathode materials. The deposition of manganese ions on the cathode is facilitated by the byproduct zinc hydroxide sulfate (ZHS), and both this process and the ion intercalation mechanism contribute substantially to the capacity. Herein, by constructing an alkaline and manganese-free substrate to decouple mechanisms, the capacity fading issues and resolution strategies based on the ZHS-assisted manganese deposition mechanism are comprehensively investigated. An "acid-in-alkali" substrate (AlO-ZnO) was designed with the fundamental principles of using the alkali (ZnO) to assist in manganese deposition and the acid (AlO) to aid in manganese dissolution. Specifically, Brønsted acidic sites (AlO) within the alkaline substrate structure capitalize on the proton self-limiting effect to generate a localized acidic environment at the cathode, in order to inhibit and activate dead Mn for enhanced energy density and cycle life. As a result, long-term cycle stability (2000 cycles with 98% retention) and high-rate performance are achieved. This work provides a new perspective for significantly improving the cycle stability of AZMBs and upgrading the mechanism cognition.
{"title":"\"Acid-in-Alkali\" structure for regulating dynamic evolution of manganese in Zn–Mn batteries","authors":"Xinyu Luo , Haoyu Wang , Mingjun Cen , Tiantian Fang , Shuya Zhang , Rui Yan , Wenchao Peng , Yang Li , Qicheng Zhang , Xiaobin Fan","doi":"10.1016/j.ensm.2026.104914","DOIUrl":"10.1016/j.ensm.2026.104914","url":null,"abstract":"<div><div>Rechargeable aqueous zinc-manganese batteries (AZMBs) have received widespread attention as next-generation large-scale energy storage devices. However, there is still some controversy regarding the energy storage mechanism of the cathode materials. The deposition of manganese ions on the cathode is facilitated by the byproduct zinc hydroxide sulfate (ZHS), and both this process and the ion intercalation mechanism contribute substantially to the capacity. Herein, by constructing an alkaline and manganese-free substrate to decouple mechanisms, the capacity fading issues and resolution strategies based on the ZHS-assisted manganese deposition mechanism are comprehensively investigated. An \"acid-in-alkali\" substrate (AlO-ZnO) was designed with the fundamental principles of using the alkali (ZnO) to assist in manganese deposition and the acid (AlO) to aid in manganese dissolution. Specifically, Brønsted acidic sites (AlO) within the alkaline substrate structure capitalize on the proton self-limiting effect to generate a localized acidic environment at the cathode, in order to inhibit and activate dead Mn for enhanced energy density and cycle life. As a result, long-term cycle stability (2000 cycles with 98% retention) and high-rate performance are achieved. This work provides a new perspective for significantly improving the cycle stability of AZMBs and upgrading the mechanism cognition.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"86 ","pages":"Article 104914"},"PeriodicalIF":20.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995085","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 : 2026-01-19DOI: 10.1016/j.ensm.2026.104913
Bayan Hijjawi, Michel L. Trudeau
Lithium metal batteries (LMBs) have shown significant interest as next-generation energy storage systems due to their ultra-high theoretical specific capacity of 3,860 mAh g−1. However, dendrite growth remains a major obstacle to commercialization, driven by instabilities in the native passivation layer (NPL) and the solid electrolyte interphase (SEI). The NPL, formed by lithium’s reactivity with ambient gases, induces uneven current distributions, while fragile SEIs crack easily, exposing fresh lithium and triggering parasitic reactions.
This review combines experimental and computational approaches to understand and improve these interfacial layers. For the NPL, mechanothermal milling, picosecond laser treatments, vacuum thermal evaporation, and engineered electrodeposition layers have been employed to smooth surfaces and lower resistance. For the SEI, approaches such as artificial SEIs, electrolyte additives, solid-state electrolytes (SSEs), anode modification, and separator engineering enhance stability and suppress dendrite growth. Complementarily, computational methods including density functional theory (DFT), molecular dynamics (MD), ab initio molecular dynamics (AIMD), kinetic Monte Carlo (KMC), and machine learning (ML) provide atomistic insights into interfacial reactions and ion transport.
Together, these experimental and computational approaches provide a unified framework that guides the design of stable interfacial layers and accelerates the safe commercialization of high-energy LMBs.
锂金属电池（lmb）由于具有3860 mAh g−1的超高理论比容量，已成为下一代储能系统的重要组成部分。然而，由于原生钝化层（NPL）和固体电解质间相（SEI）的不稳定性，枝晶生长仍然是商业化的主要障碍。NPL由锂与环境气体的反应性形成，导致电流分布不均匀，而脆弱的sei容易破裂，暴露新鲜的锂并引发寄生反应。本文将结合实验和计算方法来理解和改进这些界面层。对于NPL，机械热铣削、皮秒激光处理、真空热蒸发和工程电沉积层已被用于光滑表面和降低电阻。对于SEI，人工SEI、电解质添加剂、固态电解质（ssi）、阳极改性和分离器工程等方法可以提高稳定性并抑制枝晶生长。此外，包括密度泛函理论（DFT）、分子动力学（MD）、从头算分子动力学（AIMD）、动力学蒙特卡罗（KMC）和机器学习（ML）在内的计算方法提供了对界面反应和离子传输的原子性见解。总之，这些实验和计算方法提供了一个统一的框架，指导稳定界面层的设计，加速高能lmb的安全商业化。
{"title":"Suppressing dendrites in lithium metal anodes: A review of passivation layers and multiscale computational approaches","authors":"Bayan Hijjawi, Michel L. Trudeau","doi":"10.1016/j.ensm.2026.104913","DOIUrl":"10.1016/j.ensm.2026.104913","url":null,"abstract":"<div><div>Lithium metal batteries (LMBs) have shown significant interest as next-generation energy storage systems due to their ultra-high theoretical specific capacity of 3,860 mAh g<sup>−1</sup>. However, dendrite growth remains a major obstacle to commercialization, driven by instabilities in the native passivation layer (NPL) and the solid electrolyte interphase (SEI). The NPL, formed by lithium’s reactivity with ambient gases, induces uneven current distributions, while fragile SEIs crack easily, exposing fresh lithium and triggering parasitic reactions.</div><div>This review combines experimental and computational approaches to understand and improve these interfacial layers. For the NPL, mechanothermal milling, picosecond laser treatments, vacuum thermal evaporation, and engineered electrodeposition layers have been employed to smooth surfaces and lower resistance. For the SEI, approaches such as artificial SEIs, electrolyte additives, solid-state electrolytes (SSEs), anode modification, and separator engineering enhance stability and suppress dendrite growth. Complementarily, computational methods including density functional theory (DFT), molecular dynamics (MD), ab initio molecular dynamics (AIMD), kinetic Monte Carlo (KMC), and machine learning (ML) provide atomistic insights into interfacial reactions and ion transport.</div><div>Together, these experimental and computational approaches provide a unified framework that guides the design of stable interfacial layers and accelerates the safe commercialization of high-energy LMBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"85 ","pages":"Article 104913"},"PeriodicalIF":20.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001565","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 : 2026-01-19DOI: 10.1016/j.ensm.2026.104915
Zewei Hu , Haiying Lu , Liyang Liu , Yunqi Gao , Yuju Qi , Xin Wang , Jiayao Wang , Peng Xie , Chao Han , Weijie Li
Anode-free sodium metal batteries (AFSMBs) hold great promise for high-energy sodium storage but are plagued by unstable interfaces and dendritic sodium growth arising from uneven plating and stripping. Here, we introduce a magnetic–electric dual-field interfacial regulation strategy by engineering a FeCoNiCuSn multicomponent alloy (MA) integrated with a carbon nanotube (CNT) scaffold on commercial aluminum foil (MA@CNT). The interconnected CNT framework provides a three-dimensional conductive network that accommodates volume changes and firmly anchors MA nanoparticles. The Sn component ensures homogeneous Na nucleation, while Cu, Fe, Co, and Ni form multicomponent alloys with Sn to mitigate volume expansion during cycling. More importantly, the magnetic elements (Fe, Co, Ni) create localized magnetic fields that direct Na⁺ flux through Lorentz-force-driven migration, leading to uniform deposition and effective suppression of dendritic growth–an interfacial regulation mechanism unexplored in AFSMBs. Benefiting from these synergistic effects, MA@CNT||Na asymmetric cells deliver stable cycling for over 600 cycles at 1 mA cm–2, and the MA@CNT||Na₃V₂(PO₄)₃ full cells exhibit excellent rate capability and long-term stability. This study establishes magnetic-interface engineering as a powerful strategy to achieve dendrite-free sodium deposition, offering a new paradigm for the design of stable, high-performance anode-free sodium metal batteries.
无阳极金属钠电池（AFSMBs）在高能钠存储方面具有很大的前景，但由于镀层和剥离不均匀而导致界面不稳定和枝状钠生长而受到困扰。本文介绍了一种磁电双场界面调节策略，通过将FeCoNiCuSn多组分合金（MA）与碳纳米管（CNT）支架集成在商用铝箔上（MA@CNT）。相互连接的碳纳米管框架提供了一个三维导电网络，可以适应体积变化并牢固地锚定MA纳米颗粒。Sn成分确保了均匀的Na形核，而Cu、Fe、Co和Ni与Sn形成多组分合金，以减轻循环过程中的体积膨胀。更重要的是，磁性元素（Fe, Co, Ni）产生了局部磁场，引导Na⁺的通量通过洛伦兹力驱动的迁移，导致均匀沉积并有效抑制枝晶生长——这是afsmb中尚未探索的界面调节机制。受益于这些协同效应，MA@CNT||Na不对称电池在1 mA cm-2下提供超过600次的稳定循环，MA@CNT||Na₃V₂（PO₄）₃全电池表现出优异的速率能力和长期稳定性。本研究确立了磁界面工程作为实现无枝晶钠沉积的有力策略，为设计稳定、高性能的无阳极金属钠电池提供了新的范例。
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Pub Date : 2026-01-19DOI: 10.1016/j.ensm.2026.104916
Hee-Jae Ahn , Young-Hoon Kim , Hye-Young Cho , Young-Woon Byeon , Yong-Seok Choi , Tae-Hong Kim , Hyo-Jun Ahn , Jae-Chul Lee
Most alloying-type anodes for Na-ion batteries are fundamentally limited in ultrafast-charging applications due to the formation of Zintl phases: intermetallic compounds with intrinsically high electrical resistivity. This work demonstrates how to overcome this fundamental limitation by employing metal sulfide-based conversion anodes (NiS, CuS, and MnS), which follow a distinct electrochemical pathway that avoids Zintl-phase formation. During cycling in ether-based electrolytes, these sulfides undergo conversion reactions that spontaneously generate highly conductive, in-situ formed metal nanoparticles embedded within a self-assembled three-dimensional nanoporous Na2S matrix. This unique composite structure forms a dual-function architecture that enables both efficient ion diffusion and long-range electron transport, even when using inexpensive microsized sulfide particles. Among the tested materials, NiS exhibits the best performance, delivering a reversible capacity of 600 mAh g–1 at 1C, exceptional cycling stability over 3800 cycles at 10C, and a high-rate capacity of 358 mAh g–1 at 30C. Density functional theory and machine-learning-based molecular dynamics simulations reveal that the strong Ni–S bonding in the intermediate phases suppresses nanoparticle coarsening, resulting in uniformly distributed, nanoscale Ni particles that form an efficient percolation network. These findings establish a new design paradigm for Zintl-free conversion anodes, offering a practical and scalable route toward high-performance, fast-charging Na-ion batteries.
大多数用于钠离子电池的合金型阳极从根本上限制了超快充电应用，因为形成了Zintl相：具有固有高电阻率的金属间化合物。这项工作展示了如何通过使用金属硫化物基转换阳极（NiS， cu和MnS）来克服这一基本限制，这些阳极遵循独特的电化学途径，避免了锌相的形成。在醚基电解质中循环时，这些硫化物发生转化反应，自发地产生高导电性的原位形成的金属纳米颗粒，嵌入在自组装的三维纳米多孔Na2S基质中。这种独特的复合结构形成了一种双重功能结构，即使在使用廉价的微型硫化物颗粒时，也能实现有效的离子扩散和远程电子传输。在所测试的材料中，NiS表现出最好的性能，在1C下可提供600 mAh g-1的可逆容量，在10℃下可提供超过3800次循环的卓越循环稳定性，在30℃下可提供358 mAh g-1的高速率容量。密度泛函理论和基于机器学习的分子动力学模拟表明，中间相的强Ni - s键抑制了纳米颗粒的粗化，导致均匀分布的纳米级Ni颗粒形成有效的渗透网络。这些发现为无锌转换阳极建立了一个新的设计范例，为高性能、快速充电的钠离子电池提供了一条实用且可扩展的途径。
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Pub Date : 2026-01-18DOI: 10.1016/j.ensm.2026.104912
Biao Ran , Mingwei Li , Jin Song , Tianshuo Zhao , Wenqi Tang , Boyi Pang , Huanxin Li , Chao Yang , Jiao Zhang , Chaopeng Fu
Triggering the anionic redox reaction (ARR) of manganese rich cathode materials has become a prevalent strategy for developing low-cost and high-energy sodium-ion batteries. However, the practical implementation of ARR is substantially hindered by irreversible oxygen loss, structural degradation, and continuous voltage decay, which are often associated with weak Mn–O hybridization. Strengthening the Mn–O interaction is therefore crucial to activate and stabilize the lattice oxygen and achieve reversible redox chemistry. To tackle this issue, we design a superlattice cathode with the composition of (Na0.69Li0.01)Mn0.5Ni0.18Fe0.06Li0.06Cu0.05Ti0.15O2 through a high-entropy strategy to optimize the Mn–O orbital interaction. The tailored multi-cation configuration enhances Mn–O hybridization, suppressing cation migration and oxygen release. The inherent superlattice structure further stabilizes the structure through orbital hybridization, as confirmed by spectroscopic and structural analyses. As a result, the cathode delivers a high specific capacity of 164.4 mAh g-1 with an average voltage of 3.54 V, achieving a high practical energy density of 210.4 Wh kg-1 in full cells, and demonstrates exceptional long-term cycling stability. This work highlights the critical role of high entropy-mediated Mn–O hybridization enabling reversible anionic redox chemistry, presenting a transformative design strategy for high-energy and long-life sodium-ion batteries.
触发富锰正极材料的阴离子氧化还原反应（ARR）已成为开发低成本高能量钠离子电池的普遍策略。然而，ARR的实际实施受到不可逆氧损失、结构降解和连续电压衰减的极大阻碍，这些通常与弱Mn-O杂化有关。因此，加强Mn-O相互作用对于激活和稳定晶格氧和实现可逆氧化还原化学至关重要。为了解决这一问题，我们设计了一种由（Na0.69Li0.01）Mn0.5Ni0.18Fe0.06Li0.06Cu0.05Ti0.15O2组成的超晶格阴极，通过高熵策略优化Mn-O轨道相互作用。量身定制的多阳离子结构增强了Mn-O杂化，抑制了阳离子迁移和氧释放。光谱和结构分析证实，固有的超晶格结构通过轨道杂化进一步稳定了结构。因此，阴极提供了164.4 mAh g-1的高比容量，平均电压为3.54 V，在充满电池的情况下实现了210.4 Wh kg-1的高实用能量密度，并表现出出色的长期循环稳定性。这项工作强调了高熵介导的Mn-O杂化在可逆阴离子氧化还原化学中的关键作用，提出了一种高能长寿命钠离子电池的变革性设计策略。
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