麦立强, 安琴友, 马鑫泉. Zn²⁺介导界面催化储能：水系多价金属离子电池新视角[J]. 金属学报, DOI: 10.11900/0412.1961.2026.00090.

摘要 相关文章 Metrics 全文: PDF(890 KB)   摘要: 水系多价金属离子(Mn+ (n为金属(M)离子的价态，n ³ 2))电池兼具低成本、高安全性与高能量密度，是极具前景的新一代电化学储能体系。然而，酸性水系电解液环境与多价金属离子较大的离子半径，易在循环过程中引发正极结构失效，导致可用于多价金属离子可逆存储的电极材料长期匮乏，严重限制了该体系的发展。针对这一关键瓶颈，本文系统凝练本团队围绕钒基电极材料开展的两项代表性工作，并成功验证了钒基材料在多价电池体系中的应用潜力。(1) 核心经典成果为“Zn2+介导水解离的界面催化储能模型”。在基于VN@rGO (负载在多孔石墨烯气凝胶上的纯氮化钒纳米晶)正极的水系锌离子电池中，Zn2+可极化界面H2O分子并诱导水解离，使生成的*OH (*代表正极表面提供的吸附位点)中间体在钒基界面发生可逆吸附/脱附，从而参与快速电荷存储。该模型将水系电池中的水由潜在副反应来源转化为可调控的储能反应参与者，突破了传统的离子嵌入/脱出和赝电容模型对快充行为的解释。实验结果表明，Zn2+-VN配位体系可实现近乎最优的*OH吸附/脱附平衡，使水系锌离子电池兼具高比容量、长循环寿命与优异快充性能。(2) 具有隧道结构的单斜VO2(B)电极应用于水系锰离子电池，作为上述界面水/质子化学认识的进一步拓展。研究揭示了Mn2+/H+协同嵌入行为及其对电极结构演化的影响，阐明了高质子活性诱导V元素不可逆溶解、进而造成容量衰减的内在机理。在此基础上，提出氢键重构驱动的质子转移调控策略，实现了电极/电解液界面双电层结构的优化，有效抑制界面过度质子活性与副反应，使VO2(B)电极展现出优异的倍率性能与循环稳定性。展望未来，水系多价金属离子电池的发展不仅依赖高容量电极材料的发现，更需要建立“金属离子-H2O分子-电极界面”协同调控的新型储能化学。 关键词 ： 锌离子电池,  锰离子电池,  循环稳定性,  储能机制     Abstract：The aqueous multivalent metal-ion (Mn+ (n ≥ 2)) battery is a promising new generation of electrochemical energy storage systems. This battery has several advantages, such as low cost, high safety, and high energy density. However, the acidic aqueous electrolyte environment and the large ionic radius of multivalent metal ions tend to cause failure of the positive electrode structure during cycling. This failure results in a long-term shortage of electrode materials suitable for the reversible storage of multivalent metal ions, severely restricting the development of this system. To address this key bottleneck, this study systematically examines two representative studies conducted by our research group on vanadium-based electrode materials and successfully verifies them in different battery systems: (1) The core achievement is the “Zn2+-mediated water dissociation interfacial catalytic storage model.” In aqueous zinc-ion batteries using VN@rGO (pure vanadium nitride nanocrystals supported on a porous graphene aerogel) cathodes, Zn2+ can polarize interfacial water molecules and induce water dissociation. This enables the generated *OH (where * denotes adsorption sites on the cathode surface) intermediates to undergo reversible adsorption/desorption on vanadium-based interfaces and participate in fast charge storage. This model converts water from a potential source of side reactions into a controllable participant in energy storage, extending the conventional understanding based on ion intercalation/deintercalation and pseudocapacitive mechanisms. Experimental results show that the Zn2+–VN coordination system achieves a near-optimal *OH adsorption/desorption balance, thereby endowing aqueous zinc-ion batteries with high specific capacity, long cycle life, and excellent fast-charging performance. (2) As an extension of this interfacial water/proton chemistry, monoclinic VO2 nanorod electrodes with tunnel structures are further applied in aqueous manganese-ion batteries to realize efficient Mn2+ storage. This storage efficiency is achieved via a reversible ion intercalation/deintercalation mechanism. Thus, this study reveals the Mn2+/H+ cointercalation behavior and clarifies the intrinsic mechanism of irreversible vanadium dissolution induced by high proton activity. Based on these results, a hydrogen-bond reconfiguration-driven proton-transfer regulation strategy is proposed to optimize the electric double-layer structure at the electrode/electrolyte interface, effectively suppress excessive interfacial proton activity and side reactions, and enable the VO2 electrodes to achieve excellent rate performance and cycling stability. This work indicates that the development of aqueous multivalent metal-ion batteries requires high-capacity electrode materials and coordinated storage chemistry involving metal ions, water molecules, and electrode interfaces. 收稿日期: 2026-03-30      基金资助:国家自然科学基金(No. 52127816); 海南省重点研发项目(No. ZDYF2025GXJS008); 教育部基础学科与交叉学科突破计划(No.JYB2025XDXM408) 服务 把本文推荐给朋友 加入引用管理器 E-mail Alert RSS 作者相关文章 麦立强 安琴友 马鑫泉 44.8K 链接本文: https://www.ams.org.cn/CN/Y0/V/I/0 [1] 陈卫祥;刘伟;陈昀;潘洪革;陈长聘. Ml_(1-x)Ca_x(Ni,Co,Al)_5贮氢合金的电化学性能[J]. 金属学报, 1998, 34(6): 640-644. [2] 杨晓光;雷永泉;张文魁;朱光明;王启东. (Zr,Ti)(V,Mn,Pd,Ni,Fe)_2系贮氢电极合金的循环稳定性[J]. 金属学报, 1996, 32(8): 852-856. Viewed Full text Abstract Cited   Shared      Discussed