水系多价金属离子(Mⁿ⁺ (n为金属(M)离子的价态，n ≥ 2))电池兼具低成本、高安全与高容量，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，本文系统凝练了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离子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 (三维多孔还原氧化石墨烯气凝胶限域型VN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H₂O分子适度解离，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H₂O由潜在的副反应来源转变为可调控的储能反应参与者，为理解其快充行为提供了区别于传统离子嵌入/脱出与赝电容机制的新视角。(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，有效抑制界面过高质子活性与副反应，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，更需要构建“金属离子-H₂O分子-电极界面”协同调控的新型储能化学体系。

The aqueous multivalent metal-ion (Mⁿ⁺ (n denotes the valence/charge number of metal (M) ion, 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 capacity. 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 (three-dimensional porous reduced graphene oxide (rGO) aerogel confined vanadium nitride (VN) nanocrystals) cathodes, Zn²⁺ can polarize interfacial H₂O 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 transforms H₂O in aqueous batteries from a potential source of parasitic reactions into a tunable participant in energy-storage reactions, thereby providing a new perspective on their fast-charging behavior that differs from the conventional ion intercalation/deintercalation and pseudocapacitive mechanisms. Experimental results demonstrate that the Zn²⁺-VN coordination system achieves the theoretically predicted optimal balance between *OH adsorption and desorption. (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 system involving metal ions, H₂O molecules, and electrode interfaces.