界面水解离调控：水系多价金属离子电池新视角

doi:10.11900/0412.1961.2026.00090

金属学报

2026, Vol. 62

Issue (8): 1323-1330 DOI: 10.11900/0412.1961.2026.00090

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界面水解离调控：水系多价金属离子电池新视角

麦立强(

), 安琴友, 马鑫泉

武汉理工大学材料复合新技术全国重点实验室武汉 430070

Interfacial Water Dissociation Regulation: A New Perspective on Aqueous Multivalent Metal-Ion Batteries

MAI Liqiang(

), AN Qinyou, MA Xinquan

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

引用本文:

麦立强, 安琴友, 马鑫泉. 界面水解离调控：水系多价金属离子电池新视角[J]. 金属学报, 2026, 62(8): 1323-1330.
Liqiang MAI, Qinyou AN, Xinquan MA. Interfacial Water Dissociation Regulation: A New Perspective on Aqueous Multivalent Metal-Ion Batteries[J]. Acta Metall Sin, 2026, 62(8): 1323-1330.

全文: PDF(1636 KB) HTML

摘要:

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。

关键词 ：锌离子电池, 锰离子电池, 钒基材料, 储能机制

Abstract：

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.

Key words： zinc-ion battery manganese-ion battery vanadium-based material energy storage mechanism

收稿日期: 2026-03-30

ZTFLH:

TM912.9

基金资助:国家自然科学基金项目(52127816);教育部基础学科与交叉学科突破计划项目(JYB2025XDXM408);海南省重点研发项目(ZDYF2025GXJS008)

通讯作者: 麦立强，mlq518@whut.edu.cn，主要从事新型储能材料与器件研究

Corresponding author: MAI Liqiang, professor, Tel: 13554628578, E-mail: mlq518@whut.edu.cn

作者简介: 麦立强，男，1975年生，教授，博士，英国皇家化学会会士
麦立强，武汉理工大学副校长，二级教授，博士生导师，国家杰出青年科学基金获得者(2014)、教育部长江学者特聘教授(2016)、国家“万人计划”科技创新领军人才(2016)。
长期从事纳米储能材料与器件研究。针对容量衰减机制不明、高能量密度与高功率密度极难兼顾等关键科学难题，提出了电子/离子双连续输运思想，创建了单根纳米线器件电子/离子输运原位表征的普适新模型，建立了“麦-晏”场效应储能理论，突破了储能材料与器件的批量化制备技术，并实现成果转化与应用。

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https://www.ams.org.cn/CN/10.11900/0412.1961.2026.00090 或 https://www.ams.org.cn/CN/Y2026/V62/I8/1323

图1 用于描述水系锌离子电池(AZIBs)的催化模型[16](a) correlation between Imax × capacity (multiplication product of the maximum current (Imax) and corresponding capacity) and the charge-to-radius ratio (q / r) for different metal ions (The red data points and grey region respectively represent 41 selected examples from the top values of AZIBs and 10 selected examples from the top values of other aqueous metal-ion batteries (AMBs))(b) schematic showing Zn2+ polarization-induced water dissociation and reversible *OH adsorption at the electrode surface (Mn+ : M denotes a metal element and n denotes the valence/charge number; δ⁺/δ⁻ denote partial positive and partial negative charges, respectively; S1 and S2 denote the steps of *OH adsorption and desorption, respectively)

图2 Zn2+介导的VN@rGO正极界面*OH存储[16](a) contour plot of water dissociation activity as a function of *OH adsorption energy, comparing different metal ions and cathode materials (ΔG*OH(E) and ΔG*OH(C) are the Gibbs energy changes on the electrode and solvated cations, respectively. The color bar represents the overpotential (η, in volts) for water dissociation in AMBs using different cathode materials. The specific chemical compositions of the 20 cathode materials on the horizontal axis are shown in the box below the plot)(b) volcano plot of the capacity of AMBs under galvanostatic charge-discharge (at a current density of 2000 mA/g based on three-electrode cells) versus the ionic electronegativity of metal ions (The dashed lines represent the volcano trends)(c) comparison of rate performance between water dissociation rendered *OH storage and conventional Zn2+ intercalation (VN@rGO—three-dimensional porous reduced graphene oxide (rGO) aerogel confined vanadium nitride (VN) nanocrystals. MOF—metal-organic-framework)

图3 杂化锰盐电解液的性质[27](a) schematic illustrating the typical formation of hydrogen bond between H2O and ethylene glycol (EG), along with the corresponding hydrogen bond length(b) water evaporative test in different electrolytes and corresponding weight changes

图4 界面吸附机理及双电层调控[27](a) zeta (ζ) potential of VO2 in H2O, pure aqueous electrolytes, and 50%EG electrolyte(b) schematic of the interface adsorption corresponding to Fig.4a(c) schematic of the EDL structure and bulk electrolyte in various electrolytes (left: 50%EG electrolyte, right: pure aqueous electrolyte) and a corresponding mechanism for suppressing V species dissolution (IHP—inner Helmholtz plane, OHP—outer Helmholtz plane)

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