水系锌离子电池硫酸锌电解液添加剂的研究进展
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成都大学 机械工程学院, 四川 成都 610106

作者简介:

胡倚嘉(2002—),男,四川广安人,硕士研究生,主要研究方向为水系锌离子电池电解液。

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TM912

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成都大学人才工程科研启动项目(2081921012)


Progress of zinc sulfate electrolyte additives for aqueous zinc-ion batteries
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School of Mechanical Engineering, Chengdu University, Chengdu 610106 , China

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    摘要:

    水系锌离子电池(AZIBs)因其高比容量、卓越安全性和经济优势成为极具发展潜力的新一代电化学储能装置,但是ZnSO4电解液体系存在电压窗口较窄、离子传输性欠佳、高水活性易诱发锌负极腐蚀钝化及锌枝晶生长等问题,极大阻碍了AZIBs的性能提升及工业化应用。诸多学者采用在ZnSO4电解液中引入添加剂的方式进行改性。在电解液中引入有机添加剂(壳聚糖、D-木糖、四氢糠醇等),是通过构建动态界面保护层、重构溶剂化结构、抑制副反应等机制,有效提升电池循环寿命与离子传输性能,部分改性电池循环次数可达数千小时;在电解液中引入无机添加剂(硫酸氧钒、三磷酸五钾、氯化铕等),是借助离子协同效应、诱导晶体取向生长及原位形成致密SEI层,实现了锌的均匀沉积与电极保护,显著改善了电池的容量与倍率特性;在电解液中引入离子添加剂(十六烷基三甲基硫酸氢铵、碳酸氢铵、水杨酸铵等),是通过静电屏蔽、pH缓冲、优化界面电荷分布等作用,高效抑制锌枝晶生长与析氢反应,拓宽电解液电化学窗口;在电解液中引入聚合物添加剂(聚丙烯酸、聚乙烯亚胺、碳化聚合物等),是通过选择性吸附、调节界面电场、降低去溶剂化势垒等方式,优化电极/电解液界面环境,大幅提升电池的循环稳定性与可逆性。在电解液中引入添加剂的方式针对性地解决了ZnSO4电解液的部分关键问题,但仍然存在各类添加剂作用机制尚未完全明确,单一添加剂难以同时破解电解液所有缺陷等问题,且AZIBs的长期循环稳定性、规模化应用适应性等仍需进一步验证;未来,还需从开发多功能型添加剂(锌沉积调控、双界面钝化、溶剂化结构重构)、复合型添加剂(多组分杂化协同、成分/浓度优化)等方面进行深入研究,来提升AZIBs的性能及推进其工业化应用。

    Abstract:

    Aqueous zinc-ion batteries (AZIBs) have emerged as a promising new generation of electrochemical energy storage devices due to their high specific capacity, excellent safety, and economic advantages. However, the ZnSO4 electrolyte system is plagued by issues such as a narrow voltage window, poor ionic conductivity, high water activity leading to zinc anode corrosion and dendrite growth, which significantly hinders the performance improvement and industrial application of AZIBs. Many researchers have attempted to modify the ZnSO4 electrolyte by introducing additives. The introduction of organic additives (such as chitosan, D-xylose, tetrahydrofurfuryl alcohol, etc.) into the electrolyte can effectively enhance the battery s cycle life and ionic conductivity through mechanisms such as forming a dynamic interface protective layer, reconfiguring the solvation structure, and suppressing side reactions. Some modified batteries can achieve thousands of hours of cycling. The addition of inorganic additives (such as vanadium sulfate, potassium tripolyphosphate, europium chloride, etc.) can achieve uniform zinc deposition and electrode protection by leveraging the ion synergy effect, inducing crystal orientation growth, and in-situ forming a dense SEI layer, significantly improving the battery s capacity and rate performance. The introduction of ionic additives (such as ammonium hexadecyltrimethyl sulfate, ammonium bicarbonate, ammonium salicylate, etc.) can effectively inhibit zinc dendrite growth and hydrogen evolution reactions, and broaden the electrochemical window of the electrolyte through electrostatic shielding, pH buffering, and optimizing the interface charge distribution. The addition of polymer additives (such as polyacrylic acid, polyethyleneimine, carbonized polymers, etc.) can optimize the electrode/electrolyte interface environment through selective adsorption, regulating the interface electric field, and reducing the desolvation barrier, significantly enhancing the battery s cycle stability and reversibility. Although the introduction of additives in the electrolyte has targeted solutions to some key problems of the ZnSO4 electrolyte, there are still issues such as the unclear mechanism of action of various additives and the difficulty of a single additive to simultaneously address all defects of the electrolyte. Moreover, the long-term cycle stability and scalability of AZIBs still need further verification. In the future, in-depth research is needed in areas such as developing multifunctional additives (zinc deposition regulation, dual-interface passivation, solvation structure reconstruction) and composite additives (multi-component hybrid synergy, composition/concentration optimization) to enhance the performance of AZIBs and promote their industrial application.

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胡倚嘉,卢超. 水系锌离子电池硫酸锌电解液添加剂的研究进展[J].中国有色冶金,2025,54(6):80-90.

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  • 收稿日期:2025-08-28
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  • 在线发布日期: 2025-12-26
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