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研究论文

锌阳极的三维ZnO层修饰实现超长循环寿命的水系锌离子电容器

周平凡, 邓玉雪, 黄鹏, 马洪芳, 吴岭, 曲会鑫, 申来法*, 许真铭*, 张校刚*, 佟浩*   

  1. 南京航空航天大学 材料与科学技术学院 江苏省高效储能材料与技术重点实验室 南京 211106
  • 投稿日期:2025-12-05
  • 基金资助:
    项目受到国家自然科学基金(22579085, 22075142); 教育部智能纳米材料与器件重点实验室,中央高校基础研究基金(NJ2024001)的资助.

3D ZnO Layer-Modified Zinc Anodes with Ultra-Long Cycle Life in Aqueous Zinc-Ion Capacitors

Pingfan Zhou, Yuxue Deng, Peng Huang, Hongfang Ma, Ling Wu, Huixin Qu, Laifa Shen*, Zhenming Xu*, Xiaogang Zhang*, Hao Tong*   

  1. School of Materials and Science and Technology, Nanjing University of Aeronautics and Astronautics, Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, Nanjing 211106
  • Received:2025-12-05
  • Contact: *E-mail: lfshen@nuaa.edu.cn(L.F.Shen); xuzhenming@nuaa.edu.cn(Z.M.Xu); azhangxg@nuaa.edu.cn (X.G. Zhang); tongh@nuaa.edu.cn (H. Tong)
  • Supported by:
    Project supported by National Natural Science Foundation of China (22579085, 22075142); MOE Key Laboratory for Intelligent Nano Materials and Devices, the Fundamental Research Funds for the Central Universities (NJ2024001).

电化学储能技术因其高能效、模块化和环境友好性,已成为新型储能体系研究的重点方向。相比于成本高、安全性差的锂离子电池,水系锌离子电池(ZIBs)因其高安全性、低成本及绿色可持续性,被视为大规模储能的理想候选。然而,锌阳极在长期循环过程中易发生枝晶生长和副反应,导致循环稳定性差与库仑效率低,严重制约了其应用发展。针对上述问题,本研究通过过硫酸铵(APS)处理在锌电极表面构建多孔三维结构ZnO层的简便策略,制备新型APS@Zn电极。所得ZnO层兼具晶态结构的稳定性与非晶态相的高离子扩散特性,可在锌沉积过程中诱导均匀成核,优化电场与浓度分布,有效抑制枝晶生长及副反应的发生。电化学测试结果表明,APS@Zn对称电池在5 mA cm-2、1 mAh cm-2条件下可稳定循环4500 h。该研究通过构建三维多孔ZnO界面层,实现了锌负极界面调控与结构稳定性的协同优化,为高稳定性水系锌离子电池的设计提供了一种简便、可扩展的新思路。

关键词: 锌离子电容器, 锌阳极改性, ZnO, 3D结构, 人工界面层

Electrochemical energy storage technology has emerged as a crucial research focus in the development of advanced energy storage systems, owing to its high energy conversion efficiency, flexible modular design, and environmental benignity. In recent years, the growing demand for large-scale energy storage in renewable energy integration and smart grids has further accelerated research in this field. Compared with conventional lithium-ion batteries, which are constrained by high production costs, limited lithium resources, and potential safety risks associated with flammable organic electrolytes, aqueous zinc-ion capacitors (ZICs) have attracted considerable attention as promising alternatives for large-scale energy storage applications. This advantage mainly stems from the intrinsic merits of zinc metal anodes, including high theoretical capacity, low redox potential, natural abundance, low cost, and excellent safety when operated in aqueous electrolytes.Despite these advantages, the practical application of ZIBs is still severely restricted by the intrinsic challenges associated with zinc metal anodes. During repeated zinc plating/stripping processes, non-uniform Zn deposition tends to occur, leading to the formation of zinc dendrites. Meanwhile, unavoidable side reactions such as hydrogen evolution, corrosion, and by-product formation further deteriorate the anode surface and electrolyte environment. These issues collectively result in rapid capacity decay, poor cycling stability, and low Coulombic efficiency, ultimately impeding the long-term reliability and commercial viability of aqueous zinc-ion batteries. In order to solve the above problems, this study proposed a zinc electrode (APS@Zn) strategy to construct a compact three-dimensional ZnO layer by ammonium persulfate (APS) treatment. The method is simple and controllable, and the dense ZnO layer formed can not only effectively regulate the nucleation behavior of Zn2+, inhibit dendrite growth and side reactions, but also significantly improve ion transport kinetics and cycle reversibility, and realize uniform electroplating and stripping of zinc. Therefore, APS@Zn electrode shows better electrochemical performance than bare zinc electrode. The assembled symmetrical battery can be stably cycled for 4500 h under the conditions of 5 mA cm-2 and 1 mA cm-2, and can still run stably for 1800 h even under the high current density of 20 mA cm-2 and 0.5 mA cm-2. The zinc ion capacitor paired with active carbon anode can be stably cycled for more than 40000 cycles under the condition of 2 A g-1. It can be seen that the three-dimensional porous compact ZnO layer formed by APS treatment not only effectively improves the stability and reversibility of the electrode, but also makes the battery show higher and more stable specific capacity.

Key words: Zinc-ion capacitors, Zinc anode modification, ZnO, 3D Structure, Solid Electrolyte Interphase(SEI)