高等学校化学学报

高等学校化学学报

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微纳与晶格结构协同调控构筑高性能水系锌离子电池MnO2正极

杨婷1,宋亚轩1,张晋玉1,冯效玉1,葛玉凤1,景晓霞1,常盼盼2   

  1. 1. 运城学院应用化学系 2. 广西科技大学生物与化学工程学院

  • 收稿日期:2026-01-26 修回日期:2026-04-02 网络首发:2026-04-07 发布日期:2026-04-07
  • 通讯作者: 景晓霞 E-mail:jingxiaoxia@ycu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号：No.21905061)、山西省基础研究计划项目(批准号：No.202403021212304)、优秀博士来晋科研专项(批准号：No.QZX-2023015)、2025年运城市科技计划项目(批准号：No.YCKJYD-202537)和运城学院应用研究计划(批准号：No.YY-202207、QZX-2023015、YQ-2023021)资助

Synergistic Modulation of Nanostructure and Lattice Structure for High-Performance Aqueous Zinc-Ion Battery MnO2 Cathodes

YANG Ting1, SONG Yaxuan1, ZHANG Jinyu1, FENG Xiaoyu1, GE Yufeng1, JING Xiaoxia1*, CHANG Panpan2*   

  1. 1. Department of Applied Chemistry, Yuncheng University 2. School of Biological and Chemical Engineering, Guangxi University of Science and Technology
  • Received:2026-01-26 Revised:2026-04-02 Online First:2026-04-07 Published:2026-04-07
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21905061), the Fundamental Research Program of Shanxi Province, China(No.202403021212304), the Scientific Research Program for PhDs coming to Shanxi Province, China(No.QZX-2023015), the Technology Plan Project of Yuncheng City for 2025, China(No.YCKJYD-202537) and the Applied Research Projects of Yuncheng University, China(Nos. YY-202207, QZX-2023015, YQ-2023021)

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摘要： 针对水系锌离子电池δ-MnO2正极材料存在的反应动力学迟缓、结构不稳定及容量衰减快等问题，提出一种结合Ni2+离子掺杂与纳米结构调控的协同改性策略，成功制备了Ni2+掺杂的δ-MnO2纳米花正极材料（NiMnO2-n）。纳米结构调控使NiMnO2-n具有纳米级片层尺寸和大的比表面积(142 m2·g-1)，能有效缩短离子扩散路径并增加电化学活性位点。同时，Ni2+掺杂进一步减薄纳米片厚度并扩大层间距，在促进H+/Zn2+嵌入/脱出动力学的同时，显著提升了材料的结构稳定性。此外，Ni2+掺杂引入的丰富氧空位可削弱离子插层时的空间位阻，降低离子扩散能垒，从而加速反应动力学。得益于上述结构优势，NiMnO2-n表现出更快的H+和Zn2+扩散特性与嵌入/脱出动力学特性，具备良好的倍率性能和循环稳定性：在1.0 A·g-1电流密度下可提供150.7 mAh·g-1的可逆容量，循环900周后每圈容量衰减率仅为0.040%。机理研究初步证实，NiMnO2-n的储能过程为H?与Zn2?嵌入/脱出和沉积-溶解共存的混合反应机制。

关键词: 水系锌离子电池, 掺杂, 结构调控, 氧空位, 动力学

Abstract: The δ-MnO2 cathode materials in aqueous zinc-ion batteries suffers from sluggish reaction kinetics, structural instability and rapid capacity degradation. To address these issues, this study proposes a synergistic modification strategy combining Ni2+ doping and nanostructure regulation, successfully preparing Ni2+-doped δ-MnO2 nanoflower spheres (NiMnO2-n). Nanostructure regulation endows NiMnO2-n with nanosized sheet structures and a large specific surface area of 142 m2·g-1, effectively shortening ion diffusion paths and increasing electrochemical active sites. Besides, Ni2+ doping further reduces the thickness of nanosheet and expands the interlayer spacing, which not only promotes H+/Zn2+ intercalation/extraction kinetics but also significantly enhances the structural stability of NiMnO2-n. Moreover, the abundant oxygen vacancies introduced by Ni2+ doping weaken the spatial potential resistance for ion intercalation and lower the ion diffusion barrier, thereby accelerating the reaction kinetics. Benefiting from these structural advantages, NiMnO2-n exhibits faster H+ and Zn2+ diffusion characteristics and improved intercalation/extraction kinetics, leading to improved rate capability and cycling stability: it delivers a reversible capacity of 150.7 mAh·g-1 at a current density of 1.0 A·g-1 with a decay as low as 0.040% per cycle over 900 cycles. Mechanistic studies preliminarily confirm that the energy storage process in NiMnO2-n originates from the intercalation/extraction of H+ and Zn2+ and the dissolution-deposition of MnO2.

Key words: Aqueous zinc-ion battery, Doping, Structural regulation, Oxygen vacancy, Kinetics

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