锌电池中锰氧化物正极的循环机制：一种基于理论的方法
The cycling mechanism of manganese-oxide cathodes in zinc batteries: A theory-based approach
AI总结：
本文构建结合DFT计算的连续介质全电池模型，阐明近中性硫酸锌电解质中锰氧化物正极的两相循环与主导电荷存储机制，并据实验验证以优化电池性能。
摘要：
锌基电池具有良好的体积能量密度，并与环境友好的水性电解质相容。锌离子电池（ZIBs）依赖类似锂离子电池的Zn²⁺穿梭机制，与锌空气电池相比，可实现更高的往返效率和更好的循环寿命。近中性硫酸锌电解质中的锰氧化物正极是ZIBs最突出的候选材料。研究提出，Zn²⁺嵌入、H⁺嵌入和Mn²⁺溶解均对电荷存储机制有贡献。在放电和充电过程中，可观察到两个不同的相。值得注意的是，在第二放电阶段检测到由pH驱动的碱式硫酸锌沉淀。然而，目前仍缺乏对这些ZIBs两相机制完整且一致的理解。本文提出一个由DFT计算支持的连续介质全电池模型，以研究这些观察结果的意义。将近中性水性电解质的络合物形成反应纳入电池模型，并结合DFT计算，描绘出循环机制的一致图景。研究考察了电解质pH与锰氧化物正极反应机制之间的相互作用，并确定了占主导地位的电荷存储机制。该模型通过电化学循环数据、循环伏安图和原位pH测量得到验证，从而能够分析电池设计和电解质组成对循环的影响，并优化电池性能。
英文摘要：
Zinc-based batteries offer good volumetric energy densities and are compatible with environmentally friendly aqueous electrolytes. Zinc-ion batteries (ZIBs) rely on a lithium-ion-like Zn$^{2+}$-shuttle, which enables higher roundtrip efficiencies and better cycle life than zinc-air batteries. Manganese-oxide cathodes in near-neutral zinc sulfate electrolytes are the most prominent candidates for ZIBs. Zn$^{2+}$-insertion, H$^+$-insertion, and Mn$^{2+}$-dissolution are proposed to contribute to the charge-storage mechanism. During discharge and charge, two distinct phases are observed. Notably, the pH-driven precipitation of zinc-sulfate-hydroxide is detected during the second discharge phase. However, a complete and consistent understanding of the two-phase mechanism of these ZIBs is still missing. This paper presents a continuum full cell model supported by DFT calculations to investigate the implications of these observations. We integrate the complex-formation reactions of near-neutral aqueous electrolytes into the battery model and, in combination with the DFT calculations, draw a consistent picture of the cycling mechanism. We investigate the interplay between electrolyte pH and reaction mechanisms at the manganese-oxide cathodes and identify the dominant charge-storage mechanism. Our model is validated with electrochemical cycling data, cyclic voltammograms, and in-situ pH measurments. This allows us to analyse the influence of cell design and electrolyte composition on cycling and optimize the battery performance.
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