Spontaneous grain refinement effect of rare earth zinc alloy anodes enables stable zinc batteries

作     者：Manjing Chen Yuxiang Gong Yunxiang Zhao Yexin Song Yan Tang Zhiyuan Zeng Shuquan Liang Peng Zhou Bingan Lu Xiaotan Zhang Jiang Zhou 

作者机构：School of Materials Science&Engineering Hunan Provincial Key Laboratory of Electronic Packaging and Advanced Functional MaterialsCentral South University Institute of Materials Research Tsinghua Shenzhen International Graduate School Tsinghua University Department of Materials Science and Engineering City University of Hong Kong Hunan Provincial Key Defense Laboratory of High Temperature Wear-Resisting Materials and Preparation Technology Hunan University of Science and Technology School of Physics and Electronics Hunan University School of Chemistry and Materials Science University of Science and Technology of China Suzhou Institute for Advanced Research University of Science and Technology of China 

出 版 物：《National Science Review》 (国家科学评论(英文版))

年 卷 期：2024年第07期

页      面：252-262页

核心收录：

学科分类：0808[工学-电气工程] 08[工学] 

基　　金：supported by the National Natural Science Foundation of China (52372252  52202339 and 51932011) 

摘      要：Irreversible interfacial reactions at the anodes pose a significant challenge to the long-term stability and lifespan of zinc（Zn） metal batteries, impeding their practical application as energy storage devices. The plating and stripping behavior of Zn ions on polycrystalline surfaces is inherently influenced by the microscopic structure of Zn anodes, a comprehensive understanding of which is crucial but often overlooked. Herein, commercial Zn foils were remodeled through the incorporation of cerium（Ce）elements via the ‘pinning effect’ during the electrodeposition process. By leveraging the electron-donating effect of Ce atoms segregated at grain boundaries（GBs）, the electronic configuration of Zn is restructured to increase active sites for Zn nucleation. This facilitates continuous nucleation throughout the growth stage,leading to a high-rate instantaneous-progressive composite nucleation model that achieves a spatially uniform distribution of Zn nuclei and induces spontaneous grain refinement. Moreover, the incorporation of Ce elements elevates the site energy of GBs, mitigating detrimental parasitic reactions by enhancing the GB stability. Consequently, the remodeled ZnCe electrode exhibits highly reversible Zn plating/stripping with an accumulated capacity of up to 4.0 Ah cm-2in a Zn symmetric cell over 4000 h without short-circuit behavior. Notably, a ～0.4 Ah Zn||NH4V4O10pouch cell runs over 110 cycles with 83% capacity retention with the high-areal-loading cathode(≈20 mg cm-2). This refining-grains strategy offers new insights into designing dendrite-free metal anodes in rechargeable batteries.