Correlating local structure and migration dynamics in Na/Li dual ion conductor Na5YSi4O12

• 成果类型: Article
• 署名作者: Lou, Chenjie; Liu, Jie; Sun, Xuan; Zhang, Wenda; Xu, Ligang; Luo, Huajie; Chen, Yongjin; Gao, Xiang; Kuang, Xiaojun; Fu, Jipeng; Xu, Jun; Su, Lei; Ma, Jiwei; Tang, Mingxue
• 署名单位: China Jiliang University; Guilin University of Technology; University of Science & Technology Beijing; Nankai University; Nankai University; Tongji University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-12330
• DOI: 10.1073/pnas.2401109121
• 发表日期: 2024-08-13
• 关键词: coordination environments; silicate crystals; nmr; na-23; na; batteries; diffusion; CHALLENGES; parameters; insights

摘要

Na5YSi4O12 (NYSO) is demonstrated as a promising electrolyte with high ionic conductivity and low activation energy for practical use in solid Na-ion batteries. Solid- state NMR was employed to identify the six types of coordination of Na+ ions and migration pathway, which is vital to master working mechanism and enhance performance. The assignment of each sodium site is clearly determined from high- quality 23 Na NMR spectra by the aid of Density Functional Theory calculation. Well- resolved 23 Na exchangespectroscopy and electrochemical tracer exchange spectra provide the first experimental evidence to show the existence of ionic exchange between sodium at Na5 and Nab sites, revealing that Na transport route is possibly along three- dimensional chain of open channel-Na4-open channel. Variable- temperature NMR relaxometry is developed to evaluate Na jump rates and self- diffusion coefficient to probe the sodium- ion dynamics in NYSO. Furthermore, NYSO works well as a dual ion conductor in Na and Li metal batteries with Na3V2(PO4)3 and LiFePO4 as cathodes, respectively.