Solid-state Li batteries require solid electrolytes which have high Li⁺ conductivity and good chemical/mechanical compatibility with Li metal anodes and high energy cathodes. Structure/function correlations which relate local bonding to macroscopic properties are needed to guide development of new solid electrolyte materials. This study combines diffraction measurements with solid-state nuclear magnetic resonance spectroscopy (ssNMR) and neutron pair distribution function (nPDF) analysis to probe the short-range vs. long-range structure of glass-ceramic Li₃PS₄-based solid electrolytes. This work demonstrates how different synthesis conditions (e.g., solvent selection and thermal processing) affect the resulting polyanionic network. More specifically, structures with high P coordination numbers (e.g., PS₄³⁻ and P₂S₇⁴⁻) correlate with higher Li⁺ mobility compared to other polyanions (e.g., (PS₃)_n^n– chains and P₂S₆⁴⁻). Overall, this work demonstrates how ssNMR and nPDF can be used to draw key structure/function correlations for solid-state superionic conductors.

固态锂电池需要具有高 Li ⁺电导率以及与锂金属负极和高能正极具有良好化学/机械相容性的固体电解质。需要将局部键合与宏观性质相关的结构/功能相关性来指导新固体电解质材料的开发。本研究将衍射测量与固态核磁共振光谱 (ssNMR) 和中子对分布函数 (nPDF) 分析相结合，以探测玻璃陶瓷 Li ₃ PS _{4的短程与长程结构}基固体电解质。这项工作展示了不同的合成条件（例如，溶剂选择和热处理）如何影响所得的聚阴离子网络。_{更具体地说，与其他聚阴离子（例如，(PS 3} ) _n ^n-链和 P ₂ S ₆相比，具有高 P 配位数的结构（例如，PS ₄ ^3-和 P ₂ S ₇ ^4-）与更高的 Li ⁺迁移率相关^4- )。总体而言，这项工作展示了如何使用 ssNMR 和 nPDF 绘制固态超离子导体的关键结构/功能相关性。