UCl 3 -Type Crystalline Oxychloride Electrolytes for All-Solid-State Lithium-Ion Batteries

作者：Junlong Yang, Shiwei Chen, Qiong Yuan, Guangsu Tan, Qinzhe Liu, Shaoyu Yang, Yanxin Deng, Yingbo Zhao, Wei Liu, Yi Yu, Yanming Cui, Jian Wang, Shou‐Hang Bo, Chao Xu · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c11480 · 被引用次数：21 · 研究领域：Advanced Battery Materials and Technologies、Advancements in Battery Materials、Inorganic Chemistry and Materials

Halide solid-state electrolytes are promising for next-generation all-solid-state lithium-ion batteries due to their high ionic conductivity and wide electrochemical windows. While most research focuses on close-packed crystal structures, nonclose-packed frameworks─exemplified by UCl 3 -type structures─offer unique advantages in enhancing lithium-ion transport via reduced diffusion barriers. Here, we report a new family of UCl 3 -type crystalline oxychloride electrolytes, Li 0.388+ x La 0.475 Ta 0.238 Cl 3– x O x (0 ≤ x ≤ 0.388, LLTCO), synthesized via rapid high-energy shake milling. The material with an optimized composition ( x = 0.15) exhibits high ionic conductivity above 2 mS cm –1 at 30 °C, oxidative stability exceeding 5 V vs Li/Li +, and excellent mechanical compressibility. Moreover, the LLTCO-based Li–Li symmetric cells show a long cycle life, indicating their strong capacity to suppress lithium dendrite formation. Spectroscopy analyses reveal the successful incorporation of oxygen, which preferentially substitutes Cl – around Ta 5+ sites without compromising crystallinity, even at a high oxygen content. The oxygen incorporation further promotes the formation of Li environments with fast dynamics, accounting for the enhanced conductivity. All-solid-state batteries utilizing the optimized oxychloride electrolyte in conjunction with Ni-rich cathodes demonstrate enhanced reversible capacities compared to their undoped counterparts. This work highlights the benefits of...