Oxychloride Polyanion Clustered Solid‐State Electrolytes via Hydrate‐Assisted Synthesis for All‐Solid‐State Batteries
Guanzhi Wang, Simeng Zhang, Han Wu, Matthew Zheng, Changtai Zhao, Jianwen Liang, Liyu Zhou, Junyi Yue, Xiangzhen Zhu, Yang Xu, Nian Zhang, Tianlu Pang, Jiamin Fu, Weihan Li, Yuanguang Xia, Wen Yin, Xueliang Sun, Xiaona Li
Abstract
Abstract Solid‐state electrolytes (SSEs) play a vital role in the development of high‐energy all‐solid‐state batteries. However, most adopted mechanical ball milling and/or high‐temperature annealing are ineffective approaches for large‐scale synthesis. Herein, a universal and scalable hydrate‐assisted strategy for the synthesis of oxychloride SSEs is developed based on the chemical reaction among alkali chlorides, AlCl 3 , and AlCl 3 ·6H 2 O. The synthesized aluminum‐based oxychloride SSEs possess a high Li + conductivity over 1 mS cm −1 at 30 °C. The final aluminum‐based oxychloride SSEs are structurally heterogeneous with nm‐sized LiCl‐like and LiAlCl 4 crystallites and large amounts of amorphous [Al a O b Cl c ] (2 b + c −3 a )− components. Faster local mobility of Li + ions in amorphous structures is verified and is attributable to weakened Li + ‐X − interactions ensured by the [Al a O b Cl c ] (2 b + c −3 a )− polyanions. The potential applications for this synthesis technique are further demonstrated by kilogram‐scale reactions and synthesis of other oxychloride SSEs including zirconium‐based and tantalum‐based analogs. These findings not only provide a new simple, scalable, and energy‐efficient synthesis route for oxychloride SSEs but also further promote their application in all‐solid‐state batteries.