Amorphous AlOCl Compounds Enabling Nanocrystalline LiCl with Abnormally High Ionic Conductivity

作者：Hui Duan, Changhong Wang, Xusheng Zhang, Jiamin Fu, Weihan Li, Jing Wan, Ruizhi Yu, Min Fan, Fucheng Ren, Shuo Wang, Matthew Zheng, Xiaona Li, Jianwen Liang, Rui Wen, Sen Xin, Yu‐Guo Guo, Xueliang Sun · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c06498 · 被引用次数：93 · 研究领域：Advanced Battery Materials and Technologies、Thermal Expansion and Ionic Conductivity、Advancements in Battery Materials

LiCl is a promising solid electrolyte, providing it possesses high ionic conductivity. Numerous efforts have been made to enhance its ionic conductivity through aliovalent doping. However, aliovalent substitution changes the intrinsic structure of LiCl, compromising its cost-effectiveness and electrochemical stability. Here, we report nanocrystalline LiCl embedded in amorphous AlOCl compounds with a heterogeneous structure to enhance its ionic conductivity. Nanocrystallization enlarges the LiCl unit cell, while amorphization facilitates interfacial ion transport. As a result, the amorphous AlOCl-modified LiCl nanocrystal (AlOCl-nanoLiCl) demonstrates a high ionic conductivity of 1.02 mS cm –1, which is 5 orders of magnitude higher than that of LiCl. Additionally, it exhibits high oxidative stability, low cost ($19.87 US kg –1 ), and low Young’s modulus (2–3 GPa). When AlOCl-nanoLiCl is coupled with Li-rich cathodes (Li 1.17 Mn 0.55 Ni 0.24 Co 0.05 O 2, 4.8 V vs Li + /Li), all-solid-state batteries exhibit remarkable long-term cycling stability (>1000 cycles). This work presents a novel strategy to enhance the ionic conductivity of alkaline chlorides without compromising their intrinsic advantages.