Amorphous AlOCl Compounds Enabling Nanocrystalline LiCl with Abnormally High Ionic Conductivity

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_1.17Mn_0.55Ni_0.24Co_0.05O₂, 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.