Designing highly conductive and (electro)chemically stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. This work reports halide nanocomposite solid electrolytes (HNSES) ZrO2(-ACI)-A2ZrCl6 (A = Li or Na) exhibiting improved ionic conductivities at 30 °C and improved compatibility with sulfide solid electrolytes. The mechanochemical synthesis method creates nanostructured networks that enhance interfacial superionic conduction, attributed to interfacial oxygen-substituted compounds. A fluorinated HNSE shows improved high-voltage stability and interfacial compatibility with Li9PS5Cl and layered lithium transition metal oxide positive electrodes. A Li-In||LiNi0.88Co0.11Mn0.01O2 all-solid-state cell demonstrates a specific discharge of 115 mAh g−1 after nearly 2000 cycles at 400 mA g−1.

Hiram Kwak, Jae-Seung Kim, Daseul Han, Jong Seok Kim, Juhyoun Park, Gihan Kwon, Seong-Min Bak, Unseon Heo, Changhyun Park, Hyun-Wook Lee, Kyung-Wan Nam, Dong-Hwa Seo, Yoon Seok Jung