Abstract

Abstract Solid‐state Li batteries using Na + superionic conductor type solid electrolyte attracts wide interest because of its safety and high theoretical energy density. The NASCION type solid electrolyte LAGP (Li 1. 5 Al 0.5 Ge 0.5 P 3 O 12 ) shows favorable conductivity as well as good mechanical strength to prevent Li dendrite penetration. However, the instability of LAGP with Li metal remains a great challenge. In this work, an amorphous Ge thin film is sputtered on an LAGP surface, which can not only suppress the reduction reaction of Ge 4+ and Li, but also produces intimate contact between the Li metal and the LAGP solid electrolyte. The symmetric cell with the Ge‐coated LAGP solid electrolyte shows superior stability and cycle performance for 100 cycles at 0.1 mA cm −2 . A quasi‐solid‐state Li–air battery has also been assembled to further demonstrate this advantage. A stable cycling performance of 30 cycles in ambient air can be obtained. This work helps to achieve a stable and ionic conducting interface in solid‐state Li batteries.