Abstract

AbstractSolid‐oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air as H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell with a solid–electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, with a lithium‐ion conductivity of σLi=4.8×10−4 S cm−1 at 25 °C that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+‐conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low‐impedance dendrite‐free plating/stripping of a lithium anode. It is also stable upon contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all‐solid‐state Li/LiFePO4 cell, a Li‐S cell with a polymer‐gel cathode, and a supercapacitor.

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