Lithium-Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid-State Batteries

Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6718-6723. doi: 10.1002/anie.202015238. Epub 2021 Feb 1.

Abstract

Owing to high ionic conductivity and good oxidation stability, halide-based solid electrolytes regain interest for application in solid-state batteries. While stability at the cathode interface seems to be given, the stability against the lithium metal anode has not been explored yet. Herein, the formation of a reaction layer between Li3 InCl6 (Li3 YCl6 ) and lithium is studied by sputter deposition of lithium metal and subsequent in situ X-ray photoelectron spectroscopy as well as by impedance spectroscopy. The interface is thermodynamically unstable and results in a continuously growing interphase resistance. Additionally, the interface between Li3 InCl6 and Li6 PS5 Cl is characterized by impedance spectroscopy to discern whether a combined use as cathode electrolyte and separator electrolyte, respectively, might enable long-term stable and low impedance operation. In fact, oxidation stable halide-based lithium superionic conductors cannot be used against Li, but may be promising candidates as cathode electrolytes.

Keywords: electrochemical energy storage; lithium metal anode; solid electrolyte interphase; solid-state batteries; x-ray photoelectron spectroscopy.