Suppression of Electrochemical and Chemical Degradation of Li10GeP2S12 by an Elastomeric Artificial Solid Electrolyte Interphase

The family of thio-LISICON solid-state electrolytes (SSEs) is one of the most promising material systems for the realization of fully solid state batteries due to comparable performance with liquid electrolyte-based counterparts. Among this SSE family, Li₁₀GeP₂S₁₂ (LGPS) is one of the most promising candidates due to its high theoretical ionic conductivity (1 × 10^–2 S cm^–1). However, the narrow electrochemical and chemical stability windows of LGPS make it unstable in direct contact with both Li metal and conventional transition metal oxide cathode materials, leading to dramatic degradation during battery cycling and even during battery storage prior to battery operation. In this study, we employ an elastomeric artificial solid electrolyte interphase (ASEI) as a protective layer grown directly on Li metal by electrochemically polymerizing 1,3-dioxolane prior to assembling Li/LGPS/Li test cells. This ASEI serves as a Li⁺-conducting interlayer capable of halving the chemical degradation rate as compared to untreated pristine Li at the Li/LGPS interface, while also significantly lowering the absolute impedance and overpotential of Li/LGPS/Li symmetric cells during galvanostatic cycling at 0.1 mA h cm^–2. The elemental composition and spatial structure of this ASEI layer were investigated using X-ray photoelectron spectroscopy and scanning electron microscopy characterization techniques. Density functional theory calculations were performed to understand the impact of the elastomeric ASEI layer on chemical aging at the Li/LGPS interface.