In situ XPS investigation of the SEI formed on LGPS and LAGP with metallic lithium

In situ X-ray photoelectron spectroscopy (XPS) techniques have proven to be powerful tools for the characterisation of the solid electrolyte interphase (SEI) formed between the anode and solid electrolyte (SE) in solid-state batteries. XPS offers access to time and operational condition-resolved information on the SEI's chemical composition in the absence of destructive sample preparation. Here we present a Virtual Electrode Plating XPS (VEP-XPS) investigation of the composition and stability of the SEI formed between lithium metal and two different solid electrolytes: Li₁₀GeP₂S₁₂ (LGPS) and Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP). LAGP shows slower SEI formation kinetics, as proven by the emergence of a metallic lithium signal, while LGPS exhibits rapid SEI growth that prevents metallic lithium from plating. We attribute these observations to the SEI composition, distribution and physical properties of secondary decomposition products and in particular to the mixed ion-electron conductive Li₃P which can be observed in LGPS and not in LAGP.