Visualizing the SEI formation between lithium metal and solid-state electrolyte

Abstract

The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li₃PS₄ interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li₃PS₄. This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (∼40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li₃PS₄ interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li₂S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. This information is crucial for better understanding interfacial ion mobility.