The resistive nature of decomposing interfaces of solid electrolytes with alkali metal electrodes

Abstract

A crucial ingredient in lithium (Li) and sodium (Na)-ion batteries (LIBs and NIBs) is the electrolyte. The use of Li metal (Na metal) as the anode in liquid electrolyte LIBs (NIBs) is constrained by several issues including thermal runaway, flammability, electrolyte leakage, and limited chemical stability. Considerable effort has been devoted toward the development of solid electrolytes (SEs) and all-solid-state batteries, which are presumed to mitigate some of the issues of Li metal (Na metal) in contact with flammable liquid electrolytes. However, most SEs, such as Li₃PS₄, Li₆PS₅Cl and Na₃PS₄ readily decompose against the highly reducing Li-metal and Na-metal anodes. Using first-principles calculations we elucidate the stability of more than 20 solid‖solid interfaces formed between the decomposition products of Li₃PS₄, Li₆PS₅Cl (and Na₃PS₄) against the Li-metal (Na-metal) electrode. We suggest that the work of adhesion needed to form a heterogenous interface is an important descriptor to quantify the stability of interfaces. Subsequently, we clarify the atomistic origins of the resistance to Li-ion transport at interfaces of the Li-metal anode and selected decomposition products (Li₃P, Li₂S and LiCl) of SEs, via a high-fidelity machine learning potential. Utilising an machine learning potential enables nano-second-long molecular dynamics simulations on ‘large’ interface models (here with 8320 atoms), but with similar accuracy to first-principles approaches. Our simulations demonstrate that the interfaces formed between Li metal and argyrodite (e.g., Li₆PS₅Cl) decomposition products are resistive to Li-ion transport. The implications of this study are important since binary compounds are commonly found in the vicinity of the Li(Na) metal anode upon chemical and/or electrochemical decomposition of ternary and quaternary SEs.