Ab initio Study on Lithium Anode Interface Instability and Stabilization of Superionic Li3InCl6 and Li6PS5Cl Solid Electrolytes

Abstract: Emerging superionic conductors Li3InCl6 (LIC) and Li6PS5Cl (LPSC) are very promising for solid-state electrolytes (SSEs) in all-solid-state lithium batteries (ASSLBs). However, unstable lithium-anode interfaces in LIC and LPSC have been observed through experiments and ab initio calculations, while the interphases formed in determining interfacial stability remain unclear. In this study, we investigate the ab initio stability of LIC-Li and LPSC-Li interfaces and interphases. Our ab initio calculations revealed that both interfaces are not chemically or electrochemically thermodynamically stable. Interestingly, the LPSC-Li has a stable interphase, but the LIC-Li doesn't. Moreover, the interlayers were systematically evaluated for the LIC-Li and LPSC-Li interfaces, and the desired interlayer materials are clarified for the two interfaces. This ab initio understanding of the interfaces, interphases and interlayers would help the development of a variety of stable interfaces in ASSLBs.