Predicting Wettability and the Electrochemical Window of Lithium-Metal/Solid Electrolyte Interfaces

The development of solid electrolytes (SEs) is expected to enhance the safety of lithium-ion batteries. Additionally, a viable SE could allow the use of a Li-metal negative electrode, which would increase energy density. Recently, several antiperovskites have been reported to exhibit high ionic conductivities, prompting investigations of their use as an SE. In addition to having a suitable conductivity, phenomena at the interface between an SE and an electrode are also of great importance in determining the viability of an SE. For example, interfacial interactions can change the positions of the band edges of the SE, altering its stability against undesirable oxidation or reduction. Furthermore, the wettability of the SE by the metallic anode is desired to enable low interfacial resistance and uniform metal plating and stripping during cycling. The present study probes several properties of the SE/electrode interface at the atomic scale. Adopting the antiperovskite SE Li₃OCl (LOC)/Li-metal anode interface as a model system, the interfacial energy, work of adhesion, wettability, band edge shifts, and the electrochemical window are predicted computationally. The oxygen-terminated interface was determined to be the most thermodynamically stable. Moreover, the large calculated work of adhesion for this system implies that Li will wet LOC, suggesting the possibility for low interfacial resistance. Nevertheless, these strong interfacial interactions come at a cost to electrochemical stability: strong interfacial bonding lowers the energy of the conduction band minimum (CBM) significantly and narrows the local band gap by 30% in the vicinity of the interface. Despite this interface-induced reduction in electrochemical window, the CBM in LOC remains more negative than the Li/Li⁺ redox potential, implying stability against reduction by the anode. In sum, this study illustrates a comprehensive computational approach to assessing electrode/electrolyte interfacial properties in solid-state batteries.