First-Principles Prediction of the Electrochemical Stability and Reaction Mechanisms of Solid-State Electrolytes

Solid-state batteries have significant advantages over conventional liquid batteries, providing improved safety, design freedom, and potentially reaching higher power and energy densities. The major obstacle in the commercial realization of solid-state batteries is the high resistance at the interfaces. To overcome this bottleneck, it is essential to achieve an in-depth fundamental understanding of the crucial electro- chemical processes at the interface. Conventional electrochemical stability calculations for solid electrolytes, determining the formation energy toward the energetically favorable decomposition products, often underestimate the stability window because kinetics are not included. In this work, we introduce a computational scheme that takes the redox- activity of the solid electrolytes into account in calculating the electrochemical stability, and it in many cases appears to dictate the electrochemical stability. This methodology is applied to
different chemical and structural classes of solid electrolytes, exhibiting excellent agreement with experimentally observed electrochemical stability. In contrast with current perception, the results suggest that the electrochemical stability of solid electrolytes is not always determined by the decomposition products but often originates from the intrinsic stability of the material itself. The processes occurring outside the stability window can lead toward phase separation or solid solution depending on the reaction mechanism of the material. These newly gained insights provide better predictions of the practical voltage ranges and structural stabilities of solid electrolytes, guiding solid-state batteries toward better interfaces and material design.