Thermodynamics and Kinetics of the Cathode–Electrolyte Interface in All-Solid-State Li–S Batteries

[Image: see text] Lithium–sulfur batteries (LSBs) are among the most promising energy storage technologies due to the low cost and high abundance of S. However, the issue of polysulfide shuttling with its corresponding capacity fading is a major impediment to its commercialization. Replacing traditional liquid electrolytes with solid-state electrolytes (SEs) is a potential solution. Here, we present a comprehensive study of the thermodynamics and kinetics of the cathode–electrolyte interface in all-solid-state LSBs using density functional theory based calculations and a machine learning interatomic potential. We find that among the major solid electrolyte chemistries (oxides, sulfides, nitrides, and halides), sulfide SEs are generally predicted to be the most stable against the S(8) cathode, while the other SE chemistries are predicted to be highly electrochemically unstable. If the use of other SE chemistries is desired for other reasons, several binary and ternary sulfides (e.g., LiAlS(2), Sc(2)S(3), Y(2)S(3)) are predicted to be excellent buffer layers. Finally, an accurate moment tensor potential to study the S(8)|β-Li(3)PS(4) interface was developed using an active learning approach. Molecular dynamics (MD) simulations of large interface models (>1000s atoms) revealed that the most stable Li(3)PS(4)(100) surface tends to form interfaces with S(8) with 2D channels and lower activation barriers for Li diffusion. These results provide critical new insights into the cathode–electrolyte interface design for next-generation all-solid-state LSBs.