Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium Thiophosphates.

We determined the interatomic potentials of the Li-[PS] building block in (LiS)(PS) (LPS) and predicted the Li-ion conductivity (σ) of glass-ceramic LPS from molecular dynamics. The Li-ion conduction characteristics in the crystalline/interfacial/glassy structure were decomposed by considering the structural ordering differences. The superior σ of the glassy LPS could be attributed to the fact that ∼40% of its structure consists of the short-ranged cubic S-sublattice instead of the hexagonally close-packed γ-phase. This glassy LPS has a σ of 4.08 × 10 mS cm, an improvement of ∼100 times relative to that of the γ-phase, which is in agreement with the experiments.