Deciphering How Anion Clusters Govern Lithium Conduction in Glassy Thiophosphate Electrolytes through Machine Learning

Glasses such as lithium thiophosphates (Li2S-P2S5) show promise as solid electrolytes for batteries, but a poor understanding of how the disordered structure affects lithium transport properties limits the development of glassy electrolytes. To address this, we here simulate glassy Li2S-P2S5 electrolytes with varying fractions of polyatomic anion clusters, i.e., P2S64-, P2S74-, and PS43-, using classical molecular dynamics. Based on the determined variation in ionic conductivity, we use a classification-based machine-learning metric termed softness -a structural fingerprint that is correlated to the atomic rearrangement probability -to unveil the structural origin of lithium-ion mobility. The softness distribution of lithium ions is highly spatially correlated: that is, the soft (high mobility) lithium ions are predominantly found around PS43- units, while the hard (low mobility) ions are found around P2S64- units. We also show that soft lithium-ion migration requires a smaller energy barrier to be overcome relative to that observed for hard lithium-ion migration.

Automated summary

By simulating glassy Li2S-P2S5 electrolytes with different fractions of polyatomic anion clusters, this study reveals the structural origins of lithium-ion mobility and identifies that soft (high mobility) lithium ions are predominantly found around PS43- units, while hard (low mobility) ions are found around P2S64- units. The soft lithium-ion migration requires a smaller energy barrier to be overcome compared to the hard lithium-ion migration.