Li‐Ion Transport Mechanisms in Selenide‐Based Solid‐State Electrolytes in Lithium‐Metal Batteries: A Study of Li8SeN2, Li7PSe6, and Li6PSe5X (X = Cl, Br, I)

To achieve high‐energy‐density and safe lithium‐metal batteries (LMBs), solid‐state electrolytes (SSEs) that exhibit fast Li‐ion conductivity and good stability against lithium metal are of great importance. This study presents a systematic exploration of selenide‐based materials as potential SSE candidates. Initially, Li 8 SeN 2 and Li 7 PSe 6 were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal. Subsequently, their favorable electronic insulation and mechanical properties were verified. Furthermore, extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li‐ion migration in Li 8 SeN 2 , Li 7 PSe 6 , and derived Li 6 PSe 5 X (X = Cl, Br, I). Notably, the highly favorable Li‐ion conduction mechanism of vacancy diffusion was identified in Li 6 PSe 5 Cl and Li 7 PSe 6 , which exhibited remarkably low activation energies of 0.21 and 0.23 eV, and conductivity values of 3.85 × 10 −2 and 2.47 × 10 −2 S cm −1 at 300 K, respectively. In contrast, Li‐ion migration in Li 8 SeN 2 was found to occur via a substitution mechanism with a significant diffusion energy barrier, resulting in a high activation energy and low Li‐ion conductivity of 0.54 eV and 3.6 × 10 −6 S cm −1 , respectively. Throughout this study, it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li‐ion conduction mechanisms. Utilizing both methods proved to be efficient, as relying on only one of them would be insufficient. The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.