First‐Principles Design of Na‐ion Superionic Conductors: Interstitial‐Based Na Diffusion in NaCuZrS3.

In recent years all‐solid‐state sodium‐ion batteries (SS‐SIBs) have drawn significant attention due to their potential to be safer and lower cost than lithium‐ion batteries. However, the lack of sodium solid‐state electrolytes with high ionic conductivity has become one of the major challenges. Here, with first‐principles computation we took NaCuZrS3, consisting of earth‐abundant and environmentally benign elements only, as an example to study Na‐ion transport in the post‐perovskite‐like structure and used computation‐guided design to improve its potential as a solid‐state electrolyte. With ab initio molecular dynamics simulation and nudged elastic band calculation, we studied possible diffusion mechanisms in this material and found that Na ion interstitials have a favorable migration barrier of 0.22 eV, which is among the smallest in the literature reported values. Considering the large formation energy of Frenkel defects, we proposed doping strategy to introduce extra Na interstitials in the material. Our study suggests that the post‐perovskite‐like sulfides are worth of exploration for applications in SS‐SIBs. [ABSTRACT FROM AUTHOR]