Sulfide-based conductors are one class of the most promising solid electrolytes for next-generation of all-solid-state batteries due to their advantages on high ionic conductivity and favorable mechanical properties of easy densification. Besides new material chemistry to be explored, understanding the pressure effect on structure and property is equally important from both fundamental and practical considerations, as pressure is one way to tune the properties of such solid electrolytes. Here we report the pressure-driven structural evolution and conductivity change of Na₃SbS₄ solid electrolyte through the integration of molecular dynamics (MD) simulation and in-situ experiments. Theoretical calculation predicts that no phase transition happens to tetragonal Na₃SbS₄ under 10 GPa isotopically pressure. Synchrotron X-ray diffraction and Raman results confirm that Na₃SbS₄ keeps stable tetragonal structure but shows anisotropic compressibility along different directions. After pressure release, the ionic conductivity of Na₃SbS₄ increases by four folds to 1.6 mS cm⁻¹, which is resulted from the dramatic decrease of grain boundary resistance.

硫化物基导体具有高离子电导率和易于致密的良好机械性能，是下一代全固态电池最有希望的固体电解质之一。除了要探索的新材料化学外，从基本和实际考虑出发，了解压力对结构和性能的影响同样重要，因为压力是调节此类固体电解质性能的一种方法。在这里，我们通过分子动力学（MD）模拟和原位集成报道了压力驱动的Na ₃ SbS ₄固体电解质的结构演变和电导率变化实验。理论计算预测在10 GPa同位素压力下四方Na ₃ SbS ₄不会发生相变。同步加速器X射线衍射和拉曼结果证实，Na ₃ SbS ₄保持稳定的四方结构，但沿不同方向显示出各向异性可压缩性。压力释放后，Na ₃ SbS ₄的离子电导率增加了四倍，达到1.6 mS cm ^-1，这是由于晶界电阻的急剧降低所致。