Heavily Tungsten‐Doped Sodium Thioantimonate Solid‐State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion.

A strategy for modifying the structure of solid‐state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W‐doped sodium thioantimonate SSEs, Na2.895W0.3Sb0.7S4 and Na2.7W0.3Sb0.7S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At −15 °C the Na2.895W0.3Sb0.7S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo‐cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na‐ions. An all‐solid‐state battery (ASSB) using Na2.895W0.3Sb0.7S4 as the primary SSE and a sodium sulfide (Na2S) cathode achieves a reversible capacity of 400 mAh g−1. [ABSTRACT FROM AUTHOR]