Mechanochemistry in Sodium Thioantimonate Solid Electrolytes: Effects on Structure, Morphology, and Electrochemical Performance

Sodium thioantimonate (Na3SbS4) and its W-substituted analogue Na2.88Sb0.88W0.12S4 have been identified as potential electrolyte materials for all-solid-state sodium batteries due to their high Na+ conductivity. Ball milling mechanochemistry is a frequently employed synthetic approach to produce such Na+-conductive solid solutions; however, changes in the structure and morphology introduced in these systems via the mechanochemistry process are poorly understood. Herein, we combined X-ray absorption fine structure spectroscopy, Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy characterization techniques to provide an in-depth analysis of these solid electrolytes. We report unique changes seen in the structure and morphology of Na3SbS4 and Na2.88Sb0.88W0.12S4 resulting from ball milling, inducing changes in the electrochemical performance of the solid-state batteries. Specifically, we observed a tetragonal-to-cubic crystal phase transition within Na3SbS4 following the ball mill, resulting in an increase in Na+ conductivity. In contrast, the Na+ conductivity was reduced in mechanochemically treated Na2.88Sb0.88W0.12S4 due to the formation and accumulation of a WS2 phase. In addition, mechanochemical treatment alters the surface morphology of densified Na2.88Sb0.88W0.12S4 pellets, providing intimate contact at the solid electrolyte/Na interface. This phenomenon was not observed in Na3SbS4. This work reveals the structural and morphological origin of the changes seen in these materials' electrochemical performance and how mechanochemical synthesis can introduce them.