X‐ray Crystal Structure Analysis of Sodium‐Ion Conductivity in 94 Na₃PS₄⋅6 Na₄SiS₄ Glass‐Ceramic Electrolytes

Abstract

Abstract Rietveld analysis of cubic Na 3 PS 4 in the 94 Na 3 PS 4 ⋅6 Na 4 SiS 4 (mol %) glass ceramic indicates that two Na + sites (Na1 and Na2) can be found in cubic Na 3 PS 4 and that the phosphorus atoms in cubic Na 3 PS 4 are partially replaced by silicon in the 94 Na 3 PS 4 ⋅6 Na 4 SiS 4 glass ceramic. The electron‐density distribution of the cubic Na 3 PS 4 structure, obtained by the maximum‐entropy method/Rietveld method, revealed that cubic Na 3 PS 4 contains three‐dimensional Na + conduction pathways along the Na1 and Na2 sites. From the Rietveld analysis, the cubic Na 3 PS 4 in the 94 Na 3 PS 4 ⋅6 Na 4 SiS 4 glass ceramic has a larger site‐occupancy of Na2 than that in the Na 3 PS 4 glass ceramic, which may be responsible for the improvement in Na + conductivity.