Effect of anion substitution on the structural and transport properties of argyrodites Cu7PSe6-xSx.Inspired by the good performance of argyrodites as ion conducting thermoelectrics and as solid electrolytes we investigated the effect of isovalent S2- substitution for Se2- in Cu7PSe6.  At room temperature Cu7PSe6 crystallizes in the primitive cubic β-polymorph of the argyrodite structure and transforms to the face-centered high-temperature (HT) γ-modification above 320 K. The transition for the homologous Cu7PS6 occurs at 510 K. Promising thermoelectric and ion conducting properties are observed only in the HT modification, where the cations are mobile. 
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