Structural and Na-ion conduction characteristics of Na3PSxSe4−x

Abstract

The recent discovery of the isostructrual cubic Na₃PS₄ and Na₃PSe₄ as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na₃PS_xSe_4−x. Synthesis of Na₃PS₄ under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na₃PS_xSe_4−x identified a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na₃PS_xSe_4−x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.