Na11Sn2PS12: a new solid state sodium superionic conductor

Abstract

We report a new sodium superionic conductor, Na₁₁Sn₂PS₁₂, that crystallizes in an unprecedented three-dimensional structure type and exhibits an ionic conductivity of 1.4 mS cm⁻¹, with a very low activation energy barrier for Na-ion mobility of 0.25 eV. A combination of structural elucidation via single crystal X-ray diffraction and ab initio molecular dynamics simulations show that Na⁺-ion conduction pathways flow through equi-energetic sodium–sulfur octahedra interconnected by partial vacancy cross-over sites in all crystallographic dimensions, providing an understanding of the underlying isotropic 3D fast-ion conduction in this material.