A Set of New Promising Solid Chalcogenides for Na‐Ion Batteries: Yield from the Crystal Chemical, Monte‐Carlo and Quantum‐Chemical Calculations

Abstract Free crystal space in more than 600 chalcogenide structures taken out from the ICSD has been theoretically analyzed. As a result, wide voids and channels accessible for Na + ‐ion migration were found in 236 structures. Among them, 165 compounds have not been described in the literature as Na + ‐conducting materials. These materials have been subjected to stepwise quantitative calculations. The bond valence site energy method has enabled the identification of 57 entries as the most promising ion conductors in which the Na + ‐ion migration energy ( E m ) is less than 0.55 eV for 2D or 3D diffusion. The kinetic Monte‐Carlo method has been carried out for these substances; as a result, resulting in nine of the most prospective compounds with Na + ‐ionic conductivity Ϭ≥10 −4 S cm −1 at room temperature were selected, for which the density functional theory calculations have been performed yielding six best candidates. Additionally, a logarithmic relationship was established between the values of E m and the diffusion channel radii as well as a linear relationship between Ϭ and the void radius.