Fast Ion Transport Mechanism and Electrochemical Stability of Trivalent Metal Iodide-based Na Superionic Conductors Na 3 XI 6 (X = Sc, Y, La, and In).

The exploration of solid-state sodium superionic conductors with high sodium-ion conductivity, structural and electrochemical stability, and grand interface compatibility has become the key to the next-generation energy storage applications with high energy density and long cycling life. Among them, halide-based compounds exhibit great potential with the higher electronegativity of halogens than that of the sulfur element. In this work, combined with first-principles calculation and ab initio molecular dynamic simulation, the investigation of trivalent metal iodide-based Na superionic conductors C 2/ m -Na 3 XI 6 (X = Sc, Y, La, and In) was conducted, including the fast ion transport mechanism, structural stability, and interface electrochemical compatibility with electrode materials. Along with the tetrahedral-center saddle site-predominant three-dimensional octahedral-tetrahedral-octahedral diffusion network, C 2/ m -Na 3 XI 6 possesses the merits of high Na ionic conductivities of 0.36, 0.35, and 0.20 mS cm -1 for Na 3 ScI 6 , Na 3 YI 6 , and Na 3 LaI 6 , respectively. Benefiting from its structural stabilities, C 2/ m -Na 3 XI 6 exhibits lower interface reaction energy and better electrochemical compatibility in contact with both Na metal and high-voltage poly-anion (fluoro)phosphate cathode materials than those of sulfide-based ones. Our theoretical work provides rational design principles for screening and guiding iodide-based C 2/ m -Na 3 XI 6 (X = Sc, Y, La, and In) as promising Na superionic conductor candidates used in all-solid-state energy storage applications.