LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries.

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl3-based Na+ superionic conductor (Na1-xZrxLa1-xCl4) with high ionic conductivity of 2.9 × 10-4 S cm-1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na2Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P63/m) of Na1-xZrxLa1-xCl4, with Na+ ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na1-xZrxLa1-xCl4 is mainly determined by the size of Na+-channels and the Na+/La3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO2||Na0.7Zr0.3La0.7Cl4||Na3PS4||Na2Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g-1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g-1 can be maintained at 1 C current density.