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Abstract To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl 3 -based Na + superionic conductor (Na 1 − x Zr x La 1 − x Cl 4 ) with high ionic conductivity of 2.9 × 10 −4 S cm −1 (30 °C), good compressibility and high oxidative potential (3.80 V vs . Na 2 Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure ( P6 3 /m ) of Na 1 − x Zr x La 1 − x Cl 4 , 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 Na 1 − x Zr x La 1 − x Cl 4 is mainly determined by the size of Na + -channels and the Na + /La 3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO 2 ||Na 0.7 Zr 0.3 La 0.7 Cl 4 ||Na 3 PS 4 ||Na 2 Sn 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.
Fu et al. (Tue,) studied this question.