Abstract
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 × 10−4S 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.
| Original language | English |
|---|---|
| Article number | 4315 |
| Journal | Nature Communications |
| Volume | 15 |
| Issue number | 1 |
| DOIs | |
| State | Published - Dec 2024 |
Funding
This study was supported by the National Natural Science Foundation of China (U2330101 to X.F., 52072105 to H.X., 12305368 to W.X. and 22073087 to X.W.), the National Natural Science Foundation for Distinguished Young Scholars (22225301 to X.W.), the Anhui Provincial Natural Science Foundation (2108085J23 to H.X.), the Major Science and Technology Projects in Anhui Province (202203a05020032 to X.F., 2022e03020004 to X.F., 202003a05020014 to H.X. and 2021e03020001 to H.X.), the CAS Project for Young Scientists in Basic Research (YSBR-004 to X.W.), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0450101 to X.W.), the Fundamental Research Funds for the Central Universities (JZ2022HGTB0251 to X.F. and 20720220009 to X.W.). The authors would also thank the Beijing Synchrotron Radiation Facility 1W1B beamline for X-ray Absorption Fine Structure characterization and the Super Computer Center of USTCSCC and SCCAS. This research also used resources of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704 (A.A.). We acknowledge Dr. Nan Wang at Brookhaven National Laboratory for the help in handling samples for the synchrotron measurement.