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Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes

Nature Chemistry volume 16, pages 1584–1591 (2024)Cite this article

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Abstract

Halides of the family Li3MX6 (M = Y, In, Sc and so on, X = halogen) are emerging solid electrolyte materials for all-solid-state Li-ion batteries. They show greater chemical stability and wider electrochemical stability windows than existing sulfide solid electrolytes, but have lower room-temperature ionic conductivities. Here we report the discovery that the superionic transition in Li3YCl6 is triggered by the collective motion of anions, as evidenced by synchrotron X-ray and neutron scattering characterizations and ab initio molecular dynamics simulations. Based on this finding, we used a rational design strategy to lower the transition temperature and thus improve the room-temperature ionic conductivity of this family of compounds. We accordingly synthesized Li3YClxBr6−x and Li3GdCl3Br3 and achieved very high room-temperature conductivities of 6.1 and 11 mS cm−1 for Li3YCl4.5Br1.5 and Li3GdCl3Br3, respectively. These findings open new routes to the design of room-temperature superionic conductors for high-performance solid batteries.

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Fig. 1: Crystal structure of LYC.
Fig. 2: Ionic conductivity and Li diffusion paths of LYC visualized by FDMs generated from ND patterns at various temperatures.
Fig. 3: Collective motion of anion ligands and its influence on Li-ion diffusion behaviour.
Fig. 4: AIMD simulations of LYC at different temperatures.
Fig. 5: Activating 2D Li+ diffusion pathways within the a–b plane in Li3YCl6−xBrx.
Fig. 6: Design of Li3GdCl3Br3 as a solid-state electrolyte.

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All of the data that support the findings of this work are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

Z.L. and H.C. acknowledge the financial support from the US National Science Foundation (grant nos. 1706723 and 2108688) and the faculty start-up fund of Georgia Tech. The facilities at the Advanced Photon Source at Argonne National Laboratory were made available through the General User Program, supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (contract no. DE-AC02-06CH11357). Also used in this study was the 28ID-2 XPD beamline of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (contract no. DE-SC0012704). A portion of this research was carried out at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. We thank J. Bai and W. Xu for help with the synchrotron experiments. Z.L. and H.C. thank M. McDowell for help with the low-temperature EIS measurements. M.L. and S.X. acknowledge the support of the National Science Foundation (grant no. NSF-CMMI-1554393). Y.M. acknowledges funding from the US National Science Foundation (award no. 2004837) and access to the computational facilities at the University of Maryland.

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Authors and Affiliations

  1. George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Zhantao Liu, Mu Lu, Shuman Xia & Hailong Chen

  2. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Po-Hsiu Chien & Jue Liu

  3. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Shuo Wang & Yifei Mo

  4. Department of Physics and Texas Center for Superconductivity, University of Houston, Houston, TX, USA

    Shaowei Song & Shuo Chen

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Contributions

Z.L. and H.C. conceived the idea and designed the experiments. Z.L. conducted the synthesis, electrochemical tests and some of the characterizations. P.-H.C. and J.L. performed the ND characterizations and analyses. S.W. performed the computer simulations under the supervision of Y.M. S.S. and S.C. contributed to the processing of the materials. M.L., Z.L. and S.X. performed mechanical property measurements and analyses. Z.L., H.C., J.L. and S.W. wrote the paper. All authors reviewed and revised the paper.

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Correspondence to Jue Liu, Yifei Mo or Hailong Chen.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–25 and Tables 1–16.

Supplementary Video 1

Rocking motion from 100 to 400 K.

Supplementary Video 2

Rocking–breathing motion transition from 400 to 500 K.

Supplementary Video 3

BN1 change under rocking motion from 100 to 400 K.

Supplementary Video 4

BN1 change from rocking motion at 400 K to breathing motion at 500 K.

Supplementary Video 5

BN3 change under rocking motion from 100 to 400 K.

Supplementary Video 6

BN3 change from rocking motion at 400 K to breathing motion at 500 K.

Source data

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Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 5

Statistical source data.

Source Data Fig. 6

Statistical source data.

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Liu, Z., Chien, PH., Wang, S. et al. Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes. Nat. Chem. 16, 1584–1591 (2024). https://doi.org/10.1038/s41557-024-01634-6

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