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

Zhantao Liu; Po Hsiu Chien; Shuo Wang; Shaowei Song; Mu Lu; Shuo Chen; Shuman Xia; Jue Liu; Yifei Mo; Hailong Chen

doi:10.1038/s41557-024-01634-6

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

Zhantao Liu, Po Hsiu Chien, Shuo Wang, Shaowei Song, Mu Lu, Shuo Chen, Shuman Xia, Jue Liu, Yifei Mo, Hailong Chen

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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 Li₃YCl_xBr_6−x and Li₃GdCl₃Br₃ and achieved very high room-temperature conductivities of 6.1 and 11 mS cm⁻¹ for Li₃YCl_4.5Br_1.5 and Li₃GdCl₃Br₃, respectively. These findings open new routes to the design of room-temperature superionic conductors for high-performance solid batteries. (Figure presented.)

Original language	English
Pages (from-to)	1584-1591
Number of pages	8
Journal	Nature Chemistry
Volume	16
Issue number	10
DOIs	https://doi.org/10.1038/s41557-024-01634-6
State	Published - Oct 2024

Funding

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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title = "Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes",

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. (Figure presented.)",

author = "Zhantao Liu and Chien, {Po Hsiu} and Shuo Wang and Shaowei Song and Mu Lu and Shuo Chen and Shuman Xia and Jue Liu and Yifei Mo and Hailong Chen",

note = "Publisher Copyright: {\textcopyright} The Author(s), under exclusive licence to Springer Nature Limited 2024.",

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doi = "10.1038/s41557-024-01634-6",

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AU - Liu, Zhantao

AU - Chien, Po Hsiu

AU - Wang, Shuo

AU - Song, Shaowei

AU - Lu, Mu

AU - Chen, Shuo

AU - Xia, Shuman

AU - Liu, Jue

AU - Mo, Yifei

AU - Chen, Hailong

PY - 2024/10

Y1 - 2024/10

N2 - 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. (Figure presented.)

AB - 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. (Figure presented.)

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

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