Unlocking Li superionic conductivity in face-centred cubic oxides via face-sharing configurations

Yu Chen; Zhengyan Lun; Xinye Zhao; Krishna Prasad Koirala; Linze Li; Yingzhi Sun; Christopher A O'Keefe; Xiaochen Yang; Zijian Cai; Chongmin Wang; Huiwen Ji; Clare P Grey; Bin Ouyang; Gerbrand Ceder

doi:10.1038/s41563-024-01800-8

Unlocking Li superionic conductivity in face-centred cubic oxides via face-sharing configurations

Nat Mater. 2024 Apr;23(4):535-542. doi: 10.1038/s41563-024-01800-8. Epub 2024 Feb 2.

Authors

Yu Chen^{1

2}, Zhengyan Lun^{3

4}, Xinye Zhao^{1

2}, Krishna Prasad Koirala⁵, Linze Li⁶, Yingzhi Sun^{1

2}, Christopher A O'Keefe³, Xiaochen Yang^{1

2}, Zijian Cai^{1

2}, Chongmin Wang⁶, Huiwen Ji⁷, Clare P Grey⁸, Bin Ouyang⁹, Gerbrand Ceder^{10

11}

Affiliations

¹ Department of Materials Science and Engineering, University of California, Berkeley, CA, USA.
² Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
³ Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, UK.
⁴ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, China.
⁵ Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, USA.
⁶ Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA.
⁷ Department of Materials Science and Engineering, University of Utah, Salt Lake City, UT, USA. [email protected].
⁸ Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, UK. [email protected].
⁹ Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA. [email protected].
¹⁰ Department of Materials Science and Engineering, University of California, Berkeley, CA, USA. [email protected].
¹¹ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. [email protected].

Abstract

Oxides with a face-centred cubic (fcc) anion sublattice are generally not considered as solid-state electrolytes as the structural framework is thought to be unfavourable for lithium (Li) superionic conduction. Here we demonstrate Li superionic conductivity in fcc-type oxides in which face-sharing Li configurations have been created through cation over-stoichiometry in rocksalt-type lattices via excess Li. We find that the face-sharing Li configurations create a novel spinel with unconventional stoichiometry and raise the energy of Li, thereby promoting fast Li-ion conduction. The over-stoichiometric Li-In-Sn-O compound exhibits a total Li superionic conductivity of 3.38 × 10^-4 S cm^-1 at room temperature with a low migration barrier of 255 meV. Our work unlocks the potential of designing Li superionic conductors in a prototypical structural framework with vast chemical flexibility, providing fertile ground for discovering new solid-state electrolytes.

Abstract

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