Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes

Linze Li; Bin Ouyang; Zhengyan Lun; Haoyan Huo; Dongchang Chen; Yuan Yue; Colin Ophus; Wei Tong; Guoying Chen; Gerbrand Ceder; Chongmin Wang

doi:10.1038/s41467-023-43356-2

Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes

Nat Commun. 2023 Nov 17;14(1):7448. doi: 10.1038/s41467-023-43356-2.

Authors

Linze Li^#¹, Bin Ouyang^#^{2

3}, Zhengyan Lun^{4

5}, Haoyan Huo⁴, Dongchang Chen⁶, Yuan Yue⁶, Colin Ophus⁷, Wei Tong⁶, Guoying Chen⁶, Gerbrand Ceder⁸, Chongmin Wang⁹

Affiliations

¹ Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA.
² Department of Materials Science and Engineering, University of California - Berkeley, Berkeley, CA, USA. bouyang@fsu.edu.
³ Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA. bouyang@fsu.edu.
⁴ Department of Materials Science and Engineering, University of California - Berkeley, Berkeley, CA, USA.
⁵ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, China.
⁶ Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁷ National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁸ Department of Materials Science and Engineering, University of California - Berkeley, Berkeley, CA, USA. gceder@berkeley.edu.
⁹ Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA. chongmin.wang@pnnl.gov.

^# Contributed equally.

Abstract

Chemical short-range-order has been widely noticed to dictate the electrochemical properties of Li-excess cation-disordered rocksalt oxides, a class of cathode based on earth abundant elements for next-generation high-energy-density batteries. Existence of short-range-order is normally evidenced by a diffused intensity pattern in reciprocal space, however, derivation of local atomic arrangements of short-range-order in real space is hardly possible. Here, by a combination of aberration-corrected scanning transmission electron microscopy, electron diffraction, and cluster-expansion Monte Carlo simulations, we reveal the short-range-order is a convolution of three basic types: tetrahedron, octahedron, and cube. We discover that short-range-order directly correlates with Li percolation channels, which correspondingly affects Li transport behavior. We further demonstrate that short-range-order can be effectively manipulated by anion doping or post-synthesis thermal treatment, creating new avenues for tailoring the electrochemical properties. Our results provide fundamental insights for decoding the complex relationship between local chemical ordering and properties of crystalline compounds.

Abstract

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