Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling

Xiaobo Zhu; Tobias U Schülli; Xiaowei Yang; Tongen Lin; Yuxiang Hu; Ningyan Cheng; Hiroki Fujii; Kiyoshi Ozawa; Bruce Cowie; Qinfen Gu; Si Zhou; Zhenxiang Cheng; Yi Du; Lianzhou Wang

doi:10.1038/s41467-022-28963-9

Epitaxial growth of an atom-thin layer on a LiNi_0.5Mn_1.5O₄ cathode for stable Li-ion battery cycling

Nat Commun. 2022 Mar 23;13(1):1565. doi: 10.1038/s41467-022-28963-9.

Authors

Xiaobo Zhu^{1

2}, Tobias U Schülli^{3

4}, Xiaowei Yang⁵, Tongen Lin¹, Yuxiang Hu¹, Ningyan Cheng⁶, Hiroki Fujii⁷, Kiyoshi Ozawa⁷, Bruce Cowie⁸, Qinfen Gu⁸, Si Zhou^{5

6}, Zhenxiang Cheng⁶, Yi Du⁶, Lianzhou Wang⁹

Affiliations

¹ Nanomaterials Centre, School of Chemical Engineering, and Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD, 4072, Australia.
² College of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, 410114, China.
³ Nanomaterials Centre, School of Chemical Engineering, and Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD, 4072, Australia. schulli@esrf.fr.
⁴ ESRF-The European Synchrotron, 38000, Grenoble, France. schulli@esrf.fr.
⁵ Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian, 116024, China.
⁶ Australian Institute for Innovative Materials (AIIM), University of Wollongong, Squires Way, North Wollongong, NSW, 2500, Australia.
⁷ National Institute for Materials Science, 1-2-1 Sengen, Tsukuba-city, Ibaraki, 305-0047, Japan.
⁸ Australian Synchrotron, 800 Blackburn Road, Clayton, VIC, 3168, Australia.
⁹ Nanomaterials Centre, School of Chemical Engineering, and Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD, 4072, Australia. l.wang@uq.edu.au.

Abstract

Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO₃ (TM = Ni, Mn) on a LiNi_0.5Mn_1.5O₄ cathode material. Experimental measurements and theoretical analyses confirm a Stranski-Krastanov growth, where the strained wetting layer forms under thermodynamic equilibrium, and it is self-limited to monoatomic thickness due to the competition between the surface energy and the elastic energy. Being atomically thin and crystallographically connected to the spinel host lattices, the LaTMO₃ wetting layer offers long-term suppression of the transition metal dissolution from the cathode without impacting its dynamics. As a result, the epitaxially-engineered cathode material enables improved cycling stability (a capacity retention of about 77% after 1000 cycles at 290 mA g^-1) when tested in combination with a graphitic carbon anode and a LiPF₆-based non-aqueous electrolyte solution.