Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling
Authors: Zhenxiang Cheng
Ningyan Cheng
Xiaobo Zhu
Yi Du
Hiroki Fujii
Tongen Lin
Kiyoshi Ozawa
Lianzhou Wang
Bruce Cowie
Yuxiang Hu
Tobias U Schülli
Xiaowei Yang
Qinfen Gu
Si Zhou
Journal: Nature Communications (2022)
Discipline: Multidisciplinary
Keywords: Transition metal dissolution; cathode active material; Li-based batteries; epitaxial method; atomic wetting layer
Affiliations: Nanomaterials Centre, School of Chemical Engineering, and Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD, 4072, Australia., Nanomaterials Centre, School of Chemical Engineering, and Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD, 4072, Australia. ., Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian, 116024, China., Australian Institute for Innovative Materials (AIIM), University of Wollongong, Squires Way, North Wollongong, NSW, 2500, Australia., National Institute for Materials Science, 1-2-1 Sengen, Tsukuba-city, Ibaraki, 305-0047, Japan., Australian Synchrotron, 800 Blackburn Road, Clayton, VIC, 3168, Australia.

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 LiNi0.5Mn1.5O4 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. 

Retracted: No

PubPeer comments:
 For supplementary Figure 23, duplicated curves were observed for the C1 XPS of LNMO and LNMO-C05La. Can the author clarify it? ![file] , 
 We really appreciate the reader for pointing this error out, and our sincere apologies for the delayed response, as we were just aware of this issue lately. We have double checked our previous record and acknowledge that we have accidently presented the above Supplementary Figure 23 in the Supplementary Information, in which the two XPS spectra of C1s were mistakenly duplicated. We have contacted the Nature Communication Editorial office to provide the corrected XPS spectra of C1s and to make a correction note. Many thanks for your attention. Xiaobo Zhu, on behalf of the authors ,