Understanding the Onset of Surface Degradation in LiNiO2Cathodes
Li, Xinhao; Wang, Qian; Guo, Haoyue; Artrith, Nong; Urban, Alexander
(2022) ACS Applied Energy Materials, volume 5, issue 5, pp. 5730 - 5741
(Article)
Abstract
Nickel-based layered oxides offer an attractive platform for the development of energy-dense cobalt-free cathodes for lithium-ion batteries but suffer from degradation via oxygen gas release during electrochemical cycling. While such degradation has previously been characterized phenomenologically with experiments, an atomic-scale understanding of the reactions that take place at the cathode
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surface has been lacking. Here, we develop a first-principles methodology for the prediction of the surface reconstructions of intercalation electrode particles as a function of the temperature and state of charge. We report the surface phase diagrams of the LiNiO2 (001) and (104) surfaces and identify surface structures that are likely visited during the first charge and discharge. Our calculations indicate that both surfaces experience oxygen loss during the first charge, resulting in irreversible changes to the surface structures. At the end of charge, the surface Ni atoms migrate into tetrahedral sites, from which they further migrate into Li vacancies during discharge, leading to Li/Ni mixed discharged surface phases. Further, the impact of the temperature and voltage range during cycling on the charge/discharge mechanism is discussed. The present study thus provides insight into the initial stages of cathode surface degradation and lays the foundation for the computational design of cathode materials that are stable against oxygen release.
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Keywords: degradation, density functional theory, Li-ion batteries, LiNiO, surface phase diagrams, Taverne, Chemical Engineering (miscellaneous), Energy Engineering and Power Technology, Electrochemistry, Electrical and Electronic Engineering, Materials Chemistry
ISSN: 2574-0962
Publisher: American Chemical Society
Note: Funding Information: This work was supported by the Alfred P. Sloan Foundation Grant No. G-2020-12650. H.G. acknowledges financial support by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO), Contract No. DE-SC0012704, Advanced Battery Materials Research program (Tien Duong, Program Manager). We acknowledge computing resources from Columbia University’s Shared Research Computing Facility project, which is supported by NIH Research Facility Improvement Grant No. 1G20RR030893-01, and associated funds from the New York State Empire State Development, Division of Science Technology and Innovation (NYSTAR) Contract No. C090171, both awarded April 15, 2010. We thank Joaquin Rodriguez-Lopez, Zheng Li, Alan West, and Jianzhou Qu for helpful discussions. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
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