Surface Structure, Morphology, and Stability of Li(Ni 1/3Mn 1/3Co 1/3)O 2Cathode Material

Surface Structure, Morphology, and Stability of Li(Ni 1/3Mn 1/3Co 1/3)O 2Cathode Material

TitleSurface Structure, Morphology, and Stability of Li(Ni 1/3Mn 1/3Co 1/3)O 2Cathode Material
Publication TypeJournal Article
Year of Publication2017
AuthorsJuan C Garcia, Javier Bareño, Jianhua Yan, Guoying Chen, Andrew Hauser, Jason R Croy, Hakim Iddir
JournalThe Journal of Physical Chemistry C
Volume121
Issue15
Pagination8290 - 8299
Date Published03/2017
ISSN1932-7447
Abstract

Layered Li(Ni1–xyMnxCoy)O2 (NMC) oxides are promising cathode materials capable of addressing some of the challenges associated with next-generation energy storage devices. In particular, improved energy densities, longer cycle-life, and improved safety characteristics with respect to current technologies are needed. However, sufficient knowledge on the atomic-scale processes governing these metrics in working cells is still lacking. Herein, density functional theory (DFT) is employed to predict the stability of several low-index surfaces of Li(Ni1/3Mn1/3Co1/3)O2 (NMC111) as a function of Li and O chemical potentials. Predicted particle shapes are compared with those of single crystal NMCs synthesized under different conditions. The most stable surfaces for stoichiometric NMC111 are predicted to be the nonpolar (104), the polar (012) and (001), and the reconstructed, polar (110) surfaces. Results indicate that intermediate spin Co3+ ions lower the (104) surface energy. Furthermore, it was found that removing oxygen from the (012) surface was easier than from the (104) surface, suggesting a facet dependence on surface-oxygen vacancy formation. These results give important insights into design criteria for the rational control of synthesis parameters as well as establish a foundation on which future mechanistic studies of NMC surface instabilities can be developed.

DOI10.1021/acs.jpcc.7b00896
Short TitleJ. Phys. Chem. C
Refereed DesignationRefereed