Surface Structure, Morphology, and Stability of Li(Ni1/3Mn1/3Co1/3)O2 Cathode Material

Garcia, Juan C.; Bareño, Javier; Yan, Jianhua; Chen, Guoying; Hauser, Andrew; Croy, Jason R.; Iddir, Hakim

doi:10.1021/acs.jpcc.7b00896

Surface Structure, Morphology, and Stability of Li(Ni_1/3Mn_1/3Co1/3)O₂ Cathode Material

Journal Article · Tue Mar 28 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b00896· OSTI ID:1352891

^[1]; Bareño, Javier ^[2]; Yan, Jianhua ^[3]; ^[3]; Hauser, Andrew ^[4]; Croy, Jason R. ^[2]; Iddir, Hakim ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
Univ. of Wisconsin, Madison, WI (United States)

Layered Li(Ni_1-x-yMn_xCo_y)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(Ni_1/3Mn_1/3Co_1/3)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 non-polar (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. In conclusion, 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1352891

Alternate ID(s):: OSTI ID: 1379813

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 15 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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