skip to main content


Title: Surface Structure, Morphology, and Stability of Li(Ni 1/3Mn 1/3Co1/3)O 2 Cathode Material

Layered Li(Ni 1-x-yMn xCo y)O 2 (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)O 2 (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 Co 3+ 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 surfacemore » instabilities can be developed.« less
ORCiD logo [1] ;  [2] ;  [3] ; ORCiD logo [3] ;  [4] ;  [2] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
  4. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 15; Journal ID: ISSN 1932-7447
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1379813