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Title: First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry

Embedding a lithiated cobalt oxide spinel (Li 2Co 2O 4, or LiCoO 2) component or a nickel-substituted Li2Co 1-xNixO 2 analogue in structurally integrated cathodes such as xLi 2MnO 3.(1-x)LiM'O 2 (M' = Ni/Co/Mn) has been recently proposed as an approach to advance the performance of lithium-ion batteries. Here, we first revisit the phase stability and electrochemical performance of LiCoO 2 synthesized at different temperatures using density functional theory calculations. Consistent with previous studies, we find that the occurrence of low- and high-temperature structures (i.e., cubic lithiated spinel LT-LiCoO 2; or Li 2Co 2O 4 (Fd$$\overline{3m}$$) vs trigonal-layered HT-LiCoO 2 (R$$\overline{3m}$$), respectively) can be explained by a small difference in the free energy between these 20 30 40 50 60 70 80 26 two compounds. Additionally, the observed voltage profile of a Li/LiCoO 2 cell for both cubic and trigonal phases of LiCoO 2, as well as the migration barrier for lithium diffusion from an octahedral (O h) site to a tetrahedral site (T d) in Fd$$\overline{3m}$$ LT-Li 1-xCoO 2, has been calculated to help understand the complex electrochemical charge/discharge processes. A search of LiCo xM 1-xO 2 lithiated spinel (M' = Ni or Mn) structures and compositions is conducted to extend the exploration of the chemical space of Li-Co-Mn-Ni-O electrode materials. We predict a new lithiated spinel material, LiNi 0.8125Co 0.1875O 2 (Fd$$\overline{3m}$$), with a composition close to that of commercial, layered LiNi 0.8Co 0.05Al 0.05O 2, which may have the potential for exploitation in structurally integrated, layered spinel cathodes for next generation lithium-ion batteries.
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  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357; OCI-1053575; AC02-05CH11231
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 16; Journal ID: ISSN 1944-8244
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF); Dow Chemical Company; Swiss National Science Foundation (SNSF)
Country of Publication:
United States
25 ENERGY STORAGE; lithium cobalt oxide; lithium-ion battery; materials discovery; migration barrier; overlithiated spinel; overpotential; structural search
OSTI Identifier: