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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.
Authors:
 [1] ;  [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [2] ;  [2] ;  [2] ; ORCiD logo [1]
  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
Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 16; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
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
Language:
English
Subject:
25 ENERGY STORAGE; lithium cobalt oxide; lithium-ion battery; materials discovery; migration barrier; overlithiated spinel; overpotential; structural search
OSTI Identifier:
1461501

Kim, Soo, Hegde, Vinay I., Yao, Zhenpeng, Lu, Zhi, Amsler, Maximilian, He, Jiangang, Hao, Shiqiang, Croy, Jason R., Lee, Eungje, Thackeray, Michael M., and Wolverton, Chris. First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry. United States: N. p., Web. doi:10.1021/acsami.8b00394.
Kim, Soo, Hegde, Vinay I., Yao, Zhenpeng, Lu, Zhi, Amsler, Maximilian, He, Jiangang, Hao, Shiqiang, Croy, Jason R., Lee, Eungje, Thackeray, Michael M., & Wolverton, Chris. First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry. United States. doi:10.1021/acsami.8b00394.
Kim, Soo, Hegde, Vinay I., Yao, Zhenpeng, Lu, Zhi, Amsler, Maximilian, He, Jiangang, Hao, Shiqiang, Croy, Jason R., Lee, Eungje, Thackeray, Michael M., and Wolverton, Chris. 2018. "First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry". United States. doi:10.1021/acsami.8b00394.
@article{osti_1461501,
title = {First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry},
author = {Kim, Soo and Hegde, Vinay I. and Yao, Zhenpeng and Lu, Zhi and Amsler, Maximilian and He, Jiangang and Hao, Shiqiang and Croy, Jason R. and Lee, Eungje and Thackeray, Michael M. and Wolverton, Chris},
abstractNote = {Embedding a lithiated cobalt oxide spinel (Li2Co2O4, or LiCoO2) component or a nickel-substituted Li2Co1-xNixO2 analogue in structurally integrated cathodes such as xLi2MnO3.(1-x)LiM'O2 (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 LiCoO2 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-LiCoO2; or Li2Co2O4 (Fd$\overline{3m}$) vs trigonal-layered HT-LiCoO2 (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/LiCoO2 cell for both cubic and trigonal phases of LiCoO2, as well as the migration barrier for lithium diffusion from an octahedral (Oh) site to a tetrahedral site (Td) in Fd$\overline{3m}$ LT-Li1-xCoO2, has been calculated to help understand the complex electrochemical charge/discharge processes. A search of LiCoxM1-xO2 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, LiNi0.8125Co0.1875O2 (Fd$\overline{3m}$), with a composition close to that of commercial, layered LiNi0.8Co0.05Al0.05O2, which may have the potential for exploitation in structurally integrated, layered spinel cathodes for next generation lithium-ion batteries.},
doi = {10.1021/acsami.8b00394},
journal = {ACS Applied Materials and Interfaces},
number = 16,
volume = 10,
place = {United States},
year = {2018},
month = {4}
}