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

Soo Kim, Vinay I. Hegde, Zhenpeng Yao, Zhi Lu, Maximilian Amsler, Jiangang He, Shiqiang Hao, Jason R. Croy, Eungje Lee*, Michael M. Thackeray, Chris Wolverton

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

39 Scopus citations

Abstract

Embedding a lithiated cobalt oxide spinel (Li2Co2O4, or LiCoO2) component or a nickel-substituted LiCo1-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 (Fd3m) vs trigonal-layered HT-LiCoO2 (R3m), respectively) can be explained by a small difference in the free energy between these 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 Fd3m 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 (Fd3m), with a composition close to that of commercial, layered LiNi0.8Co0.15Al0.05O2, which may have the potential for exploitation in structurally integrated, layered spinel cathodes for next-generation lithium-ion batteries.

Original languageEnglish (US)
Pages (from-to)13479-13490
Number of pages12
JournalACS Applied Materials and Interfaces
Volume10
Issue number16
DOIs
StatePublished - Apr 25 2018

Funding

S.K. (conceived and designed project details; performed all the DFT calculations) was supported by Northwestern-Argonne Institute of Science and Engineering (NAISE) and partially supported by the 2016 ECS Edward G. Weston Summer Fellowship from the Electrochemical Society (ECS). V.I.H. (new structural search and stability analysis) was supported by National Science Foundation (NSF, DMR-1309957). Z.Y. (generated prototype structures) and C.W. (planned and supervised all the aspects of the research project) were supported as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (Award No. DE-AC02-06CH11357). Z.L. (generated interfacial structures) and S.H. (phonon calculation) were supported by the Dow Chemical Company. M.A. (generated LiCoO2 polymorphs via MHM) acknowledges support from the Novartis Universitat Basel Excellence Scholarship for Life Sciences and the Swiss National Science Foundation (P300P2-158407 and P300P2-174475). J.H. (collaborated on phonon calculations and performed HSE calculations) acknowledges support via ONR STTR N00014-13-P-1056. Support from the Advanced Batteries Materials Research (BMR) Program, in particular David Howell and Tien Duong, of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged by J.R.C., E.L., and M.M.T. (contributed to the main idea and to the writing of this manuscript). This research was supported in part through the computational resources and staff contributions provided for the Quest high-performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Computational resources from the Swiss National Supercomputing Center in Lugano (project s700), the Extreme Science and Engineering Discovery Environment (XSEDE) (which is supported by National Science Foundation grant number OCI-1053575), the Bridges system at the Pittsburgh Supercomputing Center (PSC) (which is supported by NSF award number ACI-1445606) and the National Energy Research Scientific Computing Center (DOE: DE-AC02-05CH11231) are gratefully acknowledged. All the authors contributed to the data analysis and in writing the manuscript. S.K. (conceived and designed project details; performed all the DFT calculations) was supported by Northwestern-Argonne Institute of Science and Engineering (NAISE) and partially supported by the 2016 ECS Edward G. Weston Summer Fellowship from the Electrochemical Society (ECS). V.I.H. (new structural search and stability analysis) was supported by National Science Foundation (NSF, DMR-1309957). Z.Y. (generated prototype structures) and C.W. (planned and supervised all the aspects of the research project) were supported as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (Award No. DE-AC02-06CH11357). Z.L. (generated interfacial structures) and S.H. (phonon calculation) were supported by the Dow Chemical Company. M.A. (generated LiCoO2 polymorphs via MHM) acknowledges support from the Novartis Universitaẗ Basel Excellence Scholarship for Life Sciences and the Swiss National Science Foundation (P300P2-158407 and P300P2-174475). J.H. (collaborated on phonon calculations and performed HSE calculations) acknowledges support via ONR STTR N00014-13-P-1056. Support from the Advanced Batteries Materials Research (BMR) Program, in particular David Howell and Tien Duong, of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged by J.R.C., E.L., and M.M.T. (contributed to the main idea and to the writing of this manuscript). This research was supported in part through the computational resources and staff contributions provided for the Quest high-performance computing facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Computational resources from the Swiss National Supercomputing Center in Lugano (project s700), the Extreme Science and Engineering Discovery Environment (XSEDE) (which is supported by National Science Foundation grant number OCI-1053575), the Bridges system at the Pittsburgh Supercomputing Center (PSC) (which is supported by NSF award number ACI-1445606), and the National Energy Research Scientific Computing Center (DOE: DE-AC02-05CH11231) are gratefully acknowledged. All the authors contributed to the data analysis and in writing the manuscript.

Keywords

  • lithium cobalt oxide
  • lithium-ion battery
  • materials discovery
  • migration barrier
  • overlithiated spinel
  • overpotential
  • structural search

ASJC Scopus subject areas

  • General Materials Science

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