Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide.

A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric lithium cobalt oxide LiCo(III)O from low-spin to intermediate and high spin is observed for the first time. These surfaces are the ones that are relevant for Li (de)intercalation. From...

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Published in:Journal of the American Chemical Society Vol. 134; no. 14; pp. 6096 - 6100
Main Authors: Qian, Danna, Hinuma, Yoyo, Hailong Chen, Lin-Shu Du, Carroll, Kyler J., Ceder, Gerbrand, Grey, Clare P., Meng, Ying S.
Format: Article
Published: American Chemical Society 4/11/2012
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 4/11/2012
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        atl: Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide.
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        au:
          Qian, Danna
          Hinuma, Yoyo
          Hailong Chen
          Lin-Shu Du
          Carroll, Kyler J.
          Ceder, Gerbrand
          Grey, Clare P.
          Meng, Ying S.
        affil:
          Department of NanoEngineering, University of California San Diego, La Jolla, California 92109, United States
          Department of Materials Science and Engineering, Kyoto University, Kyoto, Kyoto, 606-8501, Japan
          Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02142, United States
          Department of Chemistry, University of New York at Stony Brook, Stony Brook, New York 11794, United States
          Department of Chemistry, Cambridge University, CB2 1EW, U.K.
      su:
        Lithium cobalt oxide
        Electron spin
        Stoichiometry
        Density functionals
        Nanoparticles
        Oxidation-reduction reaction
        Lithium cell electrodes
      sug:
        subj:
          Lithium cobalt oxide
          Electron spin
          Stoichiometry
          Density functionals
          Nanoparticles
          Oxidation-reduction reaction
          Lithium cell electrodes
      ab: A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric lithium cobalt oxide LiCo(III)O from low-spin to intermediate and high spin is observed for the first time. These surfaces are the ones that are relevant for Li (de)intercalation. From density functional theory calculations with a Hubbard U correction, the surface energies of the layered lithium cobalt oxide can be significantly lowered as a consequence of the spin change. The crystal field splitting of Co d orbitals is modified at the surface due to missing Co-O bonds. The electronic spin transition also has a significant impact on Co(III)-Co(IV) redox potential, as revealed by the change in the lithium (de)intercalation voltage profile in a lithium half cell.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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