Electronic Spin Transition in Nano-size Stoichiometric Lithium Cobalt Oxide
Author(s)
Qian, Danna
Hinuma, Yoyo
Chen, Hailong
Du, Lin-Shu
Carroll, Kyler J.
Ceder, Gerbrand
Grey, Clare P.
Meng, Ying Shirley
Alternative Title
Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide
Date Issued
March 2012
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Qian, Danna, Yoyo Hinuma, Hailong Chen, Lin-Shu Du, Kyler J. Carroll, Gerbrand Ceder, Clare P. Grey, and Ying S. Meng. “Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide.” Journal of the American Chemical Society 134, no. 14 (April 11, 2012): 6096-6099.
Version
Author's final manuscript
Abstract
A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric lithium cobalt oxide LiCo(III)O[subscript 2] 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.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/ja300868e
