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; ... Show more Show less
Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide
MetadataShow full item record
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.
DepartmentMassachusetts Institute of Technology. Department of Materials Science and Engineering
Journal of the American Chemical Society
American Chemical Society (ACS)
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.
Author's final manuscript