Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide
- 26 March 2012
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (14), 6096-6099
- https://doi.org/10.1021/ja300868e
Abstract
A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric lithium cobalt oxide LiCo(III)O2 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.Keywords
This publication has 15 references indexed in Scilit:
- Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical31P and7Li Solid-State NMR Study of Paramagnetic Fe(III) PhosphatesJournal of the American Chemical Society, 2010
- Anisotropic Surface Effect on Electronic Structures and Electrochemical Properties of LiCoO2The Journal of Physical Chemistry C, 2009
- Tailoring the Morphology of LiCoO2: A First Principles StudyChemistry of Materials, 2009
- Surface Properties of LiCoO2 Investigated by XPS Analyses and Theoretical CalculationsThe Journal of Physical Chemistry C, 2009
- Molten Salt Synthesis and High Rate Performance of the “Desert‐Rose” form of LiCoO2Advanced Materials, 2008
- Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO2 to CoO2 Investigated by XPSChemistry of Materials, 2007
- Nanosize Effect on High-Rate Li-Ion Intercalation in LiCoO2 ElectrodeJournal of the American Chemical Society, 2007
- Understanding the NMR shifts in paramagnetic transition metal oxides using density functional theory calculationsPhysical Review B, 2003
- Oxygen Vacancies and Intermediate Spin Trivalent Cobalt Ions in Lithium-Overstoichiometric LiCoO2Chemistry of Materials, 2002
- Layered Lithium Insertion Material of LiCo1/3Ni1/3Mn1/3O2 for Lithium-Ion BatteriesChemistry Letters, 2001