DFT plus U Calculations and XAS Study: Further Confirmation of the Presence of CoO5 Square-Based Pyramids with IS-Co3+ in Li-Overstoichiometric LiCoO2

LiCoO2, one of the major positive electrode materials for Li-ion batteries, can be synthesized with excess Li. Previous experimental work suggested the existence of intermediate spin (IS) Co3+ ions in square-based pyramids to account for the defect in this material. We present here a theoretical study based on density functional theory (DFT) calculations together with an X-ray absorption spectroscopy (XAS) experimental study. In the theoretical study, a hypothetical Li4Co2O5 material, where all the Co ions are in pyramids, was initially considered as a model material. Using DFT+U, the intermediate spin state of the Co3+ ions is found stable for U values around 1.5 eV. The crystal and electronic structures are studied in detail, showing that the defect must actually be considered as a pair of such square-based pyramids, and that Co-Co bonding can explain the position of Co in the basal plane. Using a supercell corresponding to more diluted defects (as in the actual material), the calculations show that the IS state is also stabilized. In order to investigate experimentally the change in the electronic structure in the Li-overstoichiometric LiCoO2, we used X-ray absorption near edge structure (XANES) spectroscopy and propose an interpretation of the 0 Kedge spectra based on the DFT+U calculations, that fully supports the presence of pairs of intermediate spin state Co3+ defects in Li-overstoichiometric LiCoO2.