Partially Reversible Anionic Redox for Lithium-Excess Cobalt Oxides with Cation-Disordered Rocksalt Structure

Abstract

Li-excess electrode materials potentially boost the energy density of Li-ion batteries, but the origin of the instability of anionic redox in cation-disordered rocksalt material is still under debate. In this study, a binary system of Li3NbO4–CoO is targeted as electrode materials for lithium storage applications. In this binary system, stoichiometric LiCo2/3Nb1/3O2 crystallizes into a rocksalt-type structure with partial ordering of Nb ions. Upon increase of the Li3NbO4 fraction, cation ordering is lost, forming a cation-disordered rocksalt structure in Li-excess phases. Although Li-excess Li4/3Co2/9Nb4/9O2 delivers a large reversible capacity as electrode materials, inferior cyclability and large voltage hysteresis for charge/discharge curves are noted. Irreversible structural changes in electrochemical cycles are also evidenced from results of in situ XRD measurements, suggesting that anionic redox is destabilized for Li4/3Co2/9Nb4/9O2. X-ray absorption spectroscopy reveals that partial stabilization of ligand holes as observed in SrCoO3 is achieved for these oxides. Ligand holes are more effectively stabilized for Li7/6Co4/9Nb7/18O2 with less Li-excess and Co-rich composition. Through systematic study of the binary system of Li3NbO4–CoO with different chemical compositions, factors affecting reversibility and irreversibility of anionic redox are further discussed.