Lithium insertion into Co3O4: A preliminary investigation

Lithium has been inserted into the spinel Co₃O₄ both chemically and electrochemically. During lithiation the tetrahedral A-site Co²⁺ cations are displaced into neighbouring empty octahedral sites: the incoming Li⁺ ions occupy the remaining interstitial octahedra of the spinel structure to produce the partially ordered rocksalt compound LiCo₃O₄. The octahedral B-site cations of the AB₂]X₄ spinel are unperturbed by this reaction: the oxide lattice expands by 8.6%. Lithium analyses and powder X-ray diffraction spectra indicate that further lithiation is possible. However, it is demonstrated that a fast lithiation in excess of LiCo₃O₄ is followed by a slow extrusion of B-site cobalt at 50°C until all the Li on the 8a sites has moved to the octahedral vacancies thus created.