Redox Mechanisms upon the Lithiation of Wadsley–Roth Phases

The Wadsley-Roth family of transition metal oxide phases are a promising class of anode materials for Li-ion batteries due to their open crystal structures and their ability to intercalate Li at high rates. Unfortunately, most early transition metal oxides that adopt a Wadsley-Roth crystal structure intercalate Li at voltages that are too high for most battery applications. First-principles electronic structure calculations are performed to elucidate redox mechanisms in Wadsley-Roth phases with the aim of determining how they depend on crystal structure. A comparative study of two very distinct polymorphs of Nb₂O₅ reveal two redox mechanisms: (i) an atom-centered redox mechanism at early stages of Li intercalation and (ii) a redox mechanism at intermediate to high Li concentrations involving the bonding orbitals of metal-metal dimers formed by edge-sharing Nb cations. Our study motivates several design principles to guide the development of new Wadsley-Roth phases with superior electrochemical properties.