Abstract
The TiNb2O7 Wadsley-Roth phase is a promising anode material for Li-ion batteries, enabling fast cycling and high capacities. While already used in commercial batteries, many fundamental electronic and thermodynamic properties of LixTiNb2O7 remain poorly understood. We report on an in-depth first-principles study of the redox mechanisms, structural changes, and electrochemical properties of LixTiNb2O7 as a function of Li concentration. First-principles electronic structure calculations reveal an unconventional redox mechanism upon Li insertion that results in the formation of metal-metal bonds. This metal dimer redox mechanism has important structural consequences as it results in a shortening of cation-pair distances, which in turn affects lattice parameters of the host and thereby alters Li site preferences as the Li concentration is varied. The new insights about redox mechanisms in TiNb2O7 and their effect on the structure and Li site preferences provide guidance on how the electrochemical properties of a promising class of anode materials can be tailored by exploiting the tremendous structural and chemical diversity of Wadsley-Roth phases.