The electrochemical properties of Co3O4 as a lithium-ion battery electrode: a first-principles study.

Extensive first principles calculations were performed to study the structural and electrochemical features of Co3O4 during its lithiation process as an anode material for lithium-ion batteries (LIBs). We found that with up to 8 mol Li in Co3O4, the formed LinCo3O4 structures are stable for low Li concentrations of n ≤ 1, but obvious structure distortions and volume expansions occur for LinCo3O4 with n > 1. This may be the reason why Co3O4 has a high Li capability but low cycling life as a LIB anode. The ab initio molecular dynamics simulations for LinCo3O4 (n = 2, 4, 8) further suggest a two-step electrochemistry process of Co3O4 → CoO → Co upon the lithiation process. We detected a distorted surface structure as Li atoms react with the Co3O4(110) surface, which also reduces the rate capability of the Co3O4 anode.