Regulating the 4d-band center of Mo atoms in β -Mo 2 C to promote lithium-oxygen reactions

Lithium-air batteries have attracted much attention because of their high energy density. However, the sluggish kinetics of the Li-O reaction leads to high charge/discharge overpotentials and poor reversibility. Therefore, exploring efficient and low-cost cathode catalysts in promoting the Li-O reaction is crucial. Herein, the first principles calculation method, for the first time, is used to study the catalytic performance based on Pt-like β -Mo 2 C by modifying the C sites with B, N, and O. The N modification decreases the d-band center of Mo atoms from 0.11 eV ( β -Mo 2 C) to −0.23 eV, resulting in optimal adsorption energy and charge transfer. In comparison, B and O have a negative effect. The N modification changes the rate-determining step of the entire catalytic process from the decomposition of LiO 2 ( β -Mo 2 C, B- β -Mo 2 C, O- β -Mo 2 C) to the decomposition of Li 2 O 2. The electronic structure and Bader charge analysis show that N-modified β -Mo 2 C has a significantly lower work function than other structures, which increases the charge transfer ability between the catalyst and LiO 2. This work provides a valuable scheme for adjusting the transition metal electronic structure in low-cost MXene for lithium-air batteries.