Enhanced Energy Storage Properties and DFT Investigation of a Zn–Co–Mo Heterojunction Rich in Oxygen Vacancies with Dual Electron Transport Pathways

Petal-like heterojunction materials ZnCo₂O₄/CoMoO₄ with abundant oxygen vacancies are prepared on nickel foam (NF) using modified ionic hybrid thermal calcination technology. Nanoscale ion intermixing between Zn and Mo ions induces oxygen vacancies in the annealing process, thus creating additional electrochemical active sites and enhancing the electrical conductivity. The ZnCo₂O₄/CoMoO₄ conductive network skeleton forms the primary transport pathway for electrons, while the internal electric field of the heterojunction serves as the secondary pathway. ZnCo₂O₄/CoMoO₄ exhibits excellent rate performance and high capacity attributable to its unique double electron transport mode and the effect of oxygen vacancies. The initial discharge capacity at a current of 0.1 A g^-1 is approximately 1774 mAh g^-1, and the reversible capacity remains at 1100 mAh g^-1 after 200 cycles. After a high current of 1 A g^-1, the reversible capacity is observed to remain at approximately 1240 mAh g^-1. The electronic structure, crystal structure, and work function of the heterojunction interface model are then analyzed by density functional theory (DFT). The analysis results indicate that the charge at the ZnCo₂O₄/CoMoO₄ interface is unevenly distributed, which leads to an enhanced degree of electrochemical reaction. The presence of an internal electric field improves the transport efficiency of the carriers. Experimental and theoretical calculations demonstrate that the ZnCo₂O₄/CoMoO₄ anode material designed in this work provides a reference for fabricating transition metal oxide-based lithium-ion batteries.