Research on Interfacial Construction and Energy Storage Performance of Polymetallic Heterostructure Based on Zn–Ni 3d Orbital Modulation and DFT Study

In this study, ZnCo2O4 nanosheets and NiCo2O4 nanowires were successfully grown on nickel foam as anode materials for lithium-ion batteries by a low-temperature hydrothermal and immersion method. The nanosheets offered an enlarged electrically active surface area, and the nanowires provided support for the nanosheets, thereby forming a heterojunction interface. The ZnCo2O4/NiCo2O4 heterojunction demonstrated favorable electrochemical performance in electrochemical tests. In terms of its rated performance, the capacity of the composite electrode recovered to 1050 mAh g-1 when the current density ranged from 0.1 to 1 A g-1; its capacity was maintained even when the current density returned to 0.1 A g-1 after 60 cycles. The diffusion coefficient of lithium ions (DLi+) increased due to the reduction of the interfacial contact resistance under the interfacial electric field of the heterostructure, and they were continuously activated during repeated cycles. This further significantly enhanced the electrochemical activity of the electrode. The analysis results based on the density functional theory revealed the hybridization of the 3d orbitals of Ni and Zn and the augmented electronic state occupancy of the orbitals near the Fermi energy level. This process was accompanied by the migration of electrons, leading to a decrease in the band gap. Meanwhile, the Li+ diffusion barrier decreased, and the conductivity of the electrode materials was enhanced.