Cobalt oxide (Co3O4) is regarded as the anode material for lithium-ion batteries (LIBs) with great research value owing to its environmental friendliness and exceptional theoretical capacity. However, the low intrinsic conductivity, poor electrochemical kinetics, and unsatisfactory cycling performance severely limit its practical applications in LIBs. The construction of a self-standing electrode with heterostructure by introducing a highly conductive cobalt-based compound is an effective strategy to solve the above issues. Herein, Co3O4/CoP nanoflake arrays (NFAs) with heterostructure are constructed skillfully directly grown on carbon cloth (CC) by in situ phosphorization as an anode for LIBs. Density functional theory simulation results demonstrate that the construction of heterostructure greatly increases the electronic conductivity and Li ion adsorption energy. The Co3O4/CoP NFAs/CC exhibited an extraordinary capacity (1490.7 mA h g‑l at 0.1 A g‑l) and excellent performance at high current density (769.1 mA h g‑l at 2.0 A g‑l), as well as remarkable cyclic stability (451.3 mA h g‑l after 300 cycles with a 58.7% capacity retention rate). The reasonable construction of heterostructure can promote the interfacial ion transport, significantly enhance the adsorption energy of lithium ions, improve the conductivity of Co3O4 electrode material, promote the partial charge transfer throughout the charge and discharge cycles, and enhance the overall electrochemical performance of the material.

The increasing demands of electric vehicles and portable electronics have stimulated enhanced investigations on lithium‐ion batteries (LIBs) with high capacity, increased rate capability, and long cycle stability. Transition metal oxides (TMOs) are regarded as the most promising anode materials for LIBs due to their higher theoretical capacity. However, the low conductivity and poor rate‐capability of the TMOs have seriously restricted their further development in the LIBs. Herein, layered polyhedral cobalt oxide (Co3O4)/cobalt disulifde (CoS2) with heterostructure is directly grown on carbon cloth (CC) via a facile hydrothermal method and one‐step sulfuration process for use as an anode. The heterostructures can effectively enhance the charge transfer capability due to the interfacial effect between Co3O4 and CoS2. Due to the decrease of the diffusion barrier on the nanocrystalline surface, the electrical conductivity of the material is significantly increased, the ionic diffusion resistance is significantly reduced, and the interface electron transfer increases. The Co3O4/CoS2//CC can deliver a high capacity (1545.8 mAh g−1 at 2 A g−1) and outstanding cycling life (493 mAh g−1 after 300 cycles). This method provides a new idea and choice for the application of heterogeneous anode materials for LIBs.