In order to improve the conductivity of Co3O4, Co3O4/VG/CNT composite microspheres were prepared by facile spray drying method and subsequently plasma-enhanced chemical vapor deposition method. A three-dimensional conductivity network was constructed by vertical graphenes and CNTs distributed throughout the microspheres, the transmission of electrons was greatly promoted, excellent rate performance was realized, and the high average reversible specific capacity of 526 mA h g–1 was still retained at 1000 mA g–1. Besides, thanks to the abundant pores distributed in the whole microspheres, the stress could be greatly released during the repeated charging/discharging processes, long cycling stability could be achieved, and the reversible specific capacity as high as 396 mA h g–1 was retained after 1000 cycles at 800 mA g–1. The preparation of Co3O4/VG/CNT composite microspheres can provide a new idea for high-performance lithium-ion battery anode materials.

Yolk–shell urchin-like porous Co3O4/NiO@C microspheres were synthesized via solvothermal method and annealing treatment. A high reversible capacity of 502.7 mA h g−1 was maintained after 1000 cycles at 5 C, showing the long cycling stability.

The reversible specific capacity of CSHCo3O4@C microspheres was as high as 332.6 mA h g−1 at 10C, which was significantly higher than that of SCo3O4 microspheres (68.7 mA h g−1).

Li4Ti5O12@C/CNT microspheres were prepared by a facile spray drying method, which exhibited long cycling stability (85.45 mA h g−1 after 500 cycles at 500 mA g−1) and excellent rate capability (61.16 mA h g−1 after 10 cycles at 1000 mA g−1).