The design and synthesis of hollow-nanostructured transition metal oxide-based anodes is of great importance for long-term operation of lithium ion batteries. Herein, we report a two-step calcination strategy to fabricate hollow Co3O4 nanoparticles embedded in a N,S-co-doped reduced graphene oxide framework. In the first step, core-shell-like Co@Co3O4 embedded in N,S-co-doped reduced graphene oxide is synthesized by pyrolysis of a Co-based metal organic framework/graphene oxide precursor in an inert atmosphere at 800 °C. The designed hollow Co3O4 nanoparticles with an average particle size of 25 nm and wall thickness of about 4-5 nm are formed by a further calcination process in air at 250 °C via the nanoscale Kirkendall effect. Both micropores and mesopores are generated in the HoCo3O4/NS-RGO framework. Benefiting from the hierarchical porous structure of the hollow Co3O4 and the co-doping of nitrogen and sulfur atoms in reduced graphene oxide, the thus-assembled battery exhibits a high specific capacity of 1590 mAh g-1 after 600 charge-discharge cycles at 1 A g-1 and a promising rate performance from 0.2 to 10 A g-1.
Keywords: hierarchical pores; hollow Co3O4 nanoparticle; lithium ion battery; metal−organic framework; nanoscale Kirkendall effect.