General Synthesis of Transition‐Metal Oxide Hollow Nanospheres/Nitrogen‐Doped Graphene Hybrids by Metal–Ammine Complex Chemistry for High‐Performance Lithium‐Ion Batteries

We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, in synthesizing hollow transition metal oxides (Co3O4, NiO, CuO-Cu2O and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high performance lithium ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co2+, Ni2+, Cu2+, or Zn2+)-ammine complex ions. Moreover, the hollowing process is well correlated with complexing capacity between metal ions and NH3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co2+, Ni2+, Cu2+, and Zn2+ ions, and no hollow structures formed for weak and/or non-complex Mn2+ and Fe3+ ions. Simultaneously, this novel strategy can also achieve the directly doping of nitrogen atoms into graphene framework. When used as anodic materials, the electrochemical performance of two typical hollow Co3O4 or NiO/nitrogen-doped graphene hybrids are evaluated. It is demonstrated that these unique nanostructed hybrids, in contrast with the bare counterparts, solid transition metal oxides/nitrogen-doped graphene hybrids, perform the significantly improved specific capacity, superior rate capability and excellent capacity retention.