ZnO/CoO and ZnCo2O4 Hierarchical Bipyramid Nanoframes: Morphology Control, Formation Mechanism, and Their Lithium Storage Properties

Mastery over the structure of nanoscale materials can effectively tailor and regulate their electrochemical properties, enabling improvement in both rate capability and cycling stability. We report the shape-controlled synthesis of novel mesoporous bicomponent-active ZnO/CoO hierarchical multilayered bipyramid nanoframes (HMBNFs). The as-synthesized micro/nanocrystals look like multilayered bipyramids and consist of a series of structural units with similar frames and uniform sheet branches. The use of an appropriate straight-chain monoalcohol was observed to be critical for the formation of HMBNFs. In addition, the structure of HMBNFs could be preserved only in a limited range of the precursor ratio. An extremely fast crystal growth process and an unusual transverse crystallization of the ZnCo-carbonate HMBNFs were newly discovered and proposed. By calcination of ZnCo-carbonate HMBNFs at the atmosphere of nitrogen and air, ZnO/CoO and ZnCo2O4 HMBNFs were obtained, respectively. Compared to the ZnCo2O4 HMBNFs, the ZnO/CoO HMBNFs with a uniform distribution of nanocrystal ZnO and CoO subunits exhibited enhanced electrochemical activity, including greater rate capability and longer cycling performance, when evaluated as an anode material for Li-ion batteries. The superior electrochemical performance of the ZnO/CoO HMBNFs is attributed to the unique nanostructure, bicomponent active synergy, and uniform distribution of ZnO and CoO phases at the nanoscale.