Ethanol‐Induced Ni2+‐Intercalated Cobalt Organic Frameworks on Vanadium Pentoxide for Synergistically Enhancing the Performance of 3D‐Printed Micro‐Supercapacitors

The synthesis of metal-organic framework (MOF) nanocomposites with high energy density and excellent mechanical strength is limited by the degree of lattice matching and crystal surface structure. In this study, dodecahedral ZIF-67 is synthesized uniformly on vanadium pentoxide nanowires. The influence of the coordination mode on the surface of ZIF-67 in ethanol is also investigated. Benefitting from the different coordination abilities of Ni²⁺ , Co²⁺ , and N atoms, spatially separated surface-active sites are created through metal-ion exchange. Furthermore, the incompatibility between the d⁸ electronic configuration of Ni²⁺ and the three-dimensional (3D) structure of ZIF-67 afforded the synthesis of hollow structures by controlling the amount of Ni doping. The formation of NiCo-MOF@CoOOH@V₂ O₅ nanocomposites is confirmed using X-ray absorption fine structure analysis. The high performance of the obtained composite is illustrated by fabricating a 3D-printed micro-supercapacitor, exhibiting a high area specific capacitance of 585 mF cm^-2 and energy density of 159.23 µWh cm^-2 (at power density = 0.34 mW cm^-2 ). The solvent/coordination tuning strategy demonstrated in this study provides a new direction for the synthesis of high-performance nanomaterials for electrochemical energy storage applications.