Construction of Hierarchical NiCo₂O₄@Ni-MOF Hybrid Arrays on Carbon Cloth as Superior Battery-Type Electrodes for Flexible Solid-State Hybrid Supercapacitors

Metal–organic frameworks (MOFs) have been considered as a class of promising electrode materials for supercapacitors owing to their large surface area, rich porosity, and variable redox sites; however, direct application of pristine MOFs in energy storage has been largely hindered by their poor electrical conductivity and stability issues. In this work, we demonstrate a facile two-step approach to address the controlled growth of Ni-MOF arrays on the surface of NiCo₂O₄ nanowires by modulating the formation reaction of MOFs. By taking advantage of the intriguing merits from the NiCo₂O₄ core and Ni-MOF shell as well as their synergistic effects, the optimized NiCo₂O₄@Ni-MOF hybrid electrode exhibits boosted electrochemical performance, in terms of high specific capacity (208.8 mA h/g at 2 mA/cm²) and good rate capability. In addition, the assembled flexible solid-state HSC device based on the optimized NiCo₂O₄@Ni-MOF and activated carbon as the cathode and anode achieves a maximum energy density of 32.6 W h/kg at a power density of 348.9 W/kg without sacrificing its outstanding cycling performance (nearly 100% retention over 6000 cycles at 8 mA/cm²) and mechanical stability, outperforming most recently reported MOF-based HSC devices in an aqueous electrolyte. Our work demonstrates the possibility of exploiting novel MOF-based hybrid arrays as battery-type electrodes with enhanced electrochemical properties, which exhibits great potential in flexible energy storage devices.