Covalent Graphene‐MOF Hybrids for High‐Performance Asymmetric Supercapacitors

Abstract In this work, the covalent attachment of an amine functionalized metal‐organic framework (UiO‐66‐NH 2 = Zr 6 O 4 (OH) 4 (bdc‐NH 2 ) 6 ; bdc‐NH 2 = 2‐amino‐1,4‐benzenedicarboxylate) (UiO‐Universitetet i Oslo) to the basal‐plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO‐66‐NH 2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO‐66‐NH 2 acts as an effective charge storing material with a capacitance of up to 651 F g −1 , significantly higher than traditional graphene‐based materials. The results suggest that the amide linkage plays a key role in the formation of a π‐conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO‐66‐NH 2 positive electrode with Ti 3 C 2 T X MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg −1 and an energy density of up to 73 Wh kg −1 , which are comparable to several commercial devices such as Pb‐acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.