Covalent Graphene-MOF Hybrids for High-Performance Asymmetric Supercapacitors

In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2 = Zr6O4(OH)(4)(bdc-NH2)(6); bdc-NH2 = 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-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 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 p-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-NH2 positive electrode with Ti3C2TX 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.