Experimental and theoretical investigations of covalent functionalization of 1D/2D carbon-based buckypaper via aryl diazonium chemistry for high-performance energy storage

Efforts to fabricate high-conducting and high-strength free-standing graphene/carbon nanotube (CNT) bucky-paper through room-temperature functionalization have been frustrated by the defective surface of the graphene and CNTs. In this study, high-quality graphene sheets were prepared via an amino-assisted liquid phase exfoli-ation method and used to integrate with CNTs to form free-standing flexible graphene/CNTs buckypaper. After that, individual graphene and CNT of the graphene/CNTs buckypaper were linked via diazonium chemistry to generate covalent bonds. By tuning functionalization time, the functionalized graphene/CNTs buckypaper ex-hibits an electrical conductivity of 87,500 S/m and a Young's modulus of 22.3 GPa, which are 6 and 10 times higher, respectively, than unfunctionalized graphene/CNTs buckypaper. Density functional theory calculations demonstrate that charge transfer rate (Ket) of the aryl linker bonded moiety configuration via covalent func-tionalization is an order faster than without the aryl linker bonded moiety configuration. Unprecedently, the capacitance of the functionalized graphene/CNTs buckypaper is 359.6 mF/cm3 at a scan rate of 1 mV/s with no capacitance change after 10,000 cycles of testing. This work sheds the light of the value of molecular engineering in the design of novel composite for flexible electronics, energy storage and provides important insights into the understanding of basic principles of covalent functionalization of graphene/CNTs.

Automated summary

In this study, high-quality graphene sheets were prepared and integrated with carbon nanotubes to form free-standing flexible bucky paper. Covalent bonding between the graphene and CNTs was achieved through diazonium chemistry, resulting in improved electrical conductivity and Young's modulus. This work highlights the value of molecular engineering in the design of novel composites for flexible electronics and energy storage, and provides insights into the principles of covalent functionalization of graphene/CNTs.