Free-standing graphene paper with a grey metallic luster has been fabricated for the first time, by a convenient one-step method on a large scale. Herein, the assembly of graphene oxide dispersion into ordered paper occurs simultaneously with the chemical reduction of graphene oxide to graphene. The graphene paper presents the advantages of good flexibility, low weight (0.2 g cm−3) and high electrical conductivity (15 Ω sq−1). Moreover, the size and shape of the graphene paper are freely exchanged for those of the Teflon substrate used. The flexible graphene–PANI paper subsequently exhibits excellent supercapacitor performance with an enhanced specific capacitance (763 F g−1) and good cycling stability by electropolymerization of PANI nanorods on the above graphene paper. The method presented here shows great promise for the development of low-cost electrode materials in potential energy storage devices.
