A graphene oxide nanosheets/multi-walled carbon nanotubes (GO/MWCNTs) hybrid with excellent electrocatalytic redox reversibility towards VO2+/VO2+ redox couples for vanadium redox flow batteries (VRFB) has been prepared by an electrostatic spray technique after efficient ultrasonic treatment. The structures and electrochemical properties of GO/MWCNTs are investigated by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and cyclic voltammetry. GO/MWCNTs are shown to be cross-linked and form an electrocatalytic hybrid with an effective mixed conducting network, leading to efficiently fast ion and electron transport characteristics. Compared with the pure GO nanosheets and MWCNTs, GO/MWCNTs deliver a much better electrocatalytic redox reversibility towards the positive VO2+/VO2+ couple, especially for the reduction from VO2+ to VO2+. The excellent experimental results demonstrate that the newly developed hybrid material holds great promise in the application of VRFB.
