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A 3D porous graphene composite film containing Ni/NiO hybrid nanoparticles (Ni/NiO NPs) is prepared by combining electrophoresis deposition and thermal H2 annealing techniques. The Ni/NiO NPs with a mean diameter of 45 nm are uniformly embedded on both the exterior and interior surfaces of reduced graphene, forming a 3D porous reduced graphene oxide composite film (Ni/NiO rGO). The insertion of Ni/NiO NPs into rGO greatly improves the electric conductivity and charge storage capability of the resultant Ni/NiO rGO film. By directly using i