Nanocomposites that contain reinforcements with preferred orientation have attracted significant attention because of their promising applications in a wide range of multifunctional fields. Many efforts have recently been focused on developing facile methods for preparing aligned graphene sheets in solvents and polymers because of their fascinating properties including liquid crystallinity and highly anisotropic characteristics. Self-aligned in situ reduced graphene oxide (rGO)/polymer nanocomposites are prepared using an all aqueous casting method. A remarkably low percolation threshold of 0.12 vol% is achieved in the rGO/epoxy system owing to the uniformly dispersed, monolayer graphene sheets with extremely high aspect ratios (>30000). The self-alignment into a layered structure at above a critical filler content induces a unique anisotropy in electrical and mechanical properties due to the preferential formation of conductive and reinforcing networks along the alignment direction. Accompanied by the anisotropic electrical conductivities are exceptionally high dielectric constants of over 14000 with 3 wt% of rGO at 1 kHz due to the charge accumulation at the highly-aligned conductive filler/insulating polymer interface according to the Maxwell-Wagner-Sillars polarization principle. The highly dielectric rGO/epoxy nanocomposites with the engineered structure and properties present high performance electromagnetic interference shielding with a remarkable shilding efficiency of 38 dB.

Cellular-structured graphene foam (GF)/epoxy composites are prepared based on a three-step fabrication process involving infiltration of epoxy into the porous GF. The three-dimensional (3D) GF is grown on a Ni foam template via chemical vapor deposition. The 3D interconnected graphene network serves as fast channels for charge carriers, giving rise to a remarkable electrical conductivity of the composite, 3 S/cm, with only 0.2 wt % GF. The corresponding flexural modulus and strength increase by 53 and 38%, respectively, whereas the glass transition temperature increases by a notable 31 °C, compared to the solid neat epoxy. The GF/epoxy composites with 0.1 wt % GF also deliver an excellent fracture toughness of 1.78 MPa·m(1/2), 34 and 70% enhancements against their "porous" epoxy and solid epoxy counterparts, respectively. These observations signify the unrivalled effectiveness of 3D GF relative to 1D carbon nanotubes or 2D functionalized graphene sheets as reinforcement for polymer composites without issues of nanofiller dispersion and functionalization prior to incorporation into the polymer.

3D interconnected graphene aerogels (GAs) are prepared through one-step chemical reduction and rational assembly of graphene oxide (GO) sheets, so that the difficulties to uniformly disperse the individual graphene sheets in the polymer matrixes are avoided. Apart from ultralow density, high porosity, high electrical conductivity, and excellent compressibility, the resulting GAs possess a cellular architecture with a high degree of alignment when the graphene content is above a threshold, ∼0.5 wt %. The composites prepared by infiltrating GA with epoxy resin present excellent electrical conductivities, together with high mechanical properties and fracture toughness. The unusual anisotropic structure gives rise to ∼67% and ∼113% higher electrical conductivity and fracture toughness of the composites, respectively, in the alignment direction than that transverse to it.