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Graphene encapsulating paraffin (paraffin@graphene) microcapsules were fabricated by electrostatic interaction-based self-assembly. An aqueous dispersion of graphene sheets charged with cation, were mixed with a water-based emulsion containning negatively charged paraffin droplet spheres to form self-assembled microcapsules. The morphology of the microcapsules was characterized by scanning electron microscope (SEM). Results show that the microcapsules with a well-defined spherical structure were prepared successfully. Differential scanning calorimeter (DSC) results indicate that the phase change latent heat are all above 200 J g−1. With a graphene mass fraction of 8 wt%, the thermal conductivity of the fabricated composites can reach 1.73 W m−1 K−1. Attributing to the interlocking of graphene with each other, the microcapsules enable lock the paraffin in the shell thus successfully avoiding its leakage during phase change process. The prepared phase change microcapsules are expected to apply in energy storage field. [ABSTRACT FROM AUTHOR]