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Electronic structure engineering on electrode materials could bring in a new mechanism to achieve high energy and high power densities in sodium ion batteries. Herein, we design and create Co vacancies at the interface of atomically thin CoSe2 /graphene heterostructure and obtain Co1-x Se2 /graphene heterostructure electrode materials that facilitate significant Na+ intercalation pseudocapacitance. Density functional theory (DFT) calculation suggests that the Na+ adsorption energy is dramatically increased, and the Na+ diffusion barrier i