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As one of the most promising cathodes for sodium-ion batteries, the polyanionic compounds still suffer from unsatisfactory capacity and rate performance resulting from poor electron conductivity. Furthermore, the charge-transfer kinetics, especially for Na+, becomes limiting as the mass loading increases. Herein, a robust free-standing electrode coupling optimal porous Na3V2(PO4)3@C microspheres with a bicontinuous charge transport network is designed and prepared by a simple casting method. In the design, the optimal porous carbon-coa