Electrode Design for High-Performance Sodium-Ion Batteries: Coupling Nanorod-Assembled Na₃V₂(PO₄)₃@C Microspheres with a 3D Conductive Charge Transport Network

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-coated microspheres, composed of some continuous nanorods, along with interwoven carbon nanofiber networks offer efficient electron transport and facile ion diffusion. Such an elaborate design enables impressive electron/ion conductivity, contributing to remarkable rate performance (116.1 mA h g^–1 at 0.2 C; 96 mA h g^–1 at 30 C) and outstanding cycling stability (90% capacity retention in 500 cycles at 1 C; 80% capacity retention in 5000 cycles at 10 C), which has surpassed other similar Na₃V₂(PO₄)₃-based free-standing electrodes as reported. More importantly, when mass loading extends to 8 mg cm^–2, an excellent capacity retention of 75% at 10 C can be obtained. The research offers a new avenue into the rational design of porous microspheres electrode with high conductive charge transport network, indicating its superiority in practical applications.