Decoupling High‐Voltage Instability of Na 3 VCr(PO 4 ) 3 Cathodes via a Graphitized Topological Interface for Wide‐Temperature Sodium‐Ion Batteries

ABSTRACT Polyanionic Na 3 VCr(PO 4 ) 3 is a promising high‐voltage cathode for sodium‐ion batteries, yet it suffers from severe interfacial degradation at deep desodiation, including transition metal dissolution, irreversible phase transitions, and side reactions, especially under extreme temperatures. To overcome this, we design a graphitized topological interface—a 3D continuous graphitized network coating the material particles. This interface not only enhances electron/ion transport but also templates the formation of a thin, uniform, and inorganic‐rich cathode electrolyte interphase (CEI) via selective electrolyte adsorption, shifting CEI growth from passive blocking to active induction. Moreover, it suppresses transition metal leaching and mitigates lattice distortion, thereby stabilizing the bulk structure. With such dual stabilization, the modified cathode exhibits superior wide‐temperature performance: retaining 70.3% after 1000 cycles at room temperature, while delivering capacities of 69.6 mAh g −1 (74.3% capacity retention) and 86.1 mAh g −1 at −40°C and 50°C, respectively, with excellent cycling durability. This work provides a new paradigm for high‐energy cathode design.