Integrating Scalable Dry‐Processing and Metal‐Organic Framework Glass Enables Stable High‐Voltage Cathodes in Sodium‐Ion Batteries

ABSTRACT High‐voltage NASICON‐type Na 3 (VOPO 4 ) 2 F (NVOPF) has emerged as a promising cathode for sodium‐ion batteries (SIBs) because it enables higher energy density. However, its practical application is still hindered by limited cycling stability and cycling capability, which primarily stem from interfacial instability under high cut‐off voltages during charging and sluggish Na + desolvation kinetics during discharging, respectively. Herein, we design an integrated metal‐organic framework (MOF) glass interface to concurrently stabilize the cathode/electrolyte interphase and accelerate Na + desolvation. A mix‐melt‐quench transformation converts low‐melting crystalline MOF (Zn‐P‐dmbIm) into MOF glasses, which is coupled in situ with dry‐processed NVOPF electrode fabrication to achieve a uniform and ultrathin coating from the particle to the electrode level. The conformal glassy layer promotes efficient Na + desolvation while suppressing solvent co‐intercalation, solvent decomposition, and transition‐metal dissolution. Meanwhile, the dry‐processed electrode fabrication establishes a dense yet low‐tortuosity ion‐transport network, ensuring continuous Na + transport and accelerated reaction kinetics. Benefiting from this dual regulation mechanism, the modified NVOPF cathode exhibits outstanding rate capability and long‐term cycling stability, achieving 86% capacity retention after over 1000 cycles at 5 C with a high cutoff voltage of 4.3 V. This work provides a scalable, manufacturing‐compatible channel for constructing robust high‐voltage cathodes in SIBs.