Bulk-Interface Synergy Enables Stable High-Voltage P2-Type Layered Oxide Cathodes for Fast-Charging Sodium-Ion Batteries

P2-type layered oxides hold great promise for high-energy sodium-ion batteries (SIBs) but are hindered by irreversible P2–O2 transitions and interfacial degradation that accelerate capacity fading. Herein, we present a bulk-interface dual-engineering strategy through synergistic Mg 2+ doping and CeO 2 surface modulation to overcome these challenges. The designed P2-type Na 0.67 Mg 0.1 Ni 0.23 Mn 0.67 O 2 –CeO 2 (NNMMO-Ce) cathode integrates structural reinforcement and redox synergy: bulk Mg 2+ stabilizes the lattice, widens Na + diffusion channels, and suppresses destructive high-voltage transitions, while a conformal CeO 2 nanolayer buffers lattice strain (∼0.9%), prevents intragranular cracking, and enables the storage and release of (O 2 ) n − species through reversible Ce 3+ /Ce 4+ redox activity. This coupled mechanism coordinates electron–ion transport, minimizes polarization effects, and significantly reduces charge transfer resistance as well as the escape of lattice oxygen. Consequently, NNMMO-Ce exhibits superior performance with 94.0% capacity retention at 0.1 C and 66.2 mAh g –1 at 20 C, along with highly reversible P2-OP4 transitions and >35-fold enhanced Na + diffusion. When paired with a hard-carbon anode, the full cell delivers a high energy density of 258.97 Wh kg –1 and excellent cycling stability over 2–4.35 V. This work establishes a cooperative bulk-interface strategy for constructing high-capacity, fast-charging, and long-lived SIB cathodes.