Do More with Less: Breaking the Performance Dilemma of NASICON Cathode via Minimal Quadruple Doping

NASICON‐type Na 3 V 2 (PO 4 ) 3 , featuring multielectron reactions, is a prospective cathode for SIBs, but suffers from inferior conductivity and structural degradation with compromised rate/cyclic stability. Overcoming the enduring capacity‐stability trade‐off remains a pivotal challenge in the advancement of high‐performance cathodes. Herein, we break the performance dilemma of Na 3 V 2 (PO 4 ) 3 cathode through strategic minimal quadruple doping (Mn, Al, Ni, and Cr; total 8 at%) at its V‐site. As‐prepared QD‐NVP exhibits a reversible solid‐solution‐triphasic reaction mechanism across successive V 2+ /V 3+ /V 4+ /V 5+ redox processes, accompanied by low voltage polarization and small lattice stress. Theoretical calculation and in/ex situ characterizations reveal that the minimal quadruple doping endows QD‐NVP with stable [QD‐VO 6 ] octahedra, expanded channels, weakened Na + ‐O interactions, and high V‐site spin polarization, simultaneously boosting the ion/electron conductivity, the structure stability, and the vanadium utilization. Consequently, the QD‐NVP cathode achieves concurrent high capacity (179 mA h g −1 at 0.1C), exceptional rate capability (115 mA h g −1 @80C), and excellent cycling stability (97.2% retention over 4200 cycles@50C), surpassing those of the best‐performing V‐polyanionic cathodes reported to date. Moreover, the superior battery performance of QD‐NVP‐assembled full/symmetric cells further highlights its potential multi‐scenario applications. This work provides an innovative perspective by doing more with less to develop a high‐performance NASICON cathode for next‐generation SIBs.