Preferential Alkali‐Ion Occupation in NASICON Cathodes Enables High‐Power Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are gaining attention as promising large‐scale energy storage systems due to their cost‐effectiveness and resource abundance. As a cathode material, NASICON‐type Na 3 V 2 (PO 4 ) 3 (NVP) stands out for its high structural stability and energy density. However, its practical application is hindered by poor electronic conductivity and sluggish Na + diffusion kinetics. In this study, we systematically investigated the structural evolution and Na + storage behavior of NVP materials, particularly focusing on enhancing power capability through preferential substitution of Na + with other alkali metal ions (K + and Li + ). Results show that preferential K + occupation at (6b) Na1 sites can manipulate the crystal structure and regulate Na + migration behaviors, significantly influencing the energy efficiency, rate performance, and cycling stability. Consequently, the K + ‐substituted material (NKVP) delivers, at room temperature, a discharge capacity of 80.6 mAh g −1 at the ultrahigh rate of 100C but also retains 80.8% of its capacity over 10,000 cycles at 50C, along with superior high‐temperature cycling stability over 3000 cycles at 10C and 60°C. Practically, the NKVP//HC full cell exhibits superior power performance. This work provides critical insights into the rational design of high‐performance NASICON materials, offering new pathways for the development of high‐power SIBs.