Vanadium-based Na superionic conductor (NASICON) type materials (NaxVM(PO4)3, M = transition metals) have attracted extensive attention when used as sodium-ion batteries (SIBs) cathodes due to their stable structures and large Na+ diffusion channels. However, the materials have poor electrical conductivity and mediocre energy density, which hinder their practical applications. Activating the V4+/V5+ redox couple (V4+/V5+≈4.1 V vs Na+/Na) is an effective way to elevate the energy density of SIBs, whereas the irreversible phase transition of V4+/V5+ and severe structural distortion will inevitably result in fast capacity fading and unsatisfactory rate capability. Herein, a high entropy regulation strategy is proposed to optimize the detailed crystal structure and improve the reversibility of crystalline phase transformation and electrical conductivity of the material. With the activated reversible V4+/V5+ redox couple, stable structure, and fast electrochemical kinetics, the high entropy material Na3.2V1.5Fe0.1Al0.1Cr0.1Mn0.1Cu0.1(PO4)3 (NVMP-HE) exhibits an outstanding electrochemical performance with highly reversible specific capacity of 120.1 mAh g-1 at 0.1 C and excellent cycling stability (92.4% retention after 1000 cycles at 20 C). Besides, the in situ X-ray diffraction (XRD) measurement reveals that a smooth three-phase transition reaction is involved in this high-entropy cathode and the existence of mesophase facilitates a fast phase transition.
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