Abstract:Manganese-based NASICON cathodes enable high-energy-density sodium-ion batteries via multi-electron Mn2+/3+/4+ redox and fast Na+ diffusion. However,they suffer from Jahn-Teller distortion(Mn3+ ), causing structural degradation and compromised rate/cycling stability. Herein, a medium-entropy engineered Na3Mn2/3Ti2/3 V2/3(PO4)3 cathode material, synthesized via a scalable ball-milling method is reported, which integrates the Ti3+/4+,V3+/4 ,and Mn2+/3+ redox couples. The NMTVP-V2/3 achieves a reversible capacity of 178.8 mAh g-1 at 20 mA g-1 and an energy density of 509.6 Wh kg-1. After cycling 1200, its capacity retains 82.24% at 200 mA g-1. In-situ XRD reveals that near-equimolar Ti/Mn/V mixing creates a medium-entropy structure,promoting the mechanism shifted from a mixed solid-solution and two-phase reaction to dominant solid-solution reactions. Integrated with electrochemical characterization and DFT, the results indicate that the medium-entropy optimized NMTVP-V2/3 enhances ionic transport and mitigates phase degradation. Furthermore, the NMTVP- V2/3 ||hard carbon full cell exhibits a high capacity of 162.9 mAh g-1 at with an outstanding rate performance. This strategy can be generalized to other polyanionic systems, presenting a novel approach for developing SIB cathodes.

