Regulating Bond Structure in Polyanion Cathode for Long-Cycle-Life Sodium-Ion Batteries

The NASICON-type Na4MnV(PO4)3 (NMVP) cathode is a potential candidate for sodium-ion batteries (SIBs) due to its intrinsic safety and cost advantages. However, its performance is limited by intrinsic low electronic conductivity and Jahn–Teller distortion of Mn. In this study, Co is substituted at the Mn site to take advantage of the stronger polarization effect of Co2+ and the ionic radius difference, which shortens the Mn–O bond length and strengthens its bonding, stabilizing the MnO6 octahedral structure. Furthermore, Co doping lowers the Na+ migration energy barrier and facilitates more efficient Na+ transport. Therefore, the prepared NMCVP-0.05 sample exhibits a stable cycling performance (retaining 88.9% after 3800 cycles at 10 C) and rate performance (71.7 mAh g–1 at 50 C). This work reveals the mechanism by which regulating the bond structure in NMVP affects sodium storage performance and proposes a stability-enhancing strategy for Mn-based polyanionic cathodes.