A High‐Energy NASICON‐Type Na3.2MnTi0.8V0.2(PO₄)₃ Cathode Material with Reversible 3.2‐Electron Redox Reaction for Sodium‐Ion Batteries

Na superionic conductor (NASICON) structured cathode materials with robust structural stability and large Na⁺ diffusion channels have aroused great interest in sodium-ion batteries (SIBs). However, most of NASICON-type cathode materials exhibit redox reaction of no more than three electrons per formula, which strictly limits capacity and energy density. Herein, a series of NASICON-type Na3+x MnTi1-x Vx (PO₄ )₃ cathode materials are designed, which demonstrate not only a multi-electron reaction but also high voltage platform. With five redox couples from V5+/4+ (≈4.1 V), Mn4+/3+ (≈4.0 V), Mn3+/2+ (≈3.6 V), V4+/3+ (≈3.4 V), and Ti4+/3+ (≈2.1 V), the optimized material, Na3.2 MnTi0.8 V0.2 (PO₄ )₃ , realizes a reversible 3.2-electron redox reaction, enabling a high discharge capacity (172.5 mAh g⁻¹ ) and an ultrahigh energy density (527.2 Wh kg⁻¹ ). This work sheds light on the rational construction of NASICON-type cathode materials with multi-electron redox reaction for high-energy SIBs.