Improving Rate Performance by Inhibiting Jahn–Teller Effect in Mn-Based Phosphate Cathode for Na-Ion Batteries

Manganese-based phosphate cathodes are promising candidates for developing advanced sodium-ion batteries, primarily driven by their reliable elemental abundance, low toxicity, and desirable cycling performance. However, the cooperative Jahn–Teller effect of Mn³⁺ will inevitably lead to structural disorder and irreversible phase transition, thus greatly harming the reversible capacity, rate, and cycling performance. Herein, a stable NASICON-type Na₃MnHf(PO₄)₃ cathode is demonstrated with a volume variation of 1.9% upon the process of Na⁺ extraction/insertion based on the robust Hf─O bond and symmetrical MnO₆ octahedron. Moreover, making full use of the stepwise redox reactions of Mn²⁺/Mn³⁺/Mn⁴⁺, this cathode reveals excellent cycling stability with a capacity retention of 85.4% after 2500 cycles at 10 C. Matching with commercial hard carbon anodes, the assembled full cell keeps a capacity retention of 92.1% with the Coulombic efficiency close to 100% after 600 cycles at 1 C. The research promises opportunities for the structural amelioration of manganese-based phosphate cathodes toward the application in high-performance sodium-ion batteries.