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 Mn${}^{3+}$ 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 Na${}_3$MnHf(PO${}_4$)${}_3$ 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 MnO${}_6$ octahedron. Moreover, making full use of the stepwise redox reactions of Mn${}^{2+}$/Mn${}^{3+}$/Mn${}^{4+}$, 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. (© 2023 Wiley‐VCH GmbH)