Dual-Strategy of Cation-Doping and Nanoengineering Enables Fast and Stable Sodium-Ion Storage in a Novel Fe/Mn-Based Layered Oxide Cathode

Iron/manganese-based layered transition metal oxides have risen to prominence as prospective cathodes for sodium-ion batteries (SIBs) owing to their abundant resources and high theoretical specific capacities, yet they still suffer from rapid capacity fading. Herein, a dual-strategy is developed to boost the Na-storage performance of the Fe/Mn-based layered oxide cathode by copper (Cu) doping and nanoengineering. The P2-Na_0.76Cu_0.22Fe_0.30Mn_0.48O₂ cathode material synthesized by electrospinning exhibits the pearl necklace-like hierarchical nanostructures assembled by nanograins with sizes of 50-150 nm. The synergistic effects of Cu doping and nanotechnology enable high Na⁺ coefficients and low ionic migration energy barrier, as well as highly reversible structure evolution and Cu/Fe/Mn valence variation upon repeated sodium insertion/extraction; thus, the P2-Na_0.76Cu_0.22Fe_0.30Mn_0.48O₂ nano-necklaces yield fabulous rate capability (125.4 mA h g^-1 at 0.1 C with 56.5 mA h g^-1 at 20 C) and excellent cyclic stability (≈79% capacity retention after 300 cycles). Additionally, a promising energy density of 177.4 Wh kg^-1 is demonstrated in a prototype soft-package Na-ion full battery constructed by the tailored nano-necklaces cathode and hard carbon anode. This work symbolizes a step forward in the development of Fe/Mn-based layered oxides as high-performance cathodes for SIBs.