MnFe2O4 nanodots (∼3.3 nm) homogeneously dispersed in porous nitrogen-doped carbon nanofibers (denoted as MFO@C) were prepared by a feasible electrospinning technique. Meanwhile, MFO@C with the character of flexible free-standing membrane was directly used as binder- and current collector-free anode for sodium-ion batteries, exhibiting high electrochemical performance with high-rate capability (305 mA h g(-1) at 10000 mA g(-1) in comparison of 504 mA h g(-1) at 100 mA g(-1)) and ultralong cycling life (ca. 90% capacity retention after 4200 cycles). The Na-storage mechanism was systematically studied, revealing that MnFe2O4 is converted into metallic Mn and Fe after the first discharge (MnFe2O4 + 8Na(+) + 8e(-) → Mn + 2Fe + 4Na2O) and then to MnO and Fe2O3 during the following charge (Mn + 2Fe + 4Na2O → MnO + Fe2O3 + 8Na(+) + 8e(-)). The subsequent cycles occur through reversible redox reactions of MnO + Fe2O3 + 8Na(+) + 8e(-) ↔ Mn + 2Fe + 4Na2O, of which the reduction/oxidation of MnO/Mn takes place at a lower potential than that of Fe2O3/Fe. Furthermore, a soft package sodium-ion full battery with MFO@C anode and Na3V2(PO4)2F3/C cathode was assembled, delivering a stable capacity of ∼400 mA h g(-1) for MFO@C (with 100 cycles at 500 mA g(-1)) and a promising energy density of 77.8 Wh kg(-1) for the whole battery. This is owing to the distinctive structure of very-fine MnFe2O4 nanodots embedded in porous N-doped carbon nanofibers, which effectively improves the utilization rate of active materials, facilitates the transportation of electrons and Na(+) ions, and prevents the particle pulverization/agglomeration upon prolonged cycling.
Keywords: MnFe2O4 nanodots; electrospinning; free-standing anode; porous N-doped carbon nanofibers; sodium-ion batteries.