Realizing a High-Performance Na-Storage Cathode by Tailoring Ultrasmall Na2FePO4F Nanoparticles with Facilitated Reaction Kinetics.

In this paper, the synthesis of ultrasmall Na2FePO4F nanoparticles (≈3.8 nm) delicately embedded in porous N-doped carbon nanofibers (denoted as Na2FePO4F@C) by electrospinning is reported. The as-prepared Na2FePO4F@C fiber film tightly adherent on aluminum foil features great flexibility and is directly used as binder-free cathode for sodium-ion batteries, exhibiting admirable electrochemical performance with high reversible capacity (117.8 mAh g-1 at 0.1 C), outstanding rate capability (46.4 mAh g-1 at 20 C), and unprecedentedly high cyclic stability (85% capacity retention after 2000 cycles). The reaction kinetics and mechanism are explored by a combination study of cyclic voltammetry, ex situ structure/valence analyses, and first-principles computations, revealing the highly reversible phase transformation of Na2FeIIPO4F ↔ NaFeIIIPO4F, the facilitated Na+ diffusion dynamics with low energy barriers, and the desirable pseudocapacitive behavior for fast charge storage. Pouch-type Na-ion full batteries are also assembled employing the Na2FePO4F@C nanofibers cathode and the carbon nanofibers anode, demonstrating a promising energy density of 135.8 Wh kg-1 and a high capacity retention of 84.5% over 200 cycles. The distinctive network architecture of ultrafine active materials encapsulated into interlinked carbon nanofibers offers an ideal platform for enhancing the electrochemical reactivity, electronic/ionic transmittability, and structural stability of Na-storage electrodes.