Probing reaction processes and reversibility in Earth-abundant NaFeF for Na-ion batteries.

Sodium (Na)-ion batteries are the most explored 'beyond-Li' battery systems, yet their energy densities are still largely limited by the positive electrode material. NaFeF is a promising Earth-abundant containing electrode and operates through a conversion-type charge-discharge reaction associated with a high theoretical capacity (336 mA h g). In practice, however, only a third of this capacity is achieved during electrochemical cycling. In this study, we demonstrate a new rapid and environmentally-friendly assisted-microwave method for the preparation of NaFeF. A comprehensive understanding of charge-discharge processes and of the reactivity of the cycled electrode samples is achieved using a combination of electrochemical tests, synchrotron X-ray diffraction, Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, magnetometry, and Na/F solid-state nuclear magnetic resonance (NMR) complemented with first principles calculations of NMR properties. We find that the primary performance limitation of the NaFeF electrode is the sluggish kinetics of the conversion reaction, while the methods employed for materials synthesis and electrode preparation do not have a significant impact on the conversion efficiency and reversibility. Our work confirms that NaFeF undergoes conversion into NaF and Fe nanoparticles. The latter are found to be prone to oxidation prior to measurements, thus necessitating a robust analysis of the stable phases (here, NaF) formed upon conversion.