The orthorhombic NaFeF3, which is envisioned
to be an
auspicious positive electrode for Na-ion batteries, has drawn considerable
interest as an environmentally benign energy material with exceptionally
high theoretical capacity. Despite these prospects, the reaction mechanism(s)
during orthorhombic NaFeF3 operations are still not well
understood. Thus, in a bid to expound on this research space, we report
the reaction mechanism(s) of a carbon-coated orthorhombic NaFeF3 prepared through high-energy ball-milling and heat treatment
processes. A thermally stable ionic liquid electrolyte at elevated
temperatures is employed to maximize the utilization of NaFeF3. The orthorhombic NaFeF3 exhibits high electrochemical
activity and long-term cycling stability of up to 400 cycles at 90
°C. Through a combination of galvanostatic intermittent titration
technique and synchrotron X-ray powder diffraction measurements, we
discover that the (de)sodiation processes are facilitated by a multiphase
transformation mechanism. Further, we experimentally identify, for
the first time, an orthorhombic Na0.5FeF3 compound
as an intermediate phase of the transformations. The results discussed
in this work are expected to provide invaluable insights for the future
advancement of the Na–Fe–F system.