Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe₂O₃–FeF₃ Conversion Compounds by Direct Fluorination

We report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe₂O₃) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe₂O_3‑<i>x</i>F_2<i>x</i> (<i>x</i> < 1). At fluorination temperatures of 275 °C, STEM-EELS results showed porous interconnected nanodomains of FeF₃ and Fe₂O₃ coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF₃ + Fe₂O₃ composition, and correlate the results to their electrochemical performance. Further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF₃) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides

Formation of Iron Oxyfluoride Phase on the Surface of Nano-Fe₃O₄ Conversion Compound for Electrochemical Energy Storage

We have investigated a novel approach wherein we undertake surface fluorination of nanometer sized Fe₃O₄ conversion compound into corresponding oxyfluoride with the goal toward enhancing their energy density as well electrochemical performance stability. This is achieved by using direct fluorination of nano-Fe₃O₄ in a fluidized bed reactor under controlled reaction atmosphere and temperature. X-ray photoemission spectroscopy analysis shows conclusive evidence of the surface fluorination of Fe₃O₄ particles at a reaction temperature of 100 °C and higher forming a surface oxyfluoride phase that can be nominally described as FeOF. Formation of oxyfluoride phase is confirmed by the appearance of a higher potential intercalation plateau during the electrochemical charge–discharge cycling. Based on the experimental results, various pathways are discussed for the formation of oxyfluoride species on the surface