EELS spectroscopy of iron fluorides and FeFx/C nanocomposite electrodes used in Li-ion batteries

A new type of positive electrode for Li-ion batteries has been developed recently based on FeF3/C and FeF2/C nanocomposites. The microstructural and redox evolution during discharge and recharge processes was followed by electron energy loss spectroscopy (EELS) to determine the valence state of Fe by measuring the Fe L-3 line energy shift and from Fe L-3/L-2 line intensity ratios. In addition, transition metal fluorides were found to be electron beam sensitive, and the effect of beam exposure on EELS spectra was also investigated. The EELS results indicate that for both FeF3/C and FeF2/C nanocomposite systems, a complete reduction of iron to Fe-O is observed upon discharge to 1.5 V with the formation of a finer Fe-O/LiF subnanocomposite (similar to 7 nm). Upon complete recharging to 4.5 V, EELS data reveal a reoxidation process to a Fe2+ state with the formation of a carbon metal fluoride nanocomposite related to the FeF2 structure.