Electrochemical and Diffusional Investigation of (Na2FePO4F)-P-II Fluorophosphate Sodium Insertion Material Obtained from Fe-III Precursor
Sodium iron fluorophosphate ((Na2FePO4F)-P-II) was synthesized by economic solvothermal combustion technique using Fe-III precursors, developing one-step carbon-coated homogeneous product. Synchrotron diffraction and Mossbauer spectroscopy revealed the formation of single-phase product assuming an orthorhombic structure (s.g. Pbcn) with Fe-II species. This Fe-III precursor derived (NaFePO4F)-Fe-2-P-II exhibited reversible Na+ (de)intercalation with discharge capacity of 100 mAh/g at a rate of C/10 involving flat Fe-III/Fe-II redox plateaus located at 2.92 and 3.05 V (vs Na/Na+). It delivered good cycling stability and rate kinetics at room temperature. The stability of Na2FePO4F cathode was further verified by electrochemical impedance spectroscopy at different stages of galvanostatic analysis. Bond valence site energy (BVSE) calculations revealed the existence of 2-dimensional Na+ percolation pathways in the a-c plane with a moderate migration barrier of 0.6 eV. Combustion synthesized (Na2FePOF)-P-II-F-4 forms an economically viable sodium battery material. Although the capacity of this cathode is relatively low, this study continues systematic work, which attempts to broaden the scope of reversible sodium insertion materials.