Local Structure and Dynamics in the Na Ion Battery Positive Electrode Material Na3V2(PO4)2F3

Na3V2(PO4)2F3 is a novel electrode material that can be used in both Li ion and Na ion batteries (LIBs and NIBs). The long- and short-range structural changes and ionic and electronic mobility of Na3V2(PO4)2F3 as a positive electrode in a NIB have been investigated with electrochemical analysis, X-ray diffraction (XRD), and high-resolution 23Na and 31P solid-state nuclear magnetic resonance (NMR). The 23Na NMR spectra and XRD refinements show that the Na ions are removed nonselectively from the two distinct Na sites, the fully occupied Na1 site and the partially occupied Na2 site, at least at the beginning of charge. Anisotropic changes in lattice parameters of the cycled Na3V2(PO4)2F3 electrode upon charge have been observed, where a (= b) continues to increase and c decreases, indicative of solid-solution processes. A noticeable decrease in the cell volume between 0.6 Na and 1 Na is observed along with a discontinuity in the 23Na hyperfine shift between 0.9 and 1.0 Na extraction, which we suggest is due to a rearrangement of unpaired electrons within the vanadium t2g orbitals. The Na ion mobility increases steadily on charging as more Na vacancies are formed, and coalescence of the resonances from the two Na sites is observed when 0.9 Na is removed, indicating a Na1–Na2 hopping (two-site exchange) rate of ≥4.6 kHz. This rapid Na motion must in part be responsible for the good rate performance of this electrode material. The 31P NMR spectra are complex, the shifts of the two crystallograpically distinct sites being sensitive to both local Na cation ordering on the Na2 site in the as-synthesized material, the presence of oxidized (V4+) defects in the structure, and the changes of cation and electronic mobility on Na extraction. This study shows how NMR spectroscopy complemented by XRD can be used to provide insight into the mechanism of Na extraction from Na3V2(PO4)2F3 when used in a NIB.