Structural Evolution of Lithium-Exchanged Na₃(VO)₂(PO₄)₂F Cathode under Operation in Sodium Ion Batteries

Na superionic conductor (NASICON)-type Na₃(VO)₂(PO₄)₂F (NVOPF) exhibits excellent cycling stability for high-voltage sodium ion batteries. Various strategies have been developed to form ion-exchanged NVOPF which can enhance the ionic and electronic conductivity. However, the underlying ion transport mechanism and complex structural transitions during battery operation remained uninvestigated. In this work, we prepared lithium-exchanged NVOPF (namely NLVOPF) which shows improved ionic conductivity and increased capacity at high discharging rates. Solid-state nuclear magnetic resonance (SSNMR) revealed the distinctive presence of two kinds of Li-exchanged sites in the NLVOPF, which are attributed to the occupied lithium ions at the Na1 and Na2 sites (namely Li1 and Li2, respectively). The Li1 site was metastably replaced in the first cycle, yet the Li2 site participated in ion insertion/extraction in the subsequent cycles. Our characterizations show that the dynamic doping of lithium in NLVOPF could contribute to the improved cycling stability and capacity retention.