Insights into Reversible Sodium Intercalation in a Novel Sodium‐Deficient NASICON‐Type Structure:Na3.40□0.60Co0.5Fe0.5V(PO4)3

The rational design of novel high-performance cathode materials for sodium-ion batteries is a challenge for the development of the renewable energy sector. Here, a new sodium-deficient NASICON phosphate, namely Na3.40 □0.60 Co0.5 Fe0.5 V(PO4 )3 , demonstrating the excellent electrochemical performance is reported. The presence of Co allows a third Na+ to participate in the reaction thus exhibiting a high reversible capacity of ≈155 mAh g-1 in the voltage range of 2.0-4.0 V versus Na+ /Na with a reversible single-phase mechanism and a small volume shrinkage of ≈5.97% at 4.0 V. 23 Na solid-state nuclear magnetic resonance (NMR) combined with ex situ X-ray diffraction (XRD) refinements provide evidence for a preferential Na+ insertion within the Na2 site. Furthermore, the enhanced sodium kinetics ascribed to Co-substitution is also confirmed in combination with electrochemical impedance spectroscopy (EIS), galvanostatic intermittent titration technique (GITT), and theoretical calculation.