Cobalt Doping of Na₂VTi(PO₄)₃ Enables a High-Energy NASICON-Type Cathode Material for Sodium-Ion Batteries

Natrium superionic conductor (NASICON) compounds have emerged as a rising star in the field of sodium-ion batteries (SIBs) owing to their stable framework structure and high Na⁺ ionic conductivity. The NASICON-structured Na₂VTi(PO₄)₃ manifests significant potential as Na⁺ storage material, characterized by decent rate capability and cyclability. However, the low redox potential of Ti³⁺/Ti⁴⁺ and undesirable energy density limit its practical applications. We developed a NASICON-structured Na₃Co_2/3V_2/3Ti_2/3(PO₄)₃ (NCTVP) cathode material by doping an appropriate amount of cobalt into Na₂VTi(PO₄)₃. Cobalt doping introduces a Co³⁺/Co²⁺ redox couple at ~4.1 V and activates the V⁵⁺/V⁴⁺ redox at ~3.9 V, resulting in significantly increased medium discharge voltage and capacity. NCTVP demonstrates a high capacity of over 160 mAh g^-1 at 20 mA g^-1. With a medium discharge voltage of ~2.7 V, the energy density of NCTVP reaches 432.0 Wh kg^-1. NCTVP also demonstrates desirable cycling stability (87.4% retention for 100 cycles at 50 mA g^-1). In situ X-ray diffraction discloses a solid solution reaction mechanism for NCTVP, while the galvanostatic intermittent titration technique demonstrates fast Na⁺ diffusion kinetics. NCTVP also demonstrates high capacity and good cyclability in full cells. This contribution demonstrates an effective approach for the construction of NASICON materials for SIBs.