A high-energy-density NASICON-type Na3V1.25Ga0.75(PO4)3 cathode with reversible V4+/V5+ redox couple for sodium ion batteries

Abstract

The stable three-dimensional framework and high operating voltage of sodium superionic conductor (NASICON)-type Na3V2(PO4)3 has the potential to work with long cycle life and high-rate performance; however, it suffers from the poor intrinsic electronic conductivity and low energy density. Herein, Ga3+ is introduced into Na3V2(PO4)3 to activate the V4+/V5+ redox couple at a high potential of 4.0 V for enhancing energy density of the materials (Na3V2-xGax(PO4)3). After the partial substitution of Ga3+ for V3+, three redox couples (V2+/V3+, V3+/V4+ and V4+/V5+) of V are reversibly converted in the voltage range of 1.4–4.2 V, suggesting multi-electrons (>2e−) involved in the reversible reaction, and simultaneously the electronic conductivity of the materials is effectively enhanced. As a result, the cathode with x = 0.75 exhibits excellent electrochemical properties: in the voltage range of 2.2–4.2 V, delivering an initial capacity of 105 mAh/g at 1C with a capacity retention rate of 92.3% after 400 cycles, and providing a stable reversible capacity of 88.3 mAh/g at 40C; and in the voltage range of 1.4–4.2 V, presenting the reversible capacity 152.3 mAh/g at 1C (497.6 Wh kg−1), and cycling stably for 1000 cycles at 20C with a capacity decay of 0.02375% per cycle. It is found that the Na3V2-xGax(PO4)3 cathodes possess the sodium storage mechanism of single-phase and bi-phase reactions. This investigation presents a useful strategy to enhance the energy density and cycling life of NASICON-structured polyanionic phosphates by activating high-potential V4+/V5+ redox couple.