Manipulating the Phase Compositions of Na3(VO1-xPO4)2F1+2x (0 ≤ x ≤ 1) and Their Synergistic Effects with Reduced Graphene Oxide toward High-Rate Sodium-Ion Batteries.
Jiarong HeTao TaoFan YangZhipeng SunPublished in: ACS applied materials & interfaces (2021)
Sodium-ion batteries (SIBs) have aroused intense research and academic interest due to the natural abundance and cost-effectiveness of sodium resources. Presently, cathode materials based on the Na3(VO1-xPO4)2F1+2x (0 ≤ x ≤ 1, NVPF1+2x) polyanionic framework show intriguing electrochemical performances toward practical and advanced SIBs due to its high operating voltage (>3.9 V) and high energy density (>500 Wh kg-1). Different from conventional approaches focusing on delicate morphology design, metal ion substitution, and the conductive matrix's incorporation to overcome the low intrinsic electrical conductivity, here we adopt a one-step microwave-assisted hydrothermal approach to optimize the electrochemical performances of NVPF1+2x via manipulating its phase compositions with different vanadium sources and distinguishing the tetragonal (I4/mmm) symmetry of the Na3(VOPO4)2F phase from the orthorhombic symmetry (Amam) of the Na3V2(PO4)2F3 phase. The introduction of the conductive reduced graphene oxide (rGO) framework and its impacts on the phase compositions were systematically investigated. The rGO framework with different calcination temperature can alter the phase composition and the electrical conductivity of NVPF1+2x cathodes significantly, thus having a great impact on their electrochemical performances. Galvanostatic charge/discharge, cyclic voltammetry, electrochemical impedance spectroscopy, and the galvanostatic intermittent titration technique are adopted to compare their electrode polarization and kinetics difference and show that NVPF@rGO-600 °C possesses a high rate, small polarization, and fast kinetics electrochemical properties. This work provides new insights into manipulating phase compositions of the NVPF1+2x cathode by modulating the synthesis conditions and revealing their synergistic effect with a rGO conductive framework toward a superior rate capability and more realistic practical applications for SIBs.