Abstract
Hydrated vanadium(III) phosphate, K3V3(PO4)4·H2O, has been synthesized by a facile aqueous hydrothermal reaction. The crystal structure of the compound is determined using X-ray diffraction (XRD) analysis aided by density functional theory (DFT) computational investigation. The structure contains layers of corner-sharing VO6 octahedra connected by corner and edge-sharing PO4 tetrahedra with a hydrated K+ ion interlayer. The unit cell is assigned to the orthorhombic system (space group Pnna) with a = 10.7161(4) Å, b = 20.8498(10) Å, and c = 6.5316(2) Å. Earlier studies of this material report a K3V2(PO4)3 stoichiometry with a NASICON structure (space group R3®c). Previously reported XRD and electrochemical data on K3V2(PO4)3 are critically evaluated and we suggest that they display mixed phase compositions of K3V3(PO4)4·H2O and known electrochemically active phases KVP2O7 and K3V(PO4)2. In the present study, the synthesis conditions, structural parameters, and electrochemical properties (vs K/K+) of K3V3(PO4)4·H2O are clarified along with further physical characterization by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray fluorescence (XRF), Raman spectroscopy, Fourier transform infrared (FT-IR), and thermogravimetric analysis (TGA).