Crystal structure of nickel orthovanadate (Ni₃V₂O₈) at 299 (3) K and 1323 (8) K: an X-ray diffraction study

Nickel orthovanadate is a promising material with potential applications in energy storage and photocatalytic devices. The crystal structure of Ni₃V₂O₈ at 299 (3) K and 1323 (8) K was studied using X-ray powder diffraction. The sample was a single-phase orthorhombic kagome-staircase-Ni₃(VO₄)₂-type structure (space group Cmca) at both temperatures. The phase purity and morphology was studied using energy-dispersive X-ray spectroscopy and scanning electron microscopy. The refined unit-cell parameters at 299 (3) K are a = 5.93384 (4) Å, b = 11.38318 (7) Å and c = 8.23818 (5) Å, and at 1323 (8) K are a = 6.02077 (7) Å, b = 11.48838 (7) Å and c = 8.32611 (9) Å. The obtained results indicate thermal expansion anisotropy, with a largest expansivity along a. Variations in Ni-O and V-O bonds with temperature are observed. The variation in the Ni-O bond is about one order higher in magnitude than that of the V-O bond, signifying the high rigidity of V-O bonds. The unit-cell size variations with rising effective ionic volume of the divalent A ion in the A₃B₂O₈ family [A = Ni, Mg, Zn, Co, Mn (experimental data) and also A = Cu, Cd (theoretical data), B = V or As] are analyzed. Based on experimental and theoretical data, trends within the family are observed and the unit-cell size for reported solid solution of nickel (87%) and copper (13%) mixture in (Ni_1-xCu_x)₃V₂O₈ are predicted. Predictions are also provided for some hypothetical A₃B₂O₈ ternary compound and solid solutions.