Polymorphism in PbBiOXO4 compounds (X=V, P, As): Part II—PbBiOPO4 and PbBiOAsO4 structures and characterization of related solid solutions

Reinvestigation of PbBiOXO4 (X=V, P, As) thermal behaviour revealed a phase transition for V- and P-compounds, but no transition for the As-compound. As shown by single-crystal X-ray diffraction and high-resolution neutron powder diffraction, α-PbBiOVO4 transforms to β-PbBiOVO4 at 550 °C. The two PbBiOPO4 varieties are isomorph to the vanadate forms, while PbBiOAsO4 adopts the β-type structure whatever the temperature. PbBiP1−xOAsxO4 and PbBiV1−xOMxO4 (M=As, P, Cr, Mn) solid solutions display both triclinic and monoclinic domains, and the α→β transition temperature is a function of the substitution rate. The ionic conductivity of these compounds was investigated by impedance spectroscopy. The analysis of free space in the β-PbBiOVO4 structure allows to propose a one-dimensional oxygen diffusion pathway along [010] when the temperature increases.