Thermal variation of structure and electrical conductivity in Bi14WO24

Structure and electrical conductivity of Bi14WO24 as a function of temperature have been examined by X-ray and neutron powder diffraction, a.c. impedance spectroscopy and differential thermal analysis. The room temperature structure was successfully refined using a monoclinic subcell model in space group I2/m. However, additional reflections in the neutron data are consistent with a large supercell of dimensions a = 17.3780(1) Å, b = 17.3891(1) Å, c = 26.1785(2) Å and β = 90.270(1)°, as previously proposed. Transitions to tetragonal and cubic phases are observed at ca. 35 °C and 780 °C, respectively. The structure of the high temperature polymorph is confirmed as a fully disordered δ-Bi2O3 type phase. Analysis of the defect structure is consistent with a predominantly tetrahedral environment for tungsten, as seen at low temperatures. The conductivity behaviour is correlated with the appearance of the δ-phase at high temperatures and exhibits a value of 0.97 S cm− 1 at 800 °C.

► High oxide ion conduction in Bi14WO24 at elevated temperatures.
► Analysis of the ambient temperature structure confirms a large monoclinic cell.
► The defect structure of HT phase consistent with predominantly tetrahedral W.
► Conductivity behaviour is correlated with the observed phase transitions.