Phase behavior and mixed ionic–electronic conductivity of Ba4Sb2O9

The 6H-type perovskite phase Ba4Sb2O9, which decomposes in air below 600 K, is found to survive to room temperature in a CO2-free atmosphere. It shows substantial mixed protonic, oxide ionic and electronic conductivity. Compared to Ba4Nb2O9 and Ba4Ta2O9, Ba4Sb2O9 shows higher ionic conductivity due to the relatively easy reducibility of Sb5 +, but lower electronic conductivity due to the predominantly n-type conductivity provided by the Sb5 +/Sb3 + redox couple which leads to reduced hole concentration under oxidizing conditions. Variable temperature synchrotron X-ray diffraction studies carried out in situ under controlled atmospheres reveal a strong monoclinic distortion below 1150 K. The hexagonal to monoclinic transition is slow, does not show second-order behavior, is strongly dependent on atmosphere, and coincides with the loss of ~ 0.4 molecules of H2O per formula unit of Ba4Sb2O9. All of this suggests an important structural role for protons or hydroxide ions in the monoclinic phase.

► A new low-temperature monoclinic phase for Ba4Sb2O9 is discovered using in-situ XRD. ► The phase transition in Ba4Sb2O9 coincides with dehydration of the structure. ► Ba4Sb2O9 shows significant mixed ionic–electronic conductivity.