Phase behavior and mixed ionic-electronic conductivity of Ba4Sb2O9

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Date
2013-03-21
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Publisher
Elsevier Science BV.
Abstract
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. © 2013, Elsevier Ltd.
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Keywords
Perovskites, Protons, Stability, Hydration, Ceramics, Oxides
Citation
Dunstan, M. T., Pavan, A. F., Kharton, V. V., Avdeev, M., Kimpton, J. A., Kolotygin, V. A., Tsipis, E. V., & Ling, C. D. (2013). Phase behavior and mixed ionic-electronic conductivity of Ba4Sb2O9. Solid State Ionics, 235, 1-7. doi:10.1016/j.ssi.2013.01.008
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