Haile, Sossina M. and Lentz, Gisela and Kreuer, Klaus-Dieter and Maier, Joachim (1995) Superprotonic conductivity in Cs_3(HSO_4)_2(H_2PO_4). Solid State Ionics, 77 . pp. 128-134. ISSN 0167-2738. doi:10.1016/0167-2738(94)00291-Y. https://resolver.caltech.edu/CaltechAUTHORS:20131125-162531989
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Abstract
Investigations of solid solutions of CsHSO4 and CsH2PO4 have led to the discovery of a new compound with a sulfate to phosphate ratio of 2:1. Single-crystal X-ray data showed the as-synthesized phase to be monoclinic and not isostructural with any known compounds. Ac impedance measurements revealed that, upon heating, the compound undergoes a transformation into a phase of high conductivity at ~119 °C. The activation energy dropped from 0.90(2) eV to 0.45(5) eV, while the conductivity jumped from 2.5 X 10^(-5) Ω^(-1) cm^(-1) to 6.3 X 10^(-3) Ω^(-1) cm^(-1). Powder diffraction data suggest that the high-temperature phase is body-centered cubic. Although unlikely, the possibility of a Cs+ contribution to the conductivity at elevated temperatures cannot be precluded. Upon cooling, the compound remained in the high conductivity phase until 60-80 °C. At this point it transformed into a third, new phase and the conductivity dropped almost three orders of magnitude, but remained higher than in the as-synthesized compound. Given the similarities between this new compound and CsHSO_4, it is likely that high-temperature proton conduction in Cs_3(HSO_4)_2(H_2PO_4) is facilitated by sulfate and/or phosphate ion reorientations.
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| Additional Information: | Copyright © 1995 Elsevier. Many colleagues have kindly donated their time and expertise to this work. Mr. Karl Peters of MPI has provided single-crystal intensity data and Mr. Willie Rotenbach, also of MPI, performed the high-temperature powder diffraction. We gratefully thank Dr. Quintinn Johnson of MDI, who scanned in the powder film data and David McCready at PNL, who aided in the powder data analysis. Fig. 1 was drawn using the ATOMS program from Shape Software and powder data analysis was carried out using JADE software from MDI. This work was supported by the Alexander von Humboldt Foundation. | |||||||||
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| Subject Keywords: | CONDUCTIVITY-SUPERPROTONIC CS-3(HSO4)(2)(H2PO4) PHASE-TRANSITIONS DIFFRACTION CRYSTALS PRESSURE | |||||||||
| DOI: | 10.1016/0167-2738(94)00291-Y | |||||||||
| Record Number: | CaltechAUTHORS:20131125-162531989 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20131125-162531989 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 42718 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Jonathan Gross | |||||||||
| Deposited On: | 03 Dec 2013 00:34 | |||||||||
| Last Modified: | 10 Nov 2021 16:27 |
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