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New Oxide-Ion Electrolytes

Published online by Cambridge University Press:  28 February 2011

J.B. Goodenough
Affiliation:
Center for Materials Science and Engineering, ETC 5.160University of Texas at Austin, Austin, TX 78712-1084
Y.S. Zhen
Affiliation:
Center for Materials Science and Engineering, ETC 5.160University of Texas at Austin, Austin, TX 78712-1084
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Abstract

Strategic considerations for the design of new O2--ion solid electrolytes are presented, and preliminary measurements of the oxide-ion conductivity σo = (B/T) exp (-EA/kT) and transport number tO = σO/σ are reported for several oxides with perovsldte-related structures. Ba2In2O5 exhibits a first-order transition at Tt ∼ 930°C from the brownmillerite structure to a cubic perovskite with disordered oxygen vacancies and fast O2-ion conduction. Ba3In2MO8 (M = Ce, Zr, or Hf) contains oxygen vacancies ordered into every second BO2 (001) plane. An octahedralsite preference of the disordered M(IV) cations makes incomplete the oxygen-vacancy ordering, so a high extrinsic σo with EA ∼ 0.6 eV is found for T ≤ 400 °C. The transport properties of Ba3In2ZrO8 at 400 °C are equivalent to those of the stabilized zirconias at 800 °C. BagIn6O17 consists of an intergrowth of (BaO)2 rocksalt and Ba3In3O7.5 oxygen-deficient perovskite layers. Although there is no evidence of long-range ordering of the oxygen vacancies, nevertheless an EA = 1.06 eV and transport properties equivalent to stabilized zirconia indicate retention of short-range correlations to at least 950 °C. Attempts to prepare Bag Y6O17 yielded a mixture of hexagonal Ba3Y4O9 and unidentified phases. An EA = 0.45 eV above a Tt=370 °C gives a remarkable O2--ion conductivity at temperatures T > Tt in both the mixed-phase and pure Ba3Y4O9 at temperatures T > 370 °C, but the samples are extremely hygroscopic.

Type
Research Article
Copyright
Copyright © Materials Research Society 1991

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References

1. Faraday, M., Experimental Researches in Electricity (Taylor and Francis, London, 1839) Art 1339.Google Scholar
2. Lucat, C., Thesis No. 604, Univ. of Bordeaux (1980).Google Scholar
3. Estell, T.H. and Flenglass, S.N., Chem. Rev. 70, 339 (1970).Google Scholar
4. Kilner, J.A. and Brook, R.J., Solid State Ionics 6, 237 (1982).Google Scholar
5. Takahashi, T., Iwahara, M., and Nagai, J., J. Appl. Electrochem 2, 97 (1972).Google Scholar
6. Takahashi, T. and Iwahara, M., 3, 65 (1973).Google Scholar
7. Takahashi, T., Iwahara, M., and Arao, T., 5, 187 (1975).Google Scholar
8. Takahashi, T., Eseka, T., and Iwahara, M., 5, 197 (1975).Google Scholar
9. Schenck, R. Von and Buschbaum, H.M., Z. anorg. allgem Chem. 405, 197 (1974).Google Scholar
10. Goodenough, J.B., Ruiz-Diaz, J.E., and Zhen, Y.S., Solid State lonics 44, (1990).Google Scholar
11. Rodriguez-Carvajal, J., Vallet-Regi, M., and Calbet, J.M. Gonzalez, Mat. Res. Bull. 24, 423 (1989).CrossRefGoogle Scholar
12. Dixon, J.M., LaGrange, L.D., Merten, U., Miller, C.F., and Porter, J.T. II, J. Electrochem. Soc. 110, 276 (1963).Google Scholar
13. Zhen, Y.S. and Goodenough, J.B., Mat. Res. Bull 25, 785 (1990).CrossRefGoogle Scholar
14. Mader, K. and Müller-Buschbaum, Hk., J. Less Common Metals 157, 71 (1990).Google Scholar
15. Steinfink, H. and Lee, J.Y., personal communication.Google Scholar
16. Kwestroo, W., Hal, H.A.M. van, and Langereis, C., Mat. Res. Bull. 9, 1631 (1974).Google Scholar