DOI QR코드

DOI QR Code

Proton Conduction in Y2O3-doped SrZrO3

Y2O3가 도핑된 SrZrO3에서의 프로톤전도도

  • 백현덕 (홍익대하교 재료공학부)
  • Published : 2002.07.01

Abstract

Electrical conduction of $SrZrO_3$ doped with $Y_2O_3$ was measured as a function of gas atmosphere and temperature by impedance spectroscopy. Hydrogen dissolution, due to an enhanced driving force in the presence of oxygen, results in protonation by water incorporation. Proton conductivity increased with water vapor pressure, ${P_w}^{1/2}$. In the pure hydrogen atmosphere, the dissolution of hydrogen,$H_2(g)=2H_{i}$ +2e', is supposed to be driven by a reduced activity of electrons, ascribable to their trapping in oxygen vacancies. The activation energy of electrical conductivity was 50 kJ/mol, in wet argon atmosphere in the temperature range of $600~900^{\circ}C$, similar to those reported for proton conduction in the literature. Grain boundary effect in proton conduction was substantial in the 10% doped case at temperatures lower than $700^{\circ}C$.

고온 프로톤전도체인 $Y_2O_3$가 도핑된 $SrZrO_3$에 대하여 전기전도도의 가스 분위기 및 온도 의존도를 impedance spectroscopy로 측정하였다. 수소의 용해는 산소가 공존할 때 더 큰 열역학적 추진력을 갖게 되어 결과적으로 수증기 형태로 결정 속으로 유입되며, 프로톤전도도는 ${P_w}^{1/2}$ (수증기분압)에 의존하여 증가하였다. 순수 수소 분위기에서의 수소의 용해반응 $H_2(g)=2H_{i}$ +2e'은 전자가 산소이온공공에 trapping됨에 따른 열역학적 활동도의 감소에 의해 반응의 추진력이 커지며 그 결과 저온에서는 아르곤 분위기에서 보다 높은 전기전도도를 나타내었다. 전기전도도의 활성화에너지는 $600~900^{\circ}C$ 온도범위의 아르곤분위기에서 50kJ/mo1로 문헌에 나타난 프로톤전도도의 그것과 비슷한 크기를 나타냈다. 프로톤전도도의 입계저항은 10% 도핑한 경우 $700^{\circ}C$ 이하의 저온에서 현저하게 나타났다.

Keywords

References

  1. Solid State Ionics v.61 Defect Structure of SrZrO₃ J. A. Labrincha;J. R. Frade;F. M. B. Marques https://doi.org/10.1016/0167-2738(93)90336-2
  2. Solid State Ionics v.86-88 An Optical In-situ Study of BaCeO₃at High Temperatures T. He;P. Ehrhart https://doi.org/10.1016/0167-2738(96)82671-3
  3. Solid State Ionics v.97 A Conductivity and Thermal Gravimetric Analysis of a Y-doped SrZrO₃Single Crystal J. Muller;K. D. Kreuer;J. Maier;S. Matsuo;M. Ishigame https://doi.org/10.1016/S0167-2738(97)00087-8
  4. Solid State Ionics v.95 Impedance Spectroscopic Study of Thermodynamics and Kinetics of a Gd-doped BaCeO₃Single Crystal T. He;K. D. Kreuer;Y. M. Baikov;J. Maier https://doi.org/10.1016/S0167-2738(96)00613-3
  5. Solid State Ionics v.145 Water Vapor Solubility and Impedance of the High Temperature Proton Conductor $SrZr_{0.9}Y_{0.1}O_{2.95}$ T. Schober https://doi.org/10.1016/S0167-2738(01)00926-2
  6. Solid State Ionics v.59 Electrical Properties of $SrCe_{0.95}Yb_{0.05}O_3$ in Hydrogen Containing Atmospheres I. Kosacki;J. G. M. Becht;R. van Landschoot;J. Schoonman https://doi.org/10.1016/0167-2738(93)90063-9
  7. Solid State Ionics v.86-88 Investigation of N-type Electronic Defects in the Protonic Conductor $SrCe_{1-x}Y_xO_{3-δ}$ U. Reichel;R. R. Arons;W. Schilling https://doi.org/10.1016/0167-2738(96)00228-7
  8. Solid State Ionics v.97 Thermoelectric power of $SrCe_{0.95}Y_{0.05}O_{3-δ}$ E. O. Ahlgren https://doi.org/10.1016/S0167-2738(97)00072-6
  9. Solid State Ionics v.125 Structural and Electrical Characterization of $SrCe_{1-x}Y_xO_ζ R.J. Phillips;N. Bonanos;F.W. Poulsen;E.O. Ahlgren https://doi.org/10.1016/S0167-2738(99)00200-3
  10. Hong-ik Faculty J. v.7 Electrical Conduction of HTPCs in Hydrogen Atmosphere H. D. Baek
  11. Solid State Ionics v.125 Aspects on the Fromation and Mobility of Protonic Charge Carriers and the Stability of Perovskite-type Oxides K. D. Kreuer https://doi.org/10.1016/S0167-2738(99)00188-5
  12. J. Am. Ceram. Soc. v.83 no.4 Electrical Conductivity of the High-temperature Proton Conductor $BaZr_{0.9}Y_{0.1}O_{2.95}$ H. G. Bohn;T. Schober https://doi.org/10.1111/j.1151-2916.2000.tb01272.x
  13. J. Kor. Ceram. Soc. v.39 no.4 Electrical Conduction in Y-doped SrZrO₃-metal Electrode System H. D. Baek;P. H. Lee https://doi.org/10.4191/KCERS.2002.39.4.367
  14. J. Electrochem. Soc. v.142 no.5 Protonic Conduction Domain of Indium-doped Calcium Zirconate N. Kurita;N. Fukatsu;K. Ito;T. Ohashi https://doi.org/10.1149/1.2048611
  15. Kor. J. Ceram. v.5 no.3 Electrical Conduction in $SrZr_{0.95}Y_{0.05}O_{2.975}$ Ceramics H. D. Baek;J. H. Noh
  16. Ber. Bunsenges. Phys. Chem. v.101 no.7 Pressure/Composition Isotherms of Proton Conducting $SrYb_{0.05}Zr_{0.95}O_{2.975}/H_2O by Means of Nuclear Resonance Reaction Analysis R. Hempelmann;J. Eschenbaum;M. Altmayer;B. Gro-β https://doi.org/10.1002/bbpc.19971010702
  17. British Ceramic Proceedings no.56 Ceramic Oxygen Ion Conductors and their Technical Applications;Oxygen Diffusion in a Acceptor-doped SrCeO₃and CaZrO₃ R. A. De Souza;G. Gibson;J. A. Kilner;B. C. H. Steele(ed.)
  18. Solid State Ionics v.92 The High-temperature Proton Conductor$ Ba_3(Ca_{1.18}Nb_{1.82})O_{9-δ}$ : Thermogravimetry of the Water Uptake F. Krug;T. Schober https://doi.org/10.1016/S0167-2738(96)00484-5
  19. J. Am. Ceram. Soc. v.80 no.3 The High-temperature Proton Conductor Strontium Zirconate: Thermogravimetry of the Water Uptake F. Krug;T. Schober https://doi.org/10.1111/j.1151-2916.1997.tb02902.x
  20. J. Am. Ceram. Soc. v.71 no.1 Solubility of Hydrogen Defects in Doped and Undoped BaTiO₃ R. Waser https://doi.org/10.1111/j.1151-2916.1988.tb05760.x
  21. J. Chem. Phys. v.25 no.6 Hydrogen as a Donor in Zinc Oxide D. G. Thomas;J. J. Lander https://doi.org/10.1063/1.1743165
  22. Solid State Ionics v.116 Electronic Structures of Hydrogen and Acceptor Ions in Perovskite-type Oxide, SrZrO₃ M. Yoshino;K. Nakatsuka;H. Yukawa;M. Morinaga https://doi.org/10.1016/S0167-2738(98)00343-9
  23. Thermodynamics of Solids(2nd Ed.) R. A. Swalin
  24. Phys. Rev. v.123 no.5 Description of Impurity Ionization in Semiconductors by Chemical Thermodynamics W. W. Harvey https://doi.org/10.1103/PhysRev.123.1666
  25. Z. Naturforsch. v.31a Electrochemical Transient Investigations of the Diffusion and Concentration of Electrons in Yttria Stabilized Zirconia-solid Electrolytes W. Weppner
  26. J. Phys. Chem. Solids v.38 Small Polaron Electron Transport in Reduced CeO₂ Single Crystals K. L. Tuller;A. S. Nowick https://doi.org/10.1016/0022-3697(77)90124-X
  27. Solid State Ionics v.120 Electrical Conducting Properties of Proton-conducting Terbium-doped Strontium Cerate Membrane X. Qi;Y. S. Lin https://doi.org/10.1016/S0167-2738(99)00013-2
  28. Solid State Ionics v.143 Hydrogen Ion Conduction in Iron-substituted Strontium Titanate, $SrTi_{1-x}Fe_xO_{3-x/2}(0≤x≤0.8)$ S. Steinsvik;Y. Larring;T. Norby https://doi.org/10.1016/S0167-2738(01)00838-4
  29. Solid State Ionics v.82 Investigation of Protonic Conduction in Yb- and Y-doped Barium Zirconates R. C. T. Slade;S. D. Flint;N. Singh https://doi.org/10.1016/0167-2738(95)00212-8

Cited by

  1. Perovskites vol.50, pp.14, 2011, https://doi.org/10.1021/ic201008v