Study of Electrical Conductivity of BaZr0.85-xPdxY0.15O3-δ/ Carbonates Composite Materials

BaZr0.85-xPdxY0.15O3-δ/ Carbonates 복합전도체 전기적 특성 연구

  • Park, Ka-Young (Department of Nanotechnology and Advanced Materials Engineering, Sejong University) ;
  • Baek, Seung-Seok (Department of Nanotechnology and Advanced Materials Engineering, Sejong University) ;
  • Park, Jun-Young (Department of Nanotechnology and Advanced Materials Engineering, Sejong University)
  • 박가영 (세종대학교 나노신소재공학과) ;
  • 백승석 (세종대학교 나노신소재공학과) ;
  • 박준영 (세종대학교 나노신소재공학과)
  • Received : 2014.06.16
  • Accepted : 2014.07.08
  • Published : 2014.07.31


PdO-doped $BaZr_{0.85}Y_{0.15}O_{3-\delta}$ (BZPY) proton conductors have been proposed as applicable for intermediate temperature electrolytes for protonic ceramic fuel cells (PCFCs) because the PdO doping is effective for improving the proton conductivity of $BaZr_{0.85}Y_{0.15}O_{3-\delta}$ (BZY) with high affinity for hydrogen. In order to further improve the conductivity of BZPY, two-phase composite electrolytes consisting of a BZPY and molten carbonate were designed. Dense BZPY-based composite electrolytes were fabricated after sintering at $670^{\circ}C$ for 4 h, since molten carbonates fill the grain boundary of the porous BZPY matrix. Furthermore, BZPY/$(Li-0.5Na)_2CO_3$ composites show a significantly enhanced protonic conductivity at intermediate temperatures. This may be because easy proton transport is possible through the interface of the carbonate and oxide phase.


Supported by : 미래부


  1. E. D. Wachsman and K. T. Lee, "Lowering the Temperature of Solid Oxide Fuel Cells," Science, 334 [6058] 935-39 (2011).
  2. S. M. Haile, "Fuel Cell Materials and Components," Acta Mater., 51 [19] 5981-6000 (2003).
  3. B. C. H. Steele, "Appraisal of $Ce_{1-x}Gd_yO2_{-y/2}$ Electrolytes for IT-SOFC Operation at $500^{\circ}C$," Solid State Ionics, 129 [1-4] 95-110 (2000).
  4. J. G. Li, T. Ikegami, and T. Mori, "Low Temperature Processing of Dense Samarium-doped $CeO_2$ Ceramics: Sintering and Grain Growth Behaviors," Acta Mater., 52 [8] 2221-28 (2004).
  5. Y. P. Fu, "Electrochemical Performance of $La_{0.9}Sr_{0.1}Cer_{0.8}Ni_{0.2}$O_{3-{\delta}}-Ce_{0.8}Sm_{0.2}O_{1.9}$ Composite Cathode for Solid Oxide Fuel Cells," Int. J. Hydrogen Energy, 36 [9] 5574-80 (2011).
  6. H. Iwahara, T. Esaka, H. Uchida, and N. Maeda, "Proton Conduction in Sintered Oxides and Its Application to Steam Electrolysis for Hydrogen Production," Solid State Ionics, 3/4 359-63 (1981).
  7. H. Iwahara, T. Esaka, H. Uchida, and N. Maeda, "Studies on Solid Electrolysis Gas Cells with High-temperature-type Proton Conductor and Oxide Ion Conductor," Solid State Ionics, 11 109-15 (1983).
  8. K. Nomura and H. Kageyama, "Transport Properties of $Ba(Zr_{0.8}Y_{0.2}$)$O_{3-{\delta}}$ Perovskite," Solid State Ionics, 178 [7-10] 661-65 (2007).
  9. L. Malavasi, C. A. J. Fisher, and M. S. Islam, "Oxide-ion and Proton Conducting Electrolyte Materials for Clean Energy Applications: Structural and Mechanistic Features," Chem. Soc. Rev., 39 [11] 4370-87 (2010).
  10. K. D. Kreuer, "Proton-conducting Oxides," Annu. Rev. Mater. Res., 33 333-59 (2003).
  11. M. A. Azimova and S. McIntosh, "Transport Properties and Stability of Cobalt doped Proton Conducting Oxides," Solid State Ionics, 180 [2-3] 160-67 (2009).
  12. D. Han, Y. Nose, K. Shinoda, and T. Uda, "Site Selectivity of Dopants in $BaZr_{1-y}M_yO_{3-{\delta}}$ (M = Sc, Y, Sm, Eu, Dy) and Measurement of Their Water Contents and Conductivities," Solid State Ionics, 213 2-7 (2012).
  13. H. Iwahara, T. Yajima, T. Hibino, K. Ozaki, and H. Suzuki, "Protonic Conduction in Calcium, Strontium and Barium Zirconates," Solid State Ionics, 61 [1-3] 65-69 (1993).
  14. K. H. Ryu and S. M. Haile, "Chemical Stability and Proton Conductivity of Doped $BaCeO_3$-$BaZrO_3$ Solid Solutions," Solid State Ionics, 125 [1-4] 355-67 (1999).
  15. A. Magrez and T. Schober, "Preparation, Sintering, and Water Incorporation of Proton Conducting $Ba_{0.99}Zr_{0.8}Y_{0.2}O_{3-{\delta}}$: Comparison between Three Different Synthesis Techniques," Solid State Ionics, 175 [1-4] 585-88 (2004).
  16. E. Fabbri, D. Pergolesi, S. Licoccia, and E. Traversa, "Does the Increase in Y-dopant Concentration Improve the Proton Conductivity of Ba$Zr_{1-x}$Yx$O_{3-{\delta}}$ Fuel Cell Electrolytes?," Solid State Ionics, 181 [21-22] 1043-51 (2010).
  17. S. Ricote and N. Bonanos, "Enhanced Sintering and Conductivity Study of Cobalt or Nickel doped Solid Solution of Barium Cerate and Zirconate," Solid State Ionics, 181 694-700 (2010).
  18. T. Schober and H. G. Bohn, "Water Vapor Solubility and Electrochemical Characterization of the High Temperature Proton Conductor $BaZr_{0.9}Y_{0.1}O_{2.95}$," Solid State Ionics, 127 [3-4] 351-360 (2000).
  19. S. Tao and J. T. S. Irvine, "Conductivity Studies of Dense Yttrium-doped $BaZrO_3$ Sintered at $1325^{\circ}C$," J. Solid Sate Chem., 180 [12] 3493-503 (2007).
  20. D. Gao and R. Guo, "Structural and Electrochemical Properties of Yttrium-doped Barium Zirconate by Addition of CuO," J. Alloys Comp., 493 [1-2] 288-93 (2010).
  21. J. S. Park, J. H. Lee, H. W. Lee, and B. K. Kim, "Low Temperature Sintering of $BaZrO_3$-based Proton Conductors for Intermediate Temperature Solid Oxide Fuel Cells," Solid State Ionics, 181 [3-4] 163-67 (2010).
  22. S. S. Beak, K. Y. Park, T. H. Lee, N. Lee, Y. Seo, S. J. Song, and J. Y. Park, "PdO-doped $BaZr_{0.8}Y_{0.2}O_3$-${\delta}$ Electrolyte for Intermediate-temperature Protonic Ceramic Fuel Cells," Acta Mater., 66 273-83 (2014).
  23. M. Benamira, A. Ringuede, V. Albin, R. N. Vannier, L. Hildebrandt, C. Lagereren, and M. Cassir, "Gadolinia-doped Ceria Mixed with Alkali Carbonates for Solid Oxide Fuel Cell Applications: I. A Thermal, Structural and Morphological Insight," J. Power Sources, 196 [13] 5546-54 (2011).
  24. B. Zhu, X. Liu, P. Zhou, X. Yang, Z. Zhu, and W. Zhu, "Innovative Solid Carbonate-ceria Composite Electrolyte Fuel Cells," Electrochem. Commun., 3 [10] 566-71 (2001).
  25. M. Mizuhata, T. Ohashi, and A. B. Beleke, "Electrical Conductivity and Related Properties of Molten Carbonates Coexisting with Ceria-based Oxide Powder for Hybrid Electrolyte," Int. J. Hydrogen Eng., 37 [24] 19407-16 (2012).
  26. L. Fan, M. Chen, C. Wang, and Bin Zhu, "$Pr_2NiO_4$-Ag Composite Cathode for Low Temperature Solid Oxide Fuel Cells with Ceria-carbonate Composite Electrolyte," Int. J. Hydrogen Eng., 37 [24] 19388-94 (2012).
  27. K. Y. Park, T. H. Lee, J. T. Kim, N. Lee, Y. Seo, S. J. Song, and J. Y. Park. "Highly Conductive Barium Zirconate-based Carbonate Composite Electrolytes for Intermediate Temperature-protonic Ceramic Fuel Cells," J. Alloys Comp., 585 103-10 (2014).
  28. S. Shawuti and M. A. Gulgun, "Solid Oxide-molten carbonate Nano-composite Fuel Cells: Particle Size Effect," J. Power Sources, 267 128-35 (2014).
  29. X. Wang, Y. Ma, S. Li, A.-H. Kashyout, B. Zhu, and M. Muhammed, "Ceria-based Nanocomposite with Simultaneous Proton and Oxygen Ion Conductivity for Low-temperature Solid Oxide Fuel Cells," J. Power Sources, 196 2754-58 (2011).
  30. X. Wang, Y. Ma, and B. Zhu, "State of the Art Ceria-carbonate Composites (3C) Electrolyte for Advanced Low Temperature Ceramic Fuel Cells (LTCFCs)," Int. J. Hydrogen Eng., 37 [24] 19417-25 (2012).
  31. R. Huck, U. Bottger, D. Kohl, and G. Heiland, "Spillover Effects in the Detection of $H_2$ and $CH_4$ by Sputtered $SnO_2$ Films with Pd and PdO Deposits," Sens. Actuators, 17 [3-4] 355-59 (1989).