Transactions of the Korean hydrogen and new energy society (한국수소및신에너지학회논문집)

The Korean Hydrogen and New Energy Society (한국수소및신에너지학회)
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The Preparation and Characteristics of Covalently Cross-Linked SPEEK/Cs-TPA/Ceria Composite Membranes for Water Electrolysis

수전해용 공유가교 SPEEK/Cs-TPA/Ceria 복합막의 제조 및 특성 연구

  • Received : 2012.08.30
  • Accepted : 2012.10.26
  • Published : 2012.10.31
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Abstract

Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance and to increase the duration of the membrane. In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) and the organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted tungstophosphoric acid (Cs-TPA) with cross-linking agent contents of 0.01 mL. In conclusion, CL-SPEEK/Cs-TPA/ceria (1%) membrane showed the optimum results such as 0.130 S/cm of proton conductivity at $80^{\circ}C$, 2.324 meq./g-dry-membrane of ion exchange capacity and mechanical characteristics, and 65.03 MPa of tensile strength which were better than Nafion 117 membrane.

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References

  1. P. Millet, N. Mbemba, S. A. Grigoriev, V. N. Fateev, A. Aukauloo and C. Etiévant, "Electrochemical performances of PEM water electrolysis cells and perspectives", Int. J. Hydrogen Energy, Vol. 36, No. 6, 2011, pp. 4134-4142. https://doi.org/10.1016/j.ijhydene.2010.06.105
  2. P. W. T. Lu and J. H. Russel, "Advances in Water Electrolysis Technology with Emphasis on Use of the Solid Polymer Electrolyte", J. Appl. Elecrochem., Vol. 9, No. 3, 1979, pp. 269-283. https://doi.org/10.1007/BF01112480
  3. I. Y. Jang, O. W. Kweon, K. E. Kim, G. J. Hwang, S. B. Moon, and A. S. Kang, "Covalently crosslinked sulfonated poly(ether ether ketone)/tungstophosphoric acid composite memebranes for water electrolysis application", J. Power Sources, Vol. 181, No. 1, 2008, pp. 127-134. https://doi.org/10.1016/j.jpowsour.2008.03.022
  4. S. D. Mikhailenko, F. Celso and S. Kaliaguine, "Properties of SPEEK based membranes modified with a free radical scavenger", J. Membr. Sci., Vol. 345, 2009, pp. 315-322. https://doi.org/10.1016/j.memsci.2009.09.017
  5. P. Trogadas, J. Parrondo, and V. Ramani, "Degradation Mitigation in Polymer Electrolyte Membranes Using Free-Radical Scavengers", ECS Transactions, Vol. 16, No. 2, 2008, pp. 1725-1733. https://doi.org/10.1149/1.2982014
  6. D. Zhao, B. L. Yi, H. M. Zhang, H. M. Yu, L. Wang, Y. M. Ma and D. M. Xing, "Cesium substituted 12-tungstophosphoric ($C_{sx}H_{3-x}P W_{12}O_{40}$) loaded on ceria-degradation mitigation in polymer electrolyte membranes", J. Power Sources, Vol. 190, 2009, pp. 301-306. https://doi.org/10.1016/j.jpowsour.2008.12.133
  7. V. Ramani., H. R. Kunz and J. M. Fenton, "Stabilized heteropolyacid/Nafion composite membranes for elevated temperature/low relative humidity PEFC operation", Electro- -chimica Acta, Vol. 50, No. 5, 2005, pp. 1181-1187. https://doi.org/10.1016/j.electacta.2004.08.015
  8. S. Y. Oh, T. Yoshida, G. Kawamura, H. Muto, M. Sakai and A. Matsuda, "Proton conductivity and fuel cell property of composite electrolyte consisting of Cs-substituted heteropoly acids and sulfonated poly(ether-ether ketone)". J. Power Sources, Vol. 195, 2010, pp. 5822-5828. https://doi.org/10.1016/j.jpowsour.2010.01.063
  9. S. Y. Oh, T. Yoshida, G. Kawamura, H. muto, M. Sakai and A. Matsuda, "Composite electrolytes composed of Cs-substituted phosphotungstic acid and sulfonated poly(ether ether ketone) for fuel cell systems", Mater. Sci. Eng. B, Vol. 173, 2010, pp. 260-266. https://doi.org/10.1016/j.mseb.2010.03.002
  10. S. L. Rhoden and C. A. Linkous, "The optimization of SPEEK membranes using Phosphotungstic acid as a dopant", ECS Trans., Vol. 16, No. 2, 2008, 1461-1469. https://doi.org/10.1149/1.2981987
  11. C. Amold and R. A. Assink, "Structure- Property Relationships of Anionic Exchange Membranes for Fe/Cr Redox Storage Batteries", J. Appl. Polym. Sci., Vol. 29, No. 7, 1984, pp. 2317-2330. https://doi.org/10.1002/app.1984.070290708
  12. F. G. Helfferich, "Ion Exchange", MaGrawHill Book Co., New Yock, 1962.
  13. N. Li, Z. Cui, S. Zhang, S. Li and F. Zhang, "Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides", J. Power Sources, Vol. 172, 2007, pp. 511-519. https://doi.org/10.1016/j.jpowsour.2007.07.069
  14. M. L. Ponce, "Organic-Inorganic hybrid membranes with heteropolyacids for DMFC applications", Ph. D. Dissertation, University of Hamburg, Hamburg, 2004.
  15. Doo-Young Jang, In-Young Jang, Oh-Hwan Kweon, Kyoung-Eon Kim, Gab-Jin Hwang, An-Soo Kang, "Characterizations of Pt-SPE electrocatalysts prepared by an impregnation-reduction method for water electrolysis", Trans. of the Korean Hydrogen and New Energy Society, Vol. 17, No. 4, 2006, pp. 440-447.
  16. Y. S. Kim, F. Wang, M. Hickner, T. A. Zawodzinski, and J. E. McGrath, "Fabrication and Characterization of Heteropolyacid/Directly Polymerized Sulfonated Poly(arylene ether sulfone) Copolymer Composite Membranes for Higher Temperature Fuel Cell Applications", J. Membr. Sci., Vol. 212, 2003, pp. 263-282. https://doi.org/10.1016/S0376-7388(02)00507-0
  17. G. D. Yadav and N. S. Asthana, "Selective decomposition of cumene hydroperoxide into phenol and acetone by a novel cesium substituted heteropolyacid on clay", Applied Catalysis A: General, Vol. 244, No. 2, 2003, pp. 341-357. https://doi.org/10.1016/S0926-860X(02)00605-1
  18. G. R. Rao and T. Rajkumar, "Interaction of Keggin anions of 12-tungstophosphoric acid with $C_{ex}Zr_{1-x}O_{2}$ solid solutions", J. Colloid Interface Sci., Vol. 324, 2008, pp. 134-141. https://doi.org/10.1016/j.jcis.2008.04.070
  19. H. Dogan, T. Y. Inan, E. Unveren and M. Kaya, "Effect of cesium salt of tungstophosphoric acid (Cs-TPA) on the properties of sulfonated polyether ether ketone(SPEEK) composite membranes for fuel cell applications", Int. J. Hydrogen Energy, Vol. 35, 2010, pp. 7784-7795. https://doi.org/10.1016/j.ijhydene.2010.05.045
  20. Y. Zhang, Tingdong Du, Xuan An, Zhengyu Tu, Guodong Zhang, "Study on Ce-doped nonstoichiometric nanosilica for promoting properties of polysulfone membranes", Chem. Eng. Technol., Vol. 33, No. 4, 2010, pp. 676-681.
  21. R. W. Kopitzke, C. A. Linkous, H. R. Anderson and G. L. Nelson, "Conductivity and water uptake of aromatic-based proton exchange membrane electrolytes", J. Electrochem. Soc., Vol. 147, 2000, pp. 1677-1681. https://doi.org/10.1149/1.1393417
  22. P. Genova-Dimitrova, B. Baradie, D. Foscallo, C. Poinsignon and J. Y. Sanchez, "Ionomeric membranes for proton exchange membrane fuel cell (PEMFC): sulfonated polysulfone associated with phosphatoanimonic acid", J. Membr. Sci., Vol. 185, 2001, pp. 59-71. https://doi.org/10.1016/S0376-7388(00)00634-7

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  1. Research of Characterization of Covalently Cross-linked SPEEK/Cs-Substituted MoPA/Ceria 1wt% Composite Membrane for Water Electrolysis vol.25, pp.1, 2014, https://doi.org/10.7316/KHNES.2014.25.1.001