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

The Korean Hydrogen and New Energy Society (한국수소및신에너지학회)
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Study of Synthesis and Performance of Covalently Cross-Linked SPEEK/Cs-TSiA Composite Membranes with Ceria Contents for Water Electrolysis

수전해용 공유가교 SPEEK/Cs-TSiA 막의 Ceria의 함량에 따른 제조 및 성능 연구

  • Received : 2015.05.30
  • Accepted : 2015.06.30
  • Published : 2015.06.30
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Abstract

The engineering plastic of sulfonated polyether ether ketone (SPEEK) as a polymer matrix has been developed in this lab to replace Nafion, solid polymer electrolytes of perfluorosulfonic acid membrane which has several flaws such as high cost, and limited operational temperature above $80^{\circ}C$. The SPEEK was prepared in the sulfonation reaction of polyether ether ketone (PEEK). The organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted tungstosilicic acid (Cs-TSiA) with cross-linking agent contents of 0.01 mL. In conclusion, CL-SPEEK/Cs-TSiA/ceria 1% membrane showed the optimum results such as 0.1882 S/cm of proton conductivity at $80^{\circ}C$, and 99.61 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. Etievant, "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. 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
  5. D. Zhao, B. L. Yi, H. M. Zhang, H. M. Yu, L. Wang, Y. M. Ma, and D. M. Xing, "Cesium substituted 12-tungstophosphoric ($Cs_xH_{3-x}P\;W_{12}O_{40}$) 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
  6. S. S. Mohtar, A. F. Ismail, and T. Matsuura, "Preparation and characterization of SPEEK/MMTSTA composite membrane for DMFC application", J. Membrane Science, Vol. 371, 2011, pp. 10-19. https://doi.org/10.1016/j.memsci.2011.01.009
  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. M. Amirinejad, S. S. Madaeni, E. Rafiee, and S. Amirinejad, "Cesium hydrogen salt of heteropolyacids/ Nafion nanocomposite membranes for proton exchange membrane fuel cells", J. Membrane Science, Vol. 377, 2011, pp. 89-98. https://doi.org/10.1016/j.memsci.2011.04.014
  9. D. Zhao, B. L. Yi, H. M. Zhang, H. M. Yu, L. Wang, Y. M. Ma, and D. M. Xing, "Cesium substituted 12-tungstophosphoric ($Cs_xH_{3-x}P\;W_{12}O_{40}$) 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
  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, pp. 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. A. F. Ismail, N. H. Othman, and A. Mustafa, "Sulfonated polyether ether ketone composite membrane using tungstosilicic acid supported on silicaaluminium oxide for direct methanol fuel cell (DMFC)", J. Membrane Science, Vol. 329, pp. 18-29.
  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. 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
  16. G. R. Rao, and T. Rajkumar, "Interaction of Keggin anions of 12-tungstophosphoric acid with $Ce_xZr_{1-x}O_2$ solid solutions", J. Colloid Interface Sci., Vol. 324, 2008, pp. 134-141. https://doi.org/10.1016/j.jcis.2008.04.070
  17. F. Meng, N. V. Aieta, S. F. Dec, J. L. Horan, D. Williamson, M. H. Frey, P. Pham, J. A. Turner, M. A. Yandrasits, S. J. Hamrocke, and A. M. Herring, "Structural and transport effects of doping perfluorosulfonic acid polymers with the heteropoly acids, $H_3PW_{12}O_{40}orH_4SiW_{12}O_{40}$", Electrochim. Acta., Vol. 53, 2007, pp. 1372-1378. https://doi.org/10.1016/j.electacta.2007.06.047
  18. T. Okuhara, H. Watanabe, T. Nishimura, K. Inumaru, and M. Misono, "Microstructure of Cesium Hydrogen Salts of 12-Tungstophosphoric Acid Relevant to Novel Acid Catalysis", Chem. Mater., Vol. 12, 2000, pp. 2230-2238. https://doi.org/10.1021/cm9907561
  19. 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
  20. S. Guhan, and D. Sangeetha, "Evaluation of sulfonated poly(ether ether ketone) silicotungstic acid composite membranes for fuel cell applications", Int. J. Polym. Mater., Vol. 58, 2009, pp. 87-98.