The Preparation and Physicochemical Characteristics of Covalently Cross-Linked SPEEK/HPA Composite Membranes for Water Electrolysis

수전해용 공유가교 SPEEK/HPA 복합막의 제조 및 물리화학적 특성

  • Published : 2009.04.30

Abstract

In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated (SPEEK) and the organic-inorganic blend composite membranes has been prepared by loading heteropoly acids (HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA). And then these were covalently cross-linked (CL-SPEEK/HPA) as the electrolyte and MEA of polymer electrolyte membrane electrolysis (PEME). As a result, the optimum reaction conditions of CL-SPEEK/HPA was established and the electrochemical characteristics such as ion conductivity ($\sigma$) were in the order of magnitude: CL-SPEEK /TPA30 (${\sigma}=0.128\;S/cm^{-1}$) < /MoPA40 (${\sigma}=0.14\;S/cm^{-1})$ < /TSiA30 (${\sigma}=0.22\;S/cm^{-1}$) at $80^{\circ}C$, and mechanical characteristics such as tensile strength: CL-SPEEK /TSiA30 $\fallingdotseq$ /MoPA40 < /TPA30. Consequently, in regards of above characterisitics and oxidation durability, the CL-SPEEK/TPA30 exhibited a better performance in PEME than the others, but CL-SPEEK/MoPA40 showed the best electrocatalytic activity of cell voltage 1.71 V among the composite membranes. The dual effect of higher proton conductivity and electrocatalytic activity with the addition of HPAs, causes a synergy effect.

Keywords

References

  1. S. M. J. Zaidi, S. D. Mikhailenko, G. P. Robertson, and M. D. Guiver, 'Proton Conducting Composite Membrane from Polyether ether ketone and Hetero-polyacids for Fuel Cell Applications', J. Memb. Sci., Vol. 173, No. 1, 2000, pp. 17-34 https://doi.org/10.1016/S0376-7388(00)00345-8
  2. I. Y. Jang, O. H. Kweon, K. E. Kim, G. J. Hwang, S. B. Moon, A. S. Kang, 'Covalently cross-linked sulfonated poly (ether ether ketone)/ tungstophos phoric acid composite membranes 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
  3. I. Y. Jang, O. H. Kweon, K. E. Kim, G. J. Hwang, S. B. Moon, A. S. Kang, 'Application of polysulfone (PSf)– and polyether ether ketone (PEEK)–tungstophosphoric acid (TPA) composite membranes for water electrolysis', J. Memb. Sci., Vol. 322, No. 1, 2008, pp. 154-161 https://doi.org/10.1016/j.memsci.2008.05.028
  4. M. L. Ponce, L. Prado, B. Ruffmann, K. Richau, R. Mohr, S.P. Nunes, 'Reduction of methanol permeability in polyetherketone-heteropolyacid membranes', J. Memb. Sci, Vol. 217, No. 1-2, 2003, pp. 5-15 https://doi.org/10.1016/S0376-7388(02)00309-5
  5. P. Xing, G. P. Robertson, M. D. Guiver, S. D. Mikhailenko, K. Wang, and S. Kaliaguine, 'Synthesis and Characterization of Sulfonated Poly(ether ether ketone) for Proton Exchange Membranes', J. Membr. Sci, Vol. 229, No. 1-2, 2004, pp. 95-106 https://doi.org/10.1016/j.memsci.2003.09.019
  6. C. Arnold 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
  7. F. G. Helfferich, 'Ion Exchange', MaGraw-Hill Book Co., New York, 1962
  8. N. Fujiwara, K. Yasuda, T. Ioroi, Z. Siroma and Y. Miyazaki, 'Preparation of platinumruthenium onto solid polymer electrolyte membrane and the application to a DMFC anode', Electrochimica Acta, Vol. 47, 2002, pp. 4079-4084 https://doi.org/10.1016/S0013-4686(02)00414-0
  9. 장두영, 장인영, 권오환, 김경언, 황갑진, 강안수, '함침-환원법으로 제조된 수전해용 Pt-SPE 전극촉매의 특성', 한국수소 및 신에너지학회 논문집, Vol. 17, No. 4, 2006, pp.440-447
  10. 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. Memb. Sci., Vol. 212, No. 1-2, 2003, pp. 263-282 https://doi.org/10.1016/S0376-7388(02)00507-0
  11. 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. Hamrock, A. M. Herring, 'Structural and transport effects of doping perfluorosulfonic acid polymers with the heteropoly acids, $H_3PW_{12}O_{40}$ or $H_4SiW_{12}O_{40}$, Electrochimica Acta, Vol. 53, No. 3, 2007, pp. 1372-1378 https://doi.org/10.1016/j.electacta.2007.06.047
  12. J. A. Seo, D. K. Roe, J. K. Koh, and J. H. Kim, Preparation and Characterization of Proton Conducting Composite Membranes From P (VDF_CTFE)-g-PSPMA Graft Copolymer and Heteropolyacid, Kor. Membr. J., Vol. 10, No 1, 2008, pp. 20-25
  13. 황용구, '수전해용 SPEEK 전해질 막의 제조시 HPA 첨가제의 영향', 명지대학교 대학원, 박사학위논문, 용인, 2008
  14. N. E. Dowling, 'Mechanical Behaviour of Materials', Prentice-Hall, New Jersey (1993)
  15. R. J. Stanis, Mei-Chen Kuo, A. J. Rickett, J. A. Turner, A. M. Herring, 'Investigation into the activity of heteropolyacids towards the oxygen reduction reaction on PEMFC cathodes', Electrochimica Acta, Vol. 53, No. 28, 2008, pp. 8277-8286 https://doi.org/10.1016/j.electacta.2008.06.052