Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells

GAO Qijun, HUANG Mianyan, WANG Yuxin, CAI Yuquan, XU Li

PDF(332 KB)
PDF(332 KB)
Front. Chem. Sci. Eng. ›› 2008, Vol. 2 ›› Issue (1) : 95-101. DOI: 10.1007/s11705-008-0012-5

Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells

  • GAO Qijun, HUANG Mianyan, WANG Yuxin, CAI Yuquan, XU Li
Author information +
History +

Abstract

Sulfonated poly(ether ether ketone) (SPEEK) is a very promising alternative membrane material for direct methanol fuel cells. However, with a fairly high degree of sulfonation (DS), SPEEK membranes can swell excessively and even dissolve at high temperature. This restricts membranes from working above a high tolerable temperature to get high proton conductivity. To deal with this contradictory situation, insolvable zirconium tricarboxybutylphosphonate (Zr(PBTC)) powder was employed to make a composite with SPEEK polymer in an attempt to improve temperature tolerance of the membranes. SPEEK/Zr(PBTC) composite membranes were obtained by casting a homogeneous mixture of Zr(PBTC) and SPEEK in N,N-dimethylacetamide on a glass plate and then evaporating the solvent at 60°C. Many characteristics were investigated, including thermal stability, liquid uptake, methanol permeability and proton conductivity. Results showed significant improvement not only in temperature tolerance, but also in methanol resistance of the SPEEK/Zr(PBTC) composite membranes. The membranes containing 30 wt-% ∼ 40 wt-% of Zr(PBTC) had their methanol permeability around 10-7 cm2·s-1 at room temperature to 80°C, which was one order of magnitude lower than that of Nafion ¯115. High proton conductivity of the composite membranes, however, could also be achieved from higher temperature applied. At 100% relative humidity, above 90°C the conductivity of the composite membrane containing 40 wt-% of Zr(PBTC) exceeded that of the Nafion ¯115 membrane and even reached a high value of 0.36 S·cm-1 at 160°C. Improved applicable temperature and high conductivity of the composite membrane indicated its promising application in DMFC operations at high temperature.

Cite this article

Download citation ▾
GAO Qijun, HUANG Mianyan, WANG Yuxin, CAI Yuquan, XU Li. Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells. Front. Chem. Sci. Eng., 2008, 2(1): 95‒101 https://doi.org/10.1007/s11705-008-0012-5

References

1. Hogarth M P Hards G A Direct methanol fuel cells,technological advances and further requirementsPlatinum Met Rev 1996 40(4)50157
2. Li L Xu L Wang Y X Study on the preparation and properties of sulfonated polyetherether ketone membranesActa Polymeric Sinica 2003 (3)452455(in Chinese)
3. Li L Xu L Wang Y X Study on the preparation and properties of sulfonated phenolphthaleinpoly(ether sulfone) membranesActa PolymericSinica 2003 (4)465468(in Chinese)
4. Ren X Zawadzinski T A Uribe F Dai H Methanol cross-overin direct methanol fuel cellsElectrochemSoc Proc 1995 95(23)284289
5. Heinzel A Barragan V M A review of the state-of-the-artof the methanol crossover in direct methanol fuel cellsJ Power sources 1999 847074
6. Li Q F Huang R H Approaches and recent developmentof polymer electrolyte membranes for fuel cells operating above 100°CChem Mater 2003 1548964915
7. Li L Zhang J Wang Y X Sulfonated poly(ether ether ketone) membranes for directmethanol fuel cellJ Membr Sci 2003 22659167
8. Kreuer K D Onthe development of proton conducting polymer membrane for hydrogenand methanol fuel cellsJ Membr Sci 2001 1852939
9. Bauer B Jones D J Roziere J Tchicaya L Alberti G Casciola M Massinelli L Peraio A Besse S Ramunni E Electrochemical characterization of sulfonatedpolyetherketone membranesJ New Mater ElectrochemSyst 2000 38792
10. Silva V S Ruffmann B Silva H Gallego Y A Mends A Madeira L M Nunes S P Proton electrolyte membraneproperties and direct methanol fuel cell performance. I: characterizationof hybrid sulfonated poly(ether ether ketone)/zirconium oxide membranesJ Power Sources 2005 1403440
11. Silva V S Schirmer J Reissner R Ruffmann B Silva H Mendes A Madeira L M Nunes S P Proton electrolyte membrane properties and direct methanolfuel cell performance. II: fuel cell performance and membrane propertieseffectsJ Power Sources 2005 1404149
12. Alberti G Casciola M Composite membranes for medium-temperaturePEM fuel cellsAnnu Rev Mater Res 2003 33129136
13. Yamazaki Y Jang M Y Taniyama T Proton conductivity of zirconium tricarboxybutyl phosphonate/PBInanocomposite membraneSci Tech AdvancedMaterial 2004 5455459
14. Jang M Y Yamazaki Y Preparation, characterizationand proton conductivity of membrane based on zirconium tricarboxybutylphosphonateand polybenzimidazole for fuel cellsSolidState Ionics 2004 167107112
15. Stein E W Clearfield A Subramanian M A Conductivity of group IV metal sulfophosphonate and a newclass of interstratified metal amine-sulfophosphonatesSolid State Ionics 1996 83113124
16. Li L Xu L Wang Y X Novel proton conducting composite membranes for directmethanol fuel cellMater Lett 2003 57(8)14061410
17. Kim Y T Song M K Kim K H Park S B Min S K Rhee H W Nafion/ZrSPPcomposite membrane for high temperature operation of PEMFCsElectrochemical Acta 2004 50645648
18. Bishop M T Karasz F E Russo P S Langley K H Solubilityand properties of a poly(aryl ether ketone) in strong acidsMacromolecules 1985 188693
19. Tricoli V Carretta N Bartolozz M A comparative investigation of proton conductivity andmethanol transport in fluorinated ionomeric membranesJ Electrochem Soc 2000 14712861292
20. Kopitzke R W Linkous C A Anderson H R Nelson G L Conductivityand water uptake of aromatic-based proton exchange membrane electrolytesJ Electrochem Soc 2000 14716771681
AI Summary AI Mindmap
PDF(332 KB)

Accesses

Citations

Detail

Sections
Recommended

/