Radiation grafted fuel cell membranes based on co-grafting of α-methylstyrene and methacrylonitrile into a fluoropolymer base film

Journal of Membrane Science

Volumn 339, Issue 1-2, 2009, Pages 68-77

  Gubler, Lorenz ^a   Slaski, Michal ^a   Wallasch, Frank ^a   Wokaun, Alexander ^a   Scherer, Günther G ^a  

^a PAUL SCHERRER INSTITUTE   (Switzerland)

Author keywords

Copolymerization; Membrane electrode assembly; Polymer electrolyte fuel cell; Proton exchange membrane; Radiation grafting

Indexed keywords

ALTERNATING COPOLYMER; COGRAFTING; COPOLYMER STRUCTURE; DEGREE OF GRAFTING; FLUOROPOLYMER; GRAFTING RATE; ION EXCHANGE CAPACITY; ISO-PROPANOL; MEMBRANE ELECTRODE ASSEMBLY; METHACRYLONITRILE; METHYLSTYRENE; OPERATING CONDITION; OXIDATIVE DEGRADATION; POLY(STYRENE SULFONIC ACID); POLYMER DEGRADATION; POLYMER ELECTROLYTE FUEL CELL; POST MORTEM ANALYSIS; PROTON EXCHANGE; PROTON EXCHANGE MEMBRANE; PROTON EXCHANGE MEMBRANES; RADIATION GRAFTING; RADICAL MECHANISM; SINGLE CELLS; SOLUTION COPOLYMERIZATION; WATER AS SOLVENT;

ALPHA PARTICLE SPECTROMETERS; CHEMICAL STABILITY; COPOLYMERIZATION; CROSSLINKING; DEGRADATION; ELECTROCHEMISTRY; ELECTROLYTIC REDUCTION; FUEL CELLS; GRAFT COPOLYMERS; GRAFTING (CHEMICAL); HYDROGEN; ION EXCHANGE; ION EXCHANGE MEMBRANES; PHOTORESISTS; POLYELECTROLYTES; POLYMERS; PROTONS; STYRENE;

CELL MEMBRANES;

2 PROPANOL; ALPHA METHYLSTYRENE; COPOLYMER; HYDROGEN; METHACRYLONITRILE; POLYMER; POLYSTYRENESULFONIC ACID; SOLVENT; WATER;

ARTICLE; ARTIFICIAL MEMBRANE; CONTROLLED STUDY; CROSS LINKING; ENERGY CONVERSION; FUEL CELL; ION EXCHANGE; MOLECULAR STABILITY; POLYMERIZATION; PRIORITY JOURNAL; PROTON TRANSPORT; RADIATION GRAFTED FUEL CELL MEMBRANE; REACTOR; SULFONATION; TEMPERATURE;

EID: 67649268155     PISSN: 03767388     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.memsci.2009.04.031     Document Type: Article

References (50)

1. Gubler L., and Scherer G.G. A proton-conducting polymer membrane as solid electrolyte-function and required properties. Adv. Polym. Sci. 215 (2008) 1
2. Nasef M.M., and Hegazy E.S.A. Preparation and applications of ion exchange membranes by radiation-induced graft copolymerization of polar monomers onto non-polar films. Prog. Polym. Sci. 29 (2004) 499
3. Alkan Gürsel S., Gubler L., Gupta B., and Scherer G.G. Radiation grafted membranes. Adv. Polym. Sci. 215 (2008) 157
4. Gubler L., and Scherer G.G. Radiation grafted proton conducting membranes. In: Vielstich W., Gasteiger H.A., and Yokokawa H. (Eds). Handbook of Fuel Cells-Fundamentals, Technology and Applications, Volume 5: Performance Degradation (2009), John Wiley & Sons, Ltd, Chichester, United Kingdom 313-321
5. Gubler L., Alkan Gürsel S., and Scherer G.G. Radiation grafted membranes for polymer electrolyte fuel cells. Fuel Cells 5 (2005) 317
6. Gubler L., and Scherer G.G. Durability of radiation grafted fuel cell membranes. In: Inaba M., Schmidt T.J., and Büchi F.N. (Eds). Polymer Electrolyte Fuel Cell Durability (2009), Springer Science, New York 133-155
7. Hübner G., and Roduner E. EPR investigations of HO{radical dot} radical initiated degradation reactions of sulfonated aromatics as model compounds for fuel cell proton conducting membranes. J. Mater. Chem. 9 (1999) 409
8. V.F. D'Agostino, J.Y. Lee, E.H. Cook, Trifluorostyrene sulfonic acid membranes, US Patent 4,113,922, 1978.
9. Momose T., Tomiie K., Ishigaki I., and Okamoto J. Radiation grafting of α,β,β-trifluorostryrene onto various polymer films by preirradiation method. J. Appl. Polym. Sci. 37 (1989) 2165
10. C. Stone, A.E. Steck, Graft polymeric membranes and ion-exchange membranes formed therefrom, US Patent US 6,359,019, 2002.
11. Alkan Gürsel S., Yang Z., Choudhury B., Roelofs M.G., and Scherer G.G. Radiation grafted membranes using a trifluorostyrene derivative. J. Electrochem. Soc. 153 (2006) A1964
12. LaConti A.B., Hamdan H., and McDonald R.C. Mechanisms of membrane degradation. In: Vielstich W., Gasteiger H.A., and Lamm A. (Eds). Handbook of Fuel Cells-Fundamentals, Technology and Applications, Volume 3: Fuel Cell Technology and Applications, Part 1 (2003), John Wiley & Sons, Ltd, Chichester, United Kingdom 647-662
13. Chen J., Asano M., Yamaki T., and Yoshida M. Effect of crosslinkers on the preparation and properties of ETFE-based radiation-grafted polymer electrolyte membranes. J. Appl. Polym. Sci. 100 (2006) 4565
14. Chen J., Asano M., Yamaki T., and Yoshida M. Improvement of chemical stability of polymer electrolyte fuel cell membranes by grafting of new substituted styrene monomers into ETFE films. J. Mater. Sci. 41 (2006) 1289
15. Chen J., Asano M., Yamaki T., and Yoshida M. Preparation and characterization of chemically stable polymer electrolyte membranes by radiation-induced graft copolymerization of four monomers into ETFE films. J. Membr. Sci. 269 (2006) 194
16. Assink R.A., Arnold C., and Hollandsworth R.P. Preparation of oxidatively stable cation-exchange membranes by the elimination of tertiary hydrogen. J. Membr. Sci. 56 (1991) 143
17. Fleischhauer J., Schmidt-Naake G., and Scheller D. Untersuchungen zum Reaktionsverhalten beim Vorliegen von Depolymerisations reaktionen. Untersuchung von Copolymerisationen des α-Methylstyrols. Angew. Makromol. Chem. 243 (1996) 11
18. Pilcher S.C., and Ford W.T. High molecular weight poly(α-methylstyrene) formed by free radical polymerization in emulsions. J. Polym. Sci. A: Polym. Chem. 39 (2001) 525
19. Li L., Muto F., Miura T., Oshima A., Washio M., Ikeda S., Iida M., Tabata Y., Matsuura C., and Katsumura Y. Improving the properties of the proton exchange membranes by introducing α-methylstyrene in the pre-irradiation induced graft polymerization. Eur. Polym. J. (2006) 1222
20. Becker W., Bothe M., and Schmidt-Naake G. Grafting of poly(styrene-co-acrylonitrile) onto pre-irradiated FEP and ETFE films. Angew. Makromol. Chem. 273 (1999) 57
21. Fordyce R.G., Chapin E.C., Ham G.E., and Copolymerization V. Relative monomer addition rates in vinyl copolymerization. J. Am. Chem. Soc. 70 (1948) 2489
22. Becker W., and Schmidt-Naake G. Eigenschaften polymerer Protonenaustauschermembranen aus strahlungsinduzierter Pfropfpolymerisation. Chem. Eng. Technol. 72 (2000) 1541
23. Becker W., and Schmidt-Naake G. Properties of polymer exchange membranes from irradiation introduced graft polymerization. Chem. Eng. Technol. 24 (2001) 1128
24. L. Gubler, M. Slaski, G.G. Scherer, A method for preparing a radiation grafted fuel cell membrane with enhanced chemical stability and a membrane electrode assembly, Patent Application WO2006084591, 2005.
25. Kenney J.F. Monomer sequence distribution in α-methylstyrene-methacrylonitrile copolymer. J. Polym. Sci. 14 (1976) 113
26. Gubler L., Slaski M., Wokaun A., and Scherer G.G. Advanced monomer combinations for radiation grafted fuel cell membranes. Electrochem. Commun. 8 (2006) 1215
27. Gubler L., Prost N., Alkan Gürsel S., and Scherer G.G. Proton exchange membranes prepared by radiation grafting of styrene/divinylbenzene onto poly(ethylene-alt-tetrafluoroethylene) for low temperature fuel cells. Solid State Ionics 176 (2005) 2849
28. Büchi F.N., Marek A., and Scherer G.G. In situ membrane resistance measurements in polymer electrolyte fuel cells by fast auxiliary current pulses. J. Electrochem. Soc. 142 (1995) 1895
29. Ham G.E. Copolymerization (1964), Interscience Publishers, New York, London, Sydney
30. Mayo F.R., Lewis F.M., and Copolymerization I. A basis for comparing the behavior of monomers in copolymerization; the copolymerization of styrene and methyl methacrylate. J. Am. Chem. Soc. 66 (1944) 1594
31. M. Slaski, Radiation grafted fuel cell membranes with improved oxidative stability, Dissertation ETH No. 16995, Swiss Federal Institute of Technology Zürich, 2007, available at http://ecl.web.psi.ch/Publications/theses.html.
32. Rager T. Pre-irradiation grafting of styrene/divinylbenzene onto poly(tetrafluoroethylene-co-hexafluoropropylene) from non-solvents. Helv. Chim. Acta 86 (2003) 1966
33. Kenney J.F., and Patel P.J. Emulsion copolymerization behaviour of α-methylstyrene with methacrylonitrile. J. Polym. Sci. 14 (1976) 105
34. Young L.J. Copolymerization parameters. J. Polym. Sci. 54 (1961) 411
35. Johnston H.K., and Rudin A. Free-radical copolymerization of methacrylonitrile and α-methylstyrene. Macromolecules 4 (1971) 661
36. El-Naggar A.M., Zohdy M.H., Sahar S.M., and Allam E.A. Reactivity ratios during radiation-induced grafting of comonomer mixtures onto polyester fabrics. Polym. Int. 50 (2001) 1082
37. Zohdy M.H., Sahar S.M., Hassan M.S., Khalil E.M., El-Hossamy M., and El-Naggar A.M. Selective properties of polyester and cotton/polyester fabrics gamma irradiation grafted with different binary mixtures of vinyl monomers. Polym. Int. 48 (1999) 515
38. L. Gubler, F. Wallasch, A. Wokaun, G.G. Scherer, An enhanced grafting model comprising monomer transport, PSI Electrochemistry Laboratory-Annual Report 2008, ISSN 1661-5379, 6, available at http://ecl.web.psi.ch/SciRep.html.
39. Bandrup J., and Immergut E.H. Polymer Handbook. 4th ed. (1999), Wiley, New York
40. Mattsson B., Ericson H., Torel L.M., and Sundholm F. Micro-Raman investigations of PVDF-based proton-conducting membranes. J. Polym. Sci. A: Polym. Chem. 37 (1999) 3317
41. Schmidt C., Töpfer O., Langhoff A., Oppermann W., and Schmidt-Naake G. Depth profiling of graft polymer membranes via confocal laser scanning microscopy. Chem. Mater. 19 (2007) 4277
42. Gubler L., Kuhn H., Schmidt T.J., Scherer G.G., Brack H.P., and Simbeck K. Performance and durability of membrane electrode assemblies based on radiation-grafted FEP-g-polystyrene membranes. Fuel Cells 4 (2004) 196
43. 2 PEFC. J. Electrochem. Soc. 152 (2005) A93
44. Kreuer K.D. On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells. J. Membr. Sci. 185 (2001) 29
45. Zawodzinski T.A., Derouin C., Radzinski S., Sherman R.J., Smith V.T., Springer T.E., and Gottesfeld S. Water uptake by and transport through Nafion 117 membranes. J. Electrochem. Soc. 140 (1993) 1041
46. Huang X., Solasi R., Zou Y., Feshler M., Reifsnider K., Condit D., Burlatsky S., and Madden T. Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability. J. Polym. Sci. B: Polym. Phys. 44 (2006) 2346
47. L. Gubler, M. Schisslbauer, G.G. Scherer, Rapid aging studies of the PSI fuel cell membrane, PSI Electrochemistry Laboratory-Annual Report 2007, ISSN 1661-5379, 9, available at http://ecl.web.psi.ch/SciRep.html.
48. Gubler L., Ben youcef H., Alkan Gürsel S., Wokaun A., and Scherer G.G. Crosslinker effect in ETFE based radiation grafted proton conducting membranes. I. Properties and fuel cell performance characteristics. J. Electrochem. Soc. 155 (2008) B921
49. Büchi F.N., Gupta B., Haas O., and Scherer G.G. Study of radiation-grafted FEP-g-polystyrene membranes as polymer electrolytes in fuel cells. Electrochim. Acta 40 (1995) 345
50. Gubler L., Slaski M., Wokaun A., and Scherer G.G. Aging tests of radiation grafted fuel cell membranes. Electrochem. Soc. Trans. 3 (2006) 569