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Blend proton exchange membranes with high performance based on sulfonated poly(arylene ether phosphine oxide)s and poly(vinylidene fluoride)

  • Qingqi Huang
  • Yanying Cheng
  • Shanshan Zhang
  • Huiping Liu
  • Huiying Liao
Polymers
  • 22 Downloads

Abstract

A series of blend membranes based on sulfonated poly(arylene ether phosphine oxide)s (sPEPOF) and poly(vinylidene fluoride) (PVDF) were prepared and studied. The miscibility and thermal properties of blend membranes were evaluated. The morphologies were investigated by atomic force microscope. The results demonstrated that the blend membranes exhibited good compatibility and high thermal stability. The microstructures of blend membranes could be adjusted by introducing hydrophobic PVDF, thus improving the properties of membranes. Additionally, a suitable content of PVDF was in favor of promoting proton conductivity, oxidative stability, restraining water swelling, and methanol permeability. For example, the blend membrane containing 5% weight content of PVDF displayed a proton conductivity of 0.135 S cm−1, which was higher than those of the pristine sPEPOF membrane (0.124 S cm−1) and Nafion 117 (0.114 S cm−1) at 80 °C and 100% relative humidity. Meanwhile, it showed a lower swelling than that of Nafion 117, and its methanol permeability was about one-fortieth that of Nafion 117. Besides, the oxidative stability was also remarkably improved compared to the pristine sPEPOF membrane. Therefore, the achieved blend membranes exhibited excellent application prospect.

Notes

Acknowledgements

We thank the National Natural Science Foundation of China (No. 21404071) for financial support.

References

  1. 1.
    Zhang HW, Shen PK (2012) Recent development of polymer electrolyte membranes for fuel cells. Chem Rev 112:2780–2832CrossRefGoogle Scholar
  2. 2.
    Mauritz KA, Moore RB (2004) State of understanding of Nafion. Chem Rev 104:4535–4585CrossRefGoogle Scholar
  3. 3.
    Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath JE (2004) Alternative polymer systems for proton exchange membranes (PEMs). Chem Rev 104:4587–4611CrossRefGoogle Scholar
  4. 4.
    Li W, Guo X, Fang J (2014) Synthesis and properties of sulfonated polyimide–polybenzimidazole copolymers as proton exchange membranes. J Mater Sci 49:2745–2753.  https://doi.org/10.1007/s10853-013-7977-2 CrossRefGoogle Scholar
  5. 5.
    Kreuer K (2001) On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells. J Membr Sci 185(1):29–39CrossRefGoogle Scholar
  6. 6.
    Chen RM, Jin JH, Yang SL, Li G (2017) Effect of pendant group containing fluorine on the properties of sulfonated poly(arylene ether sulfone)s as proton exchange membrane. J Mater Sci 52:1028–1038.  https://doi.org/10.1007/s10853-016-0398-2 CrossRefGoogle Scholar
  7. 7.
    Wang C, Li N, Dong WS, Lee SY, Kang NR, Lee YM, Guiver M (2011) Fluorene-based poly(arylene ether sulfone)s containing clustered flexible pendant sulfonic acids as proton exchange membranes. Macromolecules 44:7296–7306CrossRefGoogle Scholar
  8. 8.
    Kim D, Robertson G, Guiver M, Lee Y (2006) Synthesis of highly fluorinated poly(arylene ether)s copolymers for proton exchange membrane materials. J Membr Sci 281(1):111–120CrossRefGoogle Scholar
  9. 9.
    He G, Chang C, Xu M, Hu S, Li L, Zhao J, Li Z, Li Z, Yin Y, Gang M, Wu H, Yang X, Guiver MD, Jiang Z (2015) Tunable nanochannels along grapheme oxide/polymer coreshell nanosheets to enhance proton conductivity. Adv Funct Mater 25(48):7502–7511CrossRefGoogle Scholar
  10. 10.
    Sana B, Jana T (2016) Polybenzimidazole composite with acidic surfactant like molecules: a unique approach to develop PEM for fuel cell. Eur Polymer J 84:421–434CrossRefGoogle Scholar
  11. 11.
    Ma XH, Zhang CJ, Xiao GY, Yan DY (2009) Synthesis and properties of sulfonated poly(arylene ether phosphine oxide)s for proton exchange membranes. J Power Sources 188:57–63CrossRefGoogle Scholar
  12. 12.
    Zhang CJ, Kang S, Ma XH, Xiao GY, Yan DY (2009) Synthesis and characterization of sulfonated poly(arylene ether phosphine oxide)s with fluorenyl groups by direct polymerization for proton exchange membranes. J Membr Sci 329:99–105CrossRefGoogle Scholar
  13. 13.
    Fu LC, Xiao GY, Yan DY (2012) High performance sulfonated poly(arylene ether phosphine oxide) membranes by self-protected cross-linking for fuel cells. J Mater Chem 22(27):13714–13722CrossRefGoogle Scholar
  14. 14.
    Liao HY, Zhang K, Tong GS, Xiao GY, Yan DY (2013) Sulfonated poly(arylene ether phosphine oxide)s with various distributions and contents of pendant sulfonic acid groups synthesized by direct polycondensation. Polym Chem 5:412–422CrossRefGoogle Scholar
  15. 15.
    Gu S, He G, Wu X, Hu Z, Wang L, Xiao G, Peng L (2010) Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane. J Appl Polym Sci 116(2):852–860CrossRefGoogle Scholar
  16. 16.
    Liu F, Hashim N, Liu Y, Abed M, Li K (2011) Progress in the production and modification of PVDF membranes. J Membr Sci 375:1–27CrossRefGoogle Scholar
  17. 17.
    Kang G, Cao Y (2014) Application and modification of poly(vinylidene fluoride) (PVDF) membranes—a review. J Membr Sci 463:145–165CrossRefGoogle Scholar
  18. 18.
    Park JW, Wycisk R, Pintauro PN (2015) Membranes from blended ionomer/PVDF nanofibers: II. interplay between properties and electric response. J Membr Sci 490:103–112CrossRefGoogle Scholar
  19. 19.
    Subramanian MS, Sasikumar G (2010) Sulfonated polyether sulfone-poly(vinylidene fluoride) blend membrane for DMFC applications. J Appl Polym Sci 117:801–808CrossRefGoogle Scholar
  20. 20.
    Wootthikanokkhan J, Seeponkai N (2006) Methanol permeability and properties of DMFC membranes based on sulfonated PEEK/PVDF blends. J Appl Polym Sci 102:5941–5947CrossRefGoogle Scholar
  21. 21.
    Wang J, Li N, Cui Z, Zhang S, Xing W (2009) Blends based on sulfonated poly[bis(benzimidazobenzisoquinolinones)] and poly(vinylidene fluoride) for polymer electrolyte membrane fuel cell. J Membr Sci 341:155–162CrossRefGoogle Scholar
  22. 22.
    Ma XH, Zhang CJ, Xiao GY, Yan DY, Sun GM (2008) Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes. J Polym Sci Part A 46:1758–1769CrossRefGoogle Scholar
  23. 23.
    Liu B, Robertson G, Kim D, Guiver M, Hu W, Jiang Z (2007) Aromatic poly(ether ketone)s with pendant sulfonic acid phenyl groups prepared by a mild sulfonation method for proton exchange membranes. Macromolecules 40:1934–1944CrossRefGoogle Scholar
  24. 24.
    Urban M, Salazar-Rojas E (1988) Ultrasonic PTC modification of poly(vinylidene fluoride) surfaces and their characterization. Macromolecules 21:372–378CrossRefGoogle Scholar
  25. 25.
    Singha S, Jana T (2014) Effect of composition on the properties of PEM based on polybenzimidazole and poly(vinylidene fluoride) blends. Polymer 55:594–601CrossRefGoogle Scholar
  26. 26.
    Hazarika M, Jana T (2013) Novel proton exchange membrane for fuel cell developed from blends of polybenzimidazole with fluorinated polymer. Eur Polymer J 49:1564–1576CrossRefGoogle Scholar
  27. 27.
    Unveren E, Inan T, Çelebi S (2013) Partially sulfonated poly(1,4-phenylene ether-ether-sulfone) and poly(vinylidene fluoride) blend membranes for fuel cells. Fuel Cell 13:862–872Google Scholar
  28. 28.
    Dhamodaran A, Arindam S, Tushar J (2008) Blends of polybenzimidazole and poly(vinylidene fluoride) for use in a fuel cell. J Phys Chem B 112:5305–5310Google Scholar
  29. 29.
    Kim D, Lee H, Nam S (2013) Sulfonated poly(arylene ether sulfone) membranes blended with hydrophobic polymers for direct methanol fuel cell applications. Int J Hydrogen Energy 39:17524–17532CrossRefGoogle Scholar
  30. 30.
    Peckham TJ, Holdcroft S (2010) Structure-morphology-property relationships of non-perfluorinated proton-conducting membrane. Adv Mater 22:4667–4690CrossRefGoogle Scholar
  31. 31.
    Xing PX, Robertson GP, Guiver MD, Mikhailenko SD, Kaliaguine S (2004) Sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety prepared by direct copolymerization as proton exchange membranes for fuel cell application. Macromolecules 37:7960–7967CrossRefGoogle Scholar
  32. 32.
    Hu H, Xiao M, Wang SJ, Meng YZ (2010) Poly (fluorenyl ether ketone) ionomers containing separated hydrophilic multiblocks used in fuel cells as proton exchange membranes. Int J Hydrogen Energy 35:682–689CrossRefGoogle Scholar
  33. 33.
    Gao Y, Robertson G, Guiver M, Mikhailenko S, Li X, Kaliaguine S (2006) Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage. Polymer 47:808–816CrossRefGoogle Scholar
  34. 34.
    Ma XH, Shen LP, Zhang CJ, Xiao GY, Yan DY, Sun GM (2008) Sulfonated poly(arylene thioether phosphine oxide)s copolymers for proton exchange membrane fuel cells. J Membr Sci 310:303–311CrossRefGoogle Scholar
  35. 35.
    Okamoto K, Yin Y, Yamada O, Islam M, Honda T, Mishima T, Suto Y, Tanaka K, Kita H (2005) Methanol permeability and proton conductivity of sulfonated co-polyimide membranes. J Membr Sci 258:115–122CrossRefGoogle Scholar
  36. 36.
    Kreuer K (1996) Proton conductivity: materials and applications. Chem Mater 8:610–808CrossRefGoogle Scholar
  37. 37.
    Uma Devi A, Neelakandan S, Nagendran A (2016) Highly selective sulfonated poly(vinylidene fluoride-cohexafluoropropylene)/poly (ether sulfone) blend proton exchange membranes for direct methanol fuel cells. J Appl Polym Sci.  https://doi.org/10.1002/APP.43907 Google Scholar
  38. 38.
    Li N, Zhang S, Liu J, Zhang F (2008) Synthesis and properties of sulfonated poly[bis(benzimidazobenzisoquinolinones)] as hydrolytically and thermo oxidatively stable proton conducting ionomers. Macromolecules 41:4165–4172CrossRefGoogle Scholar
  39. 39.
    Liu D, Yates M (2009) Electric field processing to control the structure of poly(vinylidene fluoride) composite proton conducting membranes. J Membr Sci 326:539–548CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Chemical and Environmental EngineeringShanghai Institute of TechnologyShanghaiPeople’s Republic of China
  2. 2.College of Urban Construction and Safety EngineeringShanghai Institute of TechnologyShanghaiPeople’s Republic of China

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