Skip to main content
SpringerLink
Log in

Novel cross-linked membrane for direct methanol fuel cell application: sulfonated poly(ether ether nitrile)s

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

In order to reduce water uptake, swelling ratio, and methanol permeability in sulfonated proton exchange membranes (PEM), novel-sulfonated aromatic poly(ether ether nitrile)s-bearing pendant propenyl groups had been synthesized by direct copolymerization method. All the results showed that the propenyl groups were suitable cross-linkable groups, and that this method was an effective way to overcome the drawbacks of sulfonated polymers at high ion exchange capacity (IEC) values. By cross-linking, the water uptake, swelling ratio, and methanol diffusion could be restricted owing to the formation of compact network structure. For example, CSPEN-60 membranes showed the proton conductivity of 0.072 S cm−1 at 80 °C, while the swelling ratios and water uptake (17.9 and 60.7 %) were much lower than that of the SPEN-60 membrane (60.8 and 295.2 %). Meanwhile, a 1.1 × 10−7 cm2 s−1 of methanol diffusion was obtained which was much lower than that of Nafion 117 (14.1 × 10−7 cm2 s−1). Although the proton conductivity of the CSPEN-60 membranes is lower than that of the SPEN-60 membrane, the selectivity is much higher. The CSPEN-60 membrane exhibited the highest selectivity among the tested membranes, about 5.8 times higher compared with that of Nafion117.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Reference

  1. Carrette L, Friedrich KA, Stimming U (2001) Fuel cells–fundamentals and applications. Fuel Cells 1(1):5–39

    Article  CAS  Google Scholar 

  2. Steele BC, Heinzel A (2001) Materials for fuel-cell technologies. Nature 414(6861):345–352

    Article  CAS  Google Scholar 

  3. Lemons RA (1990) Fuel cells for transportation. J Power Sources 29(1–2):251–264

    Article  CAS  Google Scholar 

  4. Strasser K (1992) Mobile fuel cell development at Siemens. J Power Sources 37(1):209–219

    Article  CAS  Google Scholar 

  5. Kordesch, K., & Simader, G. R. (1996). Fuel cells and their applications.

    Book  Google Scholar 

  6. Miyatake K, Zhou H, Watanabe M (2004) Proton conductive polyimide electrolytes containing fluorenyl groups: synthesis, properties, and branching effect. Macromolecules 37(13):4956–4960

    Article  CAS  Google Scholar 

  7. Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath JE (2004) Alternative polymer systems for proton exchange membranes (PEMs). Chem Rev 104(10):4587–4612

    Article  CAS  Google Scholar 

  8. Roziere J, Jones DJ (2003) Non-fluorinated polymer materials for proton exchange membrane fuel cells. Annu Rev Mater Res 33(1):503–555

    Article  CAS  Google Scholar 

  9. Liu B, Robertson GP, Guiver MD, Shi Z, Navessin T, Holdcroft S (2006) Fluorinated poly (aryl ether) containing a 4-bromophenyl pendant group and its phosphonated derivative. Macromol Rapid Commun 27(17):1411–1417

    Article  CAS  Google Scholar 

  10. Yang Y, Holdcroft S (2005) Synthetic strategies for controlling the morphology of proton conducting polymer membranes. Fuel Cells 5(2):171–186

    Article  CAS  Google Scholar 

  11. Rikukawa M, Sanui K (2000) Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers. Prog Polym Sci 25(10):1463–1502

    Article  CAS  Google Scholar 

  12. Sakaguchi Y, Kitamura K, Nagahara S, Takase S (2004) Preparation of sulfonated poly(ether sulfone nitrile)s and characterization as proton-conducting membranes. In: Abstracts of Papers of the American Chemical Society, vol 227, pp U427–U427

  13. Sumner MJ, Harrison WL, Weyers RM, Kim YS, McGrath JE, Riffle JS, Brink MH (2004) Novel proton conducting sulfonated poly (arylene ether) copolymers containing aromatic nitriles. J. Membrane. Sci 239(2):199–211

    Article  CAS  Google Scholar 

  14. Gao Y, Robertson GP, Guiver MD, Wang G, Jian X, Mikhailenko SD, Kaliaguine S (2006) Sulfonated copoly (phthalazinone ether ketone nitrile) s as proton exchange membrane materials. J. Membrane. Sci 278(1):26–34

    Article  CAS  Google Scholar 

  15. Kim YS, Sumner MJ, Harrison WL, Riffle JS, McGrath JE, Pivovar BS (2004) Direct methanol fuel cell performance of disulfonated poly (arylene ether benzonitrile) copolymers. J Electrochem Soc 151(12):A2150–A2156

    Article  CAS  Google Scholar 

  16. Gao Y, Robertson GP, Guiver MD, Mikhailenko SD, 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(3):808–816

    Article  CAS  Google Scholar 

  17. Kim DS, Kim YS, Guiver MD, Pivovar BS (2008) High performance nitrile copolymers for polymer electrolyte membrane fuel cells. J Membr Sci 321:199–208

    Article  CAS  Google Scholar 

  18. Fu Y, Manthiram A, Guiver MD (2006) Blend membranes based on sulfonated poly (ether ether ketone) and polysulfone bearing benzimidazole side groups for proton exchange membrane fuel cells. Electrochem Commun 8(8):1386–1390

    Article  CAS  Google Scholar 

  19. Yin Y, Hayashi S, Yamada O, Kita H, Okamoto KI (2005) Branched/crosslinked sulfonated polyimide membranes for polymer electrolyte fuel cells. Macromol Rapid Commun 26(9):696–700

    Article  CAS  Google Scholar 

  20. Zhong S, Cui X, Cai H, Fu T, Shao K, Na H (2007) Crosslinked SPEEK/AMPS blend membranes with high proton conductivity and low methanol diffusion coefficient for DMFC applications. J Power Sources 168(1):154–161

    Article  CAS  Google Scholar 

  21. Yang SJ, Jang W, Lee C, Shul YG, Han H (2005) The effect of crosslinked networks with poly (ethylene glycol) on sulfonated polyimide for polymer electrolyte membrane fuel cell. J Polym Sci B Polym Phys 43(12):1455–1464

    Article  CAS  Google Scholar 

  22. Kerres JA (2005) Blended and cross linked ionomer membranes for application in membrane fuel cells. Fuel Cells 5(2):230–247

    Article  CAS  Google Scholar 

  23. Feng S, Shang Y, Xie X, Wang Y, Xu J (2009) Synthesis and characterization of crosslinked sulfonated poly (arylene ether sulfone) membranes for DMFC applications. J Membr Sci 335:13–20

    Article  CAS  Google Scholar 

  24. Zhong S, Liu C, Na H (2009) Preparation and properties of UV irradiation-induced crosslinked sulfonated poly (ether ether ketone) proton exchange membranes. J Membr Sci 326:400–407

    Article  CAS  Google Scholar 

  25. Shen S, Pu Z, Zheng P, Liu X, Jia K (2015) Synthesis and properties of cross-linkable poly (arylene ether nitrile) s containing side propenyl groups. High Perform Polym 0954008315591188

  26. Heo KB, Lee HJ, Kim HJ, Kim BS, Lee SY, Cho E, et al. (2007) Synthesis and characterization of cross-linked poly (ether sulfone) for a fuel cell membrane. J Power Sources 172(1):215–219

    Article  CAS  Google Scholar 

  27. Sundar S, Jang W, Lee C, Shul Y, Han H (2005) Crosslinked sulfonated polyimide networks as polymer electrolyte membranes in fuel cells. J Polym Sci B Polym Phys 43(17):2370–2379

    Article  CAS  Google Scholar 

  28. Zhong S, Cui X, Cai H, Fu T, Zhao C, Na H (2007) Crosslinked sulfonated poly (ether ether ketone) proton exchange membranes for direct methanol fuel cell applications. J Power Sources 164(1):65–72

    Article  CAS  Google Scholar 

  29. Park CH, Lee CH, Guiver MD, Lee YM (2011) Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs). Prog Polym Sci 36(11):1443–1498

    Article  CAS  Google Scholar 

  30. Kreuer KD, Rabenau A, Weppner W (1982) Vehicle mechanism, a new model for the interpretation of the conductivity of fast proton conductors. Angew Chem Int Edi 21(3):208–209

    Article  Google Scholar 

  31. Beydaghi H, Javanbakht M, Amoli HS, Badiei A, Khaniani Y, Ganjali MR, et al. (2011) Synthesis and characterization of new proton conducting hybrid membranes for PEM fuel cells based on poly (vinyl alcohol) and nanoporous silica containing phenyl sulfonic acid. Int J hydrogen energ 36(20):13310–13316

    Article  CAS  Google Scholar 

  32. Zhou S, Kim J, Kim D (2010) Cross-linked poly (ether ether ketone) membranes with pendant sulfonic acid groups for fuel cell applications. J. Membrane. Sci 348(1):319–325

    Article  CAS  Google Scholar 

  33. Yamaguchi T, Zhou H, Nakazawa S, Hara N (2007) An extremely low methanol crossover and highly durable aromatic pore filling electrolyte membrane for direct methanol fuel cells. Adv Mater 19(4):592–596

    Article  CAS  Google Scholar 

  34. Xue S, Yin G (2006) Proton exchange membranes based on poly (vinylidene fluoride) and sulfonated poly (ether ether ketone). Polymer 47(14):5044–5049

    Article  CAS  Google Scholar 

  35. Jung B, Kim B, Yang JM (2004) Transport of methanol and protons through partially sulfonated polymer blend membranes for direct methanol fuel cell. J. Membrane. Sci 245(1):61–69

    Article  CAS  Google Scholar 

  36. Kim YS, Hickner MA, Dong L, Pivovar BS, McGrath JE (2004) Sulfonated poly (arylene ether sulfone) copolymer proton exchange membranes: composition and morphology effects on the methanol permeability. J Membrane Sci 243(1):317–326

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully thank the financial support from the National Natural Science Foundation of China (Project No. 51373028, No. 51403029), the “863” National Major Program of High Technology (2012AA03A212), South Wisdom Valley Innovative Research Team Program, and Ningbo Major Science and Technology Research Plan (2013B06011).

Author information

Authors and Affiliations

  1. School of Microelectronic and Solid-State Electronic, Research Branch of Advanced Functional Materials, High Temperature Resistant Polymers, and Composites Key Laboratory of Sichuan Province, University of Electronic Science and Technology of China, Chengdu, 610054, China

    Penglun Zheng, Mingzhen Xu, Xiaobo Liu & Kun Jia

Authors
  1. Penglun Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mingzhen Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaobo Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kun Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xiaobo Liu or Kun Jia.

Additional information

Penglun Zheng and Mingzhen Xu contributed equally to this work.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, P., Xu, M., Liu, X. et al. Novel cross-linked membrane for direct methanol fuel cell application: sulfonated poly(ether ether nitrile)s. Ionics 23, 87–94 (2017). https://doi.org/10.1007/s11581-016-1805-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-016-1805-z

Keywords

Search

Navigation