, Volume 24, Issue 4, pp 1097–1109 | Cite as

Anion exchange membrane from polyvinyl alcohol functionalized with quaternary ammonium groups via alkyl spacers

  • K. Hari Gopi
  • Santoshkumar D. Bhat
Original Paper


Anion exchange membranes (AEMs) functionalized with quaternary ammonium groups are prepared from polyvinyl alcohol for alkaline polymer electrolyte fuel cell (APEFC) application. A series of AEMs were synthesized by direct quaternization of PVA using flexible alkyl spacer as charge carrier added in different weight percentages. These membranes were further cross-linked chemically and thermally before evaluating their ionic conductivity and ion exchange capacity. The interaction of alkyl spacer group with the polymer backbone was confirmed by FT-IR spectroscopy. XRD pattern reveals that the introduction of quaternary ammonium group disrupts the crystalline structure of polymer, increasing its amorphous phase thereby enhancing the conductivity. The QPVA membrane with 15 wt% of alkyl spacer exhibited an improved conductivity of 0.0057 S cm−1 at 40 °C in comparison with other ratios. The cell polarization data for the optimized QPVA membrane was studied at 40 °C with varying ionomer amount. The alkaline stability and cell durability for the optimized QPVA membrane were evaluated for 300 and 25 h, respectively.


Fuel cells Alkyl spacers Morphology Alkaline stability QPVA 



The financial support from Council of Scientific and Industrial Research (CSIR) Govt. of India, under CSIR Young Scientist Award Project (Grant No.DU-MLP-0090), is gratefully acknowledged. The authors thank technical officer Mrs. Bhagyalakshmi from CSIR-CECRI-Karaikudi for helping us with AFM imaging. The authors also thank the Director, CSIR-Central Electrochemical Research Institute and Scientist-In-Charge, CECRI Madras Unit for their suggestions and support.


  1. 1.
    Varcoe JR, Atanassov P, Dekel DR, Herring AM, Hickner MA, Kohl PA, Kucernak AR, Mustain WE, Nijmeijer K, Scott K, Xu T, Zhuang L (2014) Anion-exchange membranes in electrochemical energy systems. Energy Environ Sci 7:3135–3191CrossRefGoogle Scholar
  2. 2.
    He Q, Cairns EJ (2015) Review—recent progress in electrocatalysts for oxygen reduction suitable for alkaline anion exchange membrane fuel cells. J Electrochem Soc 162:F1504–F1539CrossRefGoogle Scholar
  3. 3.
    Pan J, Chen C, Zhuang L, Lu J (2012) Designing advanced alkaline polymer electrolytes for fuel cell applications. Acc Chem Res 45:473–481CrossRefGoogle Scholar
  4. 4.
    Ran J, Wu L, Wei B, Chen Y, Xu T (2014) Simultaneous enhancements of conductivity and stability for anion exchange membranes (AEMs) through precise structure design. Sci Rep 4:6486CrossRefGoogle Scholar
  5. 5.
    Hickner MA, Herring AM, Coughlin EB (2013) Anion exchange membranes: current status and moving forward. J Polym Sci B Polym Phys 51:1727–1735CrossRefGoogle Scholar
  6. 6.
    Couture G, Alaaeddine A, Boschet F, Ameduri B (2011) Polymeric materials as anion-exchange membranes for alkaline fuel cells. Prog Polym Sci 36:1521–1557CrossRefGoogle Scholar
  7. 7.
    Manohar M, Thakur AK, Pandey RP, Shahi VK (2015) Efficient and stable anion exchange membrane: tuned membrane permeability and charge density for molecular/ionic separation. J Membr Sci 496:250–258CrossRefGoogle Scholar
  8. 8.
    Wu X, Chen W, Yan X, He G, Wang J, Zhang Y, Zhu X (2014) Enhancement of hydroxide conductivity by the di-quaternization strategy for poly(ether ether ketone) based anion exchange membranes. J Mater Chem A 2:12222–12231CrossRefGoogle Scholar
  9. 9.
    Li N, Leng Y, Hickner MA, Wang C-Y (2013) Highly stable anion conductive comb-shaped copolymers for alkaline fuel cells. J Am Chem Soc 135:10124–10133CrossRefGoogle Scholar
  10. 10.
    Zarrin H, Wu J, Fowler M, Chen Z (2012) High durable PEK-based anion exchange membrane for elevated temperature alkaline fuel cells. J Membr Sci 394–395:193–201CrossRefGoogle Scholar
  11. 11.
    Chempath S, Einsla BR, Pratt LR, Macomber CS, Boncella JM, Rau JA, Pivovar BS (2008) Mechanism of tetraalkylammonium head-group degradation in alkaline fuel cell membranes. J Phys Chem C 112:3179–3182CrossRefGoogle Scholar
  12. 12.
    Edson JB, Macomber CS, Pivovar BS, Boncella JM (2012) Hydroxide based decomposition pathways of alkyltrimethylammonium cations. J Membr Sci 399-400:49–59CrossRefGoogle Scholar
  13. 13.
    Wan Y, Peppley B, Creber KAM, Bui VT (2010) Anion-exchange membranes composed of quaternized-chitosan derivatives for alkaline fuel cells. J Power Sources 195:3785–3793CrossRefGoogle Scholar
  14. 14.
    Stoica D, Ogier L, Akrour L, Alloin F, Fauvarque J-F (2007) Anionic membrane based on polyepichlorhydrin matrix for alkaline fuel cell: synthesis, physical and electrochemical properties. Electrochim Acta 53:1596–1603CrossRefGoogle Scholar
  15. 15.
    Xiong Y, Fang J, Zeng QH, Liu QL (2008) Preparation and characterization of cross-linked quaternized poly(vinyl alcohol) membranes for anion exchange membrane fuel cells. J Membr Sci 311:319–325CrossRefGoogle Scholar
  16. 16.
    Fu J, Qiao J, Lv H, Ma J, Yuan X-Z, Wang H (2010) Alkali doped poly(vinyl alcohol) (PVA) for anion-exchange membrane fuel cells—ionic conductivity, chemical stability and FT-IR characterizations. ECS Trans 25:15–23CrossRefGoogle Scholar
  17. 17.
    Qiao J, Zhang J, Zhang J (2013) Anion conducting poly(vinyl alcohol)/ poly(diallyldimethylammonium chloride) membranes with high durable alkaline stability for polymer electrolyte membrane fuel cells. J Power Sources 237:1–4CrossRefGoogle Scholar
  18. 18.
    Shin M-S, Byun Y-J, Choi Y-W, Kang M-S, Park J-S (2014) On-site crosslinked quaternized poly(vinyl alcohol) as ionomer binder for solid alkaline fuel cells. Int J Hydrog Energy 39:16556–16561CrossRefGoogle Scholar
  19. 19.
    Gauthier MA, Luo J, Calvet D, Ni C, Zhu XX, Garon M, Buschmann MD (2004) Degree of crosslinking and mechanical properties of crosslinked poly(vinyl alcohol) beads for use in solid-phase organic synthesis. Polymer 45:8201–8210CrossRefGoogle Scholar
  20. 20.
    Gopi KH, Peera SG, Bhat SD, Sridhar P, Pitchumani S (2014) Preparation and characterization of quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) as anion exchange membrane for alkaline polymer electrolyte fuel cells. Int J Hydrog Energy 39:2659–2668CrossRefGoogle Scholar
  21. 21.
    Gopi KH, Peera SG, Bhat SD, Sridhar P, Pitchumani S (2014) 3-Methyltrimethyl ammonium poly(2,6-dimethyl-1,4-phenylene oxide) based anion exchange membrane for alkaline polymer electrolyte fuel cells. Bull Mater Sci 37:877–881CrossRefGoogle Scholar
  22. 22.
    Zhou T, Zhang J, Qiao J, Liu L, Jiang G, Zhang J, Liu Y (2013) High durable poly(vinyl alcohol)/quaternized hydroxyethylcellulose ethoxylate anion exchange membranes for direct methanol alkaline fuel cells. J Power Sources 227:291–299CrossRefGoogle Scholar
  23. 23.
    Gopi KH, Bhat SD, Sahu AK, Sridhar P (2016) Quaternized poly(phenylene oxide) anion exchange membrane for alkaline direct methanol fuel cells in KOH-free media. J Appl Polym Sci 133:43693CrossRefGoogle Scholar
  24. 24.
    Hibbs MR, Hickner MA, Alam TM, McIntyre SK, Fujimoto CH, Cornelius CJ (2008) Transport properties of hydroxide and proton conducting membranes. Chem Mater 20:2566–2573CrossRefGoogle Scholar
  25. 25.
    Liao G-M, Yang C-C, Hu C-C, Pai Y-L, Lue SJ (2015) Novel quaternized polyvinyl alcohol/quaternized chitosan nano-composite as an effective hydroxide conducting electrolyte. J Membr Sci 485:17–29CrossRefGoogle Scholar
  26. 26.
    Xu PY, Guo TY, Zhao CH, Broadwell I, Zhang QG, Liu QL (2013) Anion exchange membranes based on poly(vinyl alcohol) and quaternized polyethyleneimine for direct methanol fuel cells. J Appl Polym Sci 128:3853–3860CrossRefGoogle Scholar
  27. 27.
    Yang C-C, Chiu S-J, Lin C-T (2008) Electrochemical performance of an air-breathing direct methanol fuel cell using poly(vinyl alcohol)/hydroxyapatite composite polymer membrane. J Power Sources 177:40–49CrossRefGoogle Scholar
  28. 28.
    Yang C-C, Chiu S-S, Kuo S-C, Liou T-H (2012) Fabrication of anion-exchange composite membranes for alkaline direct methanol fuel cells. J Power Sources 199:37–45CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.CSIR-Central Electrochemical Research Institute-Madras UnitCSIR Madras ComplexChennaiIndia

Personalised recommendations