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Sulfonated poly(vinyl alcohol)/triazole blends as anhydrous proton conducting membranes for polymer electrolyte membrane fuel cells

Published online by Cambridge University Press:  16 May 2013

Mehtap Safak Boroglu*
Affiliation:
Department of Chemical Engineering, Istanbul University, 34320 Avcilar, Istanbul, Turkey
Sevim Unugur Celik
Affiliation:
Department of Chemistry, Fatih University, 34500 Buyukcekmece, Istanbul, Turkey
Ismail Boz
Affiliation:
Department of Chemical Engineering, Istanbul University, 34320 Avcilar, Istanbul, Turkey
Ayhan Bozkurt
Affiliation:
Department of Chemistry, Fatih University, 34500 Buyukcekmece, Istanbul, Turkey
*
a)Address all correspondence to this author. e-mail: mehtap@istanbul.edu.tr
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Abstract

A new type of cross-linked poly(vinyl alcohol) (PVA)-sulfosuccinic acid (SSA) polymers were synthesized by varying the amount of SSA and then blending with 3-amino-1,2,4-triazole (ATri) and 1H-1,2,4-triazole (Tri) at different stoichiometric ratios to obtain proton conductive membranes in anhydrous state. The proton conductivities of membranes were investigated as a function of azole composition, SSA composition, and operating temperature. The final structures of the copolymers were confirmed by Fourier transform infrared spectra. The resultant hybrid membranes are transparent, flexible, and showed good thermal stability up to approximately 200 °C. Differential scanning calorimetry results illustrated the homogeneity of the materials. The cross-linking of the structure was confirmed by the alteration of solubility of the membranes. Methanol permeability measurements showed that the composite membranes have lower methanol permeability compared to Nafion 112. The proton conductivity of the membranes continuously increased with increasing SO3H content and 3-amino-1,2,4-triazole (ATri) content. A maximum proton conductivity of 7.26 × 10−3 S/cm was achieved for ATri-3 at 140 °C under anhydrous conditions. Incorporation of ATri unit (according to Tri unit) significantly increased the proton conductivity of the membranes, probably due to the ion transport channel or network structures formed in the membranes.

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Articles
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

Kreuer, K.D.: Proton conductivity: Materials and applications. Chem. Mater. 8, 610 (1996).CrossRefGoogle Scholar
Pu, H.T., Meyer, W.H., and Wegner, G.: Proton conductivity in acid-blended poly(4-vinylimidazole). Macromol. Chem. Phys. 202, 1478 (2001).3.0.CO;2-8>CrossRefGoogle Scholar
Zhang, H. and Shen, P.K.: Recent development of polymer electrolyte membranes for fuel cells. Chem. Rev. 112, 2780 (2012).CrossRefGoogle ScholarPubMed
Pu, H.T. and Ye, S.: Preparation and proton conductivity of acid-doped poly(5-vinyltetrazole-co-acrylonitrile). React. Funct. Polym. 66, 856 (2006).CrossRefGoogle Scholar
Maiti, J., Kakati, N., Lee, S.H., Jee, S.H., Viswanathan, B., and Yoon, Y.S.: Where do poly(vinyl alcohol) based membranes stand in relation to Nafion for direct methanol fuel cell applications? J. Power Sources 216, 48 (2012).CrossRefGoogle Scholar
Bozkurt, A., Ise, M., Kreuer, K.D., Meyer, W.H., and Wegner, G.: Proton conducting polymer electrolytes based on phosphoric acid. Solid State Ionics 125, 225 (1999).CrossRefGoogle Scholar
Lassegues, J.C., Grondin, J., Hernandez, M., and Maree, B.: Proton conducting polymer blends and hybrid organic inorganic materials. Solid State Ionics 145, 37 (2001).CrossRefGoogle Scholar
Kreuer, K.D., Fuchs, A., Ise, M., Spaeth, M., and Maier, J.: Imidazole and pyrazole-based proton conducting polymers and liquids. Electrochim. Acta 43, 1281 (1998).CrossRefGoogle Scholar
Bose, S., Kuila, T., Nguyen, T.X.H., Kim, N.H., Lau, K., and Lee, J.H.: Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges. Prog. Polym. Sci. 36, 813 (2011).CrossRefGoogle Scholar
Tanaka, R., Yamamoto, H., Kawamura, S., and Iwase, T.: Proton conducting behavior of poly(ethylenimine)-H3PO4 systems. Electrochim. Acta 40, 2421 (1995).CrossRefGoogle Scholar
Donoso, P., Gorecki, W., Berthier, C., Defendini, F., Poinsignon, C., and Armand, M.B.: NMR, conductivity and neutron scattering investigation of ionic dynamics in the anhydrous polymer protonic conductor PEO(H3PO4)x). Solid State Ionics 28, 969 (1988).CrossRefGoogle Scholar
Petty-Week, S., Zupancic, J.J., and Swedo, J.R.: Proton conducting interpenetrating polymer networks. Solid State Ionics 31, 117 (1988).CrossRefGoogle Scholar
Bozkurt, A. and Meyer, W.H.: Proton conducting poly(4-vinylimidazol)-acid blends. Solid State Ionics 138, 259 (2001).CrossRefGoogle Scholar
Yang, C., Costamagna, P., Srinivasan, S., Benziger, J., and Bocarsly, A.B.: Approaches and technical challenges to high temperature operation of proton exchange membrane fuel cells. J. Power Sources 103, 1 (2001).CrossRefGoogle Scholar
Sevil, F. and Bozkurt, A.: Proton conducting polymer electrolytes on the basis of poly(vinylphosphonic acid) and imidazole. J. Phys. Chem. Solids 65, 1659 (2004).CrossRefGoogle Scholar
Yamada, M. and Honma, I.: Proton conducting acid–base mixed materials under water-free condition. Electrochim. Acta 48, 2411 (2003).CrossRefGoogle Scholar
Gunday, S.T., Bozkurt, A., Meyer, W.H., and Wegner, G.: Effects of different acid functional groups on proton conductivity of polymer-1,2,4-triazole blends. J. Polym. Sci., Part B: Polym. Phys. 44, 3315 (2006).CrossRefGoogle Scholar
Schuster, M.F.H., Meyer, W.H., Schuster, M., and Kreuer, K.D.: Toward a new type of anhydrous organic proton conductor based on immobilized imidazole. Chem. Mater. 16, 329 (2004).CrossRefGoogle Scholar
Bozkurt, A., Meyer, W.H., and Wegner, G.: PAA/imidazole based proton conducting polymer electrolytes. J. Power Sources 123, 126 (2003).CrossRefGoogle Scholar
Deng, W., Molinero, V., and Goddard, W.A.: Fluorinated imidazoles as proton carriers for water-free fuel cell membranes. J. Am. Chem. Soc. 126, 15644 (2004).CrossRefGoogle ScholarPubMed
Li, S., Zhou, Z., Zhang, Y., and Liu, M.: 1H-1,2,4-Triazole: An effective solvent for proton-conducting electrolytes. Chem. Mater. 17, 5884 (2005).CrossRefGoogle Scholar
Celik, S.U., Akbey, U., Bozkurt, A., Graf, R., and Spiess, H.W.: Proton-conducting properties of acid-doped poly(glycidyl methacrylate)-1,2,4-triazole systems. Macromol. Chem. Phys. 209, 593 (2008).CrossRefGoogle Scholar
Martwiset, S., Woudenberg, R.C., Granados-Focil, S., Yavuzcetin, O., Tuominen, M.T., and Coughlin, E.B.: Intrinsically conducting polymers and copolymers containing triazole moieties. Solid State Ionics 178, 1398 (2007).CrossRefGoogle Scholar
Rhim, J.W., Park, H.B., Lee, C.S., Jun, J.H., Kim, D.S., and Lee, Y.M.: Crosslinked poly(vinyl alcohol) membranes containing sulfonic acid group: Proton and methanol transport through membranes. J. Membr. Sci. 238, 143 (2004).CrossRefGoogle Scholar
Chanthad, C. and Wootthikanokkhan, J.: Effects of crosslinking time and amount of sulfophthalic acid on properties of the sulfonated poly(vinyl alcohol) membrane. J. Appl. Polym. Sci. 101, 1931 (2006).CrossRefGoogle Scholar
Seeponkai, N. and Wootthikanokkhan, J.: Proton conductivity and methanol permeability of sulfonated poly(vinyl alcohol) membranes modified by using sulfoacetic acid and poly(acrylic acid). J. Appl. Polym. Sci. 105, 838 (2007).CrossRefGoogle Scholar
Hickey, A.S. and Peppas, N.A.: Mesh size and diffusive characteristics of semicrystalline poly(vinyl alcohol) membranes prepared by freezing/thawing techniques. J. Membr. Sci. 107, 229 (1995).CrossRefGoogle Scholar
Yu, A.X. and Cao Wang, S.: Water-vapor permeability of polyvinyl alcohol films. Desalination 62, 293 (1987).Google Scholar
Bolto, B., Tran, T., Hoang, M., and Xie, Z.: Crosslinked poly(vinyl alcohol) membranes. Prog. Polym. Sci. 34, 969 (2009).CrossRefGoogle Scholar
Sen, U., Celik, S.U., Ata, A., and Bozkurt, A.: Anhydrous proton conducting membranes for PEM fuel cells based on nafion/azole composites. Int. J. Hydrogen Energy 33, 2808 (2008).CrossRefGoogle Scholar
Mansur, H.S., Oréfice, R.L., and Mansur, A.A.P., Characterization of poly(vinyl alcohol)/poly(ethylene glycol) hydrogels and PVA-derived hybrids by small-angle x-ray scattering and FTIR spectroscopy. Polymer 45, 7193 (2004).CrossRefGoogle Scholar
Wilkes, C.E., Summers, J.W., Daniels, C.A., and Berard, M.T.: PVC Handbook (Hanser, Munich, 2005).Google Scholar
Gasa, J.V., Weiss, R.A., and Shaw, M.T.: Ionic crosslinking of ionomer polymer electrolyte membranes using barium cations. J. Membr. Sci. 304, 173 (2007).CrossRefGoogle Scholar
Lebrun, L., Da Silva, E., and Metayer, M.: Elaboration of ion-exchange membrane with semi-interpenetrating polymer networks containing poly(vinyl alcohol) as polymer matrix. J. Appl. Polym. Sci. 84, 1572 (2002).CrossRefGoogle Scholar
Zhang, H.Q., Li, X.F., Zhao, C.J., Fu, T.Z., Shi, Y.H., and Na, H.: Composite membranes based on highly sulfonated PEEK and PBI: Morphology characteristics and performance. J. Membr. Sci. 308, 66 (2008).CrossRefGoogle Scholar
Dippel, T., Kreuer, K.D., Lassegues, J.C., and Rodriguez, D.: Proton conductivity in fused phosphoric acid; A 1H/31P PFG-NMR and QNS study. Solid State Ionics 61, 41 (1993).CrossRefGoogle Scholar
Celik, S.Ü., Bozkurt, A., and Hosseini, S.S.: Alternatives toward proton conductive anhydrous membranes for fuel cells: Heterocyclic protogenic solvents comprising polymer electrolytes. Prog. Polym. Sci. 37, 1265 (2012).CrossRefGoogle Scholar
Goktepe, F., Sevim, U.C., and Bozkurt, A.: Preparation and the proton conductivity of chitosan/poly(vinyl phosphonic acid) complex polymer electrolytes. J. Non-Cryst. Solids 354, 3637 (2008).CrossRefGoogle Scholar
Goktepe, F., Bozkurt, A., and Gunday, S.T.: Synthesis and proton conductivity of poly(styrene sulfonic acid)/heterocycle-based membranes. Polym. Int. 57, 133 (2008).CrossRefGoogle Scholar
Pangon, A., Tashiro, K., and Chirachanchai, S.: Polyethylenimine containing benzimidazole branching: A model system providing a balance of hydrogen bond network or chain mobility enhances proton conductivity. J. Phys. Chem. B 115, 11359 (2011).CrossRefGoogle ScholarPubMed
Silva, B.B.R., Soares, J.B., Malfatti, C.F., and Forte, M.M.C.: Benzimidazole effect on the performance of polyelectrolyte membranes based on sulfonated hydrocarbon resin. J. Membr. Sci. 374, 12 (2011).CrossRefGoogle Scholar