Hostname: page-component-cd9895bd7-q99xh Total loading time: 0 Render date: 2024-12-28T01:24:23.008Z Has data issue: false hasContentIssue false
  • English
  • Français

Nanocomposite polymer electrolyte membranes based on poly(vinylphosphonic acid)/TiO2 nanoparticles

Published online by Cambridge University Press:  05 December 2012

Ayşe Aslan  and
Ayhan Bozkurt
Ayşe Aslan
Affiliation:
Department of Chemistry, Fatih University, 34500 Büyükçekmece-İstanbul, Turkey
Ayhan Bozkurt*
Affiliation:
Department of Chemistry, Fatih University, 34500 Büyükçekmece-İstanbul, Turkey
*
a)Address all correspondence to this author. e-mail: bozkurt@fatih.edu.tr
Get access

Abstract

In the present work, proton conducting nanocomposite electrolytes containing poly(vinylphosphonic acid) (PVPA) and TiO2 have been prepared and characterized. In the nanocomposite materials, the TiO2 content was varied from 5% to 20% (w/w) to improve mechanical strength and stability. The thermal stability, proton conductivity, as well as morphology of the electrolytes were investigated. The interaction existed between PVPA and TiO2 was confirmed by Fourier transform infrared spectroscopy. Thermogravimetric analysis showed that the samples are thermally stable up to approximately 200 °C. Differential scanning calorimetry results indicate that the Tg of the materials shift to higher temperatures as TiO2 content increases. Scanning electron microscopy results confirmed that the TiO2 nanoparticles were successfully incorporated and homogeneously distributed in the PVPA matrix. In the anhydrous state, the proton conductivity of PVPA(10)TiO2(in situ) has been found to be 0.004 S/cm at 120 °C. The proton conductivity of these membranes are also measured and compared with previous studies.

Keywords

nanocomposite polymer electrolyteproton conductivity
Type
Articles
Information
Journal of Materials Research , Volume 27 , Issue 24 , 28 December 2012 , pp. 3090 - 3095
Copyright
Copyright © Materials Research Society 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Celik, S.Ü., Bozkurt, A., and Hossein, 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
Gray, F.M.: Polymer Electrolytes (Royal Society of Chemistry Monographs, Cambridge, 1997).Google Scholar
Babir, F. and Gomez, T.: Efficiency and economics of proton exchange membrane fuel cells. Int. J. Hydrogen Energy 21, 891, (1996).CrossRefGoogle Scholar
Aslan, A., Ünal, Ş., and Ayhan, B.: Preparation, properties, and characterization of polymer electrolyte membranes based on poly(1-vinyl-1,2,4 triazole) and poly(styrene sulfonic acid). J. Electrochem. Soc. 156, B1112, (2009).CrossRefGoogle Scholar
Schuster, M.F.H. and Meyer, W.H.: Anhydrous proton-conducting polymers. Ann. Rev. Mater. Res. 33, 233 (2003).CrossRefGoogle Scholar
Smitha, B., Sridhar, S., and Khan, A.A.: Solid polymer electrolyte membranes for fuel cell applications—a review. J. Membr. Sci. 259, 10 (2005).CrossRefGoogle Scholar
Mauritz, K.A. and Moore, R.B.: State of understanding of Nafion. Chem. Rev. 104, 4535 (2004).CrossRefGoogle ScholarPubMed
Allcock, H.R., Hofmann, M.A., Ambler, C.M., and Morford, R.V.: Properties of poly(phosphazene-siloxane) block copolymers synthesized via telechelic polyphosphazenes and polysiloxane. Macromolecules 34, 6915 (2001).CrossRefGoogle Scholar
Hagihara, H., Uchida, H., and Watanabe, M.: Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane. Electrochim. Acta 51, 3979 (2006).CrossRefGoogle Scholar
Bao, C., Ouyang, M.G., and Yi, B.: Analysis of the water and thermal management in proton exchange membrane fuel cell systems. Int. J. Hydrogen Energy 31, 1040 (2006).CrossRefGoogle Scholar
Balazs, A.C., Emrick, T., and Russell, T.P.: Nanoparticle polymer composites: Where two small worlds meet. Science 314, 110 (2006).CrossRefGoogle ScholarPubMed
Krishnamoorti, R. and Vaia, R.A.: Polymer nanocomposites. J. Polym. Sci., Part B: Polym. Phys. 45, 3252 (2007).CrossRefGoogle Scholar
Caseri, W.: Nanocomposites of polymers and inorganic particles. In Hybrid Materials. Synthesis, Characterization, and Applications, Kickelbick, G. ed.; Wiley-VCH 49: Weinheim, Germany, 2007.Google Scholar
Schadler, L.S., Kumar, S.K., Benicewicz, B.C., Lewis, S.L., and Harton, S.E.: Designed interfaces in polymer nanocomposites: A fundamental viewpoint. MRS Bull. 2, 335 (2007).CrossRefGoogle Scholar
Schaefer, D.W. and Justice, R.S.: How nano are nanocomposites? Macromolecules 40, 8501 (2007).CrossRefGoogle Scholar
Gao, Y. and Choudhury, N.R.: Organic-inorganic hybrid from ionomer. In Handbook of Organic-Inorganic Hybrid Materials and Nanocomposites, Vol. 2, Nalwa, H.S. ed.; American Scientific Publishers: Stevenson Ranch, CA, 2003; pp. 271–293.Google Scholar
Liu, Z.L., Guo, B., Huang, J.C., Hong, L., Han, M., and Gan, L.M.: Nano-TiO2-coated polymer electrolyte membranes for direct methanol fuel cells. J Power Sources 157, 207 (2006).CrossRefGoogle Scholar
Chalkova, E., Pague, M.B., Fedkin, M.V., Wesolowski, D.J., and Lvov, S.N.: Effect of TiO2 surface properties on performance of Nafion-based composite membranes in high temperature and low relative humidity PEM fuel cells. J. Electrochem. Soc. 152, A1035 (2005).CrossRefGoogle Scholar
Baglio, V., Aric‘o, A.S., Blasi, A.D., Antonucci, V., Antonucci, P.L., and Licoccia, S.: Nafion–TiO2 composite DMFC membranes: Physico-chemical properties of the filler versus electrochemical performance. Electrochim. Acta 50, 1241 (2005).CrossRefGoogle Scholar
Baglio, V., Blasi, A.D., Aric‘o, A.S., Antonucci, V., Antonucci, P.L., and Trakanprapai, C.J.: Composite mesoporous titania Nafion-based membranes for direct methanol fuel cell operation at high temperature batteries, fuel cells, and energy conversion. Electrochem. Soc. 152, 1373 (2005).CrossRefGoogle Scholar
Sacc’a, A., Carbone, A., Passalacqua, E., D’Epifanio, A., Licoccia, S., and Traversa, E.: Nafion–TiO2 hybrid membranes for medium temperature polymer electrolyte fuel cells (PEFCs). J Power Sources 152, 16 (2005).CrossRefGoogle Scholar
Trakanprapai, C., Esposito, V., Licoccia, S., and Traversa, E.: Alternative chemical route to mesoporous titania from a titanatrane complex. J. Mater. Res. 20, 128 (2005).CrossRefGoogle Scholar
Chen, S.Y., Han, C.C., Tsai, C.H., Huang, J., and Chen, Y.W.: Effect of morphological properties of ionic liquid-templated mesoporous anatase TiO2 on performance of PEMFC with Nafion/TiO2 composite membrane at elevated temperature and low relative humidity. J Power Sources 171, 363 (2007).CrossRefGoogle Scholar
Santiago, E.I., Isidoro, R.A., Dresch, M.A., Matos, B.R., Linardi, M., and Fonseca, F.C.: Nafion–TiO2 hybrid electrolytes for stable operation of PEM fuel cells at high temperature. Electrochim. Acta 54, 4111 (2009).CrossRefGoogle Scholar
Roziere, J. and Jones, D.J.: Non-fluorinated polymer materials for proton exchange membrane fuel cells. Ann. Rev. Mater. Res. 33, 503 (2003).CrossRefGoogle Scholar
Hamlen, R.P.: US Patent, US 5 849, 428, September 1–3, 1998.CrossRefGoogle Scholar
Bingöl, B., Meyer, W.H., Wagner, M., and Wegner, G.: Synthesis, microstructure, and acidity of poly(vinylphosphonic acid). Macromol. Rapid Commun. 27, 1719 (2006).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
Bozkurt, A., Meyer, W.H., Gutmann, J., and Wegner, G.: Proton conducting copolymers on the basis of vinylphosphonic acid and 4-vinylimidazole. Solid State Ionics, 164, 169 (2003).CrossRefGoogle Scholar
Çelik, S.U., Akbey, U., Graf, R., Bozkurt, A., and Spiess, H.W.: Anhydrous proton-conducting properties of triazole–phosphonic acid copolymers: A combined study with MAS NMR. Phys. Chem. Chem. Phys. 10, 6058 (2008).CrossRefGoogle ScholarPubMed
Mallakpour, S. and Barati, A.: Efficient preparation of hybrid nanocomposite coatings based on poly(vinyl alcohol) and silane coupling agent modified TiO2 nanoparticles. Prog. Org. Coat. 71, 391 (2011).CrossRefGoogle Scholar
Wu, H., Hou, W., Wang, J., Xiaoa, L., and Jiang, Z.: Preparation and properties of hybrid direct methanol fuel cell membranes by embedding organophosphorylated titania submicrospheres into a chitosan polymer matrix. J. Power Sources 195, 4104 (2010).CrossRefGoogle Scholar
Peighambardoust, S.J. and Pourabbas, B.: Preparation and characterization of nylon-6/PPy/MMT composite of nanocomposite. J. Appl. Polym. Sci. 106, 697 (2007).CrossRefGoogle Scholar
Eikerling, M., Kornyshev, A.A., Kuznetsov, A.M., Ulstrup, J., and Walbran, S.: Mechanisms of proton conductance in polymer electrolyte membranes. J. Phys. Chem. B 105, 3646 (2001).CrossRefGoogle Scholar
Devrim, Y., Erkan, S., Bac, N., and Eroglu, I.: Preparation and characterization of sulfonated polysulfone/titanium dioxide composite membranes for proton exchange membrane fuel cells. Int. J. Hydrogen Energy 34, 3467 (2009).CrossRefGoogle Scholar