Research Paper

Synthesis and Characterization of Sulfonated Polyimide Based Membranes for Proton Exchange Membrane Fuel Cells

[+] Author and Article Information
Hai Zheng

Polymer and Fiber Engineering Department, Auburn University, Auburn, AL 36849

Contributed by the Advanced Energy Systems Division of ASME for publication in the Journal of Fuel Cell Science and Technology. Manuscript received July 26, 2010; final manuscript received April 22, 2013; published online June 17, 2013. Assoc. Editor: Abel Hernandez.

J. Fuel Cell Sci. Technol 10(4), 041001 (Jun 17, 2013) (5 pages) Paper No: FC-10-1085; doi: 10.1115/1.4024564 History: Received July 26, 2010; Revised April 22, 2013

Sulfonated polyimide (SPI) based membranes for proton exchange membrane fuel cells (PEMFC) have been synthesized by using a one-step high temperature polymerization method. The membranes were characterized with Fourier transform infrared spectra (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC); water uptake, ion-exchange capacity, proton conductivity and mechanical stability were tested. The results showed that the membranes had good thermal and mechanical stability and exhibited good performance when they were assembled into membrane electrode assemblies (MEAs). Fuel cell testing was performed. The SPI copolymer based MEA was tested under different hydrogen flow rates to compare with the commercially available Nafion® based MEA.

Copyright © 2013 by ASME
Your Session has timed out. Please sign back in to continue.


Kreuer, K. D., 2001, “On the Development of Proton Conducting Polymer Membranes for Hydrogen and Methanol Fuel Cells,” J. Membr. Sci., 185, pp. 29–39. [CrossRef]
Appleby, A. J., and Foulkes, F. R., 1989, Fuel Cell Handbook, Van Nostrand Reinhold, New York.
Lehman, P. A., Chamberlin, C. E., Reid, R. M., and Herron, T. G., 1999, “Proton Exchange Membrane Fuel Cell,” U.S. Patent No. 5,879,826.
“Fuel Cell,” Wikipedia, accessed 23 April 2012, http://en.wikipedia.org
“Fuel Cell Technologies Program,” U.S. Department of Energy, accessed April 24, 2012, www1.eere.energy.gov/hydrogenfuelcells
Smitha, B., SridharS., and Khan, A. A., 2005, “Solid Polymer Electrolyte Membranes for Fuel Cell Applications—A Review,” J. Membr. Sci., 259(1-2), pp. 10–26. [CrossRef]
Larminie, J., and Dicks, A., 2000, Fuel Cell System Explained, Wiley, West Sussex, UK.
“Fuel Cell Basics—Applications,” accessed April 23, 2012, www.fuelcells.org/basics
Zheng, H., 2010, “Development and Characterization of Sulfonated Polyimide Membrane for Proton Exchange Membrane Fuel Cell Applications,” M.S. thesis, Auburn University, Auburn, AL.
Wilhelm, M., Jeske, M., Marschall, R., Cavalcanti, W. L., Tolle, P., Kohler, C., Koch, D., Frauenheim, T., Grathwohl, G., Caro, J., and Wark, M., 2008, “New Proton Conducting Hybrid Membranes for HT-PEMFC Systems Based on Polysiloxanes and SO3H-Functionalized Mesoporous Si-MCM-41 Particles,” J. Membr. Sci., 316, pp. 164–175. [CrossRef]
Lee, J. S., Quan, N. D., Hwang, J. M., Lee, S. D., Kim, H., Lee, H., and Kim, H. S., 2006, “Polymer Electrolyte Membranes for Fuel Cells,” J. Ind. Eng. Chem., 12(2), pp. 175–183. Available at http://infosys.korea.ac.kr/PDF/JIEC/IE12/IE12-2-0175.pdf
Cornet, N., Diat, O., Gebel, G., Jousse, F., Marsacq, D., Mercier, R., and Pineri, M., 2000, “Sulfonated Polyimide Membranes: A New Type of Ion-Conducting Membrane for Electrochemical Applications,” J. New Mater. Electrochem. Syst., 3(1), pp. 33–42. Available at http://infosys.korea.ac.kr/PDF/JIEC/IE12/IE12-2-0175.pdf
Detallante, V., Langevin, D., Chappey, C., Metayer, M., Mercier, R., and Pineri, M., 2001, “Water Vapor Sorption in Naphthalenic Sulfonated Polyimide Membranes,” J. Membr. Sci., 190(2), pp. 227–241. [CrossRef]
Detallante, V., Langevin, D., Chappey, C., Metayer, M., Mercier, R., and Pineri, M., 2002, ‘Kinetics of Water Vapor Sorption in Sulfonated Polyimide Membranes,” Desalination, 148(2), pp. 333–339. [CrossRef]
Piroux, F., Espuche, E., Mercier, R., and Pineri, M., 2003, “Water Vapor Transport Mechanism in Naphthalenic Sulfonated Polyimides,” J. Membr. Sci., 223(1), pp. 127–139. [CrossRef]
Genies, C., Mercier, R., Sillion, B., Petiaud, R., Cornet, N., Gebel, G., and Pineri, M., 2001, “Stability Study of Sulfonated Phthalic and Naphthalenic Polyimide Structures in Aqueous Medium,” Polymer, 42(12), pp. 5097–5105. [CrossRef]
Besse, S., Capron, P., Diat, O., Gebel, G., Jousse, F., Marsacq, D., Pineri, M., Marestin, C., and Mercier, R., 2002, “Sulfonated Polyimides for Fuel Cell Electrode Membrane Assemblies (MEA),” J. New Mater. Electrochem. Syst., 5(2), pp. 109–112.
Genies, C., Mercier, R., Sillion, B., Cornet, N., Gebel, G., and Pineri, M., 2000, “Soluble Sulfonated Naphthalenic Polyimides as Materials for Proton Exchange Membranes,” Polymer, 42(2), pp. 359–373. [CrossRef]
Zhang, Y., Litt, M., Savinell, R. F., and Wainright, J. S., 1999, “Molecular Design Considerations in the Synthesis of High Conductivity PEMs for Fuel Cells,” Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 40(2), pp. 480–481.
Zhang, Y., Litt, M., Savinell, R. F., Wainright, J. S., and Vendramini, J., 2000, “Molecular Design of Polyimides Toward High Proton Conducting Materials,” Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 41(2), pp. 1561–1562. [CrossRef]
Gunduz, N., and McGrath, J. E., 2000, “Synthesis and Characterization of Sulfonated Polyimides,” 2000, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 41(1), pp. 182–183.
Shobha, H. K., Sankarapandian, M., Glass, T. E., and McGrath, J. E., 2000, “Sulfonated Aromatic Diamines as Precursors for Polyimides for Proton Exchange Membranes,” Abstracts of Papers, American Chemical Society, 220th (POLY-155).
Einsla, B. R., Hong, Y. T., Kim, Y. S., Wang, F., Gunduz, N., and McGrath, J. E., 2004, “Sulfonated Naphthalene Dianhydride Based Polyimide Copolymers for Proton-Exchange-Membrane Fuel Cells. I. Monomer and Copolymer Synthesis,” J. Polym. Sci., Part A: Polym. Chem., 42(4), pp. 862–874. [CrossRef]
Fang, J., Guo, X., Harada, S., Watari, T., Tanaka, K., Kita, H., and Okamoto, K., 2002, “Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application. 1. Synthesis, Proton Conductivity, and Water Stability of Polyimides From 4,4’-Diaminodiphenyl Ether-2,2’-Disulfonic Acid,” Macromolecules, 35(24), pp. 9022–9028. [CrossRef]
Kim, Y. S., Dong, L., Hickner, M. A., Glass, T. E., Webb, V., and McGrath, J. E., 2003, “State of Water in Disulfonated Poly(Arylene Ether Sulfone) Copolymers and a Perfluorosulfonic Acid Copolymer (Nafion) and its Effect on Physical and Electrochemical Properties,” Macromolecules, 36, pp. 6281–6285. [CrossRef]
Su, Y., Liu, Y., Sun, Y., Lai, J., Liu, B., and Guiver, M. D., 2007, “Proton Exchange Membranes Modified With Sulfonated Silica Nanoparticles for Direct Methanol Fuel Cells,” J. Membr. Sci., 296, pp. 21–28. [CrossRef]
Kim, D. H., and Kim, S. C., 2008, “Transport Properties of Polymer Blend Membranes of Sulfonated and Nonsulfonated Polysulfones for Direct Methanol Fuel Cell Application,” Macromol. Res., 16, pp. 457–466. [CrossRef]
Saito, M., Arimura, N., Hayamizu, K., and Okdada, T., 2004, “Mechanisms of Ion and Water Transport in Perfluorosulfonated Ionomer Membranes for Fuel Cells,” J. Phys. Chem. B, 108, pp. 16064–16070. [CrossRef]
Fu, Y., Manthiram, A., and Guiver, M. D., 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, pp. 1386–1390. [CrossRef]
Choi, J., Kim, D. H., Kim, H. K., Shin, C., and Kim, S. C., 2008, “Polymer Blend Membranes of Sulfonated Poly(Arylene Ether Ketone) for Direct Methanol Fuel Cell,” J. Membr. Sci., 310, pp. 384–392. [CrossRef]
Zawodzinski, T. A., Derouin, C., Radzinski, S., Sherman, R. J., Smith, V. T., Springer, T. E., and Gottesfeld, S., 1993, “Water Uptake By and Transport Through Nafion 117 Membranes,” J. Electrochem. Soc., 140, pp. 1041–1047. [CrossRef]
So, S. Y., Hong, Y. T., Kim, S. C., and Lee, S. Y., 2010, “Control of Water-Channel Structure and State of Water in Sulfonated Poly(Arylene Ether Sulfone)/Diethoxydimethylsilane In Situ Hybridized Proton Conductors and Its Influence on Transport Properties for DMFC Membranes,” J. Membr. Sci., 346, pp. 131–135. [CrossRef]
Beattie, P. D., Orfino, F. P., Basura, V. I., Zychowska, K., Ding, J., Chuy, C., Schmeisser, J., and Holdcroft, S., 2001, “Ionic Conductivity of Proton Exchange Membranes,” J. Electroanal. Chem., 503, pp. 45–56. [CrossRef]
Isikel, L., Gocek, I., and Adanur, S., 2010, “Design and Characterization of Nonwoven Fabrics for Gas Diffusion Layer in Polymer Electrolyte Membrane Fuel Cell,” J. Textile Inst., 101(11), pp. 1006–1014. [CrossRef]


Grahic Jump Location
Fig. 1

Chemical reaction for synthesis of SPI

Grahic Jump Location
Fig. 2

SPI copolymer membrane (left) and MEA produced

Grahic Jump Location
Fig. 3

FTIR testing of the ODA based diamine SPI membrane

Grahic Jump Location
Fig. 4

DSC testing of the SPI membrane

Grahic Jump Location
Fig. 5

TGA testing of the SPI membrane

Grahic Jump Location
Fig. 7

Voltage versus time curve of the fuel cell

Grahic Jump Location
Fig. 6

Schematic of the membrane proton conductivity measurement



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In