This paper is a review that is focused on ionomers based on aromatic polysulfone backbone and intended to be used in proton exchange membrane fuel cells or in direct methanol fuel cells. Emphasis is placed on the different chemical routes to prepare the ionomers. Special attention is given to the impact of the ionomer structure on the conductivity performance and on the dimensional stability of the membranes at high temperatures.
Steele, B.C.H. and Heinzel, A. (2001). Materials for Fuel-cell Technologies, Nature (Lond .), 414: 345.
2.
Rikukawa, M. and Sanui, K. (2000). Proton-conducting Polymer Electrolyte Membranes based on Hydrocarbon Polymers, Prog. Polym. Sci., 25: 1463-1502.
3.
Hickner, M.A. , Ghassemi, H., Kim , Y.S., Einsla, B.R. and McGrath, J.E. (2004). Alternative Polymer Systems for Proton Exchange Membranes (PEMs) , Chem. Rev., 104: 4587-4611.
4.
Roziere, J. and Jones, D.J. (2003). Non-fluorinated Polymer Materials for Proton Exchange Membrane Fuel Cells, Annu. Rev. Mater. Res., 33: 503-535.
5.
Yang, Y. and Holdcroft, S. ( 2005). Synthetic Strategies for Controlling the Morphology of Proton Conducting Polymer Membranes, Fuel Cells, 5: 171-186.
6.
Yu, J. , Yi, B., Xing , D., Liu , F., Chao, Z., Fu , Y. and Zhang, H. (2003). Degradation Mechanism of Polystyrene Sulfonic Acid Membrane and Application of its Composite Membranes in Fuel Cells, Phys. Chem. Chem. Phys., 5: 611-615.
7.
Amarilla, J.M., Rojas, R.M., Rojo, J.M., Cubillo, M.J., Linares, A. and Acosta, J.L. (2000). Antimonic Acid and Sulfonated Polystyrene Proton-conducting Polymeric Composites , Solid State Ionics, 127: 133- 139.
8.
Iojoiu, C. , Marechal, M., Chabert , F. and Sanchez, J.-Y. (2005). The Mastery of Chemical Modifications of Aromatic Polysulfones: Crucial for Membranes in Fuel Cell Applications, Fuel Cells (Weinheim, Germany ), 5: 344-354.
9.
Iojoiu, C. , Chabert, F., Marechal , M., Kissi, N.El. , Guindet, J. and Sanchez, J.-Y. ( 2006). From Polymer Chemistry to Membrane Elaboration A Global Approach of Fuel Cell Polymeric Electrolytes , J. Power Sources , 153: 198-209.
10.
Gao, Y., Robertson, G.P., Guiver, M.D., Mikhailenko, S.D., Li , X. and Kaliaguine, S. (2004). Synthesis of Poly(arylene ether ether ketone ketone) Copolymers Containing Pendant Sulfonic Acid Groups Bonded to Naphthalene as Proton Exchange Membrane Materials, Macromolecules, 37: 6748-6754.
11.
Xing P., Robertson, G.P., Guiver, M.D., Mikhailenko, S.D. and Kaliaguine, S. ( 2004). Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization, as Proton Exchange Membranes for Fuel Cell Application, Macromolecules , 37: 7960-7967.
12.
Miyatake, K. , Zhou, H., Uchida , H. and Watanabe M. ( 2003). Synthesis and Properties of Novel Sulfonated Poly(phenylene ether), Chem. Commun., 3: 368.
13.
Chikashige, Y. , Chikyu, Y., Miyatake , K. and Watanabe, M. (2005). Poly(arylene ether) Ionomers Containing Sulfofluorenyl Groups for Fuel Cell Applications, Macromolecules, 38: 7121.
14.
Jones, D.J. and Roziere J. ( 2001). Recent Advances in the Functionalisation of Polybenzimidazole and Polyetherketone for Fuel Cell Applications, J. Membr. Sci., 185: 41-58.
15.
Zaidi, S.M.J. , Mikhailenko, S.D., Robertson, G.P., Guiver, M.D. and Kaliaguine S. (2000). Proton Conducting Composite Membranes from Polyether Ether Ketone and Heteropolyacids for Fuel Cell Applications, J. Membr. Sci., 173: 17.
16.
Kim, D.S. , Michael, B.L. and Guiver, D. (2006). Influence of Silica Content in Sulfonated Poly(arylene ether ether ketone ketone) (SPAEEKK) Hybrid Membranes on Properties for Fuel Cell Application , Polymer, 47: 7871-7880.
17.
Elabd, Y.A. , Napadensky, E., Sloan , J.M., Crawford, D.M. and Walter, C.W. ( 2003). Triblock Copolymer Ionomer Membranes: Part I. Methanol and Proton Transport , J. Membr. Sci., 217: 27-38.
18.
Kerres, J. , Ullrich, A., Meier , F. and Harina, T. (1999). Synthesis and Characterization of Novel Acid-base Polymer Blends for Application in Membrane Fuel Cells, Solid State Ionics , 125: 243-249.
19.
Kerres, J. , Ullrich, A., Haring , T., Baldauf, M., Gebhardt, U. and Preidea, W. (2000). Preparation, Characterization and Fuel Cell Application of New Acid-base Blend Membranes, J. New Mater. Electrochem. Syst., 3: 229-239.
20.
Litt, M.H. , Zhang, Y., Savinell , R.F. and Wainright , J.S. (1999). Molecular Design Considerations in the Synthesis of High Conductivity PEMs for Fuel Cells, Polym. Prep., 40: 480-481.
21.
Miyatake, K., Iyotani, H., Yamamoto , K. and Tsuchida, E. (1996), Synthesis of Poly(phenylene sulfide sulfonic acid) via Poly(sulfonium cation) as a Thermostable Proton-conducting Copolymer, Macromolecules , 29(21): 6969-6971.
22.
Xing, P.X. , Robertson, G.P., Guiver, M.D., Mikhaileuko, S.D. and Kaliaguine , S. ( 2004). Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization, as Proton Exchange Membranes for Fuel Cell Application, Macromolecules , 37: 7960- 7967.
23.
Hickner, M. and Pivovar, B.S. (2005). The Chemical and Structural Nature of Proton Exchange Membrane Fuel Cell Properties, Fuel Cells, 5: 213-229.
24.
Marechal, M., Wessel, R., Diard , J.-P., Guindet, J. and Sanchez, J.-Y. (2007). Study of PEMFC Ionomers Through Model Molecules Mimicking the Ionomer Repeat Units, Electrochim. Acta, 52: 7953-7963.
25.
Genova-Dimitrova, P., Baradie , B., Foscallo , D., Poisignon, C. and Sanchez, J.Y. ( 2001). Ionomeric Membranes for Proton Exchange Membrane Fuel Cell (PEMFC): Sulfonated Polysulfone Associated with Phosphatoantimonic Acid , J. Membr. Sci., 185: 59-71.
26.
Iojoiu, C. , Genova-Dimitrova , P., Marechal, M. and Sanchez, J.-Y. (2006). Chemical and physicochemical characterizations of ionomers, Electrochim . Acta, 51: 4789-4801.
Noshay, A. and Robeson, L.M. (1976). Sulfonated Polysulfone , J. Appl. Polym. Sci., 20: 1885-1903.
29.
Linkous, A., Anderson, H.R., Kopitzke, R.W. and Nelson, G.L. ( 1998). Development of New Proton Exchange Membrane Electrolytes for Water Electrolysis At Higher Temperature , J. Hydrogen Energy, 23: 525-529.
30.
Blaco, J.F. , Nguyen, Q.T. and Schatzel, P. (2002). Sulfonation of Polysulfones: Suitability of the Sulfonated Materials for Asymmetric Membrane Preparation , J. Appl. Polym. Sci. , 84: 2461-2473.
31.
Guiver, M.D. , Apsimon, J.W. and Kutowy, O. ( 1989). Modified Polysulfone Membranes II. Pervaporation of Aqueous Ethanol Solution through Modified Polysulfone Membranes Bearing Various Hydroxyl Groups, US Patent 4 833 219.
32.
Keres, J.A. , Cui, W. and Reichle, S. (1996). New Sulfonated Engineering Polymers via the Metalation Route. I. Sulfonated Poly(ethersulfone) PSU Udel via Metalation-Sulfination-OxidationJ. Polym. Sci., Part A: Polym. Chem., 43: 2421-2438.
33.
Jannasch, P. ( 2002). Fuel Cell Membrane Materials by Chemical Grafting of Aromatic Main-Chain Polymers, Fuel Cells, 2(5): 248-260.
34.
Vernersson, T. , Lafitte, B., Lindbergh , G. and Jannasch, P. (2006). A Sulfophenylated Polysulfone as the DMFC Electrolyte Membrane - An Evaluation of Methanol Permeability and Cell Performance, Fuel Cells , 5: 340-346.
35.
Karlsson, L.E. and Jannasch , P. (2005). Polysulfone Ionomers for Proton-conducting Fuel Cell Membranes: 2. Sulfophenylated Polysulfones and Polyphenylsulfones, Electrochim. Acta, 50: 1939-1946.
36.
Lafitte, B. , Puchner, M. and Jannasch, P. ( 2005). Proton Conducting Polysulfone Ionomers Carrying Sulfoaryloxybenzoyl Side Chains, Macromol. Rapid Commun., 26: 1464-1468.
37.
Karlsson, L.E. and Jannasch , P. (2004). Polysulfone Ionomers for Proton-Conducting Membranes: Sulfoalkylated Polysulfones , J. Membr. Sci., 230: 61-70.
38.
Lafitte, B. and Jannasch, P. ( 2007). Proton-Conducting Aromatic Polymers Carrying Hypersulfonated Side Chains for Fuel Cell Applications , Adv. Funct. Mater. , 17: 2823-2834.
39.
Kreuer, K.D. (2001). On the Development of Proton Conducting Polymer Membranes for Hydrogen and Methanol Fuel Cells , J. Membr. Sci., 185: 29-39.
40.
Nolte, R. , Ledjeff, K., Bauer , M. and Mulhaupt, R. (1993). Partially Sulfonated Poly(arylene ether sulfone) - A Versatile Proton Conducting Membrane Material for Modern Energy Conversion Technologies, J. Membr. Sci. , 83: 211-220.
41.
Kerres, J. , Zhang, W. and Cui , W. (1998). New Sulfonated Engineering Polymers via the Metalation Route. II. Sulfinated/sulfonated Poly(ether sulfone) PSU Udel and its Crosslinking, J. Polym. Sci. Polym. Chem. , 36: 1441-1448.
42.
Kerres J. , Cui, W. and Junginger, M. (1998). Development and Characterization of Crosslinked Ionomer Membranes Based upon Sulfinated and Sulfonated PSU Crosslinked PSU Blend Membranes by Alkylation of Sulfinate Groups with Dihalogenoalkanes , J. Membr. Sci. , 139: 227-241.
43.
Sanchez, J.-Y., Chabert, F., Iojoiu , C., Salomon, J., Kissi, N. El., Piffard, Y., Marechal, M., Galiano, H. and Mercier, R. (2007). Extrusion: An Environmentally Friendly Process for PEMFC Membrane Elaboration , Electrochim. Acta, 53: 1584-1595.
44.
Marechal, M., Guindet, J., Souquet , J.-L. and Sanchez, J-Y. (2003). Solvation of Sulphonic Acid Groups in NafionĀ® Membranes from Accurate Conductivity Measurements, Electrochem. Commun., 9: 1023-1028.
45.
Vallejo, E., Pourcelly, G., Gavach , C., Mercier, R. and Pineri, M. (1999). Sulfonated Polyimides as Proton Conductor Exchange Membranes. Physicochemical Properties and Separation H+/M2+ by Electrodialysis Comparison with a Perfluorosulfonic Membrane, J. Membr. Sci., 160: 127-137.
46.
Lee, H.S., Badama, A.S., Roy , A. and McGrath, J.E. (2007). Segmented Sulfonated Poly(arylene ether sulfone)-b-Polyimide Copolymers for Proton Exchange Membrane Fuel Cells. I. Copolymer Synthesis and Fundamental Properties, J. Polym. Sci., Part A: Polym. Chem., 45: 4879-4890.
47.
Yu, X. , Roy, A., Dunn , S., Yang, J. and McGrath, J.E. (2006). Synthesis and Characterization of Sulfonated-fluorinated, Hydrophilic-hydrophobic Multiblock Copolymers for Proton Exchange Membranes, Macromol. Symp., 245: 439-449.
48.
Ghassemi, H., McGrath, J.E. and Zawodzinski , T.A. (2006 ). Multiblock Sulfonated-Fluorinated Poly (arylene ether)s for A Proton Exchange Membrane Fuel Cell, Polymer, 47: 4132-4139.
49.
Lee, H.S., Roy, A., Lane , O., Dunn, S. and McGrath, J.E. (2008). Hydrophilic-hydrophobic Multiblock Copolymers based on Poly(arylene ether sulfone) via Low-Temperature Coupling Reactions for Proton Exchange Membrane Fuel Cells, Polymer, 49: 715-723.
50.
Kim, Y.S., Dong, L., Hickner , M.A., Pivovar, B.S. and McGrath, J.E. ( 2003). Processing Induced Morphological Development in Hydrated Sulfonated Poly(arylene ether sulfone) Copolymer Membranes, Polymer, 44: 5729-5736.
51.
Kim, Y.S., Einsla, B., Sankir , M., Harrison, W. and Pivovar, B.S. (2006). Structure-property-performance Relationships of Sulfonated Poly(Arylene Ether Sulfone)s as a Polymer Electrolyte for Fuel Cell Applications, Polymer, 47: 4026-4035.
52.
Wang, F., Hickner, M., Kim, Y.S., Zawodzinski, T.A. and McGrath, J.E. ( 2002). Direct Polymerization of Sulfonated Poly(arylene ether sulfone) Random (statistical) Copolymers: Candidates for New Proton Exchange Membranes, J. Membr. Sci., 197: 231-242.
53.
Harrison, W.L., Wang, F., Mecham , J., Bhanu, V., Hill, M. and Kim , Y.S. (2003). Influence of the Bisphenol Structure on the Direct Synthesis of Sulfonated Poly(arylene ether) Copolymers , J. Polym. Sci., Part A: Polym. Chem., 41: 2264-2276.
54.
Einsla, B.R. , Kim, Y.S., Hickner, M.A., Hong, Y.T., Hill, M.L. and Pivovar, B.S. ( 2005). Sulfonated Naphthalene Dianhydride Based Polyimide Copolymers for Proton-exchange Membrane Fuel Cells: II. Membrane Properties and Fuel Cell Performance, J. Membr. Sci., 255: 141-148.
55.
Brutschy, B. ( 2000). The Structure of Microsolvated Benzene Derivatives and the Role of Aromatic Substituents, Chem. Rev., 100: 3891-3920.
56.
Kryachko, E.S. and Nguyen , M.T. (2001). Hydrogen Bonding in Benzonitrile-water Complexes, J. Chem. Phys., 115: 833-841.
57.
Wang, S., Zhuang, H., Shobha, H.K., Glass, T.E., Sankarapandian, M. and Ji, Q. ( 2001). Miscibility of Poly(arylene phosphine oxide) Systems and Bisphenol A Poly(hydroxy ether), Macromolecules, 34: 8051-8063.
58.
Etter, M.C. and Reutzel, S.M. ( 1991). Hydrogen Bond Directed Cocrystallization and Molecular Recognition Properties of Acyclic Imides, J. Am. Chem. Soc. , 113: 2586-2598.
59.
Langner, R. and Zundel, G. ( 1995). FT-IR Investigation of Polarizable, Strong Hydrogen Bonds in Sulfonic Acid Sulfoxide, Phosphine Oxide, and Arsine Oxide Complexes in the Middle- and Far-Infrared Region, J. Phys. Chem., 99: 12214-12219.
60.
Roy, A. , Hickner, M., Glass T. and McGrath, J.E. ( 2005). Advances in Materials for Proton Exchange Membrane Fuel Cell Systems, PacificGrove, CA, Abs. No 55-II, February 20-23.
61.
Wang, Z., Chen, T. and Xu, J. ( 2001). Synthesis and Properties of Novel Random and Block Copolymers Composed of Phthalimidine- and Perfluoroisopropylidene-polyarylether-sulfones, Polym. Int., 50: 249- 255.
62.
Nakabayashi, K., Matsumoto, K. and Ueda, M. (2008). Synthesis and Properties of Sulfonated Multiblock Copoly(ether sulfone)s by a Chain Extender, J. Polym. Sci., Part A: Polym. Chem. , 46: 3947-3957.
63.
Nakabayashi, K., Matsumoto, K., Higashihara , T. and Ueda, M. (2008). Influence of Adjusted Hydrophilic-Hydrophobic Lengths in Sulfonated Multiblock Copoly(ether sulfone) Membranes for Fuel Cell Application, J. Polym. Sci., Part A: Polym. Chem., 46: 7332-7341.
64.
Alberti, G., Casciola, M., Costantino , U. and Levi, G. (1978). Inorganic Ion Exchange Membranes of Microcrystals of Zirconium Phosphate Supported by Kynar, J. Membr. Sci., 3: 179.
65.
Alberti, G., Casciola, M. and Costantino, U. (1983). Inorganic Ion-exchange Membranes Made of Acid Salts of Tetravalent Metals. A Short Review, J. Membr. Sci., 16: 137-149.
66.
Deng, Q., Moore, R.B. and Mauritz, K.A. ( 1995). Novel Nafion/ORMOSIL Hybrids via In Situ Sol-gel Reactions. 1. Probe of ORMOSIL Phase Nanostructures by Infrared Spectroscopy , Chem. Mater., 7(12): 2259-2268.
67.
Grot, W. and Rajendran, G. ( 1996). Fuel Cell Components including Immobilised Heteropolyacids, Int. Patent No. WO 96/29752.
68.
Mauritz, K.A. and Warren, R.M. (1989). Microstructural Evolution of a Silicon Oxide Phase in a Perfluorosulfonic Acid Ionomer by an In Situ Sol-gel Reaction. 1. Infrared Spectroscopic Studies, Macromolecules , 22: 1730-1734.
69.
Honma, I. , Takeda, Y. and Bae , J.M. (1999). Protonic Conducting Properties of Sol-gel Derived Organic/inorganic Nanocomposite Membranes Doped with Acidic Functional Molecules, Solid State Ionics, 120: 255-264.
70.
Nakajima, H. and Honma, I. (2002). Proton-conducting Hybrid Solid Electrolytes for Intermediate Temperature Fuel Cells, Solid State Ionics, 148: 607-610.
71.
Honma, I. , Nomura, S. and Nakajima, H.J. (2001). Protonic Conducting Organic/inorganic Nanocomposites for Polymer Electrolyte Membrane, Membr. Sci., 185: 83-94.
72.
Nakajima, H., Nomura, S., Sugimoto , T., Nishikawa, S. and Honma, I. ( 2002). High Temperature Proton Conducting Organic/Inorganic Nanohybrids for Polymer Electrolyte Membranes , J. Electrochem. Soc., 149: A953-A959.
73.
Nakamura, O., Kodama, T., Ogino , I. and Miyake, Y. (1979). High-conductivity Solid Proton Conductors: Dodecamolybdophosphoric Acid and Dodecatungstophosphoric Acid Crystals, Chem. Lett. , 1: 17-18.
74.
Honma, I. , Nakajima, H.and Nomura, S. (2002). High Temperature Proton Conducting Hybrid Polymer Electrolyte Membranes , Solid State Ionics, 154-155: 707-712.
75.
Honma, I. , Nakajima. H., Nishikawa , O., Sugimoto, T. and Nomura, S. (2003). Family of High-Temperature Polymer-Electrolyte Membranes Synthesized from Amphiphilic Nanostructured Macromolecules, J. Electrochem. Soc. 150: A616-A619.
76.
Lavrencic, S. , Stangar, U., Orel , B., Vince, J., Jovanovski, V., Spreizer, H., Surca, A.,Vuk , A. and Hocevar, S. (2005). Silicotungstic Acid/Organically Modified Silane Proton-Conducting MembranesJ. Solid State Electrochem., 9: 106-113.
77.
Ramani, V. , Kunz, H.R. and Fenton, J.M. ( 2004). Investigation of NafionĀ®/HPA Composite Membranes for High Temperature/Low Relative Humidity PEMFC Operation, J. Membr. Sci., 232: 31-44.
78.
Colomban, P. ( 1992). Chemistry of Solid State Materials. 2. Proton Conductors-Solids, Membranes and Gels-Materials and Devices , Cambridge University Press, Cambridge , UK.
79.
Nakamura, O. , Ogino, I. and Kodama, T. ( 1981). Temperature and Humidity Ranges of Some Hydrates of High-Proton-Conductive Dodecamolybdophosphoric Acid and Dodecatungstophosphoric Acid Crystals under an Atmosphere of Hydrogen or Either Oxygen or Air, Solid State Ionics, 3-4: 347-351.
80.
Abe, Y. , Li, G., Nogami , M., Kasuga, T. and Hench, L.L. ( 1996). Superprotonic Conductors of Glassy Zirconium Phosphates , J. Electrochem. Soc., 143: 144-147.
81.
Tatsumisago, M., Honjo, H., Sakai Y. and Minami, T. (1994), Proton-conducting Silica-gel Films Doped with a Variety of Electrolytes , Solid State Ionics , 74:105-108
82.
Pope, M.T. ( 1983). Heteropoly and Isopoly Oxometalates, Springer-Verlag, Berlin.
83.
Moffat, J.B. (1986). Cation-anion Effects in Heteropoly Compounds with Keggin Structures, Polyhedron , 5: 261-269.
Smitha, B. , Sridhar, S. and Khan, A.A. (2005). Proton Conducting Composite Membranes from Polysulfone and Heteropolyacid for Fuel Cell Applications, J. Polym. Sci., Part B: Polym. Phys., 43: 1538-1547.
86.
Baradie, B. , Denoyelle, A., Piffard , Y., Poinsignon, C., Sanchez, J.-Y. and Vitter G. ( 1996). Thermostable Ionomeric Filled Membrane for H2/O2 Fuel Cell, French Patent 9608503, EP19970401613, Publication date: /06/12/2002, Filling date: 07/07/1997
87.
Baradie, B., Poinsignon, C., Sanchez , J.-Y., Piffard, Y., Vitter, G., Bestaoui, N., Foscallo, D., Denoyelle, A., Delabouglise, D. and Vaujany, M. ( 1998). Thermostable Ionomeric Filled Membrane for H2/O2 Fuel Cell, J. Power Sources, 74: 8-16.
