本研究利用具有磺酸基之AESA-Na與聚(苯乙烯-馬來酸酐)進行加成反應，再與bis-(aminopropyl) polydimethylsiloxane (X-22)、aminopropyltriethoxysilane (Z-6011)、Tetraethyl orthosilicate (TEOS) 進行交聯及溶膠反應，製備出一系列之質子交換膜，結果顯示，所製備出之質子交換薄膜具透明性。藉由FT-IR與solid state 13C NMR鑑定薄膜結構、TEM觀察其微觀形態；從TEM結果顯示，高IEC值之質子交換膜，親水相區域之尺寸與密度皆較大，能較有效形成離子渠道，有利於質子之傳導；由TGA顯示，Td(重量減少5%時之溫度) 約為400 C，顯示有良好的熱穩定性。
　　Z-6011、TEOS所形成之聚矽氧烷網狀結構的導入增加了其機械性質與氧化穩定性。此外，也提高了薄膜之結合水率、降低甲醇穿透度。質子傳導度於30 C、完全水合狀態下可達0.0519 S/cm2；而甲醇穿透係數介於10-7至10-6 cm2/s間。從單電池組測試結果，在直接甲醇燃料電池、60 C 時，IEC1.3-B與Nafion 117所產生之最大效能分別為5.6 mW/cm2和15.8 mW/cm2；在氫氧燃料電池、30 C時，IEC1.3-C與Nafion 117所產生之最大效能則為58.0 mW/cm2 和89.8 mW/cm2。

In this study, a series of proton-conducting membranes were prepared based on poly(styrene-co-maleic anhydride) (SMA), sodium 2-aminoethanesulfonate, bis-(aminopropyl) polydimethylsiloxane(X-22), aminopropyltriethoxysilane (Z-6011) and tetraethyl orthosilicate (TEOS). The obtained proton exchange membranes were transparent. The structural characterizations of these membranes were confirmed by FT-IR and solid state 13C NMR spectra. Furthermore, TEM was used to analyze morphology of the membranes. From TEM analysis, the hydrophilic domain for high IEC value membranes had higher average size and density than low IEC value membranes. From TGA analysis, these membranes possess good thermal stability (Td = 400 C). The polysiloxane network contributed to the increase in mechanical strength and oxidative stability in Fenton’s reagent at 80 C for 1 hour. Moreover, the polysiloxane network increased the bound water degree of the membranes and drcreased methanol permeability. The highest proton conductivity of these membranes is 0.0519 S/cm2 under fully hydrated at 30 C. The methanol permeability of the membranes ranged from 10-7 to 10-6 cm2/s. The power density of IEC1.3-B membrane and Nafion 117 membrane at 60 °C for DMFC were 5.6 mW/cm2 and 15.8 mW/cm2. The power density of IEC1.3-C membrane and Nafion 117 membrane at 30 °C for PEMFC were 58.0 mW/cm2 and 89.8 mW/cm2.

[1] W. Grove, "On a new voltaic combination," Philos. Mag., vol. 14, p. 127, 1839.
[2] 鄭耀宗、徐耀昇, "燃料電池技術進展的現況," 燃料電池論文集, pp. 15-27, 1989.
[3] 林維明, 燃料電池系統: 化學工業出版社, 1996.
[4] L. Blomen and M. Mugerwa, Fuel cell systems: Plenum Press New York;, 1993.
[5] 張漢宜、曹金萍、林智汶, "PEMFC 燃料電池電解質之現況與未來發展方向," 化工第49卷第3期, 2002.
[6] D. Hwan Jung, et al., "Performance of a direct methanol polymer electrolyte fuel cell," Journal of Power Sources, vol. 71, pp. 169-173, 1998.
[7] M. Rikukawa and K. Sanui, "Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers," progress in polymer science, vol. 25, pp. 1463-1502, 2000.
[8] 李國欣, 新型化學電源導論: 復旦大學出版社, 1992.
[9] K. Kreuer, "On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells," Journal of Membrane Science, vol. 185, pp. 29-39, 2001.
[10] K. Mauritz, "Mater Sci Engng C6 (1998)," Abstract| PDF (1333 K)| View Record in Scopus| Cited By in Scopus (102), p. 121.
[11] N. Miyake, et al., "Evaluation of a sol-gel derived Nafion/silica hybrid membrane for polymer electrolyte membrane fuel cell applications: II. Methanol uptake and methanol permeability," Journal of the Electrochemical Society, vol. 148, p. A905, 2001.
[12] D. Jung, et al., "Performance evaluation of a Nafion/silicon oxide hybrid membrane for direct methanol fuel cell," Journal of Power Sources, vol. 106, pp. 173-177, 2002.
[13] K. Adjemian, et al., "Silicon oxide Nafion 117 composite membranes for proton-exchange membrane fuel cell operation at 80-140 C," Journal of the Electrochemical Society, vol. 149, p. A256, 2002.
[14] P. Staiti, et al., "Sulfonated polybenzimidazole membranes--preparation and physico-chemical characterization," Journal of Membrane Science, vol. 188, pp. 71-78, 2001.
[15] K. Miyatake, et al., "Synthesis and proton conductivity of highly sulfonated poly (thiophenylene)," Macromolecules, vol. 30, pp. 2941-2946, 1997.
[16] G. Alberti, et al., "Polymeric proton conducting membranes for medium temperature fuel cells (110-160 C)," Journal of Membrane Science, vol. 185, pp. 73-81, 2001.
[17] J. Fang, et al., "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, vol. 35, pp. 9022-9028, 2002.
[18] S. Hietala, et al., "Structural investigation of radiation grafted and sulfonated poly (vinylidene fluoride), PVDF, membranes," Journal of Materials Chemistry, vol. 7, pp. 721-726, 1997.
[19] T. Saegusa, "Organic-inorganic polymers hybrids," Pure and Applied Chemistry, vol. 67, pp. 1965-1970, 1995.
[20] 吳千舜, "新穎質子交換膜," 中央大學化學研究所, 2004.
[21] J. Qiao, et al., "A Proton Conductor Based on a Polymeric Complex of Poly (Ethylene Oxide)-Modified Poly (Methacrylate) with Anhydrous H3PO4," Chem. Mater, vol. 15, pp. 2005-2010, 2003.
[22] K. Miyatake, et al., "Nonaqueous proton conduction in poly (thiophenylenesulfonic acid)/poly (oxyethylene) composite," Chem. Mater, vol. 11, pp. 1171-1173, 1999.
[23] R. Nagarale, et al., "Organic- Inorganic Hybrid Membrane: Thermally Stable Cation-Exchange Membrane Prepared by the Sol- Gel Method," Macromolecules, vol. 37, pp. 10023-10030, 2004.
[24] D. Rodriguez, et al., "Proton conduction in poly (acrylamide)-acid blends," Solid State Ionics, vol. 61, pp. 195-202, 1993.
[25] G. Senadeera, et al., "Enhanced ionic conductivity of poly (ethylene imine) phosphate," Solid State Ionics, vol. 85, pp. 37-42, 1996.
[26] J. Grondin, et al., "Proton conducting polymer electrolyte: the Nylon 6-10/H3PO4 blends," Solid State Ionics, vol. 77, pp. 70-75, 1995.
[27] D. Mecerreyes, et al., "Porous polybenzimidazole membranes doped with phosphoric acid: highly proton-conducting solid electrolytes," Chem. Mater, vol. 16, pp. 604-607, 2004.
[28] A. Rusanov, "Novel bis (naphthalic anhydrides) and their polyheteroarylenes with improved processability," Polymer Synthesis, pp. 115-175, 1994.
[29] C. Lee, et al., "Water-stable crosslinked sulfonated polyimide-silica nanocomposite containing interpenetrating polymer network," Journal of Power Sources, vol. 163, pp. 339-348, 2006.
[30] C. Lee, et al., "Water sorption, proton conduction, and methanol permeation properties of sulfonated polyimide membranes cross-linked with N, N-bis (2-hydroxyethyl)-2-aminoethanesulfonic acid (BES)," Macromolecules, vol. 39, pp. 755-764, 2006.
[31] Y. Yin, et al., "Water stability of sulfonated polyimide membranes," Macromolecules, vol. 39, pp. 1189-1198, 2006.
[32] F. Bovey and P. Mirau, NMR of Polymers: Academic Press New York, 1996.
[33] J. Sanders and B. Hunter, "Modern NMR spectroscopy: a guide for chemists," 1993.
[34] R. Ibbett, NMR spectroscopy of polymers: Blackie Academic & Professional London, 1993.
[35] R. He, et al., "Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors," Journal of Membrane Science, vol. 226, pp. 169-184, 2003.
[36] C. Poinsignon, et al., "Control of a Running H2/O2 Fuel Cell With Filled Polymeric Membranes by Impedance Spectroscopy," 2000, pp. 273-282.
[37] M. Bender, et al., "Intramolecular catalysis of hydrolytic reactions. II. The hydrolysis of phthalamic acid," J. Am. Chem. Soc, vol. 80, pp. 5380-5384, 1958.
[38] J. Kreuz, "AL Endrey. PP Gay and CE Sroog," J Polym. Sci.: Part A, vol. 1, p. 2607, 1966.
[39] D. Wilson, et al., Polyimides: Blackie New York, 1990.
[40] Y. Kim, et al., "Kinetic and mechanistic investigations of the formation of polyimides under homogeneous conditions," Macromolecules, vol. 26, pp. 1344-1358, 1993.
[41] M. Ghosh and K. Mittal, Polyimides: fundamentals and applications: CRC, 1996.
[42] A. Endrey, "MPD PMDA DMA," ed: Google Patents, 1965.
[43] W. Hendrix, "PROCESS FOR PREPARING POLYMIDES BY TREATING POLYAMIDE-ACIDS WITH ARO-MATIC MONOCARBOSYLIC ACID ANHY-DRIDES," ed: Google Patents, 1965.
[44] C. Yang, et al., "Organosoluble and light-colored fluorinated polyimides derived from 2, 3-bis (4-amino-2-trifluoromethylphenoxy) naphthalene and aromatic dianhydrides," Polymer, vol. 44, pp. 7067-7078, 2003.
[45] T. Ioroi, et al., "Influence of PTFE coating on gas diffusion backing for unitized regenerative polymer electrolyte fuel cells," Journal of Power Sources, vol. 124, pp. 385-389, 2003.
[46] D. Liaw and B. Liaw, "Synthesis and Properties of Polyimides Derived from 1, 4-Bis (4-aminophenoxy)-2-tert-butylbenzene," Polymer Journal, vol. 28, pp. 970-975, 1996.
[47] S. Delos, et al., "Characterization of the imidization of the aromatic polyimide LARC-160," Journal of Applied Polymer Science, vol. 27, pp. 4295-4311, 2003.
[48] Z. Shi and S. Holdcroft, "Synthesis and proton conductivity of partially sulfonated poly ([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) block copolymers," Macromolecules, vol. 38, pp. 4193-4201, 2005.
[49] Z. Ping, et al., "States of water in different hydrophilic polymers--DSC and FTIR studies," Polymer, vol. 42, pp. 8461-8467, 2001.
[50] S. Brijmohan and M. Shaw, "Proton exchange membranes based on sulfonated crosslinked polystyrene micro particles dispersed in poly (dimethyl siloxane)," Polymer, vol. 47, pp. 2856-2864, 2006.
[51] H. Wang, et al., "Nafion-bifunctional silica composite proton conductive membranes," Journal of Materials Chemistry, vol. 12, pp. 834-837, 2002.
[52] M. Bruch, et al., "Melt modification of poly (styrene-co-maleic anhydride) with alcohols in the presence of 1, 3-oxazolines," Journal of Polymer Science Part A: Polymer Chemistry, vol. 38, pp. 1222-1231, 2000.
[53] J. Qiao, et al., "New highly proton conductive polymer membranes poly (vinyl alcohol)/2-acrylamido-2-methyl-1-propanesulfonic acid (PVA/PAMPS)," Journal of Materials Chemistry, vol. 15, pp. 4414-4423, 2005.
[54] A. Siu, et al., "Effect of water on the low temperature conductivity of polymer electrolytes," J. Phys. Chem. B, vol. 110, pp. 6072-6080, 2006.
[55] K. Kreuer, "Proton conductivity: materials and applications," Chem. Mater, vol. 8, pp. 610-641, 1996.
[56] K. Kreuer, et al., "Vehicle mechanism, a new model for the interpretation of the conductivity of fast proton conductors," Angewandte Chemie International Edition in English, vol. 21, pp. 208-209, 1982.
[57] K. Kreuer, "On the development of proton conducting materials for technological applications," Solid State Ionics, vol. 97, pp. 1-15, 1997.
[58] A. Morikawa, et al., "Feature article. Preparation of new polyimide/silica hybrid materials via the sol/gel process," Journal of Materials Chemistry, vol. 2, pp. 679-689, 1992.