質子交換膜燃料電池被認為在二十一世紀裡是一個有潛力的技術，許多科學家致力於發展高導電度，良好的化學、熱穩定性，良好的機械特性以及低成本的質子交換膜。本論文以實驗室長期發展的多苯環聚芳香醚作為結構，不僅價格比商業化材料Nafion便宜，預期能在高溫低濕度的環境下有較高的導電率，合成步驟利用二氟單體與二醇單體經親核性聚縮合反應，產生三種不同苯環數目取代基的高分子(A7、A8、A9)，以GPC量測分子量，介於5.6×104~2.9×105g/mol。
三種高分子的熱裂解溫度皆有在550℃以上，屬於高熱穩定性材料。經由磺酸化過後，隨著磺酸化程度上升，熱裂解溫度也跟著下降，而薄膜的IEC質在1~2.6meq./g之間。就機械強度方面，皆比Nafion薄膜(楊氏係數0.1GPa)還來的堅韌(楊氏係數0.25GPa~1.46GPa)，在氧化測試下，損失的重量並不大，顯示了良好的氧化特性。就尺寸安定性方面，SA8在高磺酸化程度，薄膜的變化率與Nafion 117相同(45%)。在80℃、相對濕度95%下，質子導電度SA7-3為9.03×10-2、SA8-3.5為2.17×10-1、SA9-2.5為7.14×10-2，比Nafion 117在相同條件下的3.2×10-2還要高，估計此結構的磺酸化聚芳香醚高分子運用於元件中很有潛力。

Proton exchange membrane fuel cell(PEMFCs) are considered to be a promising technology in the twenty-first century, the researchers have focused on reaching the proton exchange membrane with high proton conductivity, good chemical/thermal stability, good mechanical properties and low cost. In this paper, we adopt the structure of multi-benzene ring poly aromatic ether which have been studies for time in our laboratory, is not only cheap than the commercial material Nafion, but owns more higher proton conductivity at low relative humidity and high temperature as we expected. It is synthesized from the bisphenol monomers with the bisfluoro monomers via nucleophilic polycondensation reation for obtaining three polymers with different numbers of substitutent of benzene ring(A7、A8、A9). The molecular weight of the polymer is 5.6×104~2.9×105g/mol by GPC measurement.
The degradation temperature of three polymers are over than 550℃, they are belonged to the materials of high thermal stability. All high degree of sulfonation, the degradation temperature are decreased and the IEC of membranes is on 1~2.6meq./g. Three polymer membranes showed much tougher(Young’s modulus 0.25GPa~1.46GPa) than the Nafion 117 membranes(Young’s modulus 0.1GPa).The membranes demonstrated good oxidative stability with little weights loss at high temperature. The dimensional swelling of high sulfonated SA8 membrane is similar to that of Nafion(45%). Proton conductivity of SA7-3、SA8-3.5、SA9-2.5 membranes(9.03×10-2、2.17×10-1、7.14×10-2) at 80℃ and 95%RH was higher than that of Nafion 117(3.2×10-2), therefore, we can promise the aromatic poly(arylene ether)s to be good represent in applications as proton exchange membranes.

第一章 緒論 1
1.1前言 1
1.2燃料電池種類與介紹 1
1.3質子交換膜工作原理 2
1.4質子交換膜的傳導機制 3
1.5質子交換膜種類 6
1.6交替型磺酸化聚芳香醚高分子文獻回顧 9
1.7研究動機 13
第二章 實驗儀器及原理 15
2.1鑑定分析儀器 15
2-1-1高磁場液態磁殼共振儀器(Nuclear Magnetic Resonance，NMR) 15
2-1-2凝膠滲透層分儀(Gel Permeation Chromatography，GPC) 16
2.2熱分析儀器 16
2-2-1熱重量分析儀(Thermogravimetric Analyzer，TGA) 16
2-2-2熱示差掃描卡量計(Differential Scanning Calorimetr，DSC) 16
2-2-3熱機械分析儀(Thermal Mechanical Analyzer，TMA) 17
2.3物理分析 17
2-3-1尺寸安定性(Dimensional change) 17
2-3-2吸水率(Water Uptake，WU) 17
2.4化學分析 18
2-4-1離子交換容量(Ionic-exchange capacity，IEC) 18
2-4-2λ(每個磺酸根含有多少水分子量) 18
2.5微觀分析 18
2-5-1原子力顯微鏡(Atomic Force Microscopy，AFM) 18
2.6電化學分析 19
2-6-1 AC Impedance 19
第三章 實驗 20
3.1實驗流程圖 20
3.2雙酚單體合成 24
3.3氟單體製備 33
3.4高分子聚合製備 34
3.5高分子薄膜製備 37
3.6高分子磺酸化 38
3.7理論計算IEC數值 38
第四章 結果與討論 40
4.1高分子TGA熱裂解溫度分析 40
4.2高分子DSC分析 41
4.3高分子機械強度 42
4.4傅立葉紅外線光譜(FT-IR)分析 45
4.5磺酸化後的高分子TGA熱裂解溫度分析 49
第五章 結論 60
第六章 參考文獻 61

[1] 台灣燃料電池資訊網,http://www.tfci.org.tw/.(2011)
[2] Deluca NW, Elabd YA. “Polymer electrolyte membranes for the direct methanol fuel cell: a review.”, J Polym Sci Part B Polym Phys 2006,44,2201-13.
[3] S. P. Tung, B. J. Hwang, “Synthesis and characterization of hydrated phosphor-silicate glass membrane prepared by an accelerated sol-gel process with water/vapor management”, Journal of Materials Chemistry Vol.241, 2004, pp. 315.
[4] Y. Yang, A. Siu, T. J. Peckham, H. Steven, “Structural and Morphological Features of Acid-Bearing Polymers for PEM Fuel Cells”, Adv. Polym. Sci.,2008,215,55-126.
[5] M. Rikukawa, K. Sanui., “Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers.”, Progam Polymer Science,2000,25,1463-502.
[6] M. Rikukawa, K. Sanui, “Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers”, Polym. Sci. Vol. 25,2000,pp1463.
[7] S. J. Peighambardoust, S. Rowshanzamir, M. Amjadi, “Review of the proton exchange membranes for fuel cell application”, Int. J. Hydrogen Energy, 2010, 9349-9384.
[8] M. Watanabe, H. Uchida, Y. Seki, M. Emori, “V94-2, Abstract No.606, Electrochemical Society: Pennington”, The Electrochemical Society Meeting,1994,pp.946.
[9] K. Miyatake, Y. Chikashige, E. Higuchi, M. Watanabe, ”Tuned Polymer Electrolyte Membranes Based on Aromatic Polyethers for Fuel Cell Applications”, American Chemical Society,2007,129,3879-3887.
[10] B. C. Bae, K. Miyatake, M. Watanabe, ”Sulfonated poly(arylene ether sulfone) ionomers containing fluorenyl groups for fuel cell applications”, Journal of Membranes Science,2008,310,110-118.
[11] S. Takamuku, P. Jannasch, “Properties and degradation of hydrocarbon fuel cell membranes: a comparative study of sulfonated poly(arylene ether sulfone)s with different positions of the acid groups”, Polymer Chemistry,2012,3,1202.
[12] Baijun, L.,P. Robertson, D. S. Kim, Michael, D., Wei H., Zhenhua J., “Aromatic Poly(ether ketone)s with Pendant Sulfonic Acid Phenyl Groups for PEM”, Macromolecules, 2007, 40, 1934-1944.
[13] K. Miyatake, K. Oyaizu, E. Tsuchida, A. S. Hay, ”Synthesis and Properties of Novel Sulfonated Arylene Ether/Fluorinated Alkane Copolymers”, Macromolecules,2001,34,2065-2071.
[14] T. Nakagawa, K. Nakabayashi, T. Higashihara, M. Ueda, “A high performance polymer electrolyte membrane based on sulfonated poly(ether sulfone) with binaphthyl units”, Journal of Materials Chemistry,2010,20,6662-6667.
[15] 湯凱鈞，”局部密集磺酸化聚芳香醚剛高分子運用於質子交換膜之研究”，國立中山大學光電工程學系研究所碩士論文(2012).
[16] 朱孟涵，”磺酸化聚芳香醚高分子之合成及在燃料電池上質子交換膜之應用”，國立中山大學光電工程學系研究所碩士論文(2012).
[17] 何基任,”應用於質子交換膜之磺酸化聚芳香醚高分子”,國立中山大學光電工程學系碩士論文.(2009)
[18] Y. S. Ye, Y. C. Yen, C. C. Cheng, W. Y. Chen, L. T. Tsai, F. C. Chang, Polymer,2009,50,3196.
[19] W. A. Thaler, Macromolecules, 1983,16,623.
[20] Y. C. Yen, Y. S. Ye, C. C. Cheng, Polymer,2010,51,84.
[21] B. Liu, G. P. Robertson, M. D. Guiver, Y. M. Sun, Y. L. Liu, J. Y. Lai, S. Mikhailenko, S. Kaliaguine, ”Sulfonated Poly(aryl ether ether ketone ketone)s Containing Fluorinated Moieties as Proton Exchange Membrane Materials”, Journal of Polymer Science: Part B: Polymer Physics, 2006,Vol 44,2299-2310.
[22] A. K. Mohanty, E. A. Mistri, A. Ghosh, S. Banerjee, ”Synthesis and characterization of novel fluorinated poly(arylene ether sulfone)s containing pendant sulfonic acid groups for proton exchange membrane materials”, Journal of Membrane Science, 2012,409-410.
[23] (a)H. Y. Jung, K. Y. Cho, K. A. Sung, W. K. Kim, J. K. Park, J. Power Sources, 2006, 163, 56;(b)H. Y. Jung, K. A. Sung, W. K. Kim, M. Kurkuri, J. K. Park, Electrochim.Acta, 2007, 52, 4916.
[24] A. K. Khandpur, S. Farster, F. S. Bates, I. W. Hamley, A. J. Ryan, W. Bras, K. Almdal, K. Mortensen, Macromolecules, 1995, 28, 8796-8806.
[25] A. Guinier and G. Fournet, Wiley Interscience,1955, New York.
[26] Y. Chikashige, Y. Chikyu, K. Miyatake, M. Watanabe, “Poly(arylene ether) Ionomers Containing Sulfofluorenyl Groups for Fuel Cell Applications”, Macromolecules,2005,38,7121-7126.
[27] J. R. Lee, N. Y. Kim, M. S. Lee, and S.-Y. Lee, “SiO2-coated polyimide nonwoven/Nafion composite membranes for proton exchange membrane fuel cells”, J. Membr. Sci., 2011, 367 ,265-272.