臺灣博碩士論文加值系統

本研究利用帶有磺酸基之monoamine混摻polyoxyalkylene diamine依等化學計量與帶有酸酐基之聚(苯乙烯-馬來酸酐)進行熱交聯反應，製備出含有不同磺酸基之一系列質子傳導薄膜，更進一步探討與分析其特性。結果顯示，自行製備出之高分子薄膜具透明及韌性；在DSC分析方面可發現此系列高分子薄膜均具有二個玻璃轉移溫度(Tg)：一個在-30 ~ -50°C(聚醚鏈段之Tg)，另一個在40 ~ 70°C(整個高分子主鏈移動之Tg)。在TGA結果方面，其Td0.1約在420°C，顯示本系列薄膜具有良好的熱穩定性。此外，本系列氫離子傳導高分子薄膜在完全水合狀態及100°C下，其質子傳導度可達8.4×10-2 S/cm(SMEO-SO3H-1.10)。在甲醇穿透度結果方面，本系列氫離子高分子薄膜對甲醇穿透速率約在3.0 ~ 6.2 × 10-6 cm2/s。

A new class of proton-conducting membranes were prepared based on poly(styrene-co-maleic anhydride) (SMA), polyoxylalkylene diamine (XTJ-502) and sodium 2-aminoethanesulfonate. The obtained proton- conducting membranes are transparent, tough and flexible. From DSC results, these polymers show two glass transition temperatures rang from -30 ~ -50°C(ethylene oxide) and 40 ~ 70°C(polymer matrix). Form TGA analysis, these membranes possess good thermal stability (Td0.1 = 420°C). In proton conductivity measurements, it is observed that the fully-hydrated membranes with the –SO3H content of 1.1 meq/g has the protonic conductivity of 8.4×10-2 S/cm at 100°C, and the methanol permeability of 6.2 × 10-6 cm2/s at 30°C.

壹、中文摘要..................................................................................................Ⅰ
貳、英文摘要..................................................................................................Ⅱ
參、總目錄.....................................................................................................Ⅲ
肆、表目錄.....................................................................................................Ⅶ
伍、圖目錄.....................................................................................................Ⅷ
柒、主文
第一章 緒論.....................................................................................................1
1-1 前言............................................................................................................1
1-2 燃料電池的歷史及其優點........................................................................2
1-3 燃料電池的種類........................................................................................4
1-4 質子交換膜燃料電池................................................................................6
1-5 直接甲醇燃料電池....................................................................................8
1-6 質子交換膜................................................................................................9
1-6.1 放質型氟素系質子交換膜...................................................................11
1-6.2 磺酸化之碳氫系質子交換膜...............................................................12
1-6.3有機-無機複合膜...................................................................................13
1-6.4含酸鹼對之質子交換膜........................................................................16
1-7本研究動機...............................................................................................16
第二章 實驗及儀器之原理...........................................................................18
2-1 固態核磁共振(Solid-State Nuclear Magnetic Resonance)........................18
2-1.1 魔術角旋轉(Magic Angle Spinning，MAS).........................................19
2-1.2 交叉極化(Cross-Polarization，CP).......................................................20
2-2 交流阻抗分析(Alternating Current Impedance Spectroscopy).................22
2-2.1 基礎電路學簡介...................................................................................22
2-2.2 交流阻抗分析.......................................................................................24
2-3 聚醯胺酸之合成與醯亞胺化(Imidization)..............................................28
2-3.1 熱閉環(Thermal Imidization).................................................................29
2-3.2 溶液環化法(Solution imidization).........................................................30
2-3.3 化學環化法(Chemical Imidization).......................................................30
第三章 實驗方法與步驟...............................................................................32
3-1 實驗藥品..................................................................................................32
3-2 儀器設備..................................................................................................32
3-3 含聚乙烯醚交聯型苯乙烯-馬來酸酐之醯亞胺質子傳導膜之製.........33
3-3.1 Sodium 2-Aminoethanesulfonate (SAES)之合成...................................33
3-3.2 鈉式-高分子電解質薄膜之製備..........................................................34
3-4 質子傳導膜之鑑定..................................................................................37
3-4.1 傅立葉轉換紅外線光譜儀(FT-IR).......................................................37
3-4.2 醯亞胺化程度(Degree Imidization)......................................................37
3-4.3 13C固態核磁共振光譜(13C Solid-State NMR)....................................37
3-4.4 離子交換當量(Ion Exchange Capacity, IEC)之測定...........................38
3-4.5 熱性質分析..........................................................................................38
3-4.5.1 微差式掃描卡計(Differential Scanning Calorimeter, DSC) ..............38
3-4.5.2 熱重分析(thermogravimetric analysis, TGA).....................................39
3-4.6 含水量測試(Water uptake)...................................................................39
3-4.7 結合水(bound water)............................................................................39
3-4.8 X光繞射分析(XRD).............................................................................40
3-4.9交流阻抗分析(AC Impedance Measurements)......................................40
3-4.10 甲醇穿透(Methanol permeability).......................................................41
第四章 結果與討論.......................................................................................43
4-1 質子傳導膜之製備與結構之鑑定..........................................................43
4-1.1 Sodium 2-Aminoethanesulfonate (SAES)結構之鑑定...........................43
4-1.1 傅立葉轉換紅外線光譜(FT-IR)...........................................................44
4-1.2 離子交換當量(Ion Exchange Capacity)及醯亞胺化程度(Degree of
Imidization).....................................................................................................44
4-1.3 13C 交叉極化/魔術轉角固態核磁共振光譜(13C CP/MAS NMR).....45
4-2 熱性質分析..............................................................................................46
4-3 X光繞射(XRD).........................................................................................47
4-4 水在質子傳導膜(SMEO-SO3H-x)中的狀態...........................................47
4-5 甲醇穿透度(Methanol Permeability)........................................................48
4-6 質子傳導度..............................................................................................49
4-7 氧化穩定..................................................................................................50
第五章 結論.................................................................... ..............................51
第六章 參考文獻...........................................................................................52
第七章 自述...................................................................................................68

[1] W. R. Grove, Philos. Mag. Ser., 3, 14, 127 (1839).
[2] M. A. Hickner, H. Ghassemi, Y. S. Kim, B. R. Einsla, J. E. McGrath , Chem. Rev., 104, 4587 (2004).
[3] 張漢宜, 曹金萍, 林智汶, “PEMFC 燃料電池電解質之現況興未來發展方向”, 化工第49卷第3期 (2002).
[4] D. H. Jung, C. H. Lee, C. S. Kim, D. R. Shin, J. Power Sources, 71, 169 (1998).
[5] X. X. Guo, J. H. Fang, T. Watari, K. Tanaka, H. Kita, K. I. Okamoto, Macromlecules, 35, 6707 (2002).
[6] M. Rikukawa, K. Sanui, Prog. Polym. Sci., 25, 1463 (2000).
[7] W. Y.Hsu, T. D.Gierke, J. Membr. Sci., 13, 307 (1983).
[8] O. Savadogo, J. New Mater. Electrochem. Systems, 1, 47 (1998).
[9] Z. Y. Yang, R.G. Rajendran, Angew. Chem. Int. Ed., 44, 564 (2005).
[10] Q. F. Li, R. H. He, J. O. Jensen, N. J. Bjerrum, Chem. Mater., 15, 4896 (2003).
[11] K. D. Kreuer, J. Membr. Sci., 185, 29 (2001).
[12] H. Ghassemi, J. E. McGrath, polymer, 45, 5847 (2004).
[13] G. Alberti, M. Casciola, L. Massinelli, B. Bauer. J. Membr. Sci., 185, 73 (2001).
[14] Y. Z. Fu; A. Manthiram, J. Power Source, 157, 222 (2006).
[15] F. Wang, M. Hickner, Y. S. Kim, T. A. Zawodzinski, J. E. McGrath., J. Membr. Sci., 197, 231 (2002).
[16] P. Staiti, F. Lufrano, A. S. Arico, E. Passalacqua, V. Antonucci, J. Membr. Sci., 188, 71 (2001).
[17] N. Carretta, V. Tricoli, F. Picchioni., J. Membr. Sci., 166, 189 (2000).
[18] K. Miyatake, E. Shouji, K. Yamamoto, E. Tsuchida, Macromolecules, 30, 2941 (1997).
[19] J. H. Fang, X. X. Guo, S. Harada, T. Watari, K. Tanaka, H. Kita, K. I. Okamoto, Macromolecules, 35, 9022 (2002).
[20] I. Honma, Y. Takeda, J. M. Bae, Solid State Ionics, 120, 255 (1999).
[21] H. Nakajima, I. Honma, Solid State Ionics, 148, 607 (2002).
[22] I. Honma, S. Nomura, H. Nakajima, J. Membr. Sci., 185, 83 (2001).
[23] H. Nakajima, S. Nomura, T. Sugimoto, S. Nishikawa, I. Honma, J. Electrochem. Soc., 149, A953 (2002).
[24] P. Staiti, M. Minutoli, S. Hocevar, J. Power Sources, 90, 231 (2000).
[25] P. Staiti, M. Minutoli, J. Power Sources, 94, 9 (2001).
[26] P. Staiti, Mater. Lett., 47, 241 (2001).
[27] J. M. Amarilla, R. M. Rojas, J. M. Rojo, M. J. Cubillo, A. Linares, J. L. Acosta, Solid State Ionics, 127, 133 (2000).
[28] P. Genova-Dimitrova, B. Baradie, D. Foscallo, C. Poinsignon, J. Y. Sanchez, J. Membr. Sci., 185, 59 (2001).
[29] B. Baradie, C. Poinsignon, J. Y. Sanchez, Y. Piffard, G. Vitter, N. Bestaoui, D. Foscallo, A. Denoyelle, D. Delabouglise, M. Vaujany, J. Power Sources, 74, 8 (1998).
[30] C. Poinsignon, I. Amodio, D. Foscallo, J. Y. Sanchez, Mater.Res. Soc. Symp. Proc., 548, 307 (2000).
[31] B. Bonnet, D. J. Jones, J. Roziere, L. Tchicaya, G. Alberti, M. Casciola, L. Massinelli, B. Baner, A. Peraio, E. Ramunni, J. New Mater. Electrochem. Syst., 3, 87 (2000).
[32] S. M. J. Zaidi, S. D. Mikhailenko, G. P. Robertson, M. D. Guiver, S. Kaliaguine, J. Membr. Sci, 173, 17 (2000).
[33] S. P. Nunes, B. Ruffmann, E. Rikowski, S. Vetter, K. Richau, J. Membr. Sci., 203, 215 (2002).
[34] S. D. Mikhailenko, S. M. J. Zaidi, S. Kaliaguine, Catal. Today, 67, 225 (2001).
[35] I. Honma, Y. Takeda, J. M. Bae, Solid State Ion., 120, 255 (1999).
[36] M. Popall, X. M. Du, Electrochim. Acta., 40, 2305 (1995).
[37] J. Qiao, N. Yoshimoto, M. Ishikawa, M. Morita, Chem. Mater., 15, 2005 (2003).
[38] K. Miyatake, K. Fukushima, S. Takeoka, E. Tsuchida, Chem. Mater., 11, 1171 (1999).
[39] R. K. Nagarale, G. S. Gohil, V. K. Shahi, R. Rangarajan, Macromolecules, 37, 10023 (2004).
[40] D. Rogriguez, T. Jegat, O. Trinquet, J. Grondin, J. C. Lassegues, Solid State Ion., 61, 195 (1993).
[41] G. K. R. Senadeera, M. A. Careem, S. Skaarup, K. West, Solid State Ion., 85, 37 (1996).
[42] J. Grondin, D. Rodriguez, J. C. Lassegues, Solid State Ion., 77, 70 (1995).
[43] D. Mecerreyes, H. Grande, O. Miguel, E. Ochoteco, R. Marcilla, I. Cantero, Chem. Mater., 16, 604 (2004).
[44] F. A. Bovey, P. A. Mirau, NMR of Polymers, Academic Press, San Diego (1996).
[45] J. K. M. Sanders, B. K. Hunter, Modern NMR Spectroscopy: a Guide for Che-mists, Oxford University Press, New York, Chap. 9 (1993).
[46] R. N. Ibbett, NMR Spectroscopy of Polymers, Chapman & Hall, London (1993).
[47] X. Qian, N. Gu, Z. Cheng, X. Yang, E. Wang, S. Dong, Mater. Chem. Phys., 74, 98 (2002).
[48] F. M. Gray, Solid Polymer Electrolytes: Fundamentals and Technological Application, VCH, New York (1991).
[49] R. G. Linford, Electrochemical Science and Technology of Polymers-2, (1990).
[50] M. L. Bender, Y. L. Chow, F. Chloupek, J. Am. Chem. Soc., 80, 5380 (1958).
[51] J. A. Kreuz, A. L. Endrey, F. P. Gay, C. E. Sroog, J. Appl. Polym. Sci., A-1, 4, 2607 (1966).
[52] Y. J. Kim, T. E. Glass, G. D. Lyle, J. E. Mcgrath, Macromolecules, 26, 1344 (1993)
[53] M. K. Ghosh, K. L. Mittal, Polyimides : Fundamentals and Applications, New York : Dekker (1996).
[54] D. J. Liaw, B. Y. Liaw, Polym. J., 28, 970 (1996).
[55] S. E. Delos, R. K. Schellenberg, J. E. Smedley, D. E. Kranbehl, J. Appl. Polym. Sci., 27, 4295 (1982).
[56] Z. Shi, S. Holdcroft, Macromolecules, 38, 4193 (2005).
[57] Z. H. Ping, Q. T. Nguyen, S. M. Chen, J. Q. Zhou, Y. D. Ding, Polymer, 42, 8461 (2001).
[58] S. B. Brijmohan, M. T. Shaw, Polymer, 47, 2856 (2006).
[59] J. Qiao, T. Hamaya, T. Okada, Chem. Mater., 17, 2413 (2005).
[60] S. M. Lee, W. L. Yeh, C. C. Wang, C. Y. Chen, Electrochim. Acta, 49, 2667 (2004).
[61] M. Bruch, D. Mäder, F. Bauers, T. Loontjens, R. Mülhaupt, J. Appl. Sci.:Part A, 38, 1222 (2000).
[62] J. D. Van Heumen, J. R. Stevens, Macromolecules, 28, 4268 (1995).
[63] A. Ferry, P. Jacobsson, Polymer, 37, 737 (1996).
[64] F. Alloin, J. Y. Sanchez., Electrochim. Acta, 43, 1199 (1998).
[65] H. Ba, X. Peng, Y. Qi, D. Chen, F. Wang., Makromol. Chem., 191, 2529 (1990).
[66] D. W. Kim, J. K. Park, H. W. Rhee., Solid State Ionics, 83, 49 (1996).
[67] J. L. Acosta, E. Morales., Solid State Ionics, 85, 85 (1996).
[68] W. J. Liang, C. L. Kuo, C. L. Lin, P. L. Kuo, J. Polym. Sci. Pol. Chem., 40, 1226 (2002).
[69] M. Tasaka, S. Suzuki, Y. Ogawa, J. Membr. Sci., 38, 175 (1988).
[70] Z. H. Ping, Q. T. Nguyen, S. M. Chen, J. Q. Zhou, Y. D. Ding, Polymer, 42, 8461 (2001).
[71] Y. S. Kim, L. Dong, M. A. Hickner, T. E. Glass, V. Webb, J. E. McGrath, Macromolecules, 36, 6281 (2003).
[72] Z. H. Ping, Q. T. Nguyen, S. M. Chen, J. Q. Zhou, Y. D. Ding, Polymer., 42, 8461 (2001).
[73] A. Siu, J. Schmeisser, S. Holdcroft, J. Phys. Chem. B, 110, 6072 (2006).
[74] K. D. Kreuer, Chem. Mater., 8, 610 (1996).
[75] K. D. Kreuer, A. Rabenau, W. Weppner, Angew, Chem. Int. Ed. Engl., 21, 208 (1982).
[76] K. Miyatake, K. Oyaizu, E. Tsuchida, A. S. Hay, Macromolecules, 34, 2065 (2001).