博碩士論文 942203023 詳細資訊


姓名 白哲勳(Che-hsun Pai)  查詢紙本館藏   畢業系所 化學學系
論文名稱 酸鹼高分子電解質質子傳遞研究
(Proton Transport Properties of Acid-Base Polyelectrolyte)
檔案 [Endnote RIS 格式]    [Bibtex 格式]    [檢視]  [下載]
  1. 本電子論文使用權限為同意立即開放。
  2. 已達開放權限電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。
  3. 請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。

摘要(中) 本研究成功合成所需的鹼性高分子ABPBI,並與三種酸性高分子PVSA、PVPA與PAA混合製成酸鹼混合高分子電解質薄膜。由FT-IR及XRD可知,酸鹼官能基之間產生的作用力使酸鹼高分子之間有好的相容性,而且只要加入少量酸性高分子即會破壞ABPBI本身所形成的規則性排列。在三種酸性高分子中,ABPBI與PVSA之間所形成的作用力最強,甚至有類似鹽類的形成。所有電解質薄膜的熱穩定性都可達200℃以上,可安全的應用在高溫燃料電池中,而且當酸鹼高分子間產生良好的配對,酸鹼官能基的裂解溫度會再提高,使薄膜的熱穩定性增加。
各薄膜之乾膜變溫質子導電度測量的數據遵循Arrhenius定律,隨著溫度的上升,質子導電度也隨之增加。在ABPBI-PVPA系統中,比例為50:50之活化能最低。藉由高解析度固態NMR測量的結果可知,當ABPBI與PVPA數量相同時,酸鹼高分子間排列的最緊密,形成了最好的酸鹼配對,因此使得質子在此薄膜中最容易被傳遞。在溼潤的條件下,各薄膜的質子導電度在薄膜開始失水前,皆會隨著溫度的上升而增加,當水分開始揮發後,質子導電度會快速的下降,代表藉由水分子在薄膜中為主要傳遞質子的媒介。由以上數據可知,藉由高分子間類似zip-unzip的運動傳遞質子,與藉由水分子傳遞質子的機制,在各薄膜中都存在。在所有薄膜中,ABPBI與PVPA混合製得之電解質薄膜,無論在濕潤條件或是乾燥條件下,其質子導電度都是最高的,代表imidazole與磷酸根之間的作用力最適合使質子被傳遞。
摘要(英) ABPBI is synthesized successfully in this research. After synthesized , ABPBI mix with three different acid polymers PVSA, PVPA, and PAA to form acid-base polyelectrolyte membranes. FT-IR and XRD data show that the compatibility between acid and base polymers is high because of the acid-base interaction, Besides, after adding small amount of acid polymer in ABPBI, the regular arrangement of ABPBI is destroyed because of the acid-base interaction. The interaction between ABPBI and PVSA is the strongest of all the membranes, even the 50ABPBI-50PVSA is similar to the formation of salt. All the membranes have high thermal stability up to 200℃, it means that the membranes can be used safely in high temperature fuel cells. If acid and base polymers mix well to form an ordered structure, the decomposition temperature of functional groups is increasing, and the thermal stability is higher.
Variable temperature conductivity for dry membranes follows the Arrhenius law. With the increase of temperature, the proton conductivity is increasing. In ABPBI-PVPA system, 50:50 ratio shows the lowest proton conductivity. High resolution solid state NMR shows that ABPBI and PVPA form a compact complex when the ratio is 50:50. This result suggests that the proton is more easily to transport in this membrane. In the wet condition, proton conductivity increase with increasing temperature before water loss temperature. When water starts to vaporize, proton conductivity drops quickly, it means water is the major medium to transport proton in membranes. According to the data above, the hopping and vehicle mechanism to transport proton both exist in membranes, and ABPBI-PVPA system shows the highest proton conductivity in dry and wet conditions. It means the interaction between imidazole and phosphonic acid is suitable for proton transport.
關鍵字(中) ★ 酸鹼高分子電解質
★ 質子傳遞
關鍵字(英) ★ acid-base polyelectrolyte
★ proton transport
論文目次 中文摘要…………………………………………………………………i
英文摘要………………………………………………………………iii
謝誌……………………………………………………………………iv
目錄………………………………………………………………………v
表目錄………………………………………………………………viii
圖目錄………………………………………………………………ix
第一章 緒論
1-1前言…………………………………………………………1
1-2研究動機……………………………………………………2
第二章 高溫電解質薄膜文獻回顧
2-1 Nafion®薄膜的修飾
2-1-1 使用非純水溶劑…………………………………......6
2-1-2 添加親水性氧化物或固態無機物………………......7
2-2使用碳氫化合物高分子取代Nafion®……………………...11
2-3 有機/無機複合物薄膜……………………………………..14
2-4 酸/鹼高分子薄膜
2-4-1 鹼性高分子/酸性小分子…………………………...21
2-4-2 鹼性小分子/酸性高分子…………………………...24
2-4-3 鹼性高分子/酸性高分子…………………………...25
第三章 實驗操作
3-1 樣品製備與實驗步驟
3-1-1 ABPBI之合成…………………………………….....29
3-1-2 電解質薄膜之製備…………………………………29
3-1-3 實驗步驟……………………………………………30
3-2 實驗藥品…………………………………………………...31
第四章 結果與討論
4-1 ABPBI之鑑定
4-1-1 13C固態核磁共振儀( 13C Solid State NMR )………….....32
4-1-2 傅立葉紅外線光譜儀(FT-IR)分析……………………...32
4-1-3 X光繞射儀(XRD)分析…………………………………...33
4-1-4 熱重損失分析儀(TGA)……………………………….....36
4-2 酸鹼混合高分子電解質薄膜結構分析
4-2-1 傅立葉紅外線光譜儀(FT-IR)分析……………………...38
4-2-2 X光繞射儀(XRD)分析…………………………………...41
4-2-3 熱重分析儀(TGA)分析……………………………….....45
4-2-4 微差掃瞄熱卡計(DSC)分析………………………….....49
4-3 酸鹼混合高分子電解質薄膜質子傳遞行為分析
4-3-1 無水條件下質子傳遞行為……………………………....52
4-3-2 含水條件下質子傳遞行為………………………………60
第五章 結論與未來展望………………………………………………...66
第六章 參考文獻………………………………………………………...69
參考文獻 1. Li, Q.; He, R.; Gao, J.; Jensen, J. O.; Bjerrum, N. J. J. Electrochem. Soc. 2003, 150, A1599.
2. G. Pourcelly ; A. Oikonomou ; H.D. Hurwitz ; C. Gavach, J. Electroanal. Chem. 1990, 287, 43.
3. Ronghuan He ; Qingfeng Li ; Gang Xiao ; Niels J. Bjerrum, Journal of Membrane Science 2003, 226, 169.
4. Qingfeng Li ; Ronghuan He ; Rolf W. Berg ; Hans A. Hjuler ; Niels J. Bjerrum, Solid State Ionics 2004, 168, 177.
5. Palanichamy Krishnan ; Jin-Soo Park ; Chang-Soo Kim, Journal of Power Sources 2006, 159, 817.
6. S. R. Narayanan ; Shiao-Pin Yen ; L. Liu ; S. G. Greenbaum, J. Phys. Chem. B 2006, 110, 3942.
7. Florjanczyk, Z.; Wielgus-Barry, E.; Poltarzewski, Z. Solid State Ionics 2001, 145,119.
8. Savinell, R.; Yeager, E.; Tryk, D.; Landau, U.; Wainright, J.; Weng, D.; Lux, K.;Litt, M.; Rogers, C. J. Electrochem. Soc. 1994, 141, L46
9. Malhotra, S.; Datta, R. J. Electrochem. Soc. 1997, 144, L23.
10. Doyle, M.; Choi, S. K.; Proulx, G. J. Electrochem. Soc. 2000, 147, 34.
11. Sun, J.; Jordan, L. R.; Forsyth, M.; MacFarlane, D. R. Electrochim. Acta 2001, 46, 1703.
12. Watanabe, M.; Uchida, H.; Seki, Y.; Emori, M. The Electrochemical Society Meeting; PV94-2, Abstract No. 606; Electrochemical Society: Pennington, NJ, 1994, 946
13. Mauritz, K. A. Mater. Sci. Eng., C 6, 1998, 121.
14. Miyake, N.;Wainwright, J.S.;Savinell, R.F. J. Electrochem. Soc. 2001, 148, A898.
15. Zoppi, R. A.; Yoshida, I. V. P.; Nunes, S. P. Polymer 1997, 39,1309.
16. Zoppi, R. A.; Nunes, S. P. J. Electroanal. Chem. 1997, 445, 39.
17. K. T. Adjemian ; S. J. Lee ; S. Srinivasan ; J. Benziger ; A. B. Bocarsly Journal of The Electrochemical Society 2002, 149, A256.
18. Antonucci, P. L.; Arico´, A. S.; Creti, P.; Ramunni, E.; Antonucci,V. Solid State Ionics 1999, 125, 431.
19. Yang, C.; Srinivasan, S.; Arico`, A. S.; Creti, P.; Baglio, V.; Antonucci, V. Electrochem. Solid-State Lett. 2001, 4, A31.
20. Adjemian, K.T.;Lee, S.J.;Srinivasan, S.;Benziger, J;Bocarsly, A.B. J. Electrochem. Soc. 2002, 149, A256.
21. Staiti, P.; Arico, A. S.; Baglio, V.; Lufrano, F.; Passalacqua, E.;Antonucci, V. Solid State Ionics 2001, 145, 101.
22. K.T. Adjemian ; S.J. Lee ; S. Srinivasan, J. Benziger ; A.B. Bocarly, J. Electrochem. Soc. 2002, 149, A256.
23. Z.G. Shao ; H. Xu ; M. Li ; I.-M. Hsing, Solid State Ionics 2006, 177, 779.
24. P. Costamagna ; C. Yang ; A.B. Bocarsly ; S. Srinivasan, Electrochim. Acta 2002, 47, 1023.
25. C. Yang ; S. Srinivasan ; A.B. Bocarsly ; S. Tulyani ; J.B. Benziger, J. Membr. Sci. 2004, 237, 145.
26. V. Ramani ; H.R. Kunz ; J.M. Fenton ; J. Membr. Sci. 2004, 232, 31.
27. V. Ramani ; H.R. Kunz ; J.M. Fenton ; Electrochim. Acta 2004, 50, 1181.
28. S.H. Kwak ; T.H. Yang ; C.S. Kim ; K.H.Yoon, Electrochim. Acta 2004, 50, 653.
29. S.H. Kwak ; T.H. Yang ; C.S. Kim ; K.H.Yoon, Solid State Ionics 2003, 160, 309.
30. Y. Si ; H.R. Kunz ; J.M. Fenton, J. Electrochem. Soc. 2004, 151, 623.
31. Y.F. Zhai ; H.M. Zhang ; J.W. Hu ; B.L. Yi, J. Membr. Sci. 2006, 280, 148.
32. Kawahara, M. ; Rikukawa, M. ; Sanui, K. ; Ogata, N. Solid State Ionics 2000, 136-137, 1193.
33. Kawahara, M. ; Rikukawa, M. ; Sanui, K. Polym. Adv. Technol. 2000, 11, 544.
34. Asensio, J.A. ; Borros, S. ; Gomez ,Romero, J. Polym. Sci. Part A :Polym. Chem. 2002, 40, 3703.
35. Kobayashi T ; Rikukawa M ; Sanui K ; Ogata N., Solid State Ionics 1998, 106, 219.
36. Bishop MT ; Karasz FE ; Russo PS ; Langley KH., Macromolecules 1985, 18 ,86.
37. Devaux J ; Delimoy D ; Daoust D ; Legras R ; Mercier JP ; Strazielle C ; Neild E., Polymer 1985, 26, 1994.
38. Nolte, R.; Ledjeff, K.; Bauer, M.; Mu lhaupt, R. J. Membr. Sci. 1993, 83, 211.
39. Kerres, J.; Zhang, W.; Cui, W. J. Polym. Sci. Part A 1998, 36, 1441
40. Kerres, L.; Cui, W.; Junginger, M. J. Membr. Sci. 1998, 139, 227.
41. Kerres, J. A. J. Membr. Sci. 2001, 185, 3.
42. Genies, C.; Mercier, R.; Sillinon, B.; Cornet, N.; Gebel, G.; Pineri, M., Polymer 2001, 42, 359.
43. Vallejo, E.; Gavach, C.; Pineri, M. J. Power Sources 1999, 160, 127.
44. Guo, X.; Fang, J.; Watari, T.; Tanaka, K.; Kita, H.; Okamoto, Macromolecules 2002, 35, 6707.
45. Child, A. D.; Reynolds, J. R. Macromolecules 1994, 27, 1975.
46.. Rulkens, R.; Schulze, M. Macromol. Rapid Commun. 1994, 15, 669.
47. Miyatake, K.; Iyotani, H.; Yamamoto, K.; Tscuchida, E. Macromolecules 1996, 29, 6969.
48. Hruszka, P.; Jurga, J.; Brycki, B. Polymer 1992, 33, 248.
49. Kosmala, B.; Schauer, J. J. Appl. Polym. Sci. 2002, 85, 1118.
50. Miyatake, K.; Shouji, E.; Yamamoto, K.; Tsuchida, E. Macromolecules 1997, 30, 2941.
51. Kopitzke, R. W.; Linkous, C. A.; Nelson, G. L. J. Polym. Sci. 1998, 36, 1197.
52. Guo, Q.; Pintauro, P. N.; Tang, H.; O’Connor, S. J. Polym. Sci. 1999, 154, 175.
53. Staiti, P.; Minutoli, M.; Hocevar, S. J. Power Sources 2000, 90, 231.
54. Staiti, P.; Minutoli, M. J. Power Sources 2001, 94, 9
55. Nakajima, H.; Honma, I. Solid State Ionics 2002, 148, 607.
56. Honma, I.; Nomura, S.; Nakajima, H. J. Membr. Sci. 2001, 185, 83.
57. Nakajima, H.; Nomura, S.; Sugimoto, T.; Nishikawa, S.; Honma, I, J. Electrochem. Soc. 2002, 149, A953.
58. Amarilla, J. M.; Rojas, R. M.; Rojo, J. M.; Cubillo, M. J.; Linares,A.; Acosta, J. L. Solid State Ionics 2000, 127, 133.
59. Bonnet, B.; Jones, D. J.; Roziere, J.; Tchicaya, L.; Alberti, G.; Casciola, M. Massinelli, L.; Baner, B.; Peraio, A.; Ramunni, E. J. New Mater. Electrochem. Syst. 2000, 3, 87.
60. Zaidi, S. M. J. Mikhailenko, S. D.; Robertson, G. P.; Guiver, M. D.; Kaliaguine, S. J. Membr. Sci. 2000, 173, 17.
61. Nunes, S. P.; Ruffmann, B.; Rikowski, E.; Vetter, S.; Richau, K. J. Membr. Sci. 2002, 203, 215.
62. Mikhailenko, S. D.; Zaidi, S. M. J.; Kaliaguine, S. Catal. Today, 2001, 67, 225.
63. Rozie´re, J.; Jones, D. J.; Tchicaya-Bouckary, L.; Bauer, B. WO 02/05370, 2000.
64. Genova-Dimitrova, P.; Baradie, B.; Foscallo, D.; Poinsignon, C.; Sanchez, J. Y. J. Membr. Sci. 2001, 185, 59.
65. Baradie, B.; Poinsignon, C.; Sanchez, J. Y.; Piffard, Y.; Vitter, G.; Bestaoui, N.; Foscallo, D.; Denoyelle, A.; Delabouglise, D.; Vaujany, M. J. Power Sources 1998, 74, 8.
66. Mauritz, K. A. Mater. Sci. Eng., C 1998, 6, 121.
67. Malhotra, S.; Datta, R. J. Electrochem. Soc. 1997, 144, L23.
68. Yang, C.; Srinivasan, S.; Arico`, A. S.; Creti, P.; Baglio, V.;Antonucci, V. Electrochem. Solid-State Lett. 2001, 4, A31.
69. Alberti, G.; Casciola, M.; Palombari, R. J. Membr. Sci. 2000, 172, 233.
70. Genova-Dimitrova, P.; Baradie, B.; Foscallo, D.; Poinsignon, C.; Sanchez, J. Y. J. Membr. Sci. 2001, 185, 59.
71. Hickner, M.;Kim, Y.S.;Wang, F.;Zawodzinski, T.A.;McGrath, J.E. SAMPE Tech. Conf. 2001, 33, 1519.
72. Staiti, P. J. New Mater. Electrochem. Syst. 2001, 4, 181.
73. Itaru Honma, Hitoshi Nakajima and Shigeki Nomura Solid State Ionics 2002, 154– 155, 707.
74. Honma, I.;Nomura, S.;Nakajima, H. J. Membr. Sci. 2001, 185, 83.
75. Honma, I.;Nomura, S.;Sugimoto, T.;Nakajima, H. J. Electrochem. Soc. 2002, 149, A953.
76. Masanori Yamada Itaru Honma J. Phys. Chem. B 2006, 110, 20486.
77. Bonnet, B.; Jones, D. J.; Roziere, J.; Tchicaya, L.; Alberti, G.; Casciola, M. Massinelli, L.; Baner, B.; Peraio, A.; Ramunni, E. J. New Mater. Electrochem. Syst. 2000, 3, 87.
78. Zaidi, S. M. J. Mikhailenko, S. D.; Robertson, G. P.; Guiver, M. D.; Kaliaguine, S. J. Membr. Sci. 2000, 173, 17.
79. Mikhailenko, S. D.; Zaidi, S. M. J.; Kaliaguine, S. Catal. Today, 2001, 67, 225.
80. Rozie´re, J.; Jones, D. J.; Tchicaya-Bouckary, L.; Bauer, B. WO 02/05370, 2000.
81. Hickner, M.; Kim, Y. S.; Wang, F.; Zawodzinski, T. A.; McGrath,J. E. Proc. 33rd Int. SAMPE Techn. Conf. 2001, 33, 1519.
82. Staiti, P.; Minutoli, M. J. Power Sources 2001, 94, 9.
83. Staiti, P.; Minutoli, M.; Hocevar, S. J. Power Sources 2000, 90, 231.
84. Boysen, D. A.; Chrisholm, C. R. I.; Haile, S. M.; Sekharipuram, V.; Narayanan, R. J. Electrochem. Soc. 2000, 147, 3610.
85. Park, Y.; Nagai, M. Solid State Ionics 2001, 145, 149.
86. Stangar, U. L.; Orel, B.; Groselj, N.; Judeinstein, P.; Decker, F.; Lianos, P. Monatsh. Chem. (Chem. Monthly) 2001, 132, 103.
87. Honma, I.; Nakajima, H.; Nishikawa, O.; Sugimoto, T.; Nomura, S. J. Electrochem. Soc. 2002, 149, A1389.
88. Lavrencic S. U.; Groselj, N.; Orel, B.; Schmitz, A.; Colomban, P. Solid State Ionics 2001, 145, 109.
89. Honma, I.; Nomura, S.; Nakajima, H. J. Membr. Sci. 2001, 185, 83.
90. Nakajima, H.; Nomura, S.; Sugimoto, T.; Nishikawa, S.; Honma, I, J. Electrochem. Soc. 2002, 149, A953.
91. Vaivars, G.; Azens, A.; Grangvist, C. G. Solid State Ionics 1999, 119, 269.
92. Park, Y.-I.; Dong, K. J.; Nagai, M. J. Mater. Sci. Lett. 2000, 19, 1735.
93. Park, Y.-I.; Kim, J.-D.; Nagai, M. Materials Research Society Symposium Proceedings 2000, 600, 305.
94. Donoso P. ; Gorecki W. ; Berthier C. ; Dfendini F. ; Poinsignon C. ; Armand MB. Solid State Ionics 1988, 28, 969.
95. Senadeera GKR. ; Gareem MA. ; Skaarup S. ; West K. Solid State Ionics 1996, 85, 37.
96. Gupta PN. ; Singh KP. Solid State Ionics 1996, 86, 319.
97. Vargas MA. ; Vargas RA. ; Mellander B-E. Electrochim Acta 1999, 44, 4227.
98. Bozkurt, A..; Meyer, W.H. Solid State Ionics 2001, 138, 259.
99. Tsuruhara K. ; Rikukawa M. ; Sanui K. ; Ogata N. ; Nagasaki Y. ; Kato M. Electrochim Acta 2000, 45, 1391.
100. Stevens JR ; Wieczorek W. ; Raducha D. ; Jeffrey KR. Solid State Ionics 1997, 97, 347.
101. Wieczorek W. ; Stevens JR. Polymer 1997, 38, 2057.
102. Qingfeng, L. ; Hjuler, H.A. ; Bjerrum, N.J. J. Appl. Electrochem. 2001, 31, 773.
103. S. R. Narayanan ; Shiao-Pin Yen ; L. Liu ; S. G. Greenbaum J. Phys. Chem. B 2006, 110, 3942
104. Hong-ting Pu ; Lei Qiao ; Qi-zhi Liu ; Zheng-long Yang European Polymer Journal 2005, 41, 2505.
105. Masanori Yamada ; Itaru Honma Polymer 2005, 46, 2986.
106. Liu Yifeng ; Yu Qinchun ; Yuan Jun ; Ma Liangliang ; Wu Yihua European Polymer Journal 2006, 42, 2199.
107. Masanori Yamada ; Itaru Honma Polymer 2004, 45, 8349.
108. Wonbong Jang ; Saimani Sundar ; Seunghyuk Choi ;Yong-Gun Shul ; Haksoo Han Journal of Membrane Science 2006, 280, 321.
109. M. Luisa Di Vona ; Alessandra D’Epifanio ; Debora Marani ; Marcella Trombetta ; Enrico Traversa ; Silvia Licoccia Journal of Membrane Science 2006, 279, 186
110. Z S.M. Javaid Zaidi Electrochimica Acta 2005, 50, 4771.
111. Jochen Kerres ; Andreas Ullrich ; Frank Meier ; Thomas Haring Solid State Ionics 1999, 125, 243.
112. Bouchet, R.; Siebert, E. Solid State Ionics 1999, 118, 287.
113. Colan E. Hughes ; Stefan Haufe ; Brigitta Angerstein ; Ratna Kalim ; Ulrich Ma1hr ; Annette Reiche ; Marc Baldus,J. Phys. Chem. B 2004, 108, 13626.
114. Adjemian, K. T.; Srinivasan, S.; Benziger, J.; Bocarsly, A. B. J. Power Sources 2002, 109, 356.
115. A.V. Anantaraman ; C.L. Gardner J. Electroanal. Chem. 1996, 414, 115.
116. Costamagna, P.; Yang, C.; Bocarsly, A. B.; Srinivasan, S. Electrochim. Acta 2002, 47, 1023.
117. Q.F. Li ; H.A. Hjuler ; N.J. Bjerrum J. Appl. Electrochem. 2001, 31, 773.
118. J.T.Wang ; R.F. Savinell ; J.S.Wainright ; M. Litt, H.Yu Electrochim. Acta 1996, 41, 193.
119. V. Deimede ; G.A. Voyiatzis ; J.K. Kallitsis ; L. Qingfeng ; N.J. Bjerrum Macromolecules 2000, 33, 7609.
120. Q.F. Li ; H.A. Hjuler ; C. Hasiotis ; J.K. Kallitsis ; C.G. Kontoyanni ; N.J. Bjerrum Electrochem. Solid State Lett. 2002, 5, A125.
121. C. Hasiotis ; L. Qingfeng ; V. Deimede ; J.K. Kallitsis ; C.G. Kontoyannis ; N. J. Bjerrum J. Electrochem. Soc. 2001, 148, A513.
122. Jochen Meier-Haack ; Antje Taeger ; Claus Vogel ; Kornelia Schlenstedt ; Wolfgang Lenk Dieter Lehmann Separation and Purification Technology 2005, 41, 207.
123. Donald L. Pavia ; Gary M, Lampman ; George S. Kriz , Introduction to Spectroscopy third edition, Brookscole, 2001.
124. Pedro G´omez-Romero ; Juan Antonio Asensio ; Salvador Borr
指導教授 諸柏仁(Peter Po-jen Chu) 審核日期 2007-7-17
推文 facebook   plurk   twitter   funp   google   live   udn   HD   myshare   reddit   netvibes   friend   youpush   delicious   baidu   

若有論文相關問題,請聯絡國立中央大學圖書館推廣服務組 TEL:(03)422-7151轉57407,或E-mail聯絡