Responsive image
博碩士論文 etd-1002109-180332 詳細資訊
Title page for etd-1002109-180332
論文名稱
Title
全共軛桿式高分子電解質分子長寬比之改質來增進其三維等向性離子導電度
Aspect Ratio Modulations of Fully Conjugated Rod-like Polymer Electrolyte for Enhanced Three-dimensionally Isotropic Ionic Conductivity
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
130
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2009-10-01
繳交日期
Date of Submission
2009-10-02
關鍵字
Keywords
離子導電性、磺酸離子懸垂基、硬桿式高分子
Ionic Conductivity, Sulfonated ionomer pendant, Rigid-rod polymer
統計
Statistics
本論文已被瀏覽 5659 次,被下載 0
The thesis/dissertation has been browsed 5659 times, has been downloaded 0 times.
中文摘要
本研究利用縮聚合成反應來合成出全共軛硬桿式高分子dihydroxy-PBI,並經由化學改質分別接枝上硫化丙烷懸垂基軟鏈的dihydroxy-PBI-PS與末端含有磺酸根鋰離子苯環的懸垂基的dihydroxy-PBI-AS。dihydroxy-PBI-PS的側鏈接枝率為42.27 %;dihydroxy-PBI-AS因為立體障礙的緣故導致接枝率僅為0.04 %。所合成出的高分子具有良好的熱穩定性,dihydroxy-PBI於467.8 oC開始裂解,於800 oC時仍殘留60.5 wt. %未裂解;經過改質接枝上硫化丙烷懸垂基軟鏈的dihydroxy-PBI-PS其側鏈於295.3 oC開始裂解;改質後接枝上末端含有磺酸根鋰離子苯環懸垂基的dihydroxy-PBI-AS側鏈於314.4 oC開始裂解。
Dihydroxy-PBI將其澆鑄成固態薄膜,掺雜LiClO4濃度2.02 wt. %時平行膜面室溫導電度(σ||)可達最大值為1.71×10-4 S/cm,垂直膜面室溫導電度(σ⊥) 可達最大值為1.49×10-5 S/cm。改質後接枝上硫化丙烷懸垂基軟鏈的dihydroxy-PBI-PS,掺雜LiClO4濃度為0.49 wt. %時平行膜面室溫導電度(σ||)可達最大值為1.05×10-3 S/cm,垂直膜面導室溫電度(σ⊥) 可達最大值為1.05×10-4 S/cm。改質後接枝上末端含有磺酸根鋰離子苯環懸垂基的dihydroxy-PBI-AS,平行膜面室溫導電度(σ||)在掺雜濃度為2.02 wt. %時可達最大值為1.32×10-3 S/cm,垂直膜面室溫導電度(σ⊥)可達最大值為2.26×10-5 S/cm。
經由掃瞄式電子顯微鏡(SEM)及廣角X光散射(WAXS)檢測得知:dihydroxy-PBI及dihydroxy-PBI-AS分子在其澆鑄膜皆有平行膜面排列的驅勢,dihydroxy-PBI-PS者少此結構和導電度特性。
Abstract
This study utilized polycondensation reaction to synthesize fully conjugated rod-like polymer dihydroxy-PBI. Chemical derivatizations were applied to attach pendants of propane sulfonic coil for dihydroxy-PBI-PS and to attach aromatic phenylene ring with Li ionic moiety for dihydroxy-PBI-AS. The attachment of pendants for dihydroxy-PBI-PS was 42.27 % and for dihydroxy-PBI-AS was only for 0.04 % causing by stereo hindrance of this molecule. These polymers seemed to have good thermal stability. Dihydroxy-PBI started to show degradation at 467.8 oC and retained 60.5 wt. % at 800 oC. Derivatized dihydroxy- PBI-PS and dihydroxy-PBI-AS lost their pendants at 295.3 oC and 314.4 oC, respectively.
Dihydroxy-PBI was cast into thin film. Upon doping with lithium salt of LiClO at 2.02 wt. %, dihydroxy-PBI cast film showed the highest room-temperature dc conductivity parallel to the film (σ∥) of 1.71 x 10-4 S/cm and perpendicular to the film (σ⊥) of 1.49 x 10-5 S/cm. For dihydroxy-PBI-PS cast film, the highest conductivity was at 0.49 wt. % of LiClO4 with σ∥ of 1.05 x 10-3 S/cm and σ⊥ of 1.05 x 10-4 S/cm. For dihydroxy-PBI-AS cast film, the highest conductivity was at 2.02 wt. % of LiClO4 with σ∥ of 1.32 x 10-3 S/cm and σ⊥ of 2.26 x 10-5 S/cm.
From scanning electron microscopy and wide-angle x-ray scattering, it was learned that cast films of dihydroxy-PBI and dihydroxy-PBI-AS had anisotropic layered structure parallel to the film, and that of dihydroxy-PBI-PS showed less of this anisotropy.
目次 Table of Contents
流程目錄 VI
圖目錄 VII
表目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 固態高分子電解質簡介 2
1-3 雜環芳香族硬桿式高分子簡介 3
1-4 全共軛硬桿式高分子電解質簡介 4
1-5 導電機制 6
第二章 研究動機 9
2-1 高分子主鏈的改質 12
2-2 高分子側鏈的改質 12
第三章 實驗 14
3-1 單體合成 14
3-1-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride (簡稱TABTHC)的合成反應 14
3-2 硬桿式高分子合成反應介質 16
3-2-1 聚磷酸的製備 17
3-3 硬桿式聚合物 17
3-3-1 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6-diyl(2-(2,5-dihydroxyl)
-p-phenylene)] (簡稱dihydroxy-PBI)之合成反應 18
3-3-2 Dihydroxy-PBI-PS之合成反應 19
3-3-3 Dihydroxy-PBI-AS之合成反應 20
3-4 甲基磺酸(Methanesulfonic Acid,簡稱MSA)的純化 21
3-5 化學分析 21
3-5-1 傅立葉轉換紅外線光譜儀(Fourier Transform Infrared,簡稱FTIR) 21
3-5-2 核磁共振儀(Nuclear Magnetic Resonance,簡稱NMR) 22
3-5-3 固態核磁共振儀(Solid Sate Nuclear Magnetic Resonance,簡稱SSNMR) 25
3-5-4 元素分析儀(Elemental Analyzer,簡稱EA) 28
3-5-5 高分子分子量的量測 28
3-5-6 熱重分析儀(Thermal Gravimetric Analyzer,簡稱TGA) 29
3-5-7 感應耦合電漿質譜儀(Inductively Coupled Plasma Mass Spectrometry,簡稱ICP-MS) 30
3-6 鋰鹽摻雜 31
3-7 固態高分子電解質薄膜製備 31
3-8 導電度的量測 32
3-8-1 直流(Direct Current,簡稱DC)導電度的量測 32
3-8-2 交流阻抗(Alternating Current Impedance,簡稱AC-Impedance) 33
3-9 廣角X光散射(Wide-Angle X-ray Scattering,簡稱WAXS) 35
3-10 掃描式電子顯微鏡(Scanning Electron Microscope,簡稱SEM) 35
第四章 實驗結果 37
4-1 1,3-Dichloro-4,6-dinitrobenzene (簡稱DCDNB)化學分析 37
4-1-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 37
4-1-2 質子核磁共振(1H NMR) 圖譜 38
4-1-3 元素分析(EA) 39
4-2 4,6-Dinitro-1,3-benzenediamine (簡稱DNBDA)化學分析 40
4-2-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 40
4-2-2 質子核磁共振(1H NMR)圖譜 41
4-2-3 元素分析(EA) 43
4-3 1,2,4,5-Tetraaminobenzene tetrahydrochloride (簡稱TABTHC)化學分析 43
4-3-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 43
4-3-2 質子核磁共振(1H NMR)圖譜 44
4-3-3 元素分析(EA) 45
4-4 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6-diyl(2-(2,5-dihydroxyl)
-p-phenylene)] (簡稱dihydroxy-PBI)化學分析 46
4-4-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 46
4-4-2 1H-13C交叉極化魔角旋轉(1H-13C CPMAS)固態核磁共振 (SSNMR)圖譜 47
4-4-3 元素分析(EA) 49
4-5 2,5-Dihydroxyterephthalic acid 1H-13C交叉極化魔角旋轉(1H-13C CPMAS) 固態核磁共振(SSNMR)圖譜 49
4-6 TABTH 1H-13C交叉極化魔角旋轉(1H-13C CPMAS)固態核磁共振 (SSNMR)圖譜 50
4-7 Dihydroxy-PBI-PS 化學分析 51
4-7-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 51
4-7-2 1H-13C交叉極化魔角旋轉(1H-13C CPMAS)固態核磁共振 (SSNMR)圖譜 52
4-7-3 元素分析(EA) 54
4-7-4 感應耦合電漿質譜(ICP-MS)分析 55
4-8 Dihydroxy-PBI-AS 化學分析 55
4-8-1 傅立葉轉換紅外線(FTIR)吸收光譜圖 55
4-8-2 1H-13C交叉極化魔角旋轉(1H-13C CPMAS)固態核磁共振 (SSNMR)圖譜 56
4-8-3 元素分析(EA) 58
4-8-4 感應耦合電漿質譜(ICP-MS)分析 58
4-9 Dihydroxy-PBI-PS與dihydroxy-PBI-AS接枝比例討論 59
4-10 高分子黏度的量測 59
4-10-1 Dihydroxy-PBI之極限黏度的量測 59
4-10-2 Dihydroxy-PBI-PS之極限黏度的量測 61
4-10-3 Dihydroxy-PBI-AS之極限黏度的量測 63
4-10-4 高分子黏度討論 66
4-11 高分子熱分析 66
4-11-1 Dihydroxy-PBI之熱重損失分析 66
4-11-2 Dihydroxy-PBI-PS之熱重損失分析 67
4-11-3 Dihydroxy-PBI-AS之熱重損失分析 68
4-11-4高分子熱重損失比較 69
4-12 高分子電解質平行膜面的直流導電度 70
4-12-1 Dihydroxy-PBI平行膜面的直流導電度 70
4-12-2 Dihydroxy-PBI-PS平行膜面的直流導電度 74
4-12-3 Dihydroxy-PBI-AS平行膜面的直流導電度 77
4-13 高分子電解質垂直膜面的直流導電度 81
4-13-1 Dihydroxy-PBI垂直膜面的直流導電度 81
4-13-2 Dihydroxy-PBI-PS垂直膜面的直流導電度 85
4-13-3 Dihydroxy-PBI-AS垂直膜面的直流導電度 88
4-14 掃瞄式電子顯微鏡(SEM)分析 92
4-14-1 Dihydroxy-PBI掃瞄式電子顯微鏡(SEM)分析 92
4-14-2 Dihydroxy-PBI-PS掃瞄式電子顯微鏡(SEM)分析 93
4-14-3 Dihydroxy-PBI-AS掃瞄式電子顯微鏡(SEM)分析 93
4-15 廣角X光散射(WAXS)分析 94
4-15-1 Dihydroxy-PBI廣角X光散射(WAXS)分析 95
4-15-3 Dihydroxy-PBI-AS廣角X光散射(WAXS)分析 102
4-15-4 廣角X光散射(WAXS) 106
4-16 導電度的離子特徵 106
第五章 結論 107
第六章 參考文獻 109
參考文獻 References
1. 溫添進,鋰離子高分子電池之研究發展簡述,科學發展月刊,第29卷,第七期,498頁 (2001)。
2. D. E. Fenton, J. M. Parker, and P. V. Wright, Polymer, 14, 436 (1973).
3. M. B. Armand, J. M. Chabagon, and M. Duclot, "Second International Conference on Solid Polyelectrolytes," St. Andrew, England, 1.5.1 (1978).
4. C. Berthier and W. Gorecki, Solid State Ionics, 11, 91 (1983).
5. D. W. Kim, J. K. Park, J. S. Bae, and S. I. Pyun, J. Polym. Sci. Part B: Polym. Phys., 34, 2127 (1996).
6. H. Vogel and C. S. Marvel, J. Polym. Sci., 55, 511 (1961).
7. T. D. Dang, S. J. Bai, D. P. Heberer, F. E. Arnold, and R. J. Spry, J. Polym. Sci. Part B: Polym. Phys., 31, 1941 (1993).
8. F. M. Gray, "Solid Polymer Electrolytes," VCH Publishers, Inc., New York, NY (1991).
9. J. J. Fitzgerald and R. A. Weiss, J. Macromole. Sci, Rev. Marcomol. Chem. Phys., 28, 99 (1988).
10. M. Aldissi (to the United State of America as represented by the Department of Energy), U. S. Pat. 4,880,508 (14 Nov 1989).
11. T. D. Dang and F. E. Arnold, Polym. Prep., 33, 912 (1992).
12. J. R. Reynolds, Y. Lee, S. Kim, R. L. Bartling, M. B. Gieselman, and C. S. Savage, Polym. Prep., 34, 1065 (1993).
13. R. J. Spry, M. D. Alexander, Jr., S. J. Bai, T. D. Dang, G. E. Price, D. R. Dean, B. Kumar, J. S. Solomon, and F. E. Arnold, J. Polym. Sci. Part B: Polym. Phys., 35, 2925 (1997).
14. K. M. Abraham, "Application of Electroactive Polymers," edited by B. Scrosati, Chapman & Hall, London, England, Chap. 3, (1993).
15. M. C. Wintersgill and J. J. Fontanella, "Polymer Electrolyte Reviews-2," edited by J. R. MacCallum and C. A. Vincent, Elsevier Applied Science Publisher Ltd., London, England, Chap. 2, (1989).
16. M. Watanabe, T. Endo, A. Nishimoto, K. Miura, and M. Tanagida, J. Power Sour., 81-82, 786 (1999).
17. S. Ganapathiappan, K. Chen, and D. F. Shriver, J. Am. Chem. Soc., 111, 4091 (1989).
18. S. Hossain, in: D. Linden (Ed), Handbook of Batteries, McGraw-Hill, New York, 1995.
19. 趙宙興,鋰電池複合型聚合物電解質材料研究進展,青海大學學報(自然科學版),第24卷,第4期,54頁(2006)。
20. W. A. Gazotti, M. A. S. Spinace, E. M. Cirotto, and M.-A. De Paoli, Solid State Ionics, 130, 281 (2000).
21. K. M. Abraham and V. R. Koch, J. Electrochem. Soc., 147(4), 1251 (2000).
22. A. Kills, J. F. Le Nest, A. Gandini, and H. Cheradame, Solid State Ionics,14 , 231 (1984).
23. M. Watanabe, T. Hirakimoto, S. Mutoh, and A.Nishimoto, Solid State Ionics, 148, 399 (2002).
24. Y. Wang and R. Steiner, Solid State Ionics, 176, 41 (2005).
25. C. C. Yang, S. T. Lin, and S. T. Hsu, Journal of Power Sources, 122, 210 (2003).
26. J. E. Weston and B. C. Steele, Solid State Ionics, 7, 75 (1982).
27. F. Croce, C. B. Appetechi, and L. Perai, Nature, 394, 456 (1998).
28. D. W. Kim, Solid State Ionics, 123, 243 (1999).
29. X. Glipa, M. E. Haddad, D. J. Jones, and J. Roziere, Solid State Ionics, 97, 323 (1997).
30. W. W. Moyer, Jr., C. Cole, and T. Anyos, J. Polym. Sci. Part A: Polym. Chem., 3, 2107 (1965).
31. J. F. Wolfe, B. H. Loo, and F. E. Arnold, Macromolecules, 14, 915 (1981).
32. J. F. Wolfe and F. E. Arnold, Macromolecules, 14, 909 (1981).
33. E. S. Krongauz, A. L. Rusanov, and T. L. Renard, Russ. Chem. Rev., 39(9), 747 (1970).
34. Y. H. So, J. P. Heeschen, B. Bell, P. Park, M. Briggs, and R. Decaire, Macromolecules, 31, 5229 (1998).
35. R. A. Storer, "Annual Book of ASTM Standards," 08. 01., D2857 – 95, American Society of Testing Materials (ASTM) International, Easton, Maryland (2007).
36. R. G. Pearson, J. Am. Chem. Soc., 85, 3533 (1963).
37. R. G. Pearson, J. Chem. Ed., 45, 581 (1968).
38. J. R. MacCallum and C. A. Vincent, "Polymer Electrolyte Reviews-1, "Elsevier Science Publishing Co., Inc., New York (1987).
39. M. W. Wellman, W. W. Adams, R. A. Wolff, D. S. Dudis, D. R. Wiff, and A. V. Fratini, Macromolecules, 14, 935 (1981).
電子全文 Fulltext
本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。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。
論文使用權限 Thesis access permission:校內校外均不公開 not available
開放時間 Available:
校內 Campus:永不公開 not available
校外 Off-campus:永不公開 not available

您的 IP(校外) 位址是 34.239.148.106
論文開放下載的時間是 校外不公開

Your IP address is 34.239.148.106
This thesis will be available to you on Indicate off-campus access is not available.

紙本論文 Printed copies
紙本論文的公開資訊在102學年度以後相對較為完整。如果需要查詢101學年度以前的紙本論文公開資訊,請聯繫圖資處紙本論文服務櫃台。如有不便之處敬請見諒。
開放時間 available 已公開 available

QR Code