Responsive image
博碩士論文 etd-0622113-154705 詳細資訊
Title page for etd-0622113-154705
論文名稱
Title
PVCA-co-P(PEGMA)固態高分子電解質之合成與鑑定
Synthesis and Characterizations of PVCA-co-P(PEGMA) Solid Polymer Electrolytes
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
94
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
2013-06-24
繳交日期
Date of Submission
2013-07-22
關鍵字
Keywords
聚乙二醇、碳酸亞乙烯酯、交流阻抗、嵌段共聚物、固態高分子電解質
poly(ethylene glycol), vinylene carbonate, AC-impedance, block copolymer, solid polymer electrolyte
統計
Statistics
本論文已被瀏覽 5714 次,被下載 656
The thesis/dissertation has been browsed 5714 times, has been downloaded 656 times.
中文摘要
本研究以碳酸亞乙烯酯(vinylene carbonate, VC)及在側鏈具有低聚乙二醇鏈段的poly(ethylene glycol)methyl ether methacrylate (PEGMA)做為單體,利用自由基聚合法合成出PVCA-co-P(PEGMA)嵌段共聚物,之後加入雙(三氟甲基磺醯)亞胺鋰(LiTFSI)製備出固態高分子電解質。接著在不同鋰鹽濃度情況下,透過傅立葉轉換紅外線光譜儀(Fourier transform infrared spectroscopy, FT-IR)、固態核磁共振(7Li Magic angle spinning NMR, 7Li MAS NMR)、微差式掃描熱卡計(Differential scanning calorimetry, DSC)、熱重分析(Thermogravimetric analyzer, TGA)及掃描式電子顯微鏡(Scanning electron microscope, SEM),對此系列高分子電解質進行探討。可得知鋰離子會與PVCA的C=O基團及P(PEGMA)的醚基基團產生配位作用,而形成暫時性的交聯結構,使得共聚高分子的玻璃轉移溫度上升,且其具有良好的熱穩定性及兩鏈段高分子間有不錯的相容性。最後藉由交流阻抗法(AC-impedance)測量導電度,從導電度(log σ)對溫度倒數(1/T)做圖呈一線性關係,即鋰離子傳導行為是遵循Arrhenius方程式,並且以activated hopping方式進行傳導。
Abstract
PVCA-co-P(PEGMA) block copolymers were synthesize by free- radical polymerization using vinylene carbonate (VC) and poly(ethylene glycol)methyl ether methacrylate (PEGMA) as monomers. The block copolymers were doped with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) to form solid polymer electrolytes. Fourier transform infrared spectroscopy (FT-IR), 7Li magic angle spinning NMR (7Li MAS NMR), differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA) and scanning electron microscope (SEM) showed the interaction of Li+ with both the carbonyl group of PVCA and the ether group of P(PEGMA) segments. The glass transition temperatures increased for the block copolymers doped with LiTFSI, and these results indicated the interaction of Li+ with both the carbonyl group of PVCA and the ether group of P(PEGMA) segments form transient cross-linking. Moreover, the thermal stability and compatibility between the polymer segments were good for the polymer electrolytes. The conductivity (log σ) versus reciprocal temperature (1/T) plot was linear which indicated the conduction mechanism following Arrhenius equation and Li+ transport via a activated hopping mechanism.
目次 Table of Contents
摘要 i
Abstract ii
目錄 iii
圖目錄 vi
表目錄 ix
第一章 文獻回顧 1
1.1 前言 1
1.2 高分子電解質的介紹 3
1.3 高分子電解質的種類 5
1.3.1 固態高分子電解質 6
1.3.2 膠態高分子電解質 8
1.3.3 高分子電解質的改質 12
1.4 高分子電解質的離子傳導機制 16
1.5 研究動機 18
第二章 實驗儀器原理 20
2.1 阻抗分析法 20
2.1.1 交流阻抗分析 21
2.2 固態核磁共振光譜 24
2.2.1 魔術角旋轉 25
2.2.2 交叉極化 26
第三章 實驗部分 28
3.1 實驗藥品與器材 28
3.2 實驗步驟 29
3.2.1 Poly(vinylene carbonate) (PVCA)的合成 29
3.2.2 Poly(poly(ethylene glycol) methyl ether methacrylate) (Poly(PEGMA))的合成 30
3.2.3 PVCA-co-P(PEGMA)共聚高分子的合成 31
3.2.4 固態高分子電解質薄膜的製備 31
3.3 實驗儀器 32
3.3.1 傅立葉轉換紅外線光譜儀 (Fourier Transform Infrared Spectroscopy, FT-IR) 32
3.3.2 液態核磁共振光譜分析 (Nuclear Magnetic Resonance, NMR) 33
3.3.3 固態核磁共振光譜分析 (Solid-State Nuclear Magnetic Resonance, SS-NMR) 33
3.3.4 場發射型掃描式電子顯微鏡 (Field-Emission Scanning Electron Microscope, FE-SEM) 33
3.3.5 熱重分析儀 (Thermogravimetric Analyzer, TGA) 34
3.3.6 微差式掃描熱卡計 (Differential Scanning Calorimetry, DSC) 35
3.3.7 交流阻抗分析 (AC-impedance) 36
第四章 結果與討論 38
4.1 PVCA-co-P(PEGMA)共聚高分子之結構鑑定:核磁共振 (NMR)、傅立葉轉換紅外線光譜儀 (FT-IR) 38
4.2 添加LiTFSI對PVCA-co-P(PEGMA)共聚高分子之影響 43
4.2.1 傅立葉轉換紅外線光譜儀 (FT-IR) 43
4.2.2 固態核磁共振光譜分析 (7Li-NMR) 47
4.2.3 場發射型掃描式電子顯微鏡 (FE-SEM) 51
4.2.4 熱重分析儀 (TGA) 52
4.2.5 微差式掃描熱卡計 (DSC) 54
4.2.6 固態高分子電解質的導電度分析 59
第五章 結論 66
第六章 參考文獻 68
附錄 73
參考文獻 References
(1) Tarascon, J.-M.; Armand, M. Nature 2001, 414, 359–367.
(2) Fenton, D. E.; Parker, J. M.; Wright, P. V. Polymer 1973, 14, 589.
(3) Wright, P. V. Br. Polym. J. 1975, 7, 319–327.
(4) Armand, M. B.; Chabagno, J. M.; Duclot, M. St. Andrews Ecosse 1978, 2022.
(5) Armand, M. B.; Chabagno, J. M.; Duclot, M. J.; Vashishta, P.; Mundy, J. N.; Shenoy, G. K. by P. Vashishta, JN Mundy, and GK Shennoy 1979, 131.
(6) Song, J. Y.; Wang, Y. Y.; Wan, C. C. J. Power Sources 1999, 77, 183–197.
(7) Gray, F. M. VCH, New York 1991.
(8) Pistoia, G. Lithium batteries: new materials, developments, and perspectives; Elsevier Science Ltd, 1994; Vol. 5.
(9) Koksbang, R.; Olsen, I. I.; Shackle, D. Solid State Ionics 1994, 69, 320–335.
(10) Agrawal, R. C.; Pandey, G. P. J. Phys. D: Appl. Phys. 2008, 41, 223001.
(11) Armand, M.; Gorecki, W.; Andreani, R. In Second International Symposium on Polymer Electrolytes; 1990; p. 91.
(12) Olsen, I.; Koksbang, R.; Skou, E. Electrochim. Acta 1995, 40, 1701–1706.
(13) Petersen, G.; Jacobsson, P.; Torell, L. M. Electrochim. Acta 1992, 37, 1495–1497.
(14) Bruce, P. G.; Vincent, C. A. Faraday Discuss. Chem. Soc. 1989, 88, 43–54.
(15) Berthier, C.; Gorecki, W.; Minier, M.; Armand, M. B.; Chabagno, J. M.; Rigaud, P. Solid State Ionics 1983, 11, 91–95.
(16) Benrabah, D.; Baril, D.; Sanchez, J.-Y.; Armand, M.; Gard, G. G. J. Chem. Soc., Faraday Trans. 1993, 89, 355–359.
(17) Feuillade, G.; Perche, P. J. Appl. Electrochem. 1975, 5, 63–69.
(18) Chintapalli, S.; Frech, R. Solid State Ionics 1996, 86–88, 341–346.
(19) North, J. M. EP0279554 A 1998, 2.
(20) Borghini, M. C.; Mastragostino, M.; Zanelli, A. Electrochim. Acta 1996, 41, 2369–2373.
(21) Watanabe, M.; Kanba, M.; Nagaoka, K.; Shinohara, I. J. Appl. Polym. Sci. 1982, 27, 4191–4198.
(22) Watanabe, M.; Kanba, M.; Nagaoka, K.; Shinohara, I. J. Polym. Sci., Polym. Phys. Ed. 1983, 21, 939–948.
(23) Croce, F.; Brown, S. D.; Greenbaum, S. G.; Slane, S. M.; Salomon, M. Chem. Mater. 1993, 5, 1268–1272.
(24) Watanabe, M.; Kanba, M.; Matsuda, H.; Tsunemi, K.; Mizoguchi, K.; Tsuchida, E.; Shinohara, I. Makromol. Chem., Rapid Commun. 1981, 2, 741–744.
(25) Tsuchida, E.; Ohno, H.; Tsunemi, K. Electrochim. Acta 1983, 28, 591–595.
(26) Tsunemi, K.; Ohno, H.; Tsuchida, E. Electrochim. Acta 1983, 28, 833–837.
(27) Jiang, Z.; Carroll, B.; Abraham, K. M. Electrochim. Acta 1997, 42, 2667–2677.
(28) Gozdz, A. S.; Tarascon, J. M.; Schmutz, C. N.; Warren, P. C.; Gebizlioglu, O. S.; Shokoohi, F. K. In Extended Abstracts; Vol. 94, p. 2.
(29) Gazotti, W.; Spinacé, M. A.; Girotto, E.; De Paoli, M.-A. Solid State Ionics 2000, 130, 281–291.
(30) Kim, D.-W.; Park, J.-K.; Gong, M.-S.; Song, H.-Y. Polym. Eng. Sci. 1994, 34, 1305–1313.
(31) Kuo, P.-L.; Liang, W.-J.; Chen, T.-Y. Polymer 2003, 44, 2957–2964.
(32) Weston, J. E.; Steele, B. C. H. Solid State Ionics 1982, 7, 75–79.
(33) Capuano, F.; Croce, F.; Scrosati, B. J. Electrochem. Soc. 1991, 138, 1918–1922.
(34) Croce, F.; Appetecchi, G. B.; Persi, L.; Scrosati, B. Nature 1998, 394, 456–458.
(35) Appetecchi, G. B.; Scaccia, S.; Passerini, S. J. Electrochem. Soc. 2000, 147, 4448–4452.
(36) Bronstein, L. M.; Karlinsey, R. L.; Ritter, K.; Joo, C. G.; Stein, B.; Zwanziger, J. W. J. Mater. Chem. 2004, 14, 1812–1820.
(37) Kumar, B.; Scanlon, L. G. J. Power Sources 1994, 52, 261–268.
(38) Dupon, R.; Whitmore, D. H.; Shriver, D. F. J. Electrochem. Soc. 1981, 128, 715–717.
(39) Zoski, C. G. Handbook of electrochemistry; Elsevier Science Limited, 2007.
(40) Perez, N. Electrochemistry and corrosion science; Kluwer Academic Pub, 2004.
(41) Abragam, A. The principles of nuclear magnetism; Oxford University Press, 1961; Vol. 32.
(42) Andrew, E. R.; Bradbury, A.; Eades, R. G. Nature 1958, 182, 1659–1659.
(43) Andrew, E. R.; Bradbury, A.; Eades, R. G. Nature 1959, 183, 1802–1803.
(44) Lowe, I. J. Phys. Rev. Lett. 1959, 2, 285–287.
(45) Pines, A.; Gibby, M. G.; Waugh, J. S. J. Chem. Phys. 1972, 56, 1776–1777.
(46) Pines, A.; Gibby, M. G.; Waugh, J. S. J. Chem. Phys. 1973, 59, 569–590.
(47) Alia, A.; Ganapathy, S.; Groot, H. J. M. de Photosynth. Res. 2009, 102, 415–425.
(48) Wang, Z.; Ikeda, M.; Hirata, N.; Kubo, M.; Itoh, T.; Yamamoto, O. J. Electrochem. Soc. 1999, 146, 2209–2215.
(49) Rey, I.; Johansson, P.; Lindgren, J.; Lassègues, J. C.; Grondin, J.; Servant, L. J. Phys. Chem. A 1998, 102, 3249–3258.
(50) Liang, W.-J.; Kuo, C.-L.; Lin, C.-L.; Kuo, P.-L. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 1226–1235.
(51) Hou, W.-H.; Chen, C.-Y. Electrochim. Acta 2004, 49, 2105–2112.
(52) Wei, X.; Shriver, D. F. Chem. Mater. 1998, 10, 2307–2308.
(53) Zhao, X.; Zhang, J.; Chen, S.; Wang, X.; Wang, J. Colloid Polym. Sci. 1–8.
(54) Watanabe, M.; Nishimoto, A. Solid State Ionics 1995, 79, 306–312.
(55) McLennaghan, A. W.; Pethrick, R. A. Eur. Polym. J. 1988, 24, 1063–1071.
(56) McLennaghan, A. W.; Hooper, A.; Pethrick, R. A. Eur. Polym. J. 1989, 25, 1297–1302.
(57) Nishimoto, A.; Agehara, K.; Furuya, N.; Watanabe, T.; Watanabe, M. Macromolecules 1999, 32, 1541–1548.
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:自定論文開放時間 user define
開放時間 Available:
校內 Campus: 已公開 available
校外 Off-campus: 已公開 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