博碩士論文 942203058 詳細資訊


姓名 吳豐賢(Feng-shien Wu)  查詢紙本館藏   畢業系所 化學學系
論文名稱 具有星狀有機無機高分子電解質之結構與動力學研究
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摘要(中) 此篇論文主要是利用 jeffamine-ED serious 與三聚氯氰反應形成具有星狀結構之高分子,進一步藉由添加3-Glycidyloxypropyl trimeth- oxysilane (GLYMO) 使其固化,觀察在不同 Lithium perchloride (LiClO4) 濃度下對導電行為的影響。
此篇論文的是藉由液態核磁共振儀 (Solution NMR) 、 X光繞射儀 (XRD) 、微差掃描卡計 (DSC) 、熱重分析儀 (TGA) 、紅外吸收光譜儀 (FTIR) 、交流阻抗分析儀 (AC-Impedance) 以及固態核磁共振光譜儀 (Solid State NMR) 等儀器對具有星狀結構之的固態高分子電解質加以分析研究。藉由交流阻抗分析儀的分析結果,發現於乾式固態高分子電解質中,其導電度隨高分子鏈段運動性增加而上升。在30°C 時的最佳導電度可達6.80 × 10-5 S/cm。
摘要(英) A sol-gel synthetic route for preparing poly(oxyalkylene) block copolymers has been developed by using 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, cc) as the coupling core. The coupling reaction involves the selective substitutions of oligo(oxyalkylene)-amines onto the first two chlorides of the triazine ring in a stepwise manner at 0 and 25 oC, and then (3-aminopropyl)trimethoxysilane (APTMS) cross-linking to the third chloride site at 130 oC. Afterwards, (3-glycidyloxypropyl)
-trimethoxysilane (GLYMO) react with the NH2 end groups of
oligo(oxyalkylene)amines (Jeffamine-ED serious) and co-condensation with APTMS to form an organic-inorganic hybrid electrolyte system.
The effects of several variables on conductivity were investigated, such as length of PEO chain, percentage of EO/PO segments, extent of cross-linking, and salt concentration (LiClO4). A full characterization was made by Solution NMR, X-ray Diffraction Spectrometer (XRD), Thermo Gravimetric Analyzer (TGA), differential scanning calorimetry (DSC), ionic conductivity, IR spectroscopy, and multinuclear solid-state NMR spectroscopy. The optimal lithium ionic conductivity for the hyperbranched copolymer electrolytes thus obtained reaches 6.80 x 10-5 S/cm at 30 °C with the composition of cc: ED2000: GLYMO = 1:3:3.
關鍵字(中) ★ 電解質
★ 聚矽氧烷機
★ 三聚氯氰
關鍵字(英) ★ electrolyte
★ cyanuric chloride
★ GLYMO
論文目次 第壹章 緒論……………………………………………………………..1
1-1. 簡介………………………………………………………………1
1-2. 文獻回顧…………………………………………………………2
1-2-1. 鋰電池的發展..……………………………………………..2
1-2-2. 高分子電解質……………..………………………………..2
1-2-3. 固態高分子電解質 (Solid Polymer Electrolytes)………....3
1-2-4. 膠態 (gelled-type) 高分子電解質…………………………5
1-2-5. 含有三氮環之高分子………………………………………7
1-2-6. 有機矽高分子………………………………………………9
第貳章 研究方向………………………………………………………10
2-1. 研究目的………………………………………………………..10
2-2. 研究架構………………………………….…………………….10
第叁章 實驗部分與原理………………………………………………12
3-1. 實驗藥品………………………………………………………..12
3-2. 儀器設備………………………………………………………..13
3-3. 高分子電解質膜之製備………………………………………..13
3-3-1. 含有 APTMS 之星狀高分子…………………………….13
3-3-2. 相同手臂的星狀高分子 ( homoarm star polymer )……...14
3-4. 儀器分析原理…………………………………………………..16
3-4-1. 液態核磁共振儀 (Solution NMR)…………….……….…16
3-4-2. X光繞射儀 (X-ray Diffraction Spectrometer)…………....18
3-4-3. 微差掃瞄熱卡計 (Differential Scanning Calorimeter)…...20
3-4-4. 熱重量分析儀 (Thermo Gravimetric Analyzer)……….....22
3-4-5. 傅立葉紅外線吸收光譜儀………………………………..23
3-4-6. 交流阻抗分析儀…………………………………………..23
3-4-7. 固態核磁共振光譜儀……………………………………..27
3-4-7-1. 原理簡介……………………………………………...27
3-4-7-2. 常用固態核磁共振技術……………………………...32
第肆章 結果與討論…………………………………………………..37
4-1. 乾式星狀固態高分子電解質……………………………………..37
4-2. 液態核磁共振 (Solution NMR) 光譜分析……...………………38
4-3. X-ray 粉末繞射 (Powder X-ray Diffraction) 圖譜分析…..…...45
4-4. 微差掃瞄熱卡計 ( Differential Scanning Calorimeter) 分析.…...48
4-5. 熱重量分析……………………………………………...………...56
4-6. 紅外吸收光譜之鑑定……………………………………………..58
4-7. 固態高分子電解質之導電度量測………………………………..75
4-8. 固態核磁共振光譜分析….………………..……………………...99
4-8-1. 29Si MAS NMR………………………..…………...…......100
4-8-2. 13C MAS NMR……………………………..……….…….102
4-8-3. 13C CP/MAS NMR ……………………...….………..……106
4-8-4. 7Li 譜寬分析………………………………………….…..113
4-8-5. 7Li-{1H} MAS NMR………...............................................122
第伍章 結 論…………………………………………………………128
參考文獻………………………………………………………………131
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指導教授 高憲明(Hsien-Ming Kao) 審核日期 2007-7-23
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