含有短鏈段聚乙氧烯的星狀有機無機固(膠)態高分子電解質之結構鑑定及電化學特性研究

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林季平(Chi-pin Lin) 查詢紙本館藏

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論文名稱

含有短鏈段聚乙氧烯的星狀有機無機固(膠)態高分子電解質之結構鑑定及電化學特性研究
(Structural and Electrochemical Analysis of Solid and Plasticized Star-Branched Organic-Inorganic Hybrid Electrolytes with EO Chains)

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摘要(中)

本論文分兩大部分，第一部分是利用三聚氯氰當作結構核心，並在外圍接上三嵌段共聚高分子 ED2000和矽氧烷3-isocyanate propyltriethoxysilane (ICPTES)，使其形成具有星狀結構的高分子，並在星狀結構再添加含有短鏈段聚乙氧烯 (polyethylenoxy) 之矽氧烷2-[methoxy(polyethyleneoxy)propyl] trimethoxysilane (MPEOPS)，並摻雜不同鋰鹽 (LiClO4) 濃度，預期加入具短鏈段聚乙氧烯之矽氧烷可以降低高分子的結晶性，並幫助鋰離子的傳遞，本研究會針對固態高分子電解質做一系列的探討研究；第二部分則是將第一部份的固態高分子電解質添加PVDF-HFP以增加其機械強度，並將其吸附電解液製備成膠態高分子電解質，期望可以提高導電度並應用於鋰電池中。
本篇論文第一部分利用到熱重分析儀 (TGA)、微差掃描卡計(DSC)、傅立葉紅外線吸收光譜儀 (FTIR)、交流阻抗分析儀 (AC-Impedance) 、掃描式電子顯微鏡 (SEM) 以及固態核磁共振光譜儀 (Solid State NMR) 等儀器分析星狀固態高分子電解質，並發現在30℃下最佳導電度可達到1 × 10-4 S/cm；第二部分利用交流阻抗分析儀測試其電化學穩定性，結果此膠態高分子電解質可以承受相當高的電壓 (7.4V)，並且進一步組裝成硬幣型2032電池，和市售的聚丙烯 (PP) 隔離膜之電池作電池性能比較，發現電容量都有提升的現象。

摘要(英)

Plasticized star-branched organic-inorganic hybrid electrolyte is a promising candidate for present day battery applications as it provides good mechanical and electrochemical properties. In this presentation, the dynamic properties of hyperbranched copolymer made from inorganic siloxane and polymer alkylene oxide units connected by cyanuric chloride linkage are investigated. Cyanuric chloride is chosen as the coupling core because it provides a branching site, cation binding site to help ionic transport between polymer chains. The tri-block copolymer PPG-PEG-PPG diamine (ED2000) reacts with 3-isocyanatopropyltriethoxysilane (ICPTES) and then coupling with cyanuric chloride for selective substitutions of silane modified oligo(oxyalkylene)-amines onto three chlorides of the triazine ring in a stepwise manner at 0, 25 and 130 ?C followed by co-condensation with 2-[methoxy(polyethylenoxy) propyl]trimethoxysilane (MPEOPS) to synthesize the hybrid membrane.
The star branched hybrid electrolyte shows good resistance to crystallization. The swelling ratio of the electrolyte membrane is measured with different electrolyte solvents and found to be very high in comparison to other reported polymer electrolyte membrane. The membrane exhibits ionic conductivity value near to 10-2 Scm-1. The high ionic conductivity of the electrolyte membrane is attributed to the higher percentage of swelling as it can retain sufficient amount of electrolyte solvent, thus creating channels for free movement of ions. The membrane also depicts higher electrochemical stability window versus Li/Li+ as well
IV
as stable charge-discharge behavior, which is required for practical battery applications.

關鍵字(中)

★ 星狀高分子電解質
★ 膠態高分子電解質
★ 聚乙氧烯

關鍵字(英)

★ star-branched electrolyte
★ gel polymer electrolyte
★ polyethylene oxide

論文目次

第一章緒論……………………………………………………………..1
1-1. 簡介………………………………………………………………1
1-2. 文獻回顧…………………………………………………………3
1-2-1. 鋰二次電池……………………………………..………....3
1-2-2. 鋰高分子電池…………..………………………..………..6
1-2-3. 高分子電解質 (Polymer Electrolytes) …………..……....8
1-2-4. 固態高分子電解質 (Solid Polymer Electrolyte) .......………9
1-2-5. 膠態 (gelled-type) 高分子電解質……………..…………..15
1-2-6.微孔型高分子電解質……………………………..……20
1-2-7. 含有三氮環之高分子.………………………………….…22
1-2-8. 有機矽高分子. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1-3. 研究動機與目的. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
第二章實驗部分與原理………………………………………………27
2-1. 實驗藥品………………………………………………………..27
2-2. 儀器設備………………………………………………………..29
2-3. 高分子電解質膜之製備………………………………………..30
2-3-1.固態高分子電解質製備........................……………..30
VII
2-3-2.膠態高分子電解質製備..........….………………..32
2-3-3. 硬幣型2032電池組裝.......................……….…………..33
2-4. 儀器分析原理…………………………………………………..34
2-4-1. 熱重量分析儀....................................................……..….....34
2-4-2. 微差掃瞄熱卡計........................................................….....34
2-4-3. 傅立葉紅外線吸收光譜儀………………………..………..36
2-4-4. 交流阻抗分析儀……………………………………..……..37
2-4-5. 掃描式電子顯微鏡. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41
2-4-6. 固態核磁共振光譜儀……………………………..………..42
2-4-6-1. 原理簡介………………………………………………...42 2-4-6-2. 常用固態核磁共振技術………………………………...47
2-4-7. 線性掃描電位測試..………………………..……………..52
2-4-8. 鋰離子遷移數目測試………………………..……………..53
2-4-9. 電池性能測試........……………………..…………………..53
第三章結果與討論…………………………………………………..54
3-1.3ED-3I-3M-CC 固態高分子電解質..…………………..54
3-1-1. 固態星狀高分子電解質……………………….….....…...54
3-1-2. 熱重量分析..................................….…………….....…...55
3-1-3. 微差掃描熱卡計分析..................….…………….....…...57
VIII
3-1-4. 紅外線吸收光譜之鑑定……………….………….....…...61
3-1-5. 固態電解質膜之表面分析…….………………….....…...67
3-1-6. 固態高分子電解質之導電度量測………………….....…...70
3-1-7. 固態高分子電解質之遷移數目測試……………….....…...78
3-1-8. 固態核磁共振光譜分析....................................................81
3-1-8-1.13C MAS NMR..............................................................82
3-1-8-2.13C CP/MAS NMR............................................................84
3-1-8-3.29Si MAS NMR................................................................89
3-1-8-4.1H/13C 2D WISE NMR......................................................92
3-2. 添加 PVdF-HFP 之 3ED-3I-3M-CC 膠態高分子電解質…………………………………………………………....94
3-2-1. 膠態星狀高分子電解質......................………..…......…....94
3-2-2. 膠態高分子電解質之膨潤比測試..……….……….....…...95
3-2-3. 膠態高分子電解質之導電度量測..………..……….....….102
3-2-4. 線性掃描電位分析............……………….…..………........112
3-2-5. 電池性能測試.......................................………………...….114
第四章結論…….…………………………………………………..118
參考文獻………………………………………………...……………120

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指導教授

高憲明(Hsien-Ming Kao)

審核日期

2010-7-23

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