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研究生:陳廷彥
研究生(外文):Ting-Yen Chen
論文名稱:含聚醚鏈環氧樹酯型高分子電解質之製備與其特性探討
論文名稱(外文):Preparation and Investigation of Polyether-based Crosslinked Polymer Electrolytes
指導教授:郭炳林郭炳林引用關係
指導教授(外文):Ping-Lin Kuo
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:86
中文關鍵詞:VTF關係式7Li固態核磁共振光譜環氧基聚醚高分子電解質
外文關鍵詞:7Li MAS NMRepoxidepolymer electrolytesVTF relationshippolyether
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摘 要
本研究製備之高分子電解質薄膜係以含聚乙烯醚之環氧樹脂((polyethylene glycol) diglycidyl ether, PEGDE)與雙氨基聚丙烯醚(polyoxypropylenediamine, Jeffamine D-series)在鋰鹽(LiClO4)的存在下加熱進行交鏈反應而得。藉由FT-IR、固態13C CP/MAS NMR鑑定其結構與反應。所得之高分子電解質以不□鋼為電極,利用交流阻抗分析法(ac-impedance)測量其離子導電度,並探討溫度、鋰鹽濃度、雙氨基聚丙烯醚鏈段長短及混摻diglycidyl ether of bisphenol-A(DGEBA)對其離子導電度之影響。藉由DSC、DMA可得知高分子之熱轉移(thermal transition)及黏彈性質,有助於分析其對離子導電度之影響;透過TGA分析得知各高分子及其錯合物(complexes)之熱穩定性。藉由FT-IR與7Li之魔術轉角(MAS)固態核磁共振光譜分析鋰離子於高分子電解質中之作用力(interaction)環境變化。
另製備以無溶劑高分子錯合物吸收(soaking)碳酸丙烯(propylene carbonate)溶劑而得之膠態(gelled-type)電解質薄膜;並以交流阻抗分析法、DSC與TGA等方法,分析膠態電解質之物性對導電度表現之影響。
Abstract
A series of crosslinked polyether-based polymers and their complexes with LiClO4 have been prepared and characterized by FT-IR and solid-state NMR (13C and 7Li nucleus). Significant coordination interactions between ions and the host polymer have been observed by means of differential scanning calorimeter (DSC), FT-IR, 7Li magic angle spinning (MAS) NMR, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). All events refer that Li-ions will prefe- rentially occupy the amine crosslinking sites until saturated, and then the excess Li-ions coordinate with the polyether chain segments. The results of 7Li MAS NMR reveal that Li-salt comes into being ion pairs or aggregates in high Li-salt concentration specimens, further supported by the consequences of DSC and FT-IR. These phenomena crucially affect the conductivity of the polymer electrolytes. The dependence of ionic conductivity was investigated as functions of temperature, LiClO4 concentration and PPO-segment length, and the results were studied by Arrhenius and Vogel-Tamman-Fulcher (VTF) equations to acquire the information of Li-ion transport. The results show that the conducting behavior of the complexes obey both Arrhenius and VTF manners throughout the temperature range 288-358 K, suggesting the coordinated motion model of the ionic hopping with the moving polymer chain segment.
目 錄
摘要Ⅰ
英文摘要(Abstract)Ⅱ
表目錄Ⅴ
圖目錄Ⅵ
第一章緒論1
第二章文獻回顧
2.1 鋰離子二次電池之發展3
2.2 高分子電解質6
第三章原理
3.1 交流阻抗分析13
3.2 固態核磁共振光譜18
3.3 動態機械分析21
第四章實驗部分
4.1 實驗藥品25
4.2 儀器設備26
4.3 環氧樹脂寡聚體起始物鑑定26
4.4 固態高分子電解質薄膜製備28
4.5 高分子結構鑑定29
4.6 熱性質分析30
4.7動態機械性質分析30
4.8 7Li魔術轉角固態核磁共振光譜30
4.9 交流阻抗分析31
第五章結果與討論
5.1 無溶劑型高分子電解質32
5.2 膠態高分子電解質46
第六章 結論51
參考文獻53
圖表結果58
自述86
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