臺灣博碩士論文加值系統

摘 要
本實驗利用開環聚合反應及利用連續取代的方式合成可紫外光交聯之胺基磷□共聚物，其中含有丙烯胺基(allylamine group)及胺基(amino group)。利用NMR、元素分析(Elemental Analysis)、FTIR對共聚物比例進行分析，且鑑定合成之產物。並可利用UV吸收圖譜瞭解共聚物交聯之情形，另利用DSC了解熱轉移現象(Tg、Tm)之變化;TGA測試其熱穩定性。
進一步將所合成之胺基磷□共聚物依F值計量，添加計量之過氯酸鋰(LiClO4)，製備一系列固態共聚物電解質，由FTIR圖譜可發現鋰離子會與氮原子產生作用，使得鋰離子可在分子鏈上移動。其中以Poly- [(n-hexylamine)(allylamine)]phosphazene /F=0.7;其中正己胺基與丙烯胺基取代比例為1:1;導電度2.55×10-6S/cm為最高。而待得知各固態共聚物電解質最佳導電度之F值後，加入PC (Propylene Carbonate)、EC(Ethylene Carbonate)製備膠態共聚物電解質，可發現各共聚物製成膠態電解質，以Poly[(n-butylamine)(allylamine)]phosphazene /F=0.5;添加PC、EC比例為4比1;導電度4.53×10-5S/cm為最佳。

Abstract
In this study, a series of UV curable poly(allylamino)(amino)- phosphazene has synthesized. These cosubstituted polymers are characterized by a combination of 1H, 13C and 31PNMR, Elemental analysis and FTIR spectroscopies . The degrees of curing of the copolymers are investigated by UV spectroscopy. Also studied are the thermal properties of the cured materials by DSC and TGA measurements.
The solid electrolytes based on the cured phosphazene copolymer have been prepared with various amount of LiClO4 salt.
The highest conductivity of the as-prepared solid polymer electrolytes is HEA(1.0)AA(1.0)/F=0.7electrolyte, obtained at room temperature is 2.55×10-6S/cm
It was found that the lithium ions are solvated with both the nitrogen atoms on the back bone and those on the side chains. On the other hand, the cured gel type electrolytes based on the as-perpared phosphaze copolymer, LiClO4 and PC/EC plasticizer have also been prepared. The best value of the conductivity at room temperature obtained is 4.53×10-5 S/cm from the BUA(1.1)AA(0.9)/F=0.5/(PC/EC=4/1)electrolyte

目 錄
第一章緒論1
1-1.前言1
1-2.高分子電解質的特性5
1-3.高分子電解質的種類7
1-3-1.固態高分子電解質7
1-3-2.膠態高分子電解質11
1-4.高分子電解質之研究方向14
1-4-1.尺寸安定性14
1-4-2.熱穩定性15
1-4-3.溫度效應15
1-5.鋰高分子電池的研究18
1-6 展望22
1-7. 研究動機24
第二章 實驗藥品與儀器25
2-1.實驗藥品25
2-2.實驗儀器26
第三章 紫外光聯胺基磷□共聚物之合成與鑑定27
3-1實驗過程27
3-1-1.開環聚合反應(Ring-opening polymerization)----------------28
3-1-2.取代反應 (Substitution Reaction)29
3-2.結果與討論35
3-2-1.磷-31核磁共振光譜儀(31P-NMR)35
3-2-2.碳-13核磁共振光譜儀(13C-NMR)37
3-2-3.氫-1核磁共振光譜儀(1H-NMR)39
3-2-4.元素分析測定(EA Analysis)41
3-2-5.紅外線光譜分析(ATR-FTIR Analysis)42
3-2-6.紫外光光譜分析43
3-2-7. 熱性質之測試43
3-2-8 膠體色層分析(GPC)48
第四章 紫外光聯胺基磷□共聚物電解質之製備及其性質之研究80
4-1.簡介80
4-2製備紫外光交聯胺基磷□共聚物電解質80
4-2-1. 固態胺基磷□共聚物電解質之製備81
4-2-2. 膠態胺基磷□共聚物電解質之製備81
4-3.導電度之測量原理82
4-4.導電度測量系統的建立86
4-5 紅外線光譜分析(FTIR Analysis)90
4-6.導電度的測量91
4-6-1. 固態磷□共聚物電解質之導電度91
4-6-2.膠態磷□共聚物電解質95
4-7.導電度與溫度之關係96
第五章 結論107
參考文獻109

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