紫外光交聯胺基磷@共聚物電解質製備 及其性質之研究

Synthesis and Properties of UV Curable Poly[(amino)(allylamino)]phosphazene-Based Electrolytes

陳篤厚(Du-Hou Chen)

指導教授 ： 陳玉惠

中原大學/理學院/化學研究所/碩士(2002年)

https://doi.org/10.6840/cycu200200306

摘要

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。

關鍵字

磷@ ； 電解質 ； 紫外光

並列摘要

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

並列關鍵字

polymer electrolyte ； UV curing ； polyphosphazene

參考文獻

4. Y. Matsuda, “Stable Electrolytes for Lithium Batteries”, J. Power Source, 20,19 (1987)

5. Y. Matsuda, M. Merita and K.Kosaka“ Conductivity of the Mixed organic Electrolyte Containing Propylene Carbonate and 1,2-Dimethoxyethane”, J. Electrochem. Soc., 130,10 (1983)

8. K. M. Abraham “Application of Electroactive Polymers”, Edited by B. Scrosati, Chaptan & Hall, London, Chap.3, 1993

9. M. Watanabe and N. Ogata, “Ionic Conductivity of Polymer Electrolytes and Future Applications” Br. Polym. J., 20, 181 (1988)

11. J. M. Chabgno, Thesis, University of Grenoble, 1980, B. L. Papke, Ph.D. Thesis, Northwestern University, (1982)