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研究生:黃佩君
研究生(外文):Pei-Jan Huang
論文名稱:聚苯胺共聚合體之結構、性能與電化學行為及其在鋰二次電池的應用研究
論文名稱(外文):Studies on the structure, properties and electrochemical behavior of the polyaniline copolymer and it's application in lithium secondary battery
指導教授:陳壽安
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學工程學系
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:84
中文關鍵詞:聚苯胺聚苯胺共聚合體鋰離子電池聚苯胺衍生物鋰二次電池
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利用聚苯胺(polyaniline, PAn)具可被電化學摻雜/去摻雜的特性,可製成有機二次電池。由於聚苯胺之分子鏈結構是屬於較剛硬的,加上其平面性亦非常的好,使得聚苯胺有良好的導電度及結晶性。但是結晶性愈好,對聚苯胺電池的電容量與循環壽命會有影響。因此,當只以聚苯胺作為正極之材料時,在電池不斷進行充放電後,正極活性物質的利用率會逐漸降低,此可能是因正極材料的內部已有結晶產生,使得離子的傳遞受阻礙而不易進出,造成電池內部阻抗過大導致其電容量與循環壽命衰退的速率相當快。
為了證實聚苯胺電池結晶性的產生會影響電池的電容量與循環壽命降低,故本研究主要為在聚苯胺的苯環上接上一鄰位側鏈取代基團(如:鄰位甲基基團、鄰位甲氧基基團與鄰位乙氧基基團)以成聚苯胺共聚合體。主要是破壞整個分子鏈的平面性,而使得其結晶性降低。由X光繞射光譜鑑定出此聚苯胺共聚合體其結晶性比聚苯胺差,且其分子量與表面積均比聚苯胺大,加上其亦具有良好的電化學可逆性,因此將此聚苯胺共聚合體當作正極材料組成電池時,其具有較高的電容量、循環壽命、庫倫效率、低自身放電以及在低溫下仍可進行電池充放電之優點。
而本研究是以摻雜態之聚苯胺共聚合體進行循環伏安實驗(Cyclic voltammetry, CV),瞭解其電化學可逆性;以X光繞射光譜鑑定其結晶性,以及電池的充放電測試來證實其所具有之優點。並說明其與聚苯胺之差異。

第一章 緒論 1
1-1 前言 1
1-2 共軛導電性高分子之電子結構[10, 11] 4
1-2-1 能帶理論 4
1-2-2 偏極子 (Polaron) 與雙偏極子 (Bipolaron) 4
第二章 文獻回顧 6
2-1 聚苯胺 6
2-1-1 聚苯胺的合成 6
2-1-2 聚苯胺之合成機構 7
2-1-3 聚苯胺之分子量 7
2-1-4 聚苯胺的摻雜與去摻雜 10
2-1-5 聚苯胺紫外-可見光光譜 12
2-1-6 聚苯胺之紅外線(IR)及拉曼(Raman)光譜 13
2-2聚苯胺之電化學現象 16
2-2-1循環伏安計量分析 (Cyclic voltammetry, CV) 16
2-2-2 阻抗光譜 (Impedance spectroscopy) 17
2-3 酸摻雜聚苯胺的結晶性探討 18
2-4 聚苯胺衍生物 19
2-4-1 單體聚合而成之聚苯胺衍生物 19
2-4-2 聚氮-烷基苯胺 [Poly (alkyl aniline) ] 20
2-4-3 聚鄰位甲基苯胺 21
2-5 聚苯胺共聚合體 21
2-5-1 聚苯胺共聚合體的紫外線-可見光(UV-Vis)光譜 23
2-5-2 聚苯胺共聚合體的(IR)及拉曼(Raman)光譜 23
2-5-3 聚苯胺共聚合體的電化學現象-循環伏安計量分析 (Cyclic voltammetry, CV) 25
2-6有機二次電池 (organic secondary battery) 26
2-7 文獻分析 30
第三章 實驗內容 32
3-1 藥品 32
3-2 不同比例之兩單體聚苯胺共聚合體之合成: 33
3-3 化學結構之鑑定 34
3-4聚苯胺共聚合體之物性量測 34
3-5有機二次電池之製作與測試 36
3-5-1 電化學性質分析 36
3-5-2 正極膜製作、電池組裝與測試 37
第四章 聚苯胺共聚合體之結構與物性研究 40
4-1 元素分析(EA) 40
4-2 紅外線光譜之研究(IR) 41
4-2-1聚苯胺-鄰位甲基苯胺共聚合體(PAOT)之紅外線光譜 41
4-2-2聚苯胺-鄰位甲氧基苯胺共聚合體(PAOA)之紅外線光譜 42
4-2-3聚苯胺-鄰位乙氧基苯胺共聚合體(PAOE)之紅外線光譜 43
4-3 X-射線繞射分析(X-ray Diffractometry,XRD) 44
4-3-1聚苯胺-鄰位甲基苯胺共聚合體之X-射線繞射分析 45
4-3-2聚苯胺-鄰位甲氧基苯胺共聚合體之X-射線繞射分析 46
4-3-3聚苯胺-鄰位乙氧基苯胺共聚合體之X-射線繞射分析 47
4-3-4聚苯胺共聚合體(去摻雜態)之X-射線繞射分析 48
4-4聚苯胺共聚合體之分子量分析 51
4-4-1 GPC標準品的校正 51
4-4-2 共聚不同比例含量之苯胺單體對分子量之影響 53
4-4聚苯胺共聚合體之表面積、孔隙度 54
4-5聚苯胺共聚合體之電化學性質分析 55
4-5-1 循環伏安分析(Cyclic Voltammerty,CV) 55
第五章 聚苯胺共聚合體之有機二次電池性能研究 62
5-1 不同比例之三組聚苯胺共聚合體的有機二次電池 62
5-2 聚苯胺共聚合體有機二次電池之自放電 74
5-3 聚苯胺共聚合體有機二次電池之變溫測試 75
5-4 結論 78
第六章 參考文獻 79

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