摘 要
本論文旨在研究陰離子嵌入碳材的電化學行為，基於此儲能機制設計非對稱超高電容器。
第一部份，將應用在燃料電池中作氣體擴散層的碳紙(GDL25BC)作為電極，用於研究陰離子嵌入碳材的電化學行為。搭建三電極測試系統和電解液體系，測定碳紙正極上的電化學反應並與材料分析結果做比對。我們得到的結論：1.碳紙(GDL25BC)通過陰離子嵌入儲能是高比容量且倍率性好的電極材料；2. 碳紙(GDL25BC)經滾壓處理，可以製成可繞式電極。3.可繞式碳紙電極高倍率循環穩定性好。
第二部份，通過商業石墨型碳材的陰離子嵌入行為研究得出：1.陰離子嵌入行為需在高石墨結晶度碳材中才發生，軟碳並不可行；2.顆粒尺寸會影響電極的電荷傳輸阻抗（Rct）和Warhurg擴散阻抗，大粒徑的材料其倍率性能制約很大。3.中間相碳微球（MCMB）既有高結晶度，又擁有非晶相炭峰。這些非晶相炭使得電解質更好地在電極中擴散傳輸，電極的倍率性能得到極大改善。
第三部份，依據上述結論選擇蠕蟲結構的膨脹石墨作為新型正極，並對膨脹石墨做熱處理、超聲波振蕩、瀝青碳包覆和酚醛樹脂包覆改性處理。得到性能最佳的EG-600Up（膨脹石墨經600℃處理，超聲波振蕩4h ，75%瀝青碳包覆），具有高倍率性能（3A/g）及充放電穩定性 (500cycle，95.7% 容量保持)。將此材料作為正極，活性炭負極，溶有四氟硼酸四乙基銨（TEABF4）的碳酸丙烯酯(PC)作電解液組裝成非對稱超高電容器（AC/EG-600Up）。此電容器的電能量密度和功率密度可達： 51.47Wh/kg，10.12kW/kg。

Abstract
The thesis aims at studying the electrochemical behavior of anion intercalation into carbon materials and designing the asymmetric supercapacitors based on this energy storage mechanism.
The first part introduces using carbon paper (GDL25BC), which is a gas diffusion layer in fuel cell, as an electrode for studying the electrochemical behavior of the anion intercalation. A three-electrode test system with electrolytes system was established and comparaed the electrochemical reaction on the carbon paper positive electrode with results of material analysis in this section. In conclusion: 1. Anion intercalation type carbon paper (GDL25BC) is a high specific capacity and good rate-performance electrode; 2.Carbon paper (GDL25BC) by the rolling process, can be made to flexible electrode. 3. It has a high rate performance and good cycling stability.
The second part demonstrates comparing the electrochemical behavior of anion intercalation into commercial graphitic carbons. In summary: 1. Anion intercalation need occur at graphitic carbon materials with a high crystallinity degree, so that the soft carbon is not allowed; 2 Particle size affects on the electrode through charge transfer impedance (Rct) and Warburg diffusion impedance, a large particle size material greatly restricts its rate performance. 3. Mesosphere carbon microbeads (MCMB) has a high crystallinity degree, but also amorphous carbon peak. These amorphous carbon promote electrolyte diffusion transfer in the electrode, so that the electrode performance ratio has been greatly improved.
In the third part, worms-like type expanded graphite was selected as new cathode based on the above conclusions. Modify expanded graphite by heat treatment, ultrasonic vibration, pitch carbon coated and phenolic resin coated. Get the best performance sample EG-600Up (expanded graphite treated treatment at 600 ℃, ultrasonic oscillation 4h, 75% pitch coated), it has a high rate capability (3A / g) and discharge stability (500cycle, retention 95.7%). Assembled asymmetric supercapcitors (AC /EG-600Up) which activated carbons as a negative electrode, EG-600Up as a positive electrode, measured in TEABF4 solving in propylene carbonate (PC). It has a good performance on energy density and power density: 51.47Wh / kg, 10.12kW / kg.

目錄
誌 謝 I
Abstract II
目錄 IV
圖表目錄 VII
第一章 緒論及理論基礎 1
1-1電化學原理 1
1-1-1電化學反應系統 1
1-1-2 極化、歐姆阻抗、過電位 2
1-1-3 三電極系統介紹 3
1-2 鋰離子電池 5
1-2-1 鋰離子電池原理 5
1-2-2 鋰離子電池結構介紹 7
1-2-3 鋰離子電池碳材負極 9
1-3 電化學電容器 11
1-3-1 電容器簡介 11
1-3-2 電化學電容器分類及性能介紹 11
1-3-3 電化學電容器儲能機制 16
1-4 混合型超級電容器 21
1-4-1混合型超級電容器介紹 22
1-4-2 鋰離子電容器(Lithium ion Supcapacitors) 22
1-4-2 雙石墨電池(Dual-graphite cell) 25
1-4-3 活性炭/石墨混合型電容器 29
1-5 研究動機 31
第二章 實驗方法與步驟 32
2-1電極製作 32
2-1-1 漿料分散、塗覆 32
2-1-2 電極片組裝、處理 32
2-2 實驗藥品與儀器 33
2-2-1藥品 33
2-2-3設備 34
2-3 電化學測試系統 35
2-4 電化學分析實驗 36
2-4-1 循環伏安法 （CV） 37
2-4-2 計時電位分析法 （CP） 38
2-4-3倍率性能測試（C-Rate） 40
2-4-4 循環充放電壽命測試（Cycle Life） 41
2-4-5 交流阻抗圖譜法（AC-impedance） 41
2-5 材料分析 43
2-5-1 掃描式電子顯微鏡 43
2-5-2 穿透式電子顯微鏡 44
2-5-3 X光繞射分析 45
2-5-3 氮氣吸脫附曲線 46
2-5-4 拉曼散射光譜 49
第三章 碳紙正極上的陰離子嵌入行為應用 51
3-1 簡介 51
3-2 實驗方法介紹 54
3-3 碳紙（GDL25BC）的物理特性 55
3-4碳紙正極（GDL25BC）的電化學特性 59
3-5碳紙（GDL25BC）的可繞性改良 65
第四章 陰離子嵌入型膨胀石墨的改性研究 70
4-1 簡介 70
4-2 實驗方法介紹 71
4-2-1電極製作方法說明 71
4-2-2 天然石墨 化學膨脹處理 72
4-2-3 膨脹石墨 熱處理 73
4-2-4膨脹石墨 超聲波振蕩處理 74
4-2-5 膨脹石墨 球磨處理 74
4-2-6 表面碳包覆 75
4-3 商業石墨型碳材的陰離子嵌入行為表現 77
4-4 電化學活化與陰離子嵌入的機制比較 86
4-5 膨脹石墨正極的陰離子嵌入應用及材料改性研究 91
4-6 膨脹石墨正極的表面包覆處理研究 98
第五章 非對稱超高電容器設計 105
5-1 簡介 105
5-2非對稱設計準則 105
5-3 非對稱設計之活性炭負極研究 108
5-4 電雙層型與電池型電極研究方法比較 112
5-5 非對稱設計之質量匹配 117
5-5 電位窗移動 120
5-6 非對稱超高電容器 123
5-7 未來的工作 126
文献回顾 127

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