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研究生:黃正瑋
研究生(外文):Cheng-Wei Huang
論文名稱:碳纖維表面成長奈米碳管及含氧官能基以促進電容表現之研究
論文名稱(外文):Carbon Nanotubes Grafting and Oxygen Functionalities Introduction to Enhance the Capacitive Performance of Carbon Fibers
指導教授:鄧熙聖
指導教授(外文):Hsisheng Teng
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:2008
畢業學年度:96
語文別:中文
論文頁數:91
中文關鍵詞:碳纖維奈米碳管電雙層電容電化學電容器導電度提升氧官能基過電位氧化
外文關鍵詞:Activated carbon fiberConductivity enhancementNanotube graftingPolarization oxidationElectrochemical capacitorOxygen functional groupsCarbon nanotubeDouble layer capacitance
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本實驗以碳纖維表面成長奈米碳管及含氧官能基強化電容器的應用性。成長奈米碳管的目的是為了降低碳-碳及碳-集電器間的接觸阻力,使電容器在高速率充放電時,能維持高電容量;而含氧官能基則是形成表面擬電容以提升電容量。電容器在充放電過程受總電阻影響,使其高電流密度下的能量儲存效率較低。本研究利用濺鍍法及化學沈積法在碳纖維表面上成長奈米碳管提升碳纖維的導電性,亦維持其高表面積(與含浸法相比),而在充放電測試中,放電流150 mA時,維持相對電容量損耗僅7%,而未成長奈米碳管的碳電極則有17%,並以電子繞射探討觸媒與奈米碳管的結晶結構及成長機制。並用交流阻抗分析碳電極內阻。至於表面氧化處理方面,以過電位氧化法在碳表面生成大量含氧官能基,大幅增加碳電極的電容量。由循環伏安法測得氧化後的碳電極電容量有463 F/g,提升70%的電容量,以程溫脫附(TPD)及表面元素分析(ESCA)分析表面含氧官能基的組成,發現有效提升電容量的組成是quinone類型的含氧官能基。
Carbon nanotube (CNT)-grafting by chemical vapor deposition was conducted to reduce the resistance of activated carbon fiber serving as an electrode for electric double layer capacitors. Sputtering deposition of Ni catalyst particles led to a uniform growth of CNTs on the carbon fiber surface through the tip-growth mechanism. Because sputtering deposition ensures little pore blockage (in comparison with wet-impregnation), the surface area decrease of the carbon fiber due to Ni loading was minimized. A capacitor cell assembled with the CNT-grafted fiber showed higher electrolyte-ion and electron conductivities relative to a cell assembled with the bare fiber. By increasing the discharging current from 1 to 150 mA, the bare fiber exhibited a capacitance loss of 17% while the CNT-grafted fiber showed a mitigated capacitance loss of only 7%. This developed CNT-grafting technique renders activated carbon fiber a promising electrode material for a variety of electrochemical applications.In order to promote the performance of electrochemical capacitors, we use polarization oxidation method on activated carbon fabric for producing surface oxygen functional groups. The specific capacitance (463 F/g) of the carbon was found to increase upon polarization oxidation. Surface oxygen functional groups analysis using temperature programmed desorption and X-ray photoelectron spectroscopy showed that the double-layer capacitance was enhanced due to the presence of quinone type functional group.
摘 要 Ⅰ
Abstract Ⅱ
誌 謝 Ⅲ
總目錄 Ⅳ
表目錄 Ⅷ
圖目錄 Ⅸ

第一章 緒論 1
1-1 前言 1
1-2 超高電容器的發展與應用 2
1-3 研究動機 3

第二章 理論說明與文獻整理 4
2-1 碳纖維的性質 4
2-2 碳電極之改質方法 7
2-2.1 海膽狀碳材 7
2-2.2 表面氧化處理 8
2-3 碳材分析 9
2-3.1 吸附基本理論 9
2-3.2 拉曼光譜 13
2-3.3 程溫脫附 13
2-3.4 化學分析電子光譜 15
2-4 電容器 16
2-4.1 電容器簡介 16
2-4.2 平行板電容器 16
2-4.3 電容器串並聯 18
2-4.4 二極式及三極式電容器 21
2-5 電雙層的概念及結構 23
2-5.1 電雙層原理 23
2-5.2 Helmholtz電雙層模型 23
2-5.3 Stern電雙層模型 25
2-5.4 電雙層結構 26
2-6 電化學測試方法 28
2-6.1 循環伏安法 28
2-6.2 電化學充放電 29
2-6.3 交流阻抗理論 31

第三章 實驗設備與方法 37
3-1 操作設備及藥品 37
3-2 碳纖維表面成長奈米碳管 39
3-2.1 碳纖維表面擔載鎳觸媒 40
3-2.2 熱裂解化學沈積法成長奈米碳管 40
3-2.3 氮氣物理吸脫附實驗 41
3-2.4 SEM結構分析 42
3-2.5 TEM微結構分析 42
3-2.6 Raman分析 42
3-2.7 電容器組裝 43
3-2.8 循環伏安法 44
3-2.9 定電流充放電 44
3-2.10 交流阻抗分析 44
3-3 碳纖維表面氧化處理 45
3-3.1 熱處理 46
3-3.2 過電位氧化 47
3-3.3 X光光電子能譜分析 48
3-3.4 程溫脫附 48
3-3.5 電化學測試 49
第四章 結果與討論 50
4-1 表面成長奈米碳及碳材分析 50
4-1.1 SEM分析 50
4-1.2 HR-TEM分析 52
4-1.3 氮氣吸脫附結果分析 56
4-1.4 Raman分析 58
4-1.5 循環伏安法測試之分析與討論 60
4-1.6 定電流充放電行為與分析 63
4-1.7 交流阻抗及內部阻力之討論 68
4-2 過電位氧化處理與電容行為 73
4-2.1 三極式循環伏安測試 74
4-2.2 程溫脫附與官能基分析 78
4-2.3 XPS分析 82

第五章 結論 84

參考文獻 86
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