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研究生： 吳品儀
Wu, Pin-I
論文名稱： 石油瀝青活性碳之製程探討與電雙層電容應用
Preparation of Activated Carbon from Petroleum Pitch for Electric Double-Layer Capacitors
指導教授： 鄧熙聖
Teng, Hsisheng
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 103
中文關鍵詞： 電雙層電容器 、介相瀝青 、化學活化 、活性碳 、孔洞結構
外文關鍵詞： electric double layer capacitors, mesophase pitch, chemical activation, activated carbon, porous structure
相關次數： 點閱：82  下載：7 
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    • 本研究提出了一種分階段加熱程序，將石油瀝青轉化為中間相結構再經由KOH活化成為雙電層電容器（EDLC）的高性能碳電極材料。在前熱處理中，降低升溫速率和延長持溫時間（430℃）都增加了中間相結構的形成，導致活性碳微孔含量和微孔表面積增加，有利於儲存能量提高比電容值，但卻不利於離子的傳輸；另一方面，降低前熱處理的升溫速率可以提高碳材的導電性。為了同時具有高導電性及利於離子傳輸的結構我們使用分階段升溫程序，在升溫過程中插入兩個低溫持溫的步驟（100和200℃）。分階段升溫程序將石油瀝青的脂肪族併合到芳香族結構中，這可以大大提高產物產率，並形成了可以轉化為高導電性和低離子傳輸阻力的中間相結構。組成對稱型二極式超級電容器在有機相溶液(TEMABF4/PC)中放電速率為0.5 A g-1時，電容值可達160 F g-1；且在高放電速率下(100 A g-1)時，電容值仍可維持110 F g-1。其比能量可達40.1 Wh kg-1，且功率可達到93.2 kW kg-1。本研究的結果指出使用石油瀝青作為前驅物用於製備多孔性活性碳的可行性和脂肪族用於調控活性碳結構以利於超級電容器電荷儲存的重要性。

    This study devises a temperature-programmed pretreatment strategy to convert petroleum pitch into a mesophase framework that can be activated by KOH to become high-performance carbon electrode materials for electric double layer capacitors (EDLCs). The multi-step pretreatment incorporates the aliphatic species of petroleum pitch into the aromatic framework, which substantially increases the product yield and forms a mesophase framework that can be converted to an activated carbon with high electronic conductivity and low ion transport resistance. When assembled in a symmetric two-electrode EDLC, the multi-step carbon exhibits capacitance values of 160 and 110 F g-1 at a discharge current of 0.5 and 100 A g-1, respectively, in 1 M triethylmethylammonium tetrafluoroborate/propylene carbonate electrolyte. The EDLC delivers specific energy and power of 40.1 Wh kg-1 and 93.2 kW kg-1 (based on the total carbon mass) over a voltage of 02.7 V. The results of the present study demonstrate the feasibility of using petroleum pitch as the precursor for porous carbon production and the significance of aliphatic species incorporation to regulate the pore structure of the carbons for charge storage.

    中文摘要........................ I 英文延伸摘要.....................II 致謝........................... IX 目錄............................X 表目錄..........................XIV 圖目錄..........................XV 第一章 緒論.....................1 1-1 前言......................1 1-2 超電容研究背景與發展.......2 1-3 超電容儲能機制............ 6 1-4 超電容的構成元件...........9 1-4-1構成元件簡介...........9 1-4-2電極材料...............9 1-4-3集電器................11 1-4-4介電物質..............11 1-4-5電解質................12 1-5石油瀝青與媒焦瀝青..........14 1-6 多孔性活性碳...............15 1-6-1多孔性活性碳簡介.......15 1-6-2多孔性活性碳製備.......17 1-7 研究動機...................20 第二章 文獻回顧與理論說明........21 2-1碳材應用於超級電容器的發展.....21 2-1-1活性碳碳材 (Activated carbon, AC)....21 2-1-2 模板製備多孔碳材 (Templated porous carbon)....22 2-1-3碳化物衍生碳 (Carbide-derived carbons, CDC)....23 2-1-4石墨烯材料....23 2-2介相瀝青碳材應用於超電容的發展....25 2-3活化介相瀝青碳材原理.............................26 2-4碳材孔隙分析原理................................ 28 2-4-1等溫吸附曲線...............................28 2-4-2 BET等溫吸附模式...........................31 2-4-3 BJH理論..................................32 2-4-4 D-R 等溫吸附模式..........................33 2-4-5密度泛函理論(Density Functional Theory, DFT)...34 2-5 電雙層電容器....................................38 2-5-1電容器簡介.................................38 2-5-2電雙層原理.................................41 2-5-3 Helmholtz 電雙層模型......................43 2-5-4 Stern電雙層模型...........................44 2-6電化學測試.......................................46 2-6-1循環伏安法.................................46 2-6-2定電流充放電...............................47 2-6-3交流阻抗理論...............................49 第三章 實驗方法與儀器原理介紹.........................54 3-1 藥品、材料與儀器設備........................54 3-1-1 藥品與材料........................ ......54 3-1-2 儀器與實驗設備...........................55 3-2 實驗步驟........................................56 3-2-1 沒有前熱處理(As-received)................58 3-2-2 單步驟升溫熱處理(Single-step heat treated)..59 3-2-3 分段升溫熱處理(Multi-step heat treated).....60 3-3 電化學測量簡介........................61 3-3-1 電容器組裝........................61 3-3-2 循環伏安法測試........................61 3-3-3 定電流充放電........................62 3-3-4 交流阻抗分析........................62 3-3-5 電池長效性測試........................62 3-4 樣品鑑定......................................63 3-5 分析儀器原理簡介........................64 3-5-1 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM)....................................64 3-5-2 物理吸附分析 (Brunauer-Emmett-Teller, BET) 66 3-5-3 X光繞射儀 (X-ray Diffraction, XRD) 67 3-5-4 熱重分析儀 (Thermogravimetric Analysis, TGA) 70 3-5-5 偏光顯微鏡 (Polarization Microscopy) 70 第四章 結果與討論.....................................71 4-1 TGA結果之討論..................................71 4-2 TEM結果之討論....................................74 4-3 XRD圖譜結果之討論........................... 76 4-4 碳材孔隙結構結果之討論.............................78 4-4-1 氮氣吸脫附實驗...................................78 4-4-2 材料孔徑分布.....................................80 4-5 導電度結果之討論....................................83 4-6 孔洞機制探討.....................................84 4-7 電化學測試.....................................86 4-7-1循環伏安法分析.....................................86 4-7-2定電流充放電分析...................................88 4-7-3交流阻抗分析.....................................91 4-8 電化學行為表現.....................................95 第五章 結論.....................................97 參考文獻.....................................98

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