臺灣博碩士論文加值系統

本研究以原位聚合法方式製備帶狀奈米石墨烯/氧化鐵/聚苯胺形成混合型電容器電極材料，吾等藉由FTIR, Raman, XRD, SEM及TEM等研究其性質差異性，並以恆電位分析儀探討帶狀奈米石墨烯及不同尺寸之親水氧化鐵奈米顆粒在不同添加量下其電化學特性之差異。
首先在帶狀奈米石墨烯/聚苯胺二元奈米複合材料系統中，從充放電行為及庫倫效應之結果可得知，隨帶狀奈米石墨烯的添加量提升，整體二元奈米複合材料之電化學特性會逐漸轉由帶狀奈米石墨烯作為主導，經檢測結果發現在5wt%之帶狀奈米石墨烯的添加下可降低複合材料的尺寸，因此可降低離子擴散阻抗，提供較大的接觸面積與電解液進行氧化還原反應，使聚苯胺的比電容值由193.80 F/g提升至384.73 F/g (5mV/s)，且在1000圈之循環壽命從原本純聚苯胺的59.6%提升至70.1%。
在引入不同尺寸之親水氧化鐵奈米顆粒與帶狀奈米石墨烯/聚苯胺所形成的三元奈米複合材料中，因親水改質後之氧化鐵奈米顆粒表面的羧酸官能基可進一步提供苯胺單體良好的活性反應點，故可進一步降低三元奈米複合材料之結構尺寸，於0.5wt%的6nm親水氧化鐵奈米顆粒添加下，其比電容值達最大為499.71 F/g (5mV/s)，1000圈之循環壽命可提升至88.3%，顯示該電極材料具有更優異的電化學特性。

In this study, the GNR/Fe3O4/PANI hybrid capacitors were synthesized by in-situ polymerization. FTIR, Raman, XRD, SEM and TEM were applied to characterize the properties. Electrochemical properties of electrodes were studied by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy techniques, respectively.
The electrochemical performance of GNR/PANI binary composites with different amounts of GNR has been compared. It’s obvious that the capacitance performance of the binary composites gradually enhanced as the GNR amount increased. By adding 5wt% GNR to the composite (P-5G), it exhibited much higher specific capacitance of 384.73 F/g compared to 193.80 F/g of the pure PANI at a scan rate of 5 mV/s, and the cycle stability of the composite could be improved to 70.1% after 1000 times which is more than 10% higher than that of pure PANI (59.6%). The enhancement is due to the addition of 5wt% GNR to reduce the particle size. The lower particle size can decrease the the diffusion resistance of ions and provide a larger contact surface to react with electrolyte.
The different amount of 6 and 13nm hydrophilic Fe3O4 was added to the binary composite to fabricate the ternary composites. The P-5G-05H6 shows the hightest specific capacitance of 499.71 F/g at 5 mV/s, and the cycle stability was improved to 88.3% after 1000 times. The excellent performance is due to the carboxyl groups on the surface of the hydrophilic Fe3O4 colud further provide more active sites for aniline monomer, and more effectively reduce the particle sizes of the ternary composite.

摘要 i
Abstract ii
目錄 iv
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
1.3 研究方向及目的 3
第二章 文獻回顧 5
2.1 超級電容器 5
2.1.1 電雙層電容器 6
2.1.2 擬電容 9
2.1.3 混合型超級電容器 10
2.2 導電高分子 12
2.2.1 導電高分子簡介 12
2.2.2 導電高分子的導電原理 16
2.2.3 聚苯胺之簡介 19
2.2.4 聚苯胺之合成方式 22
2.2.5 聚苯胺之儲電原理 25
2.3 帶狀奈米石墨烯 26
2.4 氧化鐵 29
2.4.1 氧化鐵應用於超級電容器之電極研究 29
2.4.2 氧化鐵/碳材作為超級電容器之電極研究 33
2.4.3 氧化鐵/碳材/導電高分子電容性質研究 35
第三章 實驗方法與步驟 37
3.1 實驗材料 37
3.2 實驗儀器 40
3.3 實驗架構 41
3.4 實驗方法與步驟 42
3.4.1 帶狀奈米石墨烯之製備 42
3.4.2 帶狀奈米石墨烯/聚苯胺複合材料之製備 44
3.4.3 不同尺寸之奈米氧化鐵製備 46
3.4.4 Fe3O4/ GNR/ PANI三元複合材料之製備 52
3.5 實驗儀器分析原理 55
3.5.1 傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer，FTIR) 55
3.5.2 拉曼光譜儀(Raman Spectrometer) 55
3.5.3 X光繞射儀(X-ray diffractometer, XRD) 56
3.5.4 場發射式掃描電子顯微鏡(Field-emmision Scanning Electron Microscopy, FE-SEM) 57
3.5.5 高解析穿透式電子顯微鏡(HRTEM) 57
3.5.6 恆電位分析儀(Potentiostate/Gavanostat) 59
第四章 結果與討論 61
4.1 化學法製備帶狀奈米石墨烯及其性質分析 61
4.2 改變帶狀奈米石墨烯添加量與PANI形成二元複合材料 67
4.2.1 PANI/GNR二元奈米複合材料之性質分析 68
4.2.2 PANI/GNR二元奈米複合材料之電化學性質分析 77
4.3 氧化鐵奈米顆粒 85
4.3.1 不同粒徑之Fe3O4奈米顆粒製備 85
4.3.2 親水性Fe3O4奈米顆粒製備 90
4.4 改變H6及H13添加量與P-5G形成三元奈米複合材料 93
4.4.1 P-5G-H6及P-5G-H13三元奈米複合材料之性質分析 94
4.4.2 P-5G-H6及P-5G-H13三元奈米複合材料之電化學性質分析 101
第五章 結論 110
第六章 參考文獻 112

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