臺灣博碩士論文加值系統

超級電容因為具有功率密度高、循環壽命長與對環境友善之優點，使其能夠運用於通訊、醫療與工業中。而可撓式超級電容具有更加之便利性，故其有很大之潛能應用於新一代之穿戴式電子產品。本研究之目的即為製作出具有高比電容值、高能量密度、高功率密度與長循環壽命之超級電容元件。
本研究分別以碳纖維與碳布為電極基材，以電化學聚合方法，調控不同材料組成與聚合時間，製作出聚吡咯一元系統電極、石墨烯/聚吡咯與氧化奈米碳管/聚吡咯之二元系統電極、石墨烯/氧化奈米碳管/聚吡咯之三元系統電極與金屬氧化物(氧化釕、氧化錳、氧化鎳)/石墨烯/氧化奈米碳管/聚吡咯之四元系統電極。並以傅立葉轉換紅外線光譜儀與掃描式電子顯微鏡進行電極材料分子間之相互作用力鑑定與表面形貌分析，以X射線微量分析儀觀察四元系統電極之元素分布。電極之電化學性質表現由恆電流充放電法與循環伏安法進行分析。以碳布為基材系統中，於聚合時間300秒下，氧化釕/石墨烯/氧化奈米碳管/聚吡咯之四元系統電極於電流密度1A/g下有最佳之比電容值1017.1F/g，且於20A/g下具有70.8%之電容保持率；於掃描速率5mV/s下有最佳之比電容值1034.1F/g，且於100mV/s下具有70.1%之電容保持率。
本研究亦利用氧化石墨烯/1-乙基-3-甲基咪唑啉双(三氟甲基磺酰基)亞胺離之膠態電解質與不同材料之電極封裝成可撓式對稱式之超級電容元件，並以恆電流充放電法、循環伏安法、電化學交流阻抗法與充放電循環法來分析元件之電化學性質。氧化釕/石墨烯/氧化奈米碳管/聚吡咯、氧化錳/石墨烯/氧化奈米碳管/聚吡咯、氧化鎳/石墨烯/氧化奈米碳管/聚吡咯、石墨烯/氧化奈米碳管/聚吡咯與聚吡咯元件於1A/g下之最高比電容值分別為561.6F/g、517.1F/g、475.9F/g、370F/g與322.9F/g，其於20A/g下之電容保持率分別為44.3%、43.5%、44.5%、56%與41%；於5mV/s下之比電容值分別為589.5F/g、535F/g、489.8F/g、384.2F/g與335F/g，其於100mV/s下之電容保持率分別為44.1%、44.2%、44.1%、54.3%與44.2%。其中氧化釕/石墨烯/氧化奈米碳管/聚吡咯元件擁有最佳之比電容值，其能量密度可達38.11Wh/kg，且於1000次充放電循環後仍有89.5%之電容保持率，故其具有不錯之循環壽命。於應用方面，我們將四個氧化釕/石墨烯/氧化奈米碳管/聚吡咯元件串聯，能成功使紅色發光二極管發亮，證明此研究中之可撓式超級電容具有應用於新一代電子裝置之潛能。

Supercapacitors can be applied to communication and healthcare industries due to their high power density, long cycle life and friendly to environment. Because flexible supercapacitors have convenience to personal life, they have great potential to develop as a next-generation and wearable electronic gadget. Our purpose of research is to fabricate a supercapacitor device with high specific capacitance, high energy density, high power density and long cycle life.
In our research, electrode of polypyrrole(PPy), binary system electrode of graphene/PPy and oxidized carbon nanotube/PPy, ternary system electrode of graphene/oxidized carbon nanotube/PPy and quaternary system electrode of metal oxide(RuO2, MnO2 or NiO)/graphene/oxidized carbon nanotube/PPy were individualy prepared by electrochemical polymerization deposition on carbon fiber and carbon cloth respectively, and we adjusted parameters of different compositions of materials and polymerization time in this experiment. We also used Fourier transform infrared spectroscopy(FTIR) to investigate the interaction between materials, scanning electron microscopy(SEM) to investigate the surface morphology and energy dispersive X-ray microanalysis(EDX) to analyze the compositions of quaternary electrode. We used galvanic charge-discharge method and cyclic voltammetry to analyze the electrochemical properties of electrodes. For the system of carbon cloth substrate, the quaternary electrode of RuO2/graphene/oxidized carbon nanotube/PPy with polymerization time of 300s has the best specific capacitance of 1017.1F/g at current density 1A/g measured by galvanic charge-discharge method and has specific capacitance retention of 70.8% at 20A/g. It also has the best specific capacitance of 1034.1F/g at scan rate 5mV/s measured by cyclic voltammetry, and has specific capacitance retention of 70.1% at 100mV/s.
We further fabricated the flexible symmetric supercapacitor device(SSC) with above mentioned electrodes by using GO/EMITFSI as gel electrolyte and used galvanic charge-discharge, cyclic voltammetry and electrochemical impedance to analyze the electrochemical properties of devices. SSCs with symmetric electrodes of RuO2/graphene/oxidized carbon nanotube/PPy, MnO2/graphene/oxidized carbon nanotube/PPy, NiO2/graphene/oxidized carbon nanotube/PPy, graphene/oxidized carbon nanotube/PPy and PPy have the highest specific capacitance of 561.6F/g, 517.1F/g, 475.9F/g, 370F/g and 322.9F/g at current density 1A/g and have specific capacitance retention of 44.3%, 43.5%, 44.5%, 56% and 41% at 20A/g respectively. Their specific capacitances at scan rate of 5mV/s were 589.5F/g, 535F/g, 489.8F/g, 384.2F/g and 335F/g at scan rate 5mV/s with the specific capacitance retention of 44.1%, 44.2%, 44.1%, 54.3% and 44.2% at 100mV/s respectively. We found the device of RuO2/graphene/oxidized carbon nanotube/PPy has the best specific capacitance and energy density of 38.11Wh/kg and has specific capacitance retention of 89.5% after 1000 charge-discharge cycle. Finally, we use four devices of RuO2/graphene/oxidized carbon nanotube/PPy in series to light up a red LED to demonstrate our SSCs having great potential for next generation electronic gadgets.

致謝 I
中文摘要 II
ABSTRACT IV
目錄 VI
圖目錄 XI
表目錄 XXXII
第一章 緒論 1
1.1前言 1
1.2研究動機 2
1.3研究架構 3
第二章 文獻回顧 4
2.1超級電容之發展 4
2.2超級電容之特性與組成 6
2.3超級電容之分類 8
2.3.1電雙層電容 8
2.3.2贗電容 10
2.4超級電容之電化學檢測方法 11
2.4.1循環伏安法 12
2.4.2 恆電流充放電法 14
2.4.3 電化學交流阻抗法 16
2.5聚吡咯 18
2.6 奈米碳材 20
2.6.1 石墨烯 20
4.6.2 奈米碳管 21
第三章 實驗方法 22
3.1 實驗藥品與器材 22
3.2 實驗儀器與設備 24
3.3電極之製備 25
3.3.1 碳布之清洗 25
3.3.2 氧化奈米碳管之製備 25
3.3.3 Pyrrole單體水溶液之製備 26
3.3.4 含有奈米碳材與金屬氧化物之Pyrrole單體水溶液之製備 26
3.3.5電化學聚合之設定 27
3.4 可撓式對稱式超級電容元件之製備 32
3.4.1 氧化石墨烯之製備 32
3.4.2 GO/EMITFSI膠態電解質之製備 33
3.4.3 元件之組裝 34
3.5 FTIR樣品之製備 36
3.6 SEM樣品之製備 36
3.7 電化學分析之設定 37
3.7.1 三極式系統 37
3.7.2 二極式系統 37
第四章 結果與討論 38
4.1 PPy以碳纖維為基材之超級電容電極 38
4.1.1 PPy之FTIR分析 39
4.1.2 PPy於碳纖維上之表面型貌 42
4.1.3 PPy於碳纖維上之電容表現 50
4.1.4 PPy於碳纖維上之CV曲線 56
4.2奈米碳材/PPy以碳纖維為基材之超級電容電極 61
4.2.1石墨烯/PPy以碳纖維為基材之超級電容電極 62
4.2.1.1石墨烯/PPy之FTIR分析 62
4.2.1.2石墨烯/PPy於碳纖維上之表面形貌 63
4.2.1.3石墨烯/PPy於碳纖維上之電容表現 65
4.2.1.4石墨烯/PPy於碳纖維上之CV曲線 71
4.2.2氧化奈米碳管/PPy以碳纖維為基材之超級電容電極 77
4.2.2.1氧化奈米碳管/PPy之FTIR分析 77
4.2.2.2氧化奈米碳管/PPy於碳纖維上之表面形貌 78
4.2.2.3氧化奈米碳管/PPy於碳纖維上之電容表現 80
4.2.2.4氧化奈米碳管/PPy於碳纖維上之CV曲線 87
4.2.3石墨烯/氧化奈米碳管/PPy以碳纖維為基材之超級電容電極 93
4.2.3.1石墨烯/氧化奈米碳管/PPy於碳纖維上之FTIR 93
4.2.3.2石墨烯/氧化奈米碳管/PPy於碳纖維上之表面形貌 94
4.2.3.3石墨烯/氧化奈米碳管/PPy於碳纖維上之電容表現 96
4.2.3.4石墨烯/氧化奈米碳管/PPy於碳纖維上之CV曲線 109
4.3 PPy以碳布為基材之超級電容電極 121
4.3.1 PPy於碳布上之表面形貌 122
4.3.2 PPy於碳布上之電容表現 127
4.3.3 PPy於碳布上之CV曲線 132
4.4奈米碳材/PPy以碳布為基材之超級電容電極 137
4.4.1奈米碳材/PPy於碳布上之表面形貌 138
4.4.2奈米碳材/PPy於碳布上之電容表現 143
4.4.3奈米碳材/PPy於碳布上之CV曲線 149
4.5金屬氧化物/奈米碳材/PPy以碳布為基材之超級電容電極 155
4.5.1金屬氧化物/奈米碳材/PPy之FTIR分析 156
4.5.1.1 RuO2/奈米碳材/PPy之FTIR 156
4.5.1.2 MnO2/奈米碳材/PPy之FTIR 157
4.5.1.3 NiO/奈米碳材/PPy之FTIR 158
4.5.2金屬氧化物/奈米碳材/PPy於碳布上之表面形貌 159
4.5.3金屬氧化物/奈米碳材/PPy於碳布上之電容表現 166
4.5.4金屬氧化物/奈米碳材/PPy於碳布上之CV曲線 182
4.6可撓式對稱式超級電容元件之性能 197
4.6.1以GO/EMITFSI作為超級電容元件膠態電解質之性質分析 197
4.6.1.1膠化EMITFSI離子液體 198
4.6.1.2不同重量比之GO/EMITFSI作為超級電容元件膠態電解質之電容表現 199
4.6.1.3不同重量比之GO/EMITFSI作為超級電容元件膠態電解質之CV曲線 202
4.6.2 以6GO/EMITFSI電解質與不同材料電極製成超級電容元件之 性質分析 205
4.6.2.1 以6GO/EMITFSI電解質與不同材料電極製成超級電容元件之電容表現 206
4.6.2.2以6GO/EMITFSI電解質與不同材料電極組製成超級電容元件之CV曲線 209
4.6.2.3以6GO/EMITFSI電解質與不同材料電極製成超級電容元件之EIS分析 212
4.6.2.4以6GO/EMITFSI電解質與不同材料電極製成超級電容元件之Ragone plot 214
4.6.2.5可撓式對稱式超級電容元件之效能 215
4.7可撓式對稱式超級電容元件之長效性分析 216
4.7.1以6GO/EMITFSI電解質與不同材料電極製成超級電容元件於長效性分析後，電極之表面形貌 217
4.7.2以6GO/EMITFSI電解質與不同材料電極製成超級電容元件之長效性分析表現 223
第五章 結論 225
參考文獻 227

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