臺灣博碩士論文加值系統

本研究將藉由縱向切割多壁奈米碳管製備帶狀奈米石墨烯，並改變帶狀奈米石墨烯添加量，利用原位聚合法將聚吡咯包覆帶狀奈米石墨烯，形成帶狀奈米石墨烯/聚吡咯奈米複合材料，而最外層以金屬氧化物-氧化釕，均勻披覆於聚吡咯外層形成帶狀奈米石墨烯/聚吡咯/氧化釕之三元複合材料，並探討彼此之電化學表現。

首先，討論帶狀奈米石墨烯/聚吡咯二元複合材料系統，藉由SEM及TEM表面形貌觀察得知，聚吡咯顆粒大小隨著帶狀奈米石墨烯添加量上升而減小；比電容值在5 mV/s掃描速率下，則隨著帶狀奈米石墨烯添加量提升而增加，由純聚吡咯之215 F/g提升至添加帶狀奈米石墨烯7 wt%(7GP)的438 F/g，而1000圈循環壽命測試由純聚吡咯的61%提升至7GP之70.2%。

在固定帶狀奈米石墨烯/聚吡咯添加量，並改變氧化釕之添加(7GPxR)，由電化學分析後得知，隨著氧化釕披覆量提升而比電容值具有上升趨勢，並且將氧化釕添加量之最佳比例，改變製程順序，探討氧化釕包覆於外層(7GPxR)及內層(GRP)之差異，其比電容值在掃描速率5 mV/s下分別為7GP9R之1352 F/g及GRP之749 F/g，且由於低溫退火下之氧化釕具有良好之電子及質子傳導能力，於3.0 A/g高電流密度下其電容保留值由7GP之44%提升至7GP9R之64.6%。此外， GRP、7GP9R於100 mV/s掃描速率下進行1000圈之循環壽命測試，其結果為52.2%、64.6%，顯示氧化釕包覆於最外層將能有效地保護內層之聚吡咯結構並提升循環壽命。

In this study, graphene nanoribbons (GNR) were prepared by longitudinal unzipping of multiwalled carbon nanotubes (MWCNTs). The GNR/PPy nanocomposites were synthesized by in-situ polymerization with different amounts of GNR. The ruthenium oxide (RuO2-xH2O) nanoparticles were deposited directly on the surface of GNR/PPy nanocomposites using the hydrothermal method. The morphologies of the PPy、GNR/PPy 、GNR/PPy/RuO2 nanocomposites were characterized through SEM and TEM. Electrochemical behavior of the PPy、GNR/PPy 、GNR/PPy/RuO2 nanocomposites were investigated by cyclic voltammetry and galvanostatic charge-discharge.
For the GNR/PPy system, the particle size of PPy measured by SEM and TEM images was gradually decreased with increasing the loading of GNR. The specific capacity of PPy increased significantly from 215 to 438 F/g in composites with 7 wt% GNR content (7GP) at a scan rate 5 mV/s. The cycle stability of 7GP composites improved to 70.2% after 1000 times test which is higher than 61% of pure PPy.
At the system of 7 wt% GNR with various RuO2-xH2O content (7GPxR), a maximum capacitance value of 1352 F/g had been obtained for the loading of 9R ([GNR/PPy]:[ RuO2]=1:9 w/w) into GNR/PPy composite at scan rate of 5 mV/s.
To compare with the performance of specific capacitance for the loading of RuO2-xH2O inside (7GP9R) and outside (GRP) were 1352 F/g 、749 F/g. Due to the low temperature annealing,therefore, the RuO2-xH2O is provided with high electron and proton conductivity.Therefore the capacitance retention of 7GP9R was improved to 64.6% which is more 20.6% higher than the 7GP(44%) at a current density of 3.0 A/g. In addition, the cycle stability of GRP and 7GP9R were 52.2%、64.6% after 1000 times test, which is contributed to the presence of RuO2-xH2O coverd the GNR/PPy composites and could for the protect structure of PPy to improve the cycle stability.

致謝 i
摘要 i
Abstract ii
目錄 iv
圖目錄 vi
表目錄 x
第一章 緒論 1
1.1 前言 1
1.2 研究動機 4
1.3 研究方向及目的 5
第二章 文獻回顧 6
2.1 導電高分子(Conducting polymers) 6
2.1.1導電高分子簡介 6
2.1.2 基本能帶理論 10
2.1.3 導電高分子之導電機制 13
2.1.4 導電高分子種類 15
2.2 聚吡咯(Polypyrrole, PPy) 17
2.2.1 聚?咯之簡介 17
2.3 奈米碳管(Carbon Nanotubes, CNTs) 21
2.3.1 奈米碳管之簡介 21
2.3.2 帶狀奈米石墨烯(Graphene nanoribbon, GNR) 25
2.4 超級電容器(Supercapacitors) 35
2.4.1 超級電容器介紹 35
2.4.2 超級電容器之電極材料 43
2.4.3 導電高分子/奈米無機物複合材料 50
第三章 實驗方法與步驟 57
3.1 實驗材料 57
3.2 實驗儀器 60
3.3 實驗架構 61
3.4 實驗方法與步驟 62
3.4.1 帶狀奈米石墨烯之製備 62
3.4.2 帶狀奈米石墨烯/聚?咯之製備 64
3.4.3 氧化釕之製備 66
3.4.4 帶狀奈米石墨烯/聚吡咯/氧化釕之製備 68
3.5 實驗儀器分析 70
3.5.1 拉曼光譜儀 (Raman Spectrometer) 70
3.5.2 傅立葉轉換紅外光光譜儀 (Fourier Transform Infrared Spectrometer，FT-IR) 70
3.5.3 場發射掃描式電子顯微鏡 (Field-emmision Scanning Electron Microscopy，FE-SEM) 71
3.5.4 高解析穿透式電子顯微鏡 (High-Resolution Transmission Electron Microscopy，HRTEM) 71
3.5.5 電化學分析儀(Electrochemical analysis instrument) 72
第四章 結果與討論 73
4.1 化學法製備帶狀奈米石墨烯與基本性質分析 73
4.2 改變帶狀奈米石墨烯添加量:GNR-PPy複合材料 77
4.2.1 帶狀奈米石墨烯/聚吡咯二元複合材料性質分析 77
4.2.2 帶狀奈米石墨烯/聚吡咯二元複合材料電化學性質分析 83
4.3 帶狀奈米石墨烯/聚吡咯/氧化釕性質探討及電化學特性 90
4.3.1 帶狀奈米石墨烯/聚吡咯/氧化釕之製備及其性質分析 90
4.3.2 帶狀奈米石墨烯/聚吡咯/氧化釕三元複合材料電化學性質分析 95
第五章 結論 112
第六章 參考文獻 114

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