臺灣博碩士論文加值系統

本研究探討氮摻雜還原石墨烯氧化物(N-doped rGO)在非對稱性的離子液體[EMI][TFSI]中的電容相關特性。我們採用Staudenmaier法將石墨烯氧化物剝離且還原，發現氮摻雜還原石墨烯氧化物的比表面積高於1100oC下未摻雜還原石墨烯氧化物。因此本論文主要探討由氮摻雜還原石墨烯氧化物組成的電容器其如何在電解質[EMI][TFSI]中使用最大的電位窗口範圍。
由白金線作為工作電極測量出離子液體[EMI][TFSI]分解電位窗口範圍為：-1.65? +2.6 V (vs. RHE)。另由循環伏安法量測出氮摻雜還原石墨烯氧化物的離子嵌入嵌出下界電位為-1.6 V，上界電位為1.2 V。當我們在電位窗口為2.0 V的電容器做充放電時，其正、負極的電位變化皆在嵌入嵌出電位範圍內，因此其正、負極的比電容值比會符合從電雙層電容範圍中掃循環伏安圖譜所得到的比電容值比。當在沒有適當的重量比例下將工作電壓設成3.8 V時，我們往往會發現負極的電位易觸及-1.65 V而導致電解質的分解，在個別電位下仔細分析得知電容器電位窗口的主要限制在負極，因此在不對稱的電位窗口中，其正、負極重量比例(M+/M-)應該小於一，我們在正、負極重量比例(M+/M-)為0.736下探討電容器的性能。

This study explores the capacity of nitrogen doped reduced graphene oxide (N-doped rGO) in the asymmetric electrolyte [EMI][TFSI]. We employ the Staudenmaier method to exfoliate and reduce the graphene oxide, and find the sample of N-doped rGO owns a surface area, higher than 1100?aC undoped rGO. Hence, the capacitor investigation focuses on how to make most of the electrochemical window of [EMI][TFSI] with N-doped rGO.
The electrochemical window of [EMI][TFSI] is measured between -1.65 and +2.6 V (vs. RHE) with platinum electrodes. Another window rarely mentioned in the literature is the intercalation window, which is -1.6 V the lower window limit and +1.2 V (vs. RHE) the upper window limit for N-doped rGO. If we charge/discharge the capacitor in the working window of 2.0 V, the positive and negative potentials vary within the intercalation window. Consequently, the electrode capacitance ratio of positive and negative electrode is near the ratio measured with cyclic voltammetry, assuming energy storage depends on double layer capacitance entirely. When we impose the 3.8 V working window without considering a proper mass balance, we often found the negative electrode exceeds -1.65 V and decomposes the electrolyte. Careful analysis of the electrode potential variations indicates the main restriction is on the negative potential, therefore, the mass ratio of positive over negative (M+/M-) ought to be less than 1 to use the lopsided potential window sufficiently. The capacitor performance of an M+/M- ratio 0.736 is investigated with details.

摘要 I
ABSTRACT III
目錄 V
圖目錄 VII
表目錄 XI
第一章 緒論 1
1.1前言 1
1.2 研究動機 4
第二章 文獻回顧與理論基礎 6
2.1 電化學電容器 6
2.2 石墨烯 8
2.2.1機械剝離法(Mechanical exfoliation) 10
2.2.2磊晶成長法(Epitaxial growth) 11
2.2.3化學氣相沉積法(Chemical Vapor Deposition;CVD) 12
2.2.4氧化石墨烯化學還原法(Reduction from Graphene Oxides) 13
2.3 氮摻雜石墨烯 15
2.4 室溫離子液體電解液(RTILS) 17
2.5 離子液體的應用 23
2.6 離子液體應用於電雙層電容器 24
第三章 實驗方法與步驟 27
3.1 實驗藥品耗材與儀器設備 27
3.1.1 電極材料 27
3.1.2 電極漿料製備 28
3.1.3 電流收集器清洗及準備工作 28
3.1.4 電極組裝 28
3.1.5 藥品耗材 29
3.1.6 電化學量測設備 29
3.2 實驗流程 31
3.2.1電極材料的製備 31
3.2.1.1石墨烯氧化物的製備 31
3.2.1.2還原石墨烯氧化物的製備 33
3.2.1.3氮摻雜還原石墨烯氧化物的製備 34
3.2.2電極漿料的製備 35
3.2.3電極片之製備 36
3.3 電極之特性分析與電容器特性分析 38
3.3.1 X光繞射晶相分析 38
3.3.2 表面結構分析-SEM 38
3.3.3 傅立葉轉換紅外線 38
3.3.4 拉曼光譜 39
3.3.5 比表面積與微孔徑分析 40
3.3.6 電化學性質分析 41
第四章 結果與討論 43
4.1 電極材料鑑定與分析 43
4.1.1電極材料之XRD分析 43
4.1.2電極材料之SEM表面型態與EDS分析 45
4.1.3電極材料之FTIR分析 48
4.1.4電極材料之Raman分析 51
4.1.5電極材料之BET分析 56
4.2 循環伏安法分析 60
4.2.1室溫離子液體之穩定電位窗口 60
4.2.2電極材料循環伏安分析 63
4.2.2.1還原石墨烯氧化物(300 oC)之循環伏安分析 65
4.2.2.2還原石墨烯氧化物(1100 oC)之循環伏安分析 70
4.2.2.3氮摻雜還原石墨烯氧化物(1100 oC-900 oC)之循環伏安分析 75
4.3 循環伏安法在不同電極材料的比電容值 80
4.4對稱式電容器充放電時各別電極之行為 83
4.3.1正負極重量比例大於一時各別電極之行為 90
4.3.2正負極重量比例小於一時各別電極之行為 94
4.5恆電流充、放電分析 103
第五章 結論 110
參考文獻 113

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