臺灣博碩士論文加值系統

能量與功率值為工作電壓的平方比是眾所皆知的事情，所以工作窗口的大小極大影響電容器的儲存能力。而我們將證明合適的窗口大小不再一直是影響儲存能量的唯一原因，本次研究，我們探討離子液體[EMIM][TFSI]嵌入奈米碳管對於指叉式微型電容器的能量儲存影響。
原則上，可操作電位窗口受到電解液分解限制，離子液體[EMIM][TFSI]以白金片當電極測量可用電為範圍：-1.8 ? 2.6 V (vs. RHE)。然而，一維奈米碳管是層狀結構，奈米碳管經受陽離子[EMIM]和陰離子[TFSI] 的嵌入，導致剝離或是管破裂，嵌入的電位範圍小於離子液體[EMIM][TFSI]分解電位。我們用循環伏安探討上界與下界電位，且以拉曼光譜解析出嵌入限制電位，嵌入的上界電位決定在1.5和1.7 V (vs. RHE)之間，下界電位決定於-1.6 和-1.7 V (vs. RHE)之間，在循環穩定分析進一步驗證嵌入的上界與下界電位的影響。
當操作電位窗口2.0 V，微型電容器充放電10000圈後的保留率約100 %，代表有很好的循環穩定性，且庫倫效率也很快提升且穩定於100 %。然而，當操作電壓設在2.8 V或3.8 V，電容器的循環穩定逐漸下降，因為電極的電位已達到離子嵌入的電位境界，且奈米碳管有部分破裂。當電容器電壓設在2.8 V，正極的電位達到嵌入的上界內，且隨著圈數增加比電容值逐漸下降，在電流密度8 A g-1充放電10000圈後，保留率為90.8 % 。另外一方面，當電容器窗口設在3.8 V，而電流密度30 A g-1充放電10000圈後，保留率為77.5 %，由於循環測定中正負極都受到並非只有正極，造成低保留率。因此，電化學電容器的循環穩定性，主要是受電壓窗口，少數影響來自於電流密度，因此兩個因素能改變的正負電極的電位界限。

It is well-known that the energy and power values of an ultracapacitor are proportional to the square of its working voltage window. The size of working window influences the storage capability tremendously. As we shall demonstrate, the answer of proper window size is not a straightforward one. In this work, we investigate the influences of ionic liquid [EMIM][TFSI] intercalation in carbon nanotubes (CNT) on energy storage of a miniature electrochemical capacitor with interdigitated electrodes.
In principle, the workable potential window is governed by decomposition potential limits of the electrolyte. For ionic liquid [EMIM][TFSI], the measured potential range with a platinum working electrode is -1.8 ? 2.6 V (vs. RHE). Nevertheless, one-dimensional CNT is a layer structure material. [EMIM] cation and [TFSI] anion may undergo intercalation into CNT, resulting in exfoliation or tube rupture. The potential range of intercalation is narrower than the decomposition limits of ionic liquid [EMIM][TFSI]. We explore the potential upper and lower limits with cyclic voltammetry and resolve the intercalation limits with Raman spectroscopy. The upper potential limit of intercalation is determined between 1.5 and 1.7 V (vs. RHE), while the lower potential limit is decided between -1.6 and -1.7 V (vs. RHE). The upper and lower potential limits for intercalation are further validated in the cycle stability analysis.
When operated in the potential window 2.0 V, the miniature ultracapacitor was charged and discharged with excellent cycle stability, typified by a retention ratio ??00% after 104 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. However, when the applied voltage is set at 2.8 V or 3.8 V, the cycle stability of capacitor gradually declines, because the electrode potential has reached the potential limits of ion intercalation and ruptured a fraction of CNT structure. When the capacitor window is set 2.8 V, the positive electrode potential can reach the intercalation upper limit, and the capacitance value gradually decreases with increasing cycle number. The retention ratio, after 104 cycles, is 90.8% at current density 8 A g-1. On the other hand, when the capacitor window is set 3.8 V, the capacitor energy is cycled at current density 30 A g-1, the retention ratio is only 77.5% after 104 cycles. The lower retention ration results from both of the electrodes, not just positive electrode, which experienced intercalation during energy cycling. Hence the cycle stability of this electrochemical capacitor is mainly affected by the voltage window, less influenced by the current density, since both factors can change the potential boundaries of positive and negative electrodes.

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 3
第二章 文獻討論與理論基礎 5
2.1 能量儲存裝置概述 5
2.2 超高電容器 8
2.3 電極材料之奈米碳管 9
2.4 室溫離子液體電解液(RTILs) 12
2.5 離子液體應用 18
2.5.1 離子液體應用於鋰離子電池 18
2.5.2 離子液體應用於電雙層電容器 21
2.6 超高電容器之儲能及功率 24
第三章 實驗方法與步驟 26
3.1 實驗藥品耗材與儀器設備 26
3.1.1. 基材清洗與準備工作 26
3.1.2. 黃金濺鍍(Au)金屬層 26
3.1.3. 指叉式電極圖型微影/蝕刻(Photolithography)和鐵/鋁觸媒層(3/5 nm)圖案化 27
3.1.4. 沉積鐵/鋁觸媒層(3/5 Nanometer)和成長碳微管 27
3.1.5. 電容器封裝 27
3.1.6. 藥品耗材 28
3.1.7. 電化學量測設備 28
3.2 電極材料之製備 30
3.2.1 基材之清洗 30
3.2.2 黃光微影製程 (Photolithography) 30
3.2.3 CVD法成長奈米碳管 32
3.2.4 電極之轉印 34
3.2.5 試片之封裝 36
3.2.6 電容器元件量測前步驟 38
3.3 電極之特性分析與電容器特性分析 39
3.3.1 表面結構分析 39
3.3.2 電化學性質分析 39
3.3.3 拉曼光譜 40
3.3.4 傅立葉轉換紅外線 41
第四章 結果與討論 43
4.1 圖案化奈米碳管電極形貌 43
4.1.1 奈米碳管陣列形貌 43
4.1.2 反轉並移轉後的碳管陣列 46
4.2 循環伏安分析 49
4.2.1 室溫離子液體之穩定電位窗口 49
4.2.2 梳狀電極循環伏安分析 51
4.2.2.1 奈米碳管電極之循環伏安圖譜 52
4.2.2.2 電極之上界電位與下界電位循環伏安分析 56
4.3 室溫離子液體與指叉式電容器之定性分析 61
4.3.1離子液體之拉曼光譜與傅立葉轉換紅外線分析 61
4.3.1.1 離子液體之傅立葉轉換紅外線分析 61
4.3.1.2 離子液體之拉曼光譜分析 62
4.3.2 奈米碳管之拉曼分析 64
4.3.2.1 未經循環伏安之奈米碳管拉曼光譜分析 65
4.3.2.2 經歷循環伏安之奈米碳管拉曼光譜分析 67
4.3.2.3 經歷循環伏安的奈米碳管拉曼光譜之正規化拉曼光譜分析 78
4.4 恆電流充、放電分析 82
4.4.1 對稱式電容器恆電流充、放電分析 83
4.4.2 對稱式電容器充放電時各別電極之行為 93
4.4.3 充放循環穩定性分析 100
4.4.3.1 充放循環穩定性之保留率與庫倫效率分析 100
4.4.3.2 充放循環穩定性分析之能量效率分析 118
4.5 交流阻抗分析 122
第五章 結論 125
參考文獻 128

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