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研究生:邱奕鐙
研究生(外文):Yi-Deng Chiou
論文名稱:寬廣工作電位窗口圖案化碳微管之微型化電容器
論文名稱(外文):Miniature electrochemical capacitors of patterned carbon nanotubes with a wide working potential window
指導教授:蔡大翔
指導教授(外文):Dah-Shyang Tsai
口試委員:蔡大翔
口試日期:2012-07-24
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:185
中文關鍵詞:超高電容器奈米碳管軟性基板有機電解質膠態電解質離子液體
外文關鍵詞:UltracapacitorCarbon nanotubesFlexible substrateorganic electrolytegel electrolyteionic liquid
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本研究探討碳微管微型化超高電容器製作,並分析三種微型化超高電容器分別在在目前市面上常用的1M LiPF6,EC:DMC=1:1(v/v)有機電解液,PVdF-HFP為基質的膠態電解液,和1M TEABF4/PC離子液體之不同工作電位窗口的特性。此三種超高電容器特色為垂直陣列碳微管指叉式電極,電容器電極圖型製作是經由黃光微影蝕刻、化學氣相沉積法。梳狀電極的指梳間隔為20 μm,移轉前我們能先在表面濺鍍一層金以利電流收集,再將電極反轉並移轉至可饒式的電性膠帶上,以CNT_CNTx代表不同電容器。我們更進一步的利用循環伏安法、交流阻抗、恆電流充放電和穩定測試測量其電化學特性。
利用1M LiPF6,EC:DMC=1:1(v/v)有機電解液測量的對稱性電容器 CNT_CNTo可以被操作至寬廣的電位窗口4.0 V,由於電解液具有良好的離子移動性,因此較低等效串連電阻(ESR)(1.53 ? cm2)。結合了寬廣電位窗口與高導電率電解液使CNT_CNTo電容器具有良好的電化學表現,電流密度30 Ag-1充放電情況下,4.0 V電位窗口,CNT_CNTo電容器放電能量密度和功率密度分別為19.7 Whkg-1、57.54 kWkg-1;PVdF-HFP為基質的膠態電解質也可以操作至4.0 V,但CNT_CNTg電容器ESR值稍高(1.97 ? cm2)。雖然膠態電解液阻抗值較高,但膠態電解質具有固定且防止CNT電極之間短路的優點。電流密度30 Ag-1充放電情況下,4.0 V電位窗口,CNT_CNTg電容器放電能量密度和功率密度分別為16.5 Whkg-1、55.5 kWkg-1。1M TEABF4/PC離子液體的電壓窗口為2.8 V,相對於另外兩個電容器電位窗口較狹窄且CNT_CNTi的ESR值較高(2.45 ? cm2),因此其電容器能量與功率密度相較於前面兩種的電容器低。電流密度10 Ag-1充放電情況下,2.8 V電位窗口,CNT_CNTi電容器放電能量密度和功率密度分別為2.0 Wh kg-1、15.2 kWkg-1。
We have investigated preparation and properties of three miniaturized ultracapacitors with different working potential windows, which are governed by the commercial available electrolytes of 1M LiPF6,EC:DMC=1:1(v/v) organic electrolyte, PVdF-HFP-based gel electrolyte, and 1M TEABF4/PC ionic liquid. The three ultracapacitors are featured with interdigital electrodes of vertically aligned carbon nanotubes (CNTs), patterned and grown using the standard technologies of photolithography and chemical vapor deposition. The comb-like electrodes of 20 μm spacing, denoted as CNT_CNTx, are later sputtered with gold, inverted, and transferred to a plastic tape, which allows the capacitor be integrated with flexible electronics. We further measured the electrochemical properties using using cyclic voltammetry, impedance spectroscopy, galvanostatic charge/ discharge test, and stability test.

With the organic electrolyte of 1M LiPF6,EC:DMC=1:1(v/v), the symmetric capacitor CNT_CNTo can be operated in a wide potential window 4.0 V. And the sufficient ion conductivity of this electrolyte gives a minimum equivalent series resistance (ESR) 1.53 ? cm2. Combination of wide potential window and conductive electrolyte makes possible the best performance of CNT_CNTo. At a current density of 30 Ag-1 and a window 4.0 V, the CNT_CNTo cell discharges at a power level 57.5 kWkg-1 with energy density 19.7 Wh kg-1. The interdigital CNT electrodes in the PVdF-HFP-based gel electrolyte can also be operated in the potential widow 4.0 V, but the ESR value of this capacitor CNT_CNTg is slightly higher, 1.97 ? cm2. Although the resistance of gel electrolyte is slightly larger, but the gel has the advantage of preventing the probable short circuiting between two opposing CNT electrodes. The cell CNT_CNTg, at current density of 30 Ag-1 and a window 4.0V, discharges at a power level 55.5 kWkg-1 with energy density 16.5 Wh kg-1. The potential window of 1M TEABF4/PC ionic liquid of CNT_CNTi is 2.8 V, which is relatively narrow compared with the other two capacitors. And the ESR value of CNT_CNTi is also higher, 2.45 ? cm2. Hence its capacitor power and energy densities are inferior to those of the previous two cells. The CNT_CNTi cell, at current density 10 A g-1 and a window 2.8 V, discharges at a power level 15.2 kWkg-1 with energy density 2.0 Wh kg-1.
摘要 I
Abstract III
目錄 V
第一章 緒論 1
第二章 文獻回顧與理論基礎 4
2.1 能量儲存裝置概述 4
2.1.1 電容器之分類 7
2.2 超高電容器 (Ultracapacitor) 10
2.2.1 超高電容器之電極材料 11
鋰離子電解液之發展與應用 13
2.3.1 有機溶劑 13
2.3.2 鋰鹽 16
2.3.3 膠態高分子電解質 19
2.3.4 碳材/鋰離子作用與預鋰化(pre-lithiated) 22
2.3.5 電雙層電容器與鋰離子電容器(LICs) 28
2.4 離子液體電解質(RTILs) 32
有機電解液下之超級電容器 39
2.3.1 高電壓窗口電雙層電容器之研究及探討 39
2.3.2 高能量密度的混成電容器 43
2.3.3 離子液體在電雙層電容器的應用 46
第三章 實驗方法及步驟 49
3.2 電極材料之製備 53
3.2.1 基材之清洗 53
3.2.2 黃光微影製程 (Photolithography) 53
3.2.3 CVD法成長奈米碳管 56
3.2.4 電極之轉印 58
3.2.5 試片之封裝 61
3.2.6 電容器元件量測前步驟 62
3.3 PVdF-HFP為基質的膠態電解質製備流程 64
3.3 電極材料之特性分析與電性分析 66
3.3.1 表面結構分析 66
3.3.2 電化學性質分析 66
第四章 結果與討論 69
4.1 奈米碳管電極形貌 69
4.2 鋰離子有機電解液之指叉式電容器分析 76
4.2.1 鋰離子有機電解液之穩定電壓窗口分析 76
4.2.2 電極循環伏安分析 78
4.2.2.1 電極之穩定電壓窗口循環伏安分析 79
4.2.2.2 電極循環伏安分析 82
4.2.3 恆電流充、放電分析 89
4.2.3.1 對稱式電容器恆電流充、放電分析 90
4.2.3.2 對稱式電容器充放時個別電極之行為 99
4.2.3 交流阻抗分析 105
4.2.4 充放循環穩定性分析 108
4.4 PVdF-HFP膠態電解液之指叉式電容器分析 116
4.3.1 電極循環伏安分析 116
4.3.1.1 電極之穩定電壓窗口循環分析 117
4.4.1.2 電極循環伏安分析 120
4.3.2 恆電流充、放電分析 127
4.3.2.1 對稱式電容器恆電流充、放電分析 127
4.3.3 交流阻抗分析 138
4.3.4 充放循環穩定性分析 141
4.4 不同電解質之對稱性電容器比較 149
4.5 四乙基四氟硼酸銨離子液體之指叉式電容器分析 156
4.5.1 四乙基四氟硼酸銨離子液體之穩定電壓窗口分析 156
4.5.2 電極循環伏安分析 158
4.5.2.1 電極之穩定電壓窗口循環伏安分析 158
4.5.2.2 電極循環伏安分析 161
4.5.3 恆電流充、放電分析 165
4.5.3.1 對稱式電容器恆電流充、放電分析 165
4.5.4 交流阻抗分析 172
4.5.5 充放循環穩定性分析 175
第五章 結論 178
參考文獻 182
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