臺灣博碩士論文加值系統

本研究以循環伏安法製備含水釕氧化物電極於超高電容器之應用。利用循環伏安法的方式將釕氧化物沉積於多孔鎳基材上， 在製程中的釕鍍液pH值(pH=3.2)與循環伏安沉積電位(-0.6 ~ 0.15 VSCE)對於所製備之含水釕氧化物電極之擬電容特性有重要的影響。

在水溶液中以電化學合金去合金法製備多孔鎳電極材料並將其應用於釕氧化物電極，比較此具有高表面積之多孔氧化釕電極與平板氧化釕電極在硫酸水溶液中之擬電容特性，發現氧化釕電極表面積的提升有助於電容性能的提升，在掃描速率為5 mV/s下，平板氧化釕電極的比電容值為131 F/g，而多孔氧化釕電極的比電容值為352 F/g，增加率達2.68倍。另外由SEM圖觀察氧化釕電極之表面形貌，發現沉積於多孔鎳上之釕氧化物相較沉積於平板鎳更加緻密。

以製備之氧化釕電極於硫酸水溶液、含質子離子液體P-TFA與不含質子離子液體EMI-BF4中進行擬電容行為測試，結果顯示，本研究製備之氧化釕電極在含質子之電解液(硫酸水溶液、離子液體P-TFA)中具有擬電容性質，在不含質子之電解液(離子液體EMI-BF4)中也具有擬電容性質。多孔氧化釕電極於水溶液之電容性能以及在高掃描速率充放電下之維持率均有不錯的表現。
而以離子液體為電解液之下，多孔氧化釕電極於不含質子離子液體(EMI-BF4)中之電容性能優異於含質子離子液體(P-TFA)。在掃瞄速率為5 mV/s下，電解液為EMI-BF4之比電容值為311 F/g，電解液為P-TFA之比電容值為220 F/g。EMI-BF4之工作電位範圍大於P-TFA之工作電位，因此以EMI-BF4作為電解液可提供較高之能量密度及功率密度。在經過長時間之循環伏安充放電測試後，EMI-BF4與P-TFA之比電容值維持率皆有不錯的表現，顯示多孔氧化釕電極在不含質子離子液體EMI-BF4及在含質子離子液體P-TFA中具有良好的電化學穩定度，適合作為超高電容器之電解液。

In this study, hydrous ruthenium oxide electrode has been deposited on porous Ni substrate using a cyclic voltammetry method. Effects of the pH value of the plating solution and deposited sweep potential have important factors for prepared the ruthenium oxide electrodes. Further, compared to ruthenium oxide deposited on flat and porous Ni substrates, respectively. The experimental results indicated that specific capacitance of the ruthenium oxide deposited on porous Ni more than on flat Ni substrate. The specific capacitance, measured using cyclic voltammetry at a sweep rate of 5 mV/s, was 352 F/g in H2SO4 aqueous solution.
Moreover, the electrochemical behavior of CV deposited ruthenium oxides was studied in the portic 2-methylpyridine–trifluoroacetic acid (P-TFA) and the aportic 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4) ionic liquids (ILs) electrolyte. The experimental data shows that ideal pseudo-capacitive behavior of the oxide electrode in the protic P-TFA IL was observed; the specific capacitance was 220 F/g at CV scan rate 5 mV/s. In addition, it was first found that ideal pseudo-capacitive performance of the ruthenium oxide in aprotic EMI-BF4 IL, the specific capacitance was 311 F/g evaluated using cycle voltammetry; in a potential window of ~ 1.9 V. It was found that EMI-BF4 electrolyte can afford high energy density and high power density compared with aqueous solution. The experimental results also show the excellent electrochemical stability of the ruthenium oxide in ILs without involving protons electrolyte. Both of the P-TFA and EMI-BF4 IL are suitable electrolytes for ruthenium oxide super-capacitor. Moreover, the nano-structured electrode as an application of super-capacitors can improve not only the specific energy density but also the specific power density.

摘要 I
Abstract III
誌謝 V
總目錄 VII
表目錄 X
圖目錄 XI
第一章 緒論 1
第二章 背景資料與文獻回顧 3
2-1儲能元件簡介 3
2-2超高電容器的沿革與應用 5
2-3超高電容器的分類 7
2-4釕氧化物的製備方式 9
2-5 去合金化的原理 13
2-6銅鎳合金及其去合金原理 15
2-7電解液對於超高電容器的影響 16
2-8離子液體的性質 19
2-9超高電容器電容特性之測定 22
第三章 實驗方法與步驟 35
3-1 實驗儀器設備 35
3-2 電極製備 37
3-2-1 多孔洞鎳電極之製備 37
3-2-2 多孔氧化釕電極之製備 38
3-2-3 平板氧化釕電極之製備 38
3-2-4 氧化釕電極之熱處理 39
3-3 氧化釕電極之材料特性分析 39
3-3-1 表面形貌觀察 39
3-3-2 結晶結構分析 39
3-3-3化合狀態之量測 40
3-4離子液體的分子結構式 41
3-5 氧化釕電極之電化學特性評估 42
3-5-1 循環伏安曲線量測 42
3-5-2 計時電位曲線量測 42
第四章 實驗結果與討論 44
4-1 多孔鎳電極、平板氧化釕電極及多孔氧化釕電極之製備方式與原理 44
4-1-1多孔鎳的製備 44
4-1-2氧化釕電極的製備 45
4-1-3氧化釕電極的表面形貌 47
4-1-4氧化釕電極之結晶結構與化和狀態 48
4-2 多孔氧化釕與平板氧化釕電極於水溶液之擬電容特性 57
4-3 多孔氧化釕電極與平板氧化釕電極於離子液體中之擬電容特性 64
4-3-1 氧化釕電極於含質子離子液體P-TFA之電化學特性 65
4-3-2 氧化釕電極於不含質子離子液體EMI-BF4 (1-Ethyl-3-Methylimidazolium tetrafluoroborate)之電化學特性 77
4-4 多孔氧化釕電極於不同電解液之擬電容特性比較 86
第五章 結論 94
參考文獻 98

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