臺灣博碩士論文加值系統

本研究主要是利用熱分解法和溶膠凝膠法來製備多成分金屬氧化物，應用於電化學電容器電極上，以供應未來3C產業及電動汽機車之發展所需的高性能儲能元件。本研究將以提升能量密度為主軸，並藉由循環伏安法探討其電化學特性；透過X-ray 繞射儀、高解析度穿透電子顯微鏡及奈米雷射粒徑分佈儀進行材料微結構分析；利用掃瞄式電子顯微鏡觀察複合電極的表面型態。實驗所得之結果分述如下:

在第一部份以熱分解法製備Ru(1-X)Sn(X)‧Oy複合電極系統中，於Ru0.3 Sn0.7‧Oy複合電極中我們得到最大之以每克二氧化釕為基準的比電容（CRuO2）為490 F/g，透過SEM及XRD實驗結果顯示，在此比例下將得到高表面積之形態及介於晶態與非晶態的結構，兩者都間接地增加了釕氧化物的利用率。但此電容值比起近年的文獻值仍過於偏低。

為了改善上述比電容不佳的問題，故在第二部份改用溶膠凝膠法來製備具奈米級的Ru(0.3)Sn(0.7-X)V(X)‧Oy複合電極，藉導入釩氧化物來增加其釕氧化物之分散性及抑制其結晶性。結果顯示於Ru(0.3) Sn(0.1) V(0.6)‧Oy(15wt％,煅燒350℃,1hr)+Graphite(15wt％)+Carbon(55wt％)+PTFE(15wt％)/SS之複合電極，並經150℃於6hr熱處理下，得到最適化之比電容(CRuO2)為3162 F/g (20 mV/s)，為目前文獻中最高值之兩倍。並且在不同pH值電解液的測試下，展現出相當高的穩定性，經101 圈皆能維持在原電容值之81％以上。

The multi-component metal oxides were prepared by thermal decomposition and sol-gel methods in this study. It could be used on electrodes of electrochemical capacitor, to supply the high performance energy sources for 3C industry and electric vehicles. The study was focusing on increase energy density. The electrochemical characteristics was studied by cyclic voltammetry. The X-ray diffraction, high-resolution transmission electron microscope and particle size analyzer tests were applied to investigate the crystalline behavior and particle size of the multi-component metal oxides. In this study, morphology of composite electrodes were investigated by scanning electron microscopy. The result of the experiments are as following：
For the first part, the Ru(1-X)Sn(X)‧Oy composite electrodes were prepared by thermal decomposition. The maximum specific capacitance of RuO2 (CRuO2), 490 F/g, was obtained from an Ru0.3Sn0.7‧Oy composite electrode. Through the lab test result of SEM and XRD under this ratio, it showed up an enlarge surface area and their structures were between the crystalline and the amorphous, both would increase the utilization of ruthenium oxides. However, this capacitance value ware lower than recent studies.
To improve the problem of specific capacitance mentioned above. We used sol-gel methods to prepare the nanometer Ru(0.3)Sn(0.7-X)V(X)‧Oy composite electrodes for the second part. Then we added vanadium oxides to increase ruthenium oxide dispersion and then decreased its crystallization. The optimized specific capacitance of RuO2, 3162 F/g (measured at 20 mV/s), was obtained from an Ru0.3Sn0.1 V0.6‧Oy (15 wt％ ,calcinations at 350℃ for 1 hr) + graphite (15 wt％) + carbon (55 wt％) + PTFE (15 wt％)/SS composite electrode via thermal treatment at 150℃ for 6 hr. This capacitance value were more than twice of the best studies paper. Through different test of the pH value of electrolytes, it shows a high stability. Repeating this test for 101 times , it still maintained more than 81％ of original capacitance.

中文摘要………………………………………………………………… I
Abstract………………………………………………………………… II
致謝……………………………………………………………………… IV
總目錄……………………………………………………………… V
表目錄……………………………………………………………… IX
圖目錄……………………………………………………………… X



第一章 緒論………………………………………………………… 1

第二章 理論與文獻回顧…………………………………………… 2
2-1電化學電容器之簡介…………………………………………………
2
2-2電化學電容器之研革………………………………………………… 6
2-3化學電容器之儲電原理及機構……………………………………… 6
2-3.1電雙層電容器………………………………………………… 7
2-3.2偽電容電容器………………………………………………… 7
2-4電極材料……………………………………………………………… 7
2-4.1碳系材料……………………………………………………… 9
2-4.2導電性高分子………………………………………………… 11
2-4.3金屬氧化物…………………………………………………… 14
2-5影響金屬氧化物電極儲電特性之因素……………………………… 23
2-5.1金屬氧化物之結晶性………………………………………… 23
2-5.2比表面積……………………………………………………… 23
2-5.3集電板與活性物質之介面電阻……………………………… 24
2-6電解質………………………………………………………………… 24
2-7研究動機及目的……………………………………………………… 26


第三章 實驗方法與步驟…………………………………………… 30
3-1以熱分解法製備Ru(1-X)Sn(X)‧Oy複合電極…………………………… 30
3-1.1電極基材之前處理…………………………………………… 30
3-1.2 Ru(1-X)Sn(X)‧Oy複合電極之製備……………………………… 30
3-2以溶膠凝膠法製備Ru(0.3)Sn(0.7-X)V(X)‧Oy複合電極………………… 30
3-2.1電極基材之前處理…………………………………………… 30
3-2.2製備Ru(0.3)Sn(0.7-X)V(X)‧Oy活性材料之步驟………………… 33
3-2.3 Ru(0.3)Sn(0.7-X)V(X)‧Oy複合電極之製備……………………… 33
3-3材料物性之分析……………………………………………………… 33
3-3.1 X光繞射（X-Ray Diffraction）分析………………………… 33
3-3.2掃描式電子顯微鏡（Scanning Electron Microscope）………… 37
3-3.3穿透式電子顯微鏡（Transmission Electron Microscope）…… 37
3-3.4比表面積之分析……………………………………………… 37
3-3.5奈米粒徑分析儀（Particle size analyzer）…………………… 37
3-3.6熱重分析儀 （Thermogravimetric analysis）………………… 37
3-3.7示差掃描熱分析儀（Differential Scanning Calorimetry）… 37
3-3.8其他儀器……………………………………………………… 37
3-4電化學分析…………………………………………………………… 38
3-4.1循環伏安法（Cyclic Voltammetry）之分析…………………… 38
3-4.2穩定性之分析………………………………………………… 38
3-5實驗藥品與使用之儀器……………………………………………… 40

第四章 以熱分解法製備Ru(X)Sn(1-X)‧Oy複合電極……………… 41
4-1前言…………………………………………………………………… 41
4-2最佳混合金屬氧化物比例之探討…………………………………… 41
4-2.1材料分析……………………………………………………… 41
4-2.2複合電極之表面型態………………………………………… 41
4-2.3不同混合金屬氧化物比例下複合電極之電容行為………… 42
4-2.4可逆性之分析………………………………………………… 49
4-2.5複合電極之老化測試………………………………………… 49
4-3結論…………………………………………………………………… 52

第五章 以溶膠凝膠法製備Ru(0.3)Sn(0.7-X)V(X)‧Oy複合電極…… 53
5-1前言…………………………………………………………………… 53
5-2 最佳pH值之探討…………………………………………………… 52
5-3最佳混合金屬氧化物比例之探討…………………………………… 54
5-3.1材料分析……………………………………………………… 54
5-3.2純石墨電極之電容行為……………………………………… 59
5-3.3不同混合金屬氧化物比例下複合電極之電容行為………… 59
5-3.4複合電極之老化測試………………………………………… 60
5-3.5複合電極之表面型態………………………………………… 66
5-4煅燒溫度對Ru0.3Sn0.1V0.6．Oy材料之影響…………………………… 69
5-4.1材料分析……………………………………………………… 69
5-4.2不同煅燒溫度下複合電極之電容行為……………………… 70
5-4.3複合電極之老化測試………………………………………… 70
5-4.4複合電極之表面型態………………………………………… 70
5-4.5 Ru2VO6固體化合物之探討…………………………………… 83
5-5石墨添加量之探討…………………………………………………… 85
5-5.1不同石墨添加量對複合電極電容行為之影響……………… 85
5-5.2複合電極之老化測試………………………………………… 85
5-5.3可逆性之分析………………………………………………… 85
5-5.4複合電極之表面型態………………………………………… 86
5-5.5阻抗分析……………………………………………………… 86
5-6熱處理溫度之探討…………………………………………………… 97
5-6.1熱處理溫度對粉體結構之影響……………………………… 97
5-6.2不同熱處理溫度對複合電極電容行為之影響……………… 97
5-6.3複合電極之老化測試………………………………………… 97
5-6.4熱處理對擴散效應之影響…………………………………… 98
5-6.5可逆性之分析………………………………………………… 98
5-6.6複合電極之表面型態………………………………………… 98
5-7活性碳對複合電極之影響…………………………………………… 109
5-7.1純活性碳電極之電容行為…………………………………… 109
5-7.2材料分析……………………………………………………… 109
5-7.3複合電極之老化測試及可逆性分析………………………… 109
5-7.4阻抗分析……………………………………………………… 109
5-7.5複合電極之表面型態………………………………………… 110
5-8石墨/活性碳對複合電極之影響……………………………………… 120
5-8.1不同石墨/活性碳比例添加量對複合電極電容行為之影響… 120
5-8.2複合電極之老化測試………………………………………… 120
5-8.3可逆性之分析………………………………………………… 120
5-8.4複合電極之表面型態及元素分佈…………………………… 121
5-9複合電極之應用性…………………………………………………… 131
5-9.1不同電解液對複合電極電容行為之影響…………………… 131
5-9.2老化測試……………………………………………………… 131
5-9.3可逆性之分析………………………………………………… 131
5-10結論…………………………………………………………………… 137

第六章 總結………………………………………………………… 138

參考文獻…………………………………………………………… 140

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