臺灣博碩士論文加值系統

本研究利用陽極沉積法製備氧化物電極，並依不同錳含量 (0、25、50、75、100 at%) 混合硫酸氧釩與醋酸錳溶液，以定電位0.8、1.0、1.6及1.8 V進行陽極沉積於石墨基材，並對此薄膜電極進行XRD、SEM、TEM、EDS與電化學特性之分析，探討錳釩複合後對於氧化物薄膜電極之電容特性的影響。根據研究結果顯示，沉積電位改變會造成平衡相之改變，且隨著沉積電位改變，薄膜之結晶性、表面形貌、組成與電容特性亦會隨之改變。實驗結果發現利用陽極沉積法製備氧化釩電極，顆粒大小約為10 nm，隨著沉積電位增加，其表面結構趨於緻密，導致電解液不易滲入內部反應，因此最高電容值僅121 F/g；而電容穩定率僅75%，研判為CV過程中反覆氧化還原反應，使得薄膜趨於平坦，提供氧化還原反應面積下降所造成。
而氧化錳電極方面，隨著沉積電位的增加，結構尺寸無明顯改變，大約分布在20~30 nm。而在沉積電位1.0 V時主要為MnO2非晶相，其表面呈現鬆散的多孔結構，電解液容易滲入電極發生反應，最高電容值可達245 F/g。而與釩複合後，雖然電容值沒有提高，最高電容值僅在錳：釩 = 1：3、沉積電位1.0 V時為145 F/g，但是電容穩定度卻相當優異，經1200圈CV測試後仍沒有衰退的現象。顯示錳釩複合後，雖然擬電容特性欠佳，但擁有極佳的電化學穩定性。
關鍵字：超級電容器、陽極沉積法、錳氧化物、釩氧化物、電化學穩定性

In this research, manganese oxide and vanadium oxide electrodes are manufactured by anodic deposition process. Various ratios of manganese and vanadium were mixed with vanadyl sulfate and manganese acetate solution, then deposited onto graphite substrate in aqueous solution at different potentials. Besides, XRD, SEM, TEM, EDS were conducted to analyze the electrochemical characteristics of composite films. Meanwhile, the influences of the combination of Mn- and V-oxides on the capacitance characteristics of film electrode are being discussed.
According to the experimental results, the deposition potential resulted in the alteration of the equilibrium phase, as well as the crystallinity, surface morphology, composition and capacitance characteristics of the film. The microstructural observation shows that the particle size of the anodic-deposited vanadium oxide electrodes is about 10 nm. The surface structure tends to become denser with the increase of deposition potential, resulting in the difficulty of electrolyte penetration reaction. Therefore, the highest capacitance value is merely 121 F/g and the capacitive stability remains 75%. This is likely due to the repetitive redox reaction during CV process causing the flattened surface of the film, the redox reaction area is thus declined.
In terms of manganese oxide electrode, no significant change is observed in the structural size with the increase of deposition potential. The crystallite size distribution is about 20-30 nm. At the deposition potential of 1.0 V, the majority phase is amorphous MnO2, showing a loose porous structure on the film surface. The electrolyte can easily penetrate and cause the reaction with the electrodes. The maximum capacitance value can be as high as 245 F/g.
In the wake of the compound with vanadium, the maximum capacitance value of the composite film is only 145 F/g at a Mn/V ratio of 1/3 and a deposition potential of 1.0 V. Though the capacitance value is not increased, the capacitance stability is quite excellent. There is no recession phenomenon after 1200-cycle test. The experiment data suggest that instead of showing relatively good capacitance characteristics, the Mn/V oxide compound exhibits a tremendous electrochemical stability.
Key－words: Supercapacitor; Anodic deposition; Manganese oxide; Vanadium oxide; Electrochemical stability

第一章、前言 1
第二章、文獻回顧 4
2.1 電化學電容器的種類 4
2.1.1 電雙層電容器 4
2.1.2 擬電容器 5
2.2超級電容器之電極材料 9
2.3氧化物電容器電極製程 15
2.3.1淬火法(Quenching)： 15
2.3.2噴霧熱解法(Spray Pyrolysis)： 16
2.3.3溶膠凝膠法(Solgel)： 17
2.3.4離子交換層析法(Ion exchange chromatography) 19
2.3.5水熱法(Hydrothermal Method)： 19
2.3.6球磨法(Ball milling) 20
2.3.7陽極沉積法(Anodic Deposition)： 21
2.4擬電容特性之評估方式 23
2.5電解質對儲能機構之影響 24





第三章、實驗方法 36
3.1 薄膜電極製備 37
3.1.1石墨電極基材前處理 37
3.1.2陽極沉積氧化物薄膜 37
3.2薄膜電極材料分析 40
3.2.1結構分析 40
3.2.2表面形貌與元素含量分析 40
3.3電化學特性之分析 41
3.3.1線性掃描伏安法 41
3.3.2循環伏安法 41
3.3.3計時電位法 43
第四章、結果與討論 45
4.1 陽極沉積氧化物薄膜電極 45
4.1.1 線性掃描伏安 45
4.1.2 定電位定庫倫下製備氧化物薄膜電極 51
4.2 氧化物薄膜電極之性質檢測 57
4.2.1 晶體結構分析 57
4.2.2 能量散射光譜儀成分分析 60
4.2.3 SEM表面型態分析 62
4.2.4 TEM顯微結構觀察 69
4.3氧化物薄膜電極之電容特性檢測 72
4.3.1 氧化物薄膜電極之循環伏安分析 72
4.3.2循環計時定電流充放電分析 79
4.3.3 氧化物薄膜電極之循環壽命檢測 85
4.4 XPS之化學組成分析 90
第五章、結論 92
參考文獻 93

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