臺灣博碩士論文加值系統

釩液流電池大多數選用高比面積、高導電和多孔結構的碳材料作為電極，然而石墨氈材料面臨電化學活性不足及可逆性較差等問題，因此需要對石墨氈表面作處理以提升電極材料之能源轉換效率。本研究以兩種活化法分成二個部份來做處理：（1）酸處理氧官能化活化法、（2）微波輔助處理氮摻雜熱處理活化法，以提升電極材料電化學活性和增加釩液流電池的電池性能。
第一部份為將石墨氈在硫酸及硝酸體積比3:1的溶液，以水熱法之最佳參數加熱至140oC持溫50分鐘，接著在氧氣氣氛下燒結，得到酸處理氧官能化石墨氈。第二部份則是將石墨氈在三聚氰胺及硝酸濃度比0.049 M的溶液下，分別測量微波加熱以120、140及160oC熱處理溫度後，得到之微波輔助處理氮摻雜石墨氈電化學活性。兩部分處理過的石墨氈皆出現了明顯的氧化還原峰，而全電池充放電曲線圖中可以發現，酸處理氧官能化的電極庫倫效率94.8%、伏特效率81.7%與能量效率77.1%，及經140oC處理之微波輔助處理氮摻雜電極庫倫效率94.9%、伏特效率85.1%與能量效率80.8%，皆高於未處理石墨氈之庫倫效率89.8%、伏特效率76.1 %與能量效率68.3 %，全電池整體效率皆獲得改善。

High surface area, high conductivity and porous structure graphite felt materials are common choice of all vanadium redox flow battery. However, graphite felt materials have serious problems of their insufficient electrochemical activity and low electrochemical reversible ability. In order to overcome those problems, this study uses (1) acid treatment activation method and (2) microwave-assisted hydrothermal method as activation methods to solve these problems.
In the first part, the graphite felt was immersed in acid solution which was mixed with 60 mL of sulfur acid and 20 mL of nitric acid, and subsequently it was transferred into a Teflon-lined autoclave reactor and was heated at 140oC. Afterwards, the graphite felt was heated at 450oC in oxygen atmosphere. In the second part, the graphite felt was immersed in 0.049 M melamine of nitric acid solution, and it was treated by microwave-assisted hydrothermal method at various temperatures of 120oC, 140oC and 160oC.
By using the acid treatment and the microwave-assisted treatment, the graphite felt electrodes show the enhanced electrochemical activity and the highly reversible redox reaction. By using acid-treatment, the coulomb efficiency, the voltage efficiency and the energy efficiency of the graphite felt can reach 94.8%, 81.7% and 77.1%, respectively. By using the microwave-assisted treatment, the graphite felt can also reach high coulomb efficiency, voltage efficiency and energy efficiency of 94.9%, 89.8% and 85.1%, respectively.

第一章 緒論 1
1-1 前言 1
1-2 釩液流電池簡介 4
第二章 實驗原理與文獻探討 10
2-1 官能化電極之原理與發展 10
2-2 電極效率之提升 11
2-2-1 酸及熱前處理之碳基電極 11
2-2-2 奈米金屬顆粒披附之碳基電極 14
2-2-3 奈米碳管複合之碳基電極 16
2-2-4 氮摻雜之碳基電極 18
2-2-5 微波處理碳基電極 25
2-3 國內學者研究 26
2-4 官能化對電極效能的影響 29
2-5 研究動機 31
2-6 研究目的 32
第三章 研究方法 33
3-1 實驗規劃 33
3-2 實驗材料及藥品 35
3-3 實驗儀器與設備 36
3-4 電極製備 37
3-4-1 酸處理氧官能化之電極 37
3-4-2 微波輔助處理氮摻雜之電極 40
3-5 電解液製備及全電池測試 42
3-6 電極穩定度測試 43
3-7 實驗儀器 44
3-7-1 管狀高溫爐系統（Thermal CVD System） 44
3-7-2 微波消化爐（Microwave Synthesis System） 45
3-8 分析儀器原理 46
3-8-1 場發射掃描式電子顯微鏡（Scanning electron microscope, SEM） 46
3-8-2 比表面積與孔洞分析儀（Surface Area and Porosity Analyzer） 47
3-8-3 穿透式電子顯微鏡（Transmission Electron Microscope） 48
3-8-4 電化學分析儀 49
3-8-5 拉曼光譜分析儀（Raman Spectrum） 51
3-8-6 X光電子能譜儀（X-ray Photoelectron Spectroscopy, XPS） 52
3-8-7 X光繞射分析儀（X ray diffraction Spectrometer, XRD） 53
3-8-8 傅立葉轉換紅外線光譜儀（FTIR Spectrometer） 55
3-8-9 接觸角儀（Contact Angle System） 58
第四章 結果與討論 59
4-1 酸處理氧官能化之電極 59
4-1-1 酸處理氧官能化電極之循環伏安法分析 60
4-1-2 SEM 分析 70
4-1-3 接觸角分析 72
4-1-4 拉曼光譜分析 73
4-1-5 XPS分析 75
4-1-6 全電池分析 77
4-1-7 穩定性分析 79
4-2 微波輔助處理氮摻雜之電極 82
4-2-1 微波輔助處理氮摻雜電極之循環伏安法分析 84
4-2-2 SEM分析及比表面積檢測 87
4-2-3 表面元素分析測試（Mapping） 88
4-2-4 電子能量損失分析儀（Electron Energy Loss Spectroscope, EELS）分析 90
4-2-5 XPS分析 91
4-2-6 拉曼光譜分析 93
4-2-7 單電池分析 94
4-2-8 穩定性測試 96
第五章 結論 98
第六章 未來展望 102
第七章 參考文獻 103 

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