臺灣博碩士論文加值系統

超級電容是一種利用高比表面積快速將電力儲存之裝置，應用於車用電子、大型儲能建物以及太空設備上，而錳氧化物(MO)為目前常被用來作為超級電容電極之研究。但由於錳系金屬氧化物具有較差之電子導電度與比表面積，因此在本研究企圖先將碳黑(CB)置於H2O2環境中使表面改質而富含OH-官能基，再將Mn(NO3)2加入並用NH4OH調控pH值使四氧化三錳直接沉積析出於碳黑上，企圖強化四氧化三錳與碳黑間之鍵結，並增加其導電度或比表面積。本實驗藉由改變Mn(NO3)2濃度及H2O2濃度，透過場發掃描式電子顯微鏡(FE-SEM)、高解析穿透式電子顯微鏡(HRTEM)及BET測試仔細觀察合成之Mn3O4/CB複材之形貌、成分分佈與比表面積之改變，比對循環伏安圖，我們發現最佳超級電容特性之合成產物參數為0.05M Mn(NO3)2及75 wt%H2O2所製備者，其比電容值為358.8 F/g。而此最佳電容表現與Mn3O4薄膜均勻披覆於CB而表現最大之比表面積100 m2/g息息相關。

摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 vii
第一章 介紹 1
1.1. 超級電容 1
1.1.1. 電雙層電容 3
1.1.2. 擬電容 7
1.2. 研究動機與目的 9
第二章 實驗方法與步驟 10
2.1. 實驗使用之材料 10
2.2. 實驗流程 11
2.3. 製備Mn3O4/SMCB之複合電極材料 13
2.4. 材料特性分析 13
2.4.1. 傅立葉轉換紅外光譜儀 (Fourier transform infrared spectroscopy, FTIR) 13
2.4.2. X光繞射儀 (X-ray diffraction analyzer, XRD) 13
2.4.3. 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscopy, FESEM) 14
2.4.4. 場發射穿透式電子顯微鏡(Field Emission Transmission Electron Microscopy, FETEM) 14
2.4.5. X射線光電子能譜儀(X-ray Photoelectron Spectroscopy, XPS) 14
2.4.6 氣體吸附BET比表面積及微孔徑分析儀 (BET) 14
2.5 電極製備 15
2.6 超級電容電極元件之量測 15
第三章 結果與討論 17
3.1. 傅立葉轉換紅外光譜儀 (Fourier transform infrared spectroscopy, FTIR)分析 17
3.2. XRD分析 18
3.3. SEM分析 20
3.4. TEM分析 22
3.5 比表面積與孔徑分析 32
3.6 XPS分析 35
3.7. 超級電容特性測試 37
第四章 結論 44
參考文獻 45

1.A. Burke, “Ultracapacitors: why, how, and where is the technology”, J. Power Sources, 91 (2000) 37-50.
2.A. Burke, Int .J. Energ. “Ultracapacitor technologies and application in hybrid and electric vehicle” Res, 34 (2010) 133-151.
3.E. Frackowiak and F. Beguin, ”Carbon materials for the electrochemical storage of energy in capacitors”, Carbon N.Y, 39 (2001) 937-950.
4.A. G. Pandolfo and A. F. Hollenkamp, “Carbon properties and their role in supercapacitors”, J. Power Sources, 157 (2006) 11-27.
5.E. Frackowiak, “Carbon materials for supercapacitor application”, Phys. Chem. Chem. Phys, 9 (2007) 1774-1785.
6.V. Subramanian, H. W. Zhu and B. Q. Wei, “Synthesis and electrochemical characterizations of amorphous manganese oxide and single walled carbon nanotube composites as supercapacitor electrode materials”, Electrochem. Commun., 8 (2006) 827-832.
7.E. Raymundo-Pinero, V. Khomenko, E. Frackowiak and F. Beguin, “Manganese dioxide core–shell nanowires in situ grown on carbon spheres for supercapacitor application”, J. Electrochem. Soc., 152 (2005) 229-235.
8.L.Feng, Y. Zhu, H. Ding, and C. Ni, “Recent progress in nickel baesd materials for high performance pseudocpapcitor electrodes”, J. Power Sources, 267 (2014) 430-444.
9.L. L. Zhang, and X. S. Zhao, “Carbon-based materials as supercapacitor electrodes”, Chem. Soc. Rev., 38 (2009) 2520-2531.
10.Y. Zhang, H. Faeng, X. Wu, L. Wang, A. Zhang, T. Xia, H. Dong, X. Li, and L. Zhang, “Progress of electrochemical capacitor electrode materials: A review”, Int. J. Hydrogen Energy, 34 (2009) 4889-4899.
11.R. Kötz, and M. Carlen, “principles and applications of electrochemical capacitors”, Electrochim. Acta, 45 (2000) 2483-2498.
12.M. Endo, T. Maeda, T. Takeda, Y. J. Kim, K. Koshiba, H. Hara, and M. S. Dresselhaus, “Capacitance and pore-size distribution in aqueous and nonaqueous electrolytes using activated carbon electrodes”, J. Electrochem. Soc., 148(8) (2001) A910-A914.
13.J. Huang, B. G. Sumpter, and V. Meunier, “A universal model for nanoporous carbon supercapacitors applicable to diverse pore regimes, carbon materials, and electrolytes”, Chem. Eur. J., 14 (2008) 6614-6626.
14.Y. Zhang, H. Feng, X. Wu, L. Wang, A. Zhang, T. Xia, H. Dong, X. Li, and L. Zhang, “Progress of electrochemical capacitor electrode materials: A review”, Int. J. Hydrogen Energy, 34 (2009) 4889-4899.
15.J. Q. Xiao, Q. Lu, and J. G. Chen, “Nanostructured electrodes for high-performance pseudocapacitors”, Angew. Chem. Int. Ed., 52 (2013) 1882-1889.
16.T. Brezesinski, J. Wang, S. H. Tolbert, and B. Dunn, “Next generation pseudocapacitor materials from sol-gel derived transition metal oxides”, J. Sol-Gel Sci. Technol., 57 (2011) 330-335.
17.V. Augustyn, P. Simon, and B. Dunn, “Pseudocapacitive oxide materials for high-rate electrochemical energy storage”, Energy Environ. Sci., 7 (2014) 1597-1614.
18.謝淵清，電化學反應程序，1983年5月。
19.F. Gobal, and M. Faraji, “Electrodeposited polyaniline on pd-loaded TiO2 nanotubes as active material for electrochemical supercapacitor”, J. Electroanal. Chem., 691 (2013) 51-56.
20.M. Toupin, T. Brousse, and D. Belanger, “Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor”, Chem. Mater., 16 (2004) 3184-3190.