臺灣博碩士論文加值系統

在各種不同的太陽能電池的發展中，染料敏化太陽能電池(DSSC)其便宜的材料與製程簡單的優點被業界眾所矚目，而當中所使用二氧化鈦(TiO2)材料的相關研究最廣受歡迎。此研究使用TiO2-P25材料，並透過使用絲網印刷方式來製備DSSC。依據不同濃度TiO2漿料，使用絲網印刷堆疊來製備DSSC的光陽極。並探討不同的濃度TiO2漿料、堆疊厚度的TiO2 薄膜，在DSSC光陽極的薄膜表面型態與能源轉換效率之影響。在使用絲網印刷方式所製備的光陽極中，網印速度以11 mm/s的印刷參數下所製備的塗層均勻度較佳，並可藉由多次重複來回印刷，來達到適當的厚度。結果得知在不同濃的TiO2漿料中，濃度為15wt% 的TiO2醬料、堆疊厚度為40μm所製備DSSC光陽極其效率高達4.86%。

In the development of various kinds of solar cells, the advantages of dye sensitized solar cells (DSSC) for their cheap materials and simple manufacturing processes have attracted the attention of the industry, and the related research on titanium dioxide (TiO2) materials used among them is most welcome. In this research, TiO2 P25 material was used, and a DSSC was made by using screen printing. According to different concentrations of TiO2 slurry, the photoanode of DSSC was made by using screen printing stacking. The effect of different concentrations of TiO2 slurry and stack thickness of TiO2 films on the surface morphology and energy conversion efficiency of DSSC photoanodes is also discussed. In the process of preparing photoanode by screen printing, the uniformity of coating is better when the screen printing speed is 11 mm / s, and we can achieve the appropriate thickness by repeating the printing repeatedly. The results show that in different concentrations of TiO2 slurry, the concentration of 15wt%, stack thickness of 40μm TiO2 slurry prepared DSSC photoanode has an efficiency up to 4.86%.

中文摘要………………………………………………………………………………………………………………………………………………………………………………………i
英文摘要……………………………………………………………………………………………………………………………………………………………………………………ii
誌謝……………………………………………………………………………………………………………………………………………………………………………………………iii
目錄………………………………………………………………………………………………………………………………………………………………………………………………iv
表目錄…………………………………………………………………………………………………………………………………………………………………………………………vi
圖目錄………………………………………………………………………………………………………………………………………………………………………………………vii
第一章 序論………………………………………………………………………………………………………………………………………………………………………………1
1.1前言…………………………………………………………………………………………………………………………………………………………………………………1
1.2染料敏化太陽能電池簡介……………………………………………………………………………………………………………………………………2
1.3研究動機………………………………………………………………………………………………………………………………………………………………………3
第二章 理論與文獻探討………………………………………………………………………………………………………………………………………………………4
2.1二氧化鈦(TiO2)材料………………………………………………………………………………………………………………………………………………4
2.1.1二氧化鈦簡介…………………………………………………………………………………………………………………………………………………4
2.1.2二氧化鈦的特性與結構……………………………………………………………………………………………………………………………4
2.2染料敏化太陽能電池………………………………………………………………………………………………………………………………………………6
2.2.1太陽能電池的種類………………………………………………………………………………………………………………………………………6
2.2.2染料敏化太陽能電池的發展歷史…………………………………………………………………………………………………………8
2.2.3染料敏化太陽能電池的結構…………………………………………………………………………………………………………………9
2.2.4透明導電氧化物…………………………………………………………………………………………………………………………………………10
2.2.5光陽極……………………………………………………………………………………………………………………………………………………………10
2.2.6對電極……………………………………………………………………………………………………………………………………………………………10
2.2.7染料…………………………………………………………………………………………………………………………………………………………………11
2.2.8電解質……………………………………………………………………………………………………………………………………………………………13
2.2.7染料敏化太陽能電池的工作原理與傳輸損失……………………………………………………………………………14
2.3沉積與塗佈技術………………………………………………………………………………………………………………………………………………………17
2.4太陽光譜照度與空氣質量AM……………………………………………………………………………………………………………………………17
第三章 實驗步驟與設備……………………………………………………………………………………………………………………………………………………21
3.1實驗藥品與實驗設…………………………………………………………………………………………………………………………………………………21
3.1.1實驗藥品………………………………………………………………………………………………………………………………………………………21
3.1.2實驗儀器設備………………………………………………………………………………………………………………………………………………23
3.1.3實驗流程圖…………………………………………………………………………………………………………………………………………………24
3.2實驗步驟……………………………………………………………………………………………………………………………………………………………………25
3.2.1基板準備與清洗…………………………………………………………………………………………………………………………………………25
3.2.2使用絲網印刷法製備二氧化鈦光陽極……………………………………………………………………………………………25
3.2.3對電極製備…………………………………………………………………………………………………………………………………………………26
3.2.4染料與電解液的製備………………………………………………………………………………………………………………………………26
3.2.5元件封裝………………………………………………………………………………………………………………………………………………………26
3-3分析儀器運用原理…………………………………………………………………………………………………………………………………………………29
3.3.1紫外光/可見光吸收光譜儀…………………………………………………………………………………………………………………29
3.3.2全波段入射光電轉換效率測量儀………………………………………………………………………………………………………29
3.3.3電化學阻抗頻譜分析儀…………………………………………………………………………………………………………………………30
3.3.4染料敏化太陽能電池的光電轉換效率……………………………………………………………………………………………33
3.3.5場發射掃描式電子顯微鏡……………………………………………………………………………………………………………………36
第四章 結果與討論………………………………………………………………………………………………………………………………………………………………37
4-1絲網印刷法製備的染料敏化太陽能電池TiO2薄膜型態分析……………………………………………………………37
4-2不同濃度TiO2漿料製備的染料敏化太陽能電池之特性分析……………………………………………………………40
4.2.1染料敏化太陽能電池之紫外光/可見光吸收光（UV）光譜分析………………………………………40
4.2.2染料敏化太陽能電池之全波段入射光電轉換效率(IPCE)分析…………………………………………41
4.2.3染料敏化太陽能電池之電化學阻抗頻譜分析……………………………………………………………………………42
4.2.4染料敏化太陽能電池之光電轉換效率分析…………………………………………………………………………………43
4-3大面積光陽極的染料敏化太陽能電池之特性分析…………………………………………………………………………………44
4.3.1面積1cm2光陽極染料敏化太陽能電池之電化學阻抗頻譜分析…………………………………………44
4.3.2面積1cm2光陽極染料敏化太陽能電池之光電轉換效率分析………………………………………………45
4.3.3光陽極9cm2全面積、7.5cm2十字型、7.2cm2直向與橫向型之染料敏化太陽
能電池之光電轉換效率分析………………………………………………………………………………………………………………46
4.3.4鍍鋁光陽極9cm2全面積、7.5cm2十字型、7.2cm2直向與橫向型之染料敏化
太陽能電池之光電轉換效率分析………………………………………………………………………………………………………47
4.3.5鍍鋁光陽極9cm2全面積、7.5cm2十字型、7.2cm2直向與橫向型之染料敏化
太陽能電池之電化學阻抗頻譜分析…………………………………………………………………………………………………48
第五章 結論……………………………………………………………………………………………………………………………………………………………………………49
未來研究方向…………………………………………………………………………………………………………………………………………………………………………50
參考文獻……………………………………………………………………………………………………………………………………………………………………………………51
Extended Abstract……………………………………………………………………………………………………………………………………………………………52

[1] RENEWABLES 2019 GLOBAL STATUS REPORT
[2] MoneyDJ理財網財經知識庫，染料敏化太陽能電池(DSSC)
[3]H.Tributsch., 1972,“Reactions of excited chlorophyll molecules at electrodes and in photosynthesis.”Photochemistry and Photobiology, vol. 16, no.4,261 pages.
[4]H. Tsubomura, M. Matsumura, Y. Nomura, T. Amamiya, 1976, “Dye-sensitized zinc oxide/aqueous electrolyte/platinum photocell”, Nature, 261, 402-403.
[5]B.O’Regan and M. Grätzel, 1991,“A low-cost, high-efficiency solar cell based on dye sensitized colloidal TiO2 films”, Nature,353,737-740.
[6]M. Grätzel, 2001, “Photoelectrochemical cells ”,Nature,414,338-344.
[7]P. Wang, S M. Zakeeruddin , P. Comte, I. Exnar and M.Grätzel, 2003, “An efficient organogelator for ionic liquids to prepare stable quasi-solidstate dye-sensitized solar cells”, Journal of the American Chemical Society, 125, 1166-1167.
[8]M.Grätzel.,2005 ,”Solar energy conversion by dye-sensitized photovoltaic cells”, Inorganic Chemistry, 44,6841-6851.
[9]P.Wang，SM Zakeeruddin，JE Moser，MKNazeeruddin，T.Seikiguchi M.Grätzel, 2003,” A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer gel electrolyte”, Nature Material, 2, 402.
[10]D. Kuang, P. Wang, S. Ito, S.M. Zakeeruddin, M. Grätzel, 2006. “Stable mesoscopic dye sensitized solar cells based on tetracyanoborate ionic liquid electrolyte”, Journal of the American Chemical Society , 128, 7732-7733.
[11] 上海邁拓崴化工新材料科技有限公司-染料敏化太陽能電池構造
[12]Ji Young Ahn and Soo Hyung Kim, 2018, “Synergistic effects of inter- and intra-particle porosity of TiO2 nanoparticles on photovoltaic performance of dye-sensitized solar cells”, ELSEVIER- Microporous and Mesoporous Materials 266 (2018) 214–222
[13] teacher，認識鈦元素
[14] TiO2台灣光觸媒-光觸媒百科
[15]林明獻，2008，”太陽能電池技術入門”，全華圖書出版。
[16]Discover "Tag: inorganic chemistry/Titanium Dioxide in Food" ,Video & guest post by Carolyn Meyers & Edgar Rodriguez
[17] 靜宜大學應數系，”光觸媒材料”， 奈米技術與奈米科學，第六區成果展
[18]M.H.Samat, A.M.M.Ali, M.F.M.Taib and O.H.Hassan, 2016,“Hubbard U calculations on optical properties of 3d transition metal oxide TiO2”
[19] E. Rauls, M. Landmann, W G Schmidt, 2012, ” The electronic structure and optical response of rutile, anatase and brookite TiO2”, Journal of Physics Condensed Matter 24(19):195503
[20]Anh, L. T., Rai, A. K., Thi, T. V., Gim, J., Kim, S., Shin, E. C., ... & Kim, J. (2013). Improving the electrochemical performance of anatase titanium dioxide by vanadium doping as an anode material for lithium-ion batteries. Journal of Power Sources, 243, 891-898.
[21]Ludin, N. A., Mahmoud, A. A. A., Mohamad, A. B., Kadhum, A. A. H., Sopian, K., & Karim, N. S. A. (2014). Review on the development of natural dye photosensitizer for dye-sensitized solar cells. Renewable and Sustainable Energy Reviews, 31, 386-396.
[22] EnergyTrend，綠能知識-太陽能電池的分類
[23]郭明村，2003，”薄膜太陽電池發展近況”，工業材料雜誌, 203期,頁138-142。
[24]國家能源科技人才培育計畫，太陽能分類
[25]Russell F. Howe , Michael Gratzel, 1985, “EPR observation of trapped electrons in colloidal titanium dioxide”, J. Phys. Chem., 89 (21), 4495-4499.
[26]A. Hagfeldt, M. Grätzel, 2000, “Molecular photovoltaics”, Acc. Chem. Res., 33(5), 269-277.
[27]Mohammad K. Nazeeruddin, Filippo De Angelis, SimonaFantacci, AnnabellaSelloni, Guido Viscardi, Paul Liska, Seigo Ito, BesshoTakeru, and Michael Grätzel, 2005, “Combined Experimental and DFT-TDDFT Computational Study of Photoelectrochemical Cell Ruthenium Sensitizers”, J. Am. Chem. Soc., 127(48), 16835-16847.
[28]Aswani Yella, Hsuan-Wei Lee, Hoi NokTsao, Chenyi Yi, Aravind Kumar Chandir`an, Md.KhajaNazeeruddin, Eric Wei-GuangDiau, Chen-Yu Yeh, Shaik M Zakeeruddin, Michael Grätzel, 2011, “Porphyrin-Sensitized Solar Cells with Cobalt (II/III)–Based Redox Electrolyte Exceed 12 Percent Efficiency”, 334, 629-634.
[29] TOM MURPHY，2011，“Solarprint: Harvesting and Recycling light”，Technology Voice
[30]翁敏航，”太陽能電池：原理、元件、材料、製程與檢測技術”，東華書局，2010。
[31]劉茂煌，2002，”奈米光電池”，工業材料雜誌，203期，頁1~49。
[32]Ludin, N. A., Mahmoud, A. A. A., Mohamad, A. B., Kadhum, A. A. H., Sopian, K., & Karim, N. S. A. (2014). Review on the development of natural dye photosensitizer for dye-sensitized solar cells. Renewable and Sustainable Energy Reviews, 31, 386-396.
[33] Ravi Kumar Kanaparthi，2012，“Molecular Engineering of Sensitizers for Dye-Sensitized Solar Cell Applications”，ResearchGate GmbH
[34]林明獻，2007，“太陽能電池技術入門”, 第二章.
[35]K. L. Vincent Joseph, A.“Anthonysamy,Ruthenium(II) Quasi-Solid State Dye Sensitized Solar Cells with 8% Efficiency using Supramolecular Oligomer-Based Electrolyte ”, ROYAL SOCIETY OF CHEMISTRY-Journal of Materials Chemistry A, Cite this: DOI: 10.1039/c0xx00000x
[36]Md. K. Nazeeruddin, S. M. Zakeeruddin, R. Humphry-Baker, M. Jirousek, P. Liska, N. Vlachopoulos, V. Shklover, Christian-H. Fischer, M. Grätzel, 1999, “Acid−Base Equilibria of (2,2‘-Bipyridyl-4,4‘- dicarboxylic acid)ruthenium(II) Complexes and the Effect of Protonation on Charge-Transfer Sensitization of NanocrystallineTitania”, Inorg. Chem., 38(26), 6298-6305.
[37]T. Horiuchi, H. Miura, S. Uchida, 2003,“Highly-efficient metal-free organic dyes for dye-sensitized solar cells”, Chem. Commun., 24, 3036-3037.
[38]T. Horiuchi, H. Miura, K. Sumioka, S. Uchida, 2004,“High Efficiency of Dye-Sensitized Solar Cells Based on Metal-Free Indoline Dyes”, Journal of the American Chemical Society, 126(39), 12218-12219.
[39] Merck KGaA，D102 Dye
[40]Kristofer Fredin, , “Studies of Charge Transport Processes in Dye-Sensitized Solar Cells” (2007).
[41]張智信，2008，“陽極處理法製備二氧化鈦奈米管狀結構並應用於染料敏化太陽能電池之研究”，國立臺北科技大學材料科學與工程研究所碩士學位論文。
[42] 材料世界網，2008，“染料敏化太陽能電池電解質概述”
[43] Copyright，“太陽能電池”，第一部分
[44]V. Thavasi, V. Renugopalakrishnan, R. Jose, and S. Ramakrishna., 2008, “Controlled electron injection and transport at materials interfaces in dye sensitized solar cells”, Materials Science and Engineering R, 63, 81-99.
[45]黃子為，2014，”網版印刷技術應用於染料敏化太陽能電池之研究”，國立中興大學化學工程學系碩士學位論文。
[46] 中國照明學會，太陽光普照度圖
[47] Newport，Tutorial:Introduction to Solar Radiation
[48] Copyright，”獻給被電化學阻抗譜（EIS）困擾的你”，電化學天地
[49]陳政廷，2008，“混合有機色素分子共增感對色素增感太陽電池光電轉換效率的影響”。
[50]M. Adachi, Y. Murata, J. Takao, J. Jiu, M. Sakamoto, F. Wang.,2004, “Highly Efficient Dye-Sensitized Solar Cells with a Titania Thin-Film Electrode Composed of a Network Structure of Single-Crystal-like TiO2 Nanowires Made by the Oriented Attachment” Mechanism. J. Am. Chem. Soc., 126,14943-14949.
[51]Quora :What is the difference between the efficiency and the fill factor in a cell? , https://www.quora.com/What-is-the-difference-between-the-efficiency-and-the-fill-factor-in-a-cell
[52]Sandip Das, Kennesaw State University, “Development of a Low-cost, Portable, and Programmable Solar Module to Facilitate Hands-on Experiments and Improve Student Learning”,ASEE's 123rd Annual Conference & Exposition -New Orleans, LA-June 26-29,2016 ,Paper ID #17458
[53]羅聖全，2014，“探索奈米視界-科學基礎研究之重要利器-掃瞄式電子顯微鏡 (SEM)”, 第52卷第5期，國立臺灣科學教育館