本論文中，將六氯鉑酸以乙二醇還原成奈米白金粒子，並附著於碳黑表面，製成高催化性、高比表面積之白金/碳黑粉末，並以XRD與TEM比較不同白金附著量粉末間的差異。再利用白金/碳黑粉末在FTO玻璃與ITO-PET上製作白金/碳黑電極，並且以SEM、四點探針、CV與EIS分析比較不同白金附著量、不同附著劑含量與不同厚度時的差異，最後取得較佳的一組配方為: 若以FTO為基板，較好的配方是白金/碳黑重量比為20 wt%、附著劑含量為12 wt%與3 μm厚度 的C4-2-1這組。以ITO-PET為基板，則為白金/碳黑重量比為20 wt%、附著劑含量為10 wt%與4 μm厚度的C4-1-2這組。

最後將白金/碳黑電極應用於染料敏化太陽能電池的對電極上，以FTO導電玻璃為基板時得到3.84 %的光電轉換效率，而標準白金電極製作之效率為4.53 %，以ITO-PET導電塑膠板為基板的可撓式染料敏化太陽能電池轉換效率為2.24 %，標準白金電極做出的效率為2.49 %，為了使可撓式染敏太陽能電池的壽命增長，本研究使用了膠態電解質來取代原本的液態電解質，使用白金/碳黑電極製作出來的可撓式膠態染料敏化太陽能電池的效率為1.46 %，而使用白金電極製作出來的效率為1.57 %。

This study used ethylene glycol to reduced dihydrogen hexachloroplatinate.    Dihydrogen hexachloroplatinate will reduce to nano platinum and attached on the carbon black. Pt/C powder have high catalytic and high specific surface. XRD and TEM can show the difference amount of platinum adhesion. Then use the Pt/C powder to produce Pt/C electrode on the FTO and ITO-PET. SEM, four-point probe, CV and EIS analysis to compare the difference in amount of platinum adhesion, adhesion agent content and different thickness. Finally to obtain a better formula is : If used the FTO substrate, Pt/C weightratio of 20 wt%, adhesion agent content of 12 wt% and the 3 μm thickness of C4-2-1 is the better formula. If used the ITO-PET substrate, Pt/C weightratio of 20 wt%, adhesion agent content of 10 wt% and the 4 μm thickness of C4-2-1 is the better formula.

Finally, the Pt/C electrode used in dye-sensitized solar cells on the counter electrode. The photoelectric conversion efficiency on the FTO glass substrate is 3.84 %, and Pt electrode production efficiency of 4.53 %. The efficiency on the ITO-PET substrate is 2.24 %, and Pt electrode production efficiency is 2.49 %. The study used a gel electrolyte to replace the liquid electrolyte. Pt/C electrode made out of the flexible gel state dye-sensitized solar cells’ efficiency of 1.46 %, and platinum electrodes produced an efficiency of 1.57 %.

目錄

中文摘要……………………………………………………………………………I
英文摘要……………………………………………………………………………II
目錄…………………………………………………………………………………IV
圖目錄………………………………………………………………………………VI
表目錄………………………………………………………………………………IX
第一章	緒論…………………………………………………………………………1
1-1	染敏太陽能電池的原理與發展………………………………………………2
1-1-1	染料敏化太陽能電池的發展…………………………………………2
1-1-2	染料敏化太陽能電池的機制與原理…………………………………4
1-2	染料敏化太陽能電池的對電極………………………………………………6
1-3	研究動機………………………………………………………………………7
第二章	文獻回顧……………………………………………………………………8
2-1	染料敏化太陽能電池之碳材對電極…………………………………………8
2-2	白金/碳黑粉體的製作………………………………………………………10
2-3	白金/碳黑之對電極…………………………………………………………12
2-4	可撓曲式染料敏化太陽能電池……………………………………………15
第三章	實驗設備與方法……………………………………………………………18
3-1	實驗藥品與材料……………………………………………………………18
3-2	實驗步驟……………………………………………………………………24
3-2-1 白金/碳黑粉末製備……………………………………………………24
3-2-2 白金/碳黑電極製備……………………………………………………26
3-2-3 染敏太陽能電池製作…………………………………………………28
3-3	實驗儀器……………………………………………………………………31
第四章	實驗結果與討論……………………………………………………………34
4-1 白金/碳黑粉體分析…………………………………………………………34
4-2 白金/碳黑電極在FTO玻璃板之分析………………………………………37
4-2-1 電阻值量測與分析……………………………………………………37
4-2-2 薄膜形態分析…………………………………………………………39
4-2-3 CV量測與分析…………………………………………………………42
4-2-4 EIS之量測與分析………………………………………………………50
4-3 白金/碳黑電極在ITO-PET板之分析………………………………………52
4-3-1電阻值量測與分析……………………………………………………52
4-3-2薄膜形態分析…………………………………………………………54
4-3-3 CV量測與分析…………………………………………………………57
4-3-4 EIS之量測與分析………………………………………………………61
4-4 白金/碳電極於染料敏化太陽能電池之應用分析與量測…………………63
4-4-1 染敏太陽能電池在FTO板上的檢測…………………………………63
4-4-2 染敏太陽能電池在ITO-PET上的檢測………………………………66
4-4-3 膠態染敏太陽能電池在ITO-PET上的檢測…………………………69
第五章	結論…………………………………………………………………………71
參考文獻……………………………………………………………………………74
附錄A………………………………………………………………………………80
附錄B………………………………………………………………………………81
附錄C………………………………………………………………………………86

圖目錄

圖1-1 染料敏化太陽能電池的電子迴路圖…………………………………………4
圖2-1 染料敏化太陽能電池之運作機制……………………………………………9
圖2-2 以碳材為對電極之染料敏化太陽能電池結構圖……………………………9
圖2-3不同pH值製備出的白金/碳黑粉體之TEM圖與晶粒尺寸………………11
圖2-4 白金附著在碳黑表面上的TEM圖…………………………………………12
圖2-5 為白金、碳黑與白金/碳黑的CV曲線圖……………………………………13
圖3-1白金/碳黑粉末製備流程圖…………………………………………………25
圖3-2 白金/碳黑電極製備流程圖…………………………………………………26
圖3-3 白金/碳黑膜簡化命名………………………………………………………27
圖3-4 交流阻抗操作示意圖………………………………………………………33
圖4-1 白金-碳粉C0與C4之XRD分析……………………………………………34
圖4-2 白金-碳粉體C0之TEM分析………………………………………………35
圖4-3 白金/碳粉體C2之TEM分析………………………………………………35
圖4-4 白金/碳粉體C3之TEM分析………………………………………………36
圖4-5 白金/碳粉體C4之TEM分析………………………………………………36
圖4-6 在FTO基板之白金/碳黑薄膜C4-1-1表面(a,b)與截面(c,d)SEM圖………40
圖4-7在FTO基板之白金/碳黑薄膜C4-2-1表面(a,b)與截面(c,d)SEM圖………40
圖4-8在FTO基板之白金/碳黑薄膜C4-3-1表面(a,b)與截面(c,d)SEM圖………41
圖4-9比較製程中不同pH值條件下製做的C4-2-1白金/碳黑電極CV圖(在FTO)…44
圖4-10 利用CV比較製程中不同白金附著量的白金/碳黑電極(在FTO) ………44
圖4-11製程中不同附著劑含量的白金/碳黑電極CV圖(在FTO) ………………45
圖4-12不同附著劑含量及雙層膠帶厚度的白金/碳黑電極CV圖(在FTO) ……45
圖4-13 利用CV比較製程中不同膠帶層數的白金/碳黑電極(在FTO) ………46
圖4-14 白金電極之氫吸脫附CV圖(在FTO) ……………………………………46
圖4-15白金/碳黑電極之氫吸脫附CV圖(在FTO) ………………………………47
圖4-16在ITO-PET基板之白金/碳黑薄膜C4-1-2表面(a,b)與截面(c,d)SEM圖…55
圖4-17在ITO-PET基板之白金/碳黑薄膜C4-2-2表面(a,b)與截面(c,d)SEM圖…55
圖4-18在ITO-PET基板之白金/碳黑薄膜C4-3-2表面(a,b)與截面(c,d)SEM圖…56
圖4-19在ITO-PET基板上比較製程中不同膠帶層數塗佈厚度的白金/碳黑薄膜…56
圖4-20 利用CV比較製程中不同白金附著量的白金-碳電極(ITO-PET) ………58
圖4-21 利用CV比較製程中不同附著劑含量的白金-碳電極(ITO-PET) ………58
圖4-22 利用CV比較製程中不同膠帶層數的白金-碳電極(ITO-PET) …………59
圖4-23 以不同濃度之TiO2漿料製作在FTO板的染敏太陽能電池效率圖……64
圖4-24 以不同白金附著量之對電極製作在FTO板的染敏太陽能電池效率圖…64
圖4-25以不同膠帶厚度製作在ITO-PET之工作電極的染敏太陽能電池效率圖…67
圖4-26在ITO-PET板以不同白金附著量製作之對電極的染敏太陽能電池效率圖…67
圖4-27 白金/碳黑電極應用在可撓式膠態染敏太陽能電池之效率圖…………69
圖A-1 純碳黑C0-2-1與白金之CV圖(在FTO) ………………………………80
圖A-2 純碳黑C0-1-2與白金之CV圖(在ITO-PET) ……………………………80
圖B-1 利用EIS比較製程中pH值不同的白金-碳電極(在FTO) ………………81
圖B-2 利用EIS比較白金附著量不同的白金-碳電極(在FTO) …………………81
圖B-3 利用EIS比較附著劑含量不同的白金-碳電極(在FTO) …………………82
圖B-4 利用EIS比較膠帶層數不同的白金-碳電極(在FTO) ……………………82
圖B-5 純碳黑C0-2-1之EIS圖(在FTO) …………………………………………83
圖B-6 利用EIS比較白金附著量不同的白金-碳電極(ITO-PET) ………………83
圖B-7 利用EIS比較附著劑含量不同的白金-碳電極(ITO-PET) ………………84
圖B-8 利用EIS比較膠帶層數不同的白金-碳電極(ITO-PET) …………………84
圖B-9 純碳黑C0-1-2之EIS圖(在ITO-PET) ……………………………………85
圖C-1 電流-電壓曲線圖……………………………………………………………86
圖C-2 循環伏安圖…………………………………………………………………87
圖C-3 等效電路圖…………………………………………………………………88

表目錄

表4-1 不同白金附著量的白金/碳黑電極在FTO基板上的片電阻值……………38
表4-2 不同附著劑含量的白金/碳黑電極在FTO基板上的片電阻值……………38
表4-3製程中不同pH值條件下製做的C4-2-1白金/碳黑電極CV數據(在FTO) 47
表4-4 利用CV比較製程中不同白金附著量的白金/碳黑電極數據(在FTO) …48
表4-5製程中不同附著劑含量的白金/碳黑電極CV數據(在FTO) ………………48
表4-6 利用CV比較製程中不同膠帶層數的白金/碳黑電極數據(在FTO) ……48
表4-7 白金、純碳黑與白金/碳黑電極之比表面積與活性比表面基數據(在FTO)49
表4-8 利用EIS比較製程中pH值不同的白金/碳黑電極數據(在FTO) …………51
表4-9 利用EIS比較白金附著量不同的白金/碳黑電極數據(在FTO) …………51
表4-10 利用EIS比較附著劑含量不同的白金/碳黑電極數據(在FTO) …………51
表4-11 利用EIS比較膠帶層數不同的白金/碳黑電極數據(在FTO) ……………51
表4-12 不同白金附著量的白金/碳黑電極在ITO-PET基板上的片電阻值……52
表4-13 不同附著劑含量的白金/碳黑電極在ITO-PET基板上的片電阻值……53
表4-14 製程中不同膠帶層數的白金/碳黑電極在ITO-PET基板上的電阻值…53
表4-15 利用CV比較製程中不同白金附著量的白金-碳電極(ITO-PET)之數據59
表4-16 利用CV比較製程中不同附著劑含量的白金-碳電極(ITO-PET)之數據60
表4-17 利用CV比較製程中不同膠帶層數的白金-碳電極(ITO-PET)之數據…60
表4-18 利用EIS比較白金附著量不同的白金/碳黑電極(ITO-PET)之數據……61
表4-19 利用EIS比較附著劑含量不同的白金/碳黑電極(ITO-PET)之數據……62
表4-20 利用EIS比較膠帶層數不同的白金/碳黑電極(ITO-PET)之數據………62
表4-21 以不同濃度之TiO2漿料製作在FTO的染敏太陽能電池效率數據表…65
表4-22以不同白金附著量之對電極製作在FTO的染敏太陽能電池效率數據表65
表4-23以不同膠帶厚度製作在ITO-PET之工作電極的染敏太陽能電池效率表68
表4-24在ITO-PET板以不同白金附著量製作之對電極的染敏太陽能電池效率表…68
表4-25白金/碳黑電極應用在可撓式膠態染敏太陽能電池之數據表……………70

[1] B. O’Regan, M. Gratzel, “A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films”, Nature, 1991, 353, 737-740.

[2] M. Gratzel, “Photoelectrochemical cells”, Nature, 2001, 414, 338-344.

[3] M. Gratzel, “Dye-sensitized solar cells”, Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2003, 4, 145-153.

[4] J. Chen, K. Li, Y. Luo, X. Guo, D. Li, M. Deng, S. Huang, Q. Meng, “A flexible carbon counter electrode for dye-sensitized solar cells”, Carbon, 2009, 47, 2704-2708.

[5] 鍾岱麟, 含奈米二氧化矽膠態電解質製備用於染料敏化太陽能電池之研究, 淡江大學, 2010

[6] 李陸玲、陳建仲和刁維光，「染料敏化太陽能電池的基本原理與元件最佳化策略研究」，化工期刊，2009，第56卷第2期，3-15

[7] S. Nakade, T. Kanzaki, W. Kubo, T. Kitamura, Y. Wada, S. Yanagida, “Role of electrolytes on charge recombination in dye-sensitized TiO2 solar cell (1): The case of solar cells using the I-/I3- redox couple “, Journal of Physical Chemistry, 2005, 109, 3480-3487.

[8] 江明泰, 應用於染料敏化太陽能電池對電極之鉑-聚(3,4-乙烯基二氧噻吩)/聚(苯乙烯磺酸鹽)導電奈米複合薄膜的製備與性質分析, 淡江大學, 2010

[9] M. Gratzel, “Demonstrating electron transfer and nanotechnology: a natural dye-sensitized nanocrystalline energy converter “, Journal of Chemical Education, 1998, 75, 752-756.

[10] 黃桂武, “導電性聚苯胺高分子光電技術運用探討,工業技術研究院”

[11] A. M. Nardes, M. Kemerink, “Conductivity, work function, and environmental stability of PEDOT:PSS thin films treated with sorbitol”, Organic Electronics, 2008, 9, 727-734.

[12] K. M. Lee, P. Y. Chen, C. Y. Hsu, J. H. Huang, W. H. Ho, H. C. Chen, K. C. Ho, “A High Performance Counter Electrode based on Poly(3,4-alkylenedioxythiophene) for Dye-Sensitized Solar Cells”, Journal of Power Sources, 2009, 188, 313-318.

[13] J. H. Wu, Q. H. Li, L. Q. Fan, Z. Lan, P. J. Li, J. M. Lin, S. C. Hao, “High-performance polypyrrole nanoparticles counter electrode for dye sensitized solar cells”, Journal of Power Sources, 2008, 181, 172-176.

[14] Q. H. Li, J. H. Wu, Q. W. Tang, Z. Lan, P. J. Li, J. M. Lin, L. Q. Fan, ”Application of microporous polyaniline counter electrode for dye-sensitized solar cells”, Electrochemistry Communications, 2008, 10, 1299-1302.
[15] T. N. Murakami, S. Ito, Q. Wang, M. K. Nazeeruddin, T. Bessho, I. Cesar, P. Liska, R. H. Baker, P. Comte, P. Pechy, M. Gratzel, “Highly Efficient Dye-Sensitized Solar Cells Based on Carbon Black Counter Electrodes”, Journal of The Electrochemical Society, 2006, 153, A2255-A2261.

[16] A. Kay, M. Gratzel, “Low cost photovoltaic modules based on dye sensitized nanocrystalline titanium dioxide and carbon powder”, Solar Energy Materials and Solar Cells, 1996, 44, 99-117.

[17] E. Ramasamy, W. J. Lee, D. Y. Lee, J. S. Song, “Nanocarbon counterelectrode for dye sensitized solar cells”, Applied Physics Letters, 2007, 90, 173103

[18] T. Hino, Y. Ogawa, N. Kuramoto, “Preparation of functionalized and non-functionalized fullerene thin films on ITO glasses and the application to a counter electrode in a dye-sensitized solar cell”, Carbon, 2006, 44, 880-887

[19] T. Denaro, V. Baglio, M. Girolamo, V. Antonucci, A.S. Arico, F. Matteucci, R. Ornelas, “Investigation of low cost carbonaceous materials for application as counter electrode in dye-sensitized solar cells”, Journal of Applied Electrochemistry, 2009, 39, 2173-2179.

[20] K. Imoto, K. Takahashi, T. Yamaguchi, T. Komura, J. Nakamura, K. Murata, “High-performance carbon counter electrode for dye-sensitized solar cells.” Solar Energy Materials and Solar Cells, 2003, 79, 459-469.
[21] Z. Huang, X. Z. Liu, K. X. Li, D. M. Li, Y. H. Luo, H. Li, “Application of carbon materials as counter electrodes of dye-sensitized solar cells.” Electrochemistry Communications, 2007, 9, 596-598.

[22] K. Suzuki, M. Yamaguchi, M. Kumagai, S. Yanagida, “Application of carbon nanotubes to counter electrodes of dye-sensitized solar cells.” Chemistry Letters, 2003, 32, 28-29.

[23] J. E. Trancik, S. C. Barton, J. Hone, “Transparent and catalytic carbon nanotube films.” Nano Letters, 2008, 8, 982-987.

[24] T. Hino, Y. Ogawa, N. Kuramoto, “Preparation of functionalized and non-functionalized fullerene thin films on ITO glasses and the application to a counter electrode in a dye-sensitized solar cell.”, Carbon, 2006, 44, 880-887. 

[25] W. J. Hong, Y. X. Xu, G. W. Lu, C. Li, G. Q. Shi, “Transparent graphene/ PEDOT-PSS composite films as counter electrodes of dyesensitized solar cells.”, Electrochemistry Communications, 2008, 10, 1555-1558.

[26] Z. B. Wang,  C. R. Zhao, P. F. Shi, Y. S. Yang, Z. B. Yu, W. K. Wang, G. P. Yin, “Effect of a Carbon Support Containing Large Mesopores on the Performance of a Pt-Ru-Ni/C Catalyst for Direct Methanol Fuel Cells” Journal of Physical Chemistry, 2010, 114, 672-677. 



[27] Y. Y. Chu, Z. B. Wang, D. M. Gu, G. P. Yin, “Performance of Pt/C catalysts prepared by microwave-assisted polyol process for methanol electrooxidation”, Journal of Power Sources, 2010, 195, 1799-1804.

[28] L. Gan, H. D. Du, B. H. Li, F. Y. Kang, ”The effect of particle size on the interaction of Pt catalyst particles with a carbon black support”, New Carbon Materials, 2010, 25, 53-59.

[29] W. Li, C. Liang, W. Zhou, J. Qiu, Z. Zhou, G. Sun, Q. Xin, “Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells”, Journal of Physical Chemistry, 2003, 107, 6292-6299.

[30] P. J. Li, J. H. Wu, J. M. Lin, M. L. Huang, Y. F. Huang, Q. H. Li, “High-performance and low platinum loading Pt/Carbon black counter electrode for dye-sensitized solar cells”, Solar Energy, 2009, 83, 845-849.

[31] S. Y. Ang, D. A. Walsh, “Highly stable platinum electrocatalysts for oxygen reduction formed using supercritical fluid impregnation”, Journal of Power Sources, 2010, 195, 2557-2563.
[32] A. Mathew, G. M. Rao, N. Munichandraiah, “Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode”, Materials Research Bulletin, 2011, 46, 2045-2049.



[33] L. L. Chen, W. W. Tan, J. B. Zhang, X. W. Zhou, X. L. Zhang, Y. Lin, “Fabrication of high performance Pt counter electrodes on conductive plastic substrate for flexible dye-sensitized solar cells”, Electrochimica Acta, 2010, 55, 3721-3726.

[34] K. Fan, T.Y. Peng, J.N. Chen, K. Dai, “Effects of tetrabutoxytitanium on photoelectrochemical properties of plastic-based TiO2 film electrodes for flexible dye-sensitized solar cells”, Journal of Power Sources, 2011, 196, 2939-2944.

[35] L. L. Chen, J. Liu, J. B. Zhang, X. W. Zhou, X. L. Zhang, Y. Lin, “Low temperature fabrication of flexible carbon counter electrode on ITO-PEN for dye-sensitized solar cells”, Chinese Chemical Letters, 2010, 21, 1137-1140.

[36] L. Y. Lin, C. P. Lee, R. Vittal, K. C. Ho, “Selective conditions for the fabrication of a flexible dye-sensitized solar cell with Ti/TiO2 photoanode”, Journal of Power Sources, 2010, 195, 4344-4349

[37] Y. M. Xiao, J. H. Wu, G. T. Yue, J. M. Lin, M. L. Huang, Z. Lan, “Low temperature preparation of a high performance Pt/SWCNT counter electrode for flexible dye-sensitized solar cells”, Electrochimica Acta, 2011, 56, 8545-8550.