為了開發有效率且能降低成本之染料敏化太陽能電池之對電極，本研究以噴塗法將奈米碳管噴塗於氧化銦錫基板上，透過奈米碳管的催化特性將其應用於敏化染料太陽能電池之對電極。本研究主要是探討奈米碳管對電極其表面型態、結構、和轉換電抗對電池之影響。
在電極的製作部份是採用噴塗法來塗佈奈米碳管於透明導電玻璃。利用高解析掃描式電子顯微鏡來觀察對電極之表面型態與結構和利用恆電位儀分析對電極與電解液界面之電荷轉換阻抗，最後再以太陽能模擬器量測染敏太陽能電池之效率。研究結果顯示，調配奈米碳管溶液最佳的比例為碳管：竣甲基纖維素：十二烷基苯磺酸鈉：去離子水：酒精=15:4：4：3：3。以噴塗法製作面積為0.196cm2 的奈米碳管電極經由恆電位儀量測可得到最佳的串聯電阻11.9Ω-cm2電荷轉換阻抗3.2Ω-cm2 經過太陽能模擬器量測後可得短路電流1.51mA，開路電壓0.74V，填充因子介於0.57至0.65之間，最佳轉換效率為3.266%。

In order to search for an efficient and low cost counter electrode in a DSSC, Carbon Nanotube(CNT) were coated onto ITO substrates by spray coating. The CNT was used to explore the performance of the counter electrode in DSSC. Therefore effects of the morphology, structure and charge-transfer resistance were investigated.
In this study, the CNT counter electrode CE was prepared by spray coating. The surface morphology and structure of CNT films were examined by Scanning Electron Microscope (SEM). The charge-transfer resistance was examined by autolab potentiostat. The result shows that solution containg CMC 8mg,SDBS 8mg ,DI water 6ml,alcohol 6ml 30mgCNT could be used for spray coating. The lowest charge transfer impedance of approximately 3.2Ω-cm2 and series resistance of 11.9.-cm2can be obtained for an electrode area of 0.196cm2 electrode。The I-V characteristics of DSSC with CNT CE. Revealed l a VOC of 0.74V, ISC of 1.51mA, FF 0.57-0.65. The best conversion efficiency is approached 3.26%.

目錄
摘要 i
誌謝 iii
目錄 iv
表目錄 vii
圖目錄 vii
第一章 緒論 1
1.1 前言 1
1.2 研究目的 2
1.3 研究方法 3
第二章 理論基礎 4
2.1 染料敏化太陽能電池 4
2.1.1染料敏化太陽能電池的結構 4
2.1.2 染料敏化太陽能電池的工作原理 8
2.1.3 染料敏化太陽能電池對電極的研究 9
第三章 實驗步驟與實驗設備 13
3.1 實驗流程 13
3.2 實驗設備 14
3.2.1 電子束蒸鍍系統(E-beam) 14
3.2.2噴塗設備 15
3.3.實驗材料 16
3.3.1基板材料 16
3.3.2 蒸鍍靶材 16
3.3.3 分散劑 16
3.3.4 多壁奈米碳管 16
3.4. 實驗步驟 17
3.4.1 對電極基板之準備 17
3.4.2奈米碳管溶液調配與奈米碳管之噴塗 19
3.4.3鉑電極之成長 19
3.4.4 TiO2 工作電極備置 19
3.4.5染料敏化劑浸泡 21
3.4.6 試片封裝 22
3.4.7性質測試與分析 23
3.5. 量測分析設備 25
3.5.1場發射型掃描式電子顯微鏡 25
3.5.2恆電位分析儀(Autolab Potentiostat) 26
3.5.3太陽能模擬器 27
第四章 結果與討論 28
4.1不同噴塗次數之奈米碳管電極特性分析 28
4.2不同比例溶液之奈米碳管電極特性分析 36
4.3.高溫燒結對奈米碳管電極特性分析 41
4.3.1不同溫度之高溫燒結對奈米碳管電極的影響 41
4.3.2燒結時間長短對奈米碳管電極的影響 47
4.3.3燒結溫度對以B瓶噴塗製作的奈米碳管電極的影響 54
4.3.4不同燒結時間對以B瓶噴塗製作的奈米碳管電極的影響 60
4.4以奈米碳管微電極之染敏太陽能電池特性分析 62
第五章 結論 64
5.1結論 64
參考文獻 66

表目錄
表4-1-(a) ITO/Pt/electrolyte/CNT(瓶號A噴塗一次)/ITO dummy cell 等效電路特性參數………………………………………………………………………………..32
表4-1-(b) ITO/Pt/electrolyte/CNT(瓶號A噴塗二次)/ITO dummy cell 等效電
路特性參數…………………………………………………………………………..32
表4-1-(c) ITO/Pt/electrolyte/CNT(瓶號A噴塗三次)/ITO dummy cell 等效
電路特性參數…………………………………………………………………….….33
表4-1-(d) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO dummy cell 等效
電路特性參數………………………………………………………………………..33
表4-1-(e) ITO/Pt/electrolyte/CNT(瓶號A噴塗五次)/ITO dummy cell 等效
電路特性參數………………………………………………………………………..33
表4-2瓶號A，瓶號B與瓶號C溶液成分表………………………………….…36
表4-3 ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO dummy cell 之等效電路特性參數………………………………………………………………………………..…38
表4-4-ITO/Pt/electrolyte/CNT(瓶號C噴塗四次)/ITO dummy cell 之等效電路特性參數…………………………………………………………………………………..38
表4-5瓶號B與瓶號D溶液成分表………………………………………….……39
表4-6-ITO/Pt/electrolyte/CNT(瓶號D噴塗四次)/ITO dummy cell 之等效電
路特性參數………………………………………………………………………..…40
表4-7-(a) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結300℃ 60min dummy cell 等效電路特性參數……………………………………………………………..44
表4-7-(b) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結350℃ 60min dummy cell 等效電路特性參數……………………………………………………………..44
表4-7-(c) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結400℃ 60min dummy cell 等效電路特性參………………………………………………………………..44
表4-7-(d) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結450℃ 60min dummy cell 等效電路特性參數……………………………………………………………..45
表4-8-(a) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結300℃ 90min dummy cell 等效電路特性參數……………………………………………………………..49
表4-8-(b) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結350℃ 90min dummy cell 等效電路特性參數……………………………………………………………..49
表4-8-(c) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結400℃ 90min dummy cell 等效電路特性參數……………………………………………………………..50
表4-8-(d) ITO/Pt/electrolyte/CNT(瓶號A噴塗四次)/ITO燒結450℃ 90min dummy cell 等效電路特性參數……………………………………………………………..50
表4-9-(a) ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO燒結300℃ 90min dummy cell 等效電路特性參數..............................................................................................56
表4-9-(b) ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO燒結350℃ 90min dummy cell 等效電路特性參數……………………………………………………………..56
表4-9-(c) ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO燒結400℃ 90min dummy cell 等效電路特性參數……………………………………………………………..57
表4-9-(d) ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO燒結400℃ 90min dummy cell 等效電路特性參數……………………………………………………………..57
表4-10 ITO/Pt/electrolyte/CNT(瓶號B噴塗四次)/ITO燒結400℃ 60min dummy cell 等效電路特性參數……………………………………………………………..61
表4-11瓶號A噴塗四次奈米碳管之DSSC太陽能電池特性分析……….……..63
表4-12瓶號B噴塗四次奈米碳管之DSSC太陽能電池特性分析……….……..63
表4-13瓶號A噴塗四次燒結400℃ 90min奈米碳管之DSSC太陽能電池特性分析……………………………………………………………………………………..63
表4-14瓶號B噴塗四次燒結400℃ 90min奈米碳管之DSSC太陽能電池特性分析…………………………………………………………………………..….……..63

圖目錄
圖2-1染料敏化太陽能電池之內層結構示意圖……………………….…………...4
圖2-2染料敏化太陽能電池之結構示意圖……………………………….........…...5
圖2-3 (a) N3 Dye (b)N719Dye……………………………………………………...7
圖2-4染料敏化太陽能電池發電原理圖…………………………………………….8
圖2-5染料敏化太陽能電池之等效電路圖…………………………..………….…9
圖2-6染料敏化太陽能電池之EIS阻抗分析圖示……………………….…...….11
圖2-7 Pt-Ti on ITO-PEN和Pt on FTO glass EIS圖示……………………………...12
圖3-1實驗設計示意圖……………………………………………………………13
圖3-2 (a)真空蒸鍍示意圖 (b)蒸發用電子槍工作原理 (c)實體圖.........................14
圖3-3噴塗設備……………………………………………………………………..15
圖3-4 對電極基板結構示意圖(a) ITO鑽孔 (b) ITO (c) FTO厚度4mm………....18
圖3-5 燒結溫度控制圖…………………………………………………………..…20
圖3-6 (a)浸泡示意圖(b)浸泡完成示意圖 ……………………………………..….21
圖3-7 封裝示意圖……………………………………………………………….. 22
圖3-8 ITO/CNT /Electrolyte/ Pt/ CNT /ITO結構…………………………….....…23
圖3-9 ITO/TiO2/Dye/Electrolyte/ CNT /ITO結構……………………………….….24
圖3-10 FE-SEM 實體圖…………………………………………………………....25
圖3-11恆電位儀分析架構圖………………………………………………...…..…26
圖4-1-(a) Pt (20Å )/碘液/CNT(瓶號A噴塗一次)EIS量測圖………………..….…30圖4-1-(b) Pt (20Å )/碘液/CNT(瓶號A噴塗二次)EIS量測圖…………………...30圖4-1-(c) Pt (20Å )/碘液/CNT(瓶號A噴塗三次)EIS量測圖……………………31
圖4-1-(d) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)EIS量測圖………………..……31
圖4-1-(e) Pt (20Å)/碘液/CNT(瓶號A噴塗五次)EIS量測圖………………........32
圖4-2 Rs(平均值)、RCT (平均值)與瓶號A噴塗次數的關係圖………...……..…....34
圖4-3瓶號A噴塗(a)一次(b)二次(c)三次(d)四次(e)五次之SEM表面結構圖…...35
圖4-4- Pt (20Å )/碘液/CNT(瓶號B噴塗四次)EIS量測圖………………………...37
圖4-5- Pt (20Å )/碘液/CNT(瓶號C噴塗四次)EIS量測圖………………………37
圖4-6(a)瓶號B(b)瓶號C噴塗四次之SEM的表面結構圖…………………….….39
圖4-7Pt (20Å )/碘液/CNT(瓶號D噴塗四次)EIS量測圖………………………….40
圖4-8-(a) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結300℃ 60min EIS量測圖…42
圖4-8-(b) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結350℃ 60min EIS量測圖…42
圖4-8-(c) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結400℃ 60min EIS量測圖....43
圖4-8(d) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結450℃ 60min EIS量測圖….43
圖4-9瓶號A噴塗四次Rs(平均值)、RCT (平均值)與燒結溫度(60min)的關係圖..45
圖4-10瓶號A噴塗四次燒結(a)300℃(b)350℃(c)400℃(d)450℃ 60min之SEM表面結構圖…………………………………………………………....46
圖4-11-(a) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結300℃ 90min EIS量測圖..47
圖4-11-(b) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結350℃ 90min EIS量測圖..48
圖4-11-(c) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結400℃ 90min EIS量測圖..48
圖4-11-(d) Pt (20Å )/碘液/CNT(瓶號A噴塗四次)燒結450℃ 90min EIS量測圖..49
圖4-12 瓶號A噴塗四次Rs(平均值)、RCT (平均值)與燒結溫度(90min)的關係..51
圖4-13瓶號A噴塗四次燒結(a)300℃(b)350℃(c)400℃(d)450℃ 90min之SEM表面結構圖…………………………………………………………………… 52
圖4-14瓶號A噴塗四次與燒結不同溫度與時間之Rs與Rct-CNT比較圖………53
圖4-15-(a) Pt (20Å )/碘液/CNT(瓶號B噴塗四次)燒結300℃ 90min EIS量測圖..54
圖4-15-(b) Pt (20Å )/碘液/CNT(瓶號B噴塗四次)燒結350℃ 90min EIS量測圖55
圖4-15-(c) Pt (20Å )/碘液/CNT(瓶號B噴塗四次)燒結400℃ 90min EIS量測圖..55
圖4-15-(d) Pt (20Å )/碘液/CNT(瓶號B噴塗四次)燒結450℃ 90min EIS量測圖56
圖4-16瓶號A與瓶號B燒結不同溫度 90min Rs與Rct-CNT的比較圖………57
圖4-17瓶號B噴塗四次燒結(a)300℃(b)350℃(c)400℃(d)450℃ 90min之SEM表面結構圖………………………………………………………………………… 59
圖4-18- Pt (20Å )/碘液/CNT(瓶號B噴塗四次)燒結400℃ 60min EIS量測圖…...60
圖4-19瓶號B噴塗四次燒結400℃ - 60min 90min與未燒結之 Rs 、Rct-CNT與 Rct-Pt的比較圖………………………………………………………………………61

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