臺灣博碩士論文加值系統

染料敏化太陽能電池(DSSC)具有低成本、製程簡易及光電轉換 效率高等優點,目前也有許多研究團隊投入研究。由於白金背電極價 格昂貴,使商業化受到限制,因此我們希望研究出能取代白金的低成 本背電極材料,製作出高效率染料敏化太陽能電池。 本研究分為兩大部分:
一、本研究將聚鄰甲氧基苯胺(Poly(o-methoxyaniline),POMA) 以有機酸 1S-(+)-camphorsulfonic acid(CSA)進行摻雜,由於導電高分 子本身擁有不同氧化態及可以摻雜和去摻雜特性,利用摻雜後的 POMA-CSA 具有良好電化學活性,目的是希望取代昂貴的白金背電 極,製作出高效率染料敏化太陽能電池。我們研究不同比例有機酸摻 雜之 POMA,其摻雜後的高分子型態會改變,適量的有機酸摻雜的背 電極具高比表面積,為奈米顆粒結構,且可以提高電極表面粗糙度、 增加結晶性及降低背電極阻抗,因此對染料敏化太陽能電池效率可以 提升。由一系列不同比例有機酸添加之背電極比較,聚鄰甲氧基苯胺 摻雜有機酸 16%時展現最佳效果,元件效率高達 8.76%,相比於同樣 製程條件下製作之白金背電極效率佳,具有應用在染料敏化太陽能電 池之潛力。
二、利用原位聚合法製備出以共價鍵接枝方式的聚鄰甲氧基苯胺 /氧化石墨烯複合材料,石墨烯/POMA 形成分散良好之複合材料,經 有機酸摻雜後,形成 POMA-CSA 接枝於官能基化石墨烯表面,由於 POMA-CSA 有不同的氧化還原態,與碘電解液可藉由氧化還原進行 電子轉移,而具有優異的電活性;且其奈米顆粒接枝於導電石墨烯表 面,由於高比表面積及形成的導電網絡,因此可以提高背電極與電解 液間之接觸表面積,降低介面阻抗。因此本研究結合優良摻雜效應的 POMA-CSA 及良好分散性的石墨烯二者協同效應,製備出高電活性、 低阻抗、高粗糙度且元件效率高的背電極材料,其中 POMA-FGO (0.5%)-CSA (16%) 背電極元件效率高達 8.81%,優於 POMA-CSA(16%) 背電極效率 8.56%,且優於白金背電極元件效率 7.59%。

Dye-sensitized solar cells (DSSCs) have the advantages of simple process, high efficiency, and low cost. DSSCs have been investigated extensively due to their various features and merits for applications in renewable energy. However, Pt is an expensive metal element and may limit the DSSC applications.As such, replacing the expensive Pt with other materials having the required electrochemical properties for the counter electrode will be much welcome.
There are two parts in this thesis. First, a conductive polymer poly(o-methoxyaniline) (POMA) doped with an organic acid, 1S-(+)-camphorsulfonic acid (CSA), was used to fabricate counter electrodes for dye-sensitized solar cells, and the effects of POMA doped with various weight ratios of CSA on the efficiency of DSSCs were investigated. The electrodes of POMA-CSA exhibited with increased surface roughness, increased crystallinity, and decreased impedance. The characteristics of DSSCs based on POMA-CSA electrodes were analyzed using J-V, IPCE, and EIS measurements. The experimental results reveal that the POMA-CSA(16%) electrodes exhibited the optimal electrode characteristics. The DSSC based on POMA-CSA(16%) CE reached an efficiency of 8.76%, which was higher than that of DSSCs with platinum CE. Second, Covalent bond–grafted soluble poly(o-methoxyaniline)- –functional graphene oxide (POMA-FGO) nanocomposite materials were prepared and doped with 1S-(+)-camphorsulfonic acid as counter electrodes for realising dye-sensitised solar cells. DSSCs with the POMA-FGO and POMA-FGO-CSA CEs exhibited substantially reduced interfacial impedance, which may be attributed to dual improvement from the well-dispersed FGO and the doping effect of CSA. Therefore, the efficiency levels of the DSSCs fabricated with the POMA-FGO CEs were higher than those of the DSSCs fabricated with the POMA CEs. When CSA was doped with the CEs, the efficiency of the DSSC was further enhanced. In particular, the efficiency of a DSSC based on the POMA-FGO (0.5%)-CSA (16%) CEs reached 8.81%, which was higher than that of a DSSC with a conventional platinum electrode. Therefore, POMA-FGO-CSA–based CEs can serve as a potential alternative to expensive platinum CEs.

摘要............................................................................................................. I
Abstract .................................................................................................... IV
一、緒論.....................................................................................................1
1-1 前言..................................................................................................1
1-1-1 能源現況 ................................................................................1
1-2 染料敏化太陽能電池......................................................................2
1-2-1 染料敏化太陽能電池發展.......................................................2
1-2-2 染料敏化太陽能電池之原理 [1] ..............................................3
1-2-3 染料敏化太陽能電池之效率...................................................4
圖1-1 染料敏化太陽能電池基本架構及工作原理[1].............................5
1-3 奈米複合材料染料敏化太陽能電池測試......................................6
1-3-1 實驗方法....................................................................................6
1-3-2 背電極製備: ..............................................................................7
1-3-3 循環伏安法(CV):......................................................................7
1-3-4 J-V Curve....................................................................................8
1-3-5 外部量子轉換效率分析儀(IPCE)............................................9
1-3-6 電化學分析儀(EIS).................................................................10
1-4 導電高分子介紹............................................................................12
1-4-1 導電高分子的起源 .................................................................12
1-4-2 基本能帶理論與摻雜理論.....................................................13
1-4-3 共軛高分子導電理論.............................................................16
1-4-4 常見共軛高分子結構.............................................................17
1-4-5 聚苯胺(Polyaniline).................................................................18
1-4-6 聚苯胺的聚合 .........................................................................21
1-5 石墨烯簡介及製備........................................................................22
1-5-1 前言...........................................................................................22
1-5-2 石墨烯簡介..............................................................................24
1-5-3 石墨烯的化學與物理性質.....................................................26
1-5-4 石墨烯的製備方法 .................................................................28
1-6 石墨烯/高分子奈米複合材料的合成方法 ..................................32
1-7 研究動機與目的............................................................................35
二、聚鄰甲氧基苯胺導電高分子摻雜有機酸於染料敏化太陽能電池背
電極之研究...............................................................................................37
2-1 前言................................................................................................37
2-2 實驗藥品........................................................................................43
2-3 鑑定及分析儀器............................................................................45
2-4 實驗方法........................................................................................46
2-4-1 聚鄰甲氧基苯胺之合成.........................................................46
2-4-2 材料合成步驟 .........................................................................48
2-4-3 背電極製作..............................................................................49
2-4-4 元件製作..................................................................................50
2-5 結果與討論....................................................................................51
2-5-1 結構與形貌之鑑定 .................................................................51
2-5-1-1 掃描式電子顯微鏡(FESEM) ..............................................51
2-5-1-2 原子力顯微鏡(AFM)............................................................52
2-5-1-3 EDS 化學成分分析圖及各元素原子比例 ..........................53
2-5-1-4 X 射線粉末繞射儀(XRD)分析 ............................................54
2-5-1-5 穿透式電子顯微鏡(TEM)....................................................55
2-5-1-6 傅立葉轉換紅外線光譜儀(FTIR).......................................57
2-5-1-7 拉曼光譜(Raman)................................................................59
2-5-1-8 化學分析電子光譜(XPS) .....................................................60
2-5-1-9 交流阻抗圖譜(EIS)分析.....................................................62
2-5-1-10 循環伏安法(CV)................................................................63
2-5-1-11 Randles-Sevcik Plot.............................................................65
2-5-1-12 塔伏曲線(Tafel Curve) .......................................................66
2-5-2 有機酸摻雜 POMA 在染料敏化太陽能電池的應用研究.....67
2-5-2-1 J-V curve................................................................................67
2-5-2-2 IPCE.......................................................................................69
2-5-2-3 交流阻抗圖譜(EIS)分析.....................................................70
2-7 結論................................................................................................72
三、聚鄰甲氧基苯胺-石墨烯奈米複合材料於染料敏化太陽能電池背
電極之研究...............................................................................................74
3-1 前言................................................................................................74
3-2 實驗藥品........................................................................................81
3-3 鑑定及分析儀器............................................................................84
3-4 實驗方法........................................................................................85
3-4-1 改質 Hummers`method 製備氧化石墨烯之合成[52].............85
3-4-2 鄰甲氧基苯胺修飾氧化石墨烯(GO)之製備方法.................86
3-4-3 原位聚合法 FGO/POMA 奈米複合材料...............................87
3-4-4 材料合成步驟 ..........................................................................88
3-4-5 背電極製作..............................................................................89
3-4-6 元件製作..................................................................................90
3-5 結果與討論 .....................................................................................91
3-5-1 FGO 及 POMA-FGO 結構與形貌之鑑定 ..............................91
3-5-1-1 化學分析電子光譜(XPS)....................................................91
3-5-1-2 穿透式電子顯微鏡(TEM)...................................................94
3-5-1-3 傅立葉轉換紅外線光譜儀(FTIR).......................................95
3-5-1-4 拉曼光譜(Raman)................................................................97
3-5-2 背電極材料結構與形貌之鑑定 ................................................98
3-5-2-1 掃描式電子顯微鏡(FESEM) ..............................................98
3-5-2-2 原子力顯微鏡(AFM).........................................................100
3-5-2-3 穿透式電子顯微鏡(TEM).................................................101
3-5-2-4 EDS 化學成分分析圖及各元素原子比例 ........................102
3-5-2-5 化學分析電子光譜(XPS)..................................................103
3-5-2-6 X 射線粉末繞射儀(XRD)分析 ..........................................105
3-5-2-7 循環伏安法(CV)................................................................106
3-5-3 染料敏化太陽能電池的應用研究.......................................109
3-5-3-1 J-V Curve.............................................................................109
3-5-3-2 IPCE.....................................................................................112
3-5-3-3 交流阻抗圖譜(EIS)分析...................................................113
3-7 結論..............................................................................................115
第四章 總結...........................................................................................117
第五章 參考文獻 ..................................................................................119

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