具長碳鏈釕金屬錯合物染料搭配鈷金屬撮合物應用於染料敏化太陽能電池

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姓名

李佳(Chia Li) 查詢紙本館藏

畢業系所

化學學系

論文名稱

具長碳鏈釕金屬錯合物染料搭配鈷金屬撮合物應用於染料敏化太陽能電池
(Application of ruthenium-based dye with long alkyl chain using cobalt tris(bipyridine) electrolyte in dye sensitized solar cells)

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摘要(中)

染料敏化太陽能電池 ( Dye-Sensitized Solar Cells, DSSCs ) 由於具有透光性、可撓曲性、良好的光電轉換效率與低製造成本等優點，是目前相當熱門的研究領域之ㄧ。在 DSSC 中最常使用的是I-/I3-電解質，但I-/I3-沒有辦法經由結構修飾來增加元件效率。因此，使用鈷金屬錯合物電解質來提高元件的Voc是常用的策略。但是鈷金屬錯合物電解質容易與 TiO2 上的電子產生再結合，影響元件的光電轉換效率。本研究是從本實驗室所合成出的一系列染料中，選擇了尾端具有碳鏈的染料 SJW-B18 和 CYC-B11H 來搭配鈷金屬錯合物電解質組裝成染料敏化太陽能電池，探討釕金屬錯合物結構上加入了長碳鏈是否可以有效的避免鈷金屬錯合物和 TiO2 上的電子再結合，進而提高元件的光電轉換效率。將 SJW-B18 分別和鈷錯合物電解質以及碘系統電解質組裝成元件。在使用鈷錯合物電解質的元件，因為鈷錯合物的還原電位較低，因此元件的Voc值較高（0.814 V，相對於使用I-/I3-的0.781 V）。此外，為了進一步了解染料結構上碳鏈數對鈷電解質的影響，將本實驗室所合成出的另一個高效率染料 CYC-B11H 也搭配鈷電解質組裝成 DSSC 元件並測試其光電表現。實驗結果顯示，使用輔助配為基上具有四個烷基的SJW-B18為敏化劑時，由於染料在二氧化鈦電極上的覆蓋度較好，避免了鈷金屬錯合物與 TiO2 上的電子產生再結合，元件的Voc值損耗較少，讓元件有較高的Voc（0.814 V）及光電轉換效率（7.08%），而最優化的鈷錯合物電解質的組成為0.2 M Co(II), 0.02 M Co(III), 0.5 M TBP和 0.1 M LiClO4配置在乙腈溶劑中。

摘要(英)

Dye-sensitized solar cells (DSSCs), one of the third generation solar cells, are getting more popular these days, due to their light weight, low cost and easy to make. In DSSCs, electrolyte plays the role of re- generating the oxidized dye, transferring hole to the counter electrode and determining the theoretical Voc of the devices. The most common electrolyte used in DSSCs is iodide/triiodide (I-/I3-) redox couple. However, I-/I3- redox system has some disadvantages, such as the fixed redox potential and the structure of the electrolyte can not be modified, which limits it development. Many scientists are now looking for new electrolytes to increase the efficiency of DSSCs. Cobalt based electrolyte, due to it adjustable potential which can be used to increase the Voc of DSSCs, is one of the potential electrolytes. However, cobalt based electrolyte has the disadvantage of easily capture the electron on TiO2 electrode, increasing the dark current, therefore reducing Voc of the device. We use the SJW-B18 and CYC-B11H with long alkyl chain on their ancillary ligand developed by our lab to avoid the charge re- combination. In the study, we found that compared to CYC-B11H dye using SJW-B18 dye, which has 4 terminal alkyl chain, as a sesitizer can protect the surface of TiO2 electrode, increase the resistance between dye adsorbed on TiO2 electrode and electrolyte, prevent the dark current, increase the life time of the electron on TiO2 electrode and decrease the loss of Voc. The highest efficiency of the device based on SJW-B18 dye combined with cobalt electrolyte is 7.08%. The optimal composition of the electrolyte is 0.2 M Co(II), 0.02 M Co(III), 0.5 M TBP and 0.1 M LiClO4 in acetonitrile.

關鍵字(中)

★ 染料敏化太陽能電池
★ 鈷金屬錯合物
★ 染料

關鍵字(英)

論文目次

【目錄】
中文摘要 i
Abstract ii
【目錄】 iv
圖目錄 vi
表目錄 xi
第一章、緒論 1
1.1前言 1
1.2染料敏化太陽能電池（DSSC）的組成以及工作原理 2
1.2.1染料敏化太陽能電池基本工作原理 2
1.2.2 染料敏化太陽能電池光電轉換效率測試 3
1.3 影響染料敏化太陽能電池效率的因素 4
1.4 用於染料敏化太陽能電池之電解質特性 13
1.5 研究動機 21
第二章、實驗方法 23
2.1 實驗藥品與儀器 23
2.2 二氧化鈦奈米顆粒的合成與漿料製備 26
2.2.1 二氧化鈦奈米顆粒的合成 26
2.2.2 適用於網印機 ( Screen Printing )鍍膜之二氧化鈦漿料製備 27
2.3 鈷金屬錯合物氧化還原對 (Cobalt Complexes )的合成 28
2.3.1 Co(bipy)3(PF6)2與Co(bipy)3(PF6)3的合成 28
2.3.2 Cobalt (II) / Cobalt(III) 的電解液製備 29
2.4 染料敏化太陽能電池元件的組裝 29
2.4.1 二氧化鈦電極的製備與修飾 29
2.4.2 Pt對電極的製備 31
2.4.3 太陽能電池元件的組裝及效率測試 31
2.5 儀器分析與樣品製備 32
2.5.1 掃描式電子顯微鏡 32
2.5.2 太陽光模擬器及光電轉換效率測量 32
2.5.3 太陽能電池外部量子效率量測系統 33
2.5.4紫外光/可見光/近紅外光吸收光譜 34
2.5.5 光強度調製光電流/光電壓分析儀 34
2.5.6 交流阻抗分析儀 35
第三章、結果與討論 37
3.1 具有不同輔助配位基之光敏劑搭配碘系統電解質對光電轉換效率的影響 37
3.2 鈷金屬錯合物電解質組成對元件光電轉換效率的影響 39
3.3 電解質中二價鈷金屬的錯合物濃度對元件效率的影響 41
3.4 三價鈷金屬錯合物濃度對元件光電轉換效率的影響 44
3.5 電解質中TBP（4-tert-butylpyridine）濃度改變對元件光電轉換效率的影響 46
3.6 不同粒徑大小的二氧化鈦奈米顆粒對元件光電轉換效率的影響 48
3.7 TiO2漿料內乙基纖維素濃度改變對元件光電轉換效率的影響 51
3.8 不同二氧化鈦薄膜厚度對元件光電轉換效率的影響 55
3.9 改變散射層對元件光電轉換效率的影響 57
3.10 二氧化鈦奈米顆粒的合成方式對由其所組裝之元件的光電表現的影響 60
3.11 染料SJW-B18搭配鈷金屬錯合物電解質和搭配碘系統電解質的比較 63
3.11.1 使用4+4 μm電極（薄電極） 63
3.11.2 使用12+4 μm電極（厚電極） 66
3.12 染料SJW-B18和染料CYC-B11H搭配鈷金屬電解質所組裝之元件的性能比較 70
3.12.1使用4+4 μm電極（薄電極） 70
3.12.2使用12+4 μm電極（厚電極） 75
第四章結論 81
參考文獻 83
附錄 90

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2014-8-26

推文