釕與鋨錯合物染料敏化太陽能電池性能優化與特性探討

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林廖展(Liao-Chan Lin) 查詢紙本館藏

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論文名稱

釕與鋨錯合物染料敏化太陽能電池性能優化與特性探討

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摘要(中)

染料敏化太陽能電池(Dye-sensitized solar cells (DSCs))具有製程簡易等優點，在此太陽光電技術中，吸附於多孔隙二氧化鈦(TiO2)薄膜上的染料分子是影響其元件光電轉換效率的關鍵，為使元件展現最佳性能，須依據染料分子的吸光與吸附性質，調整二氧化鈦薄膜厚度，並須嘗試添加共吸附劑以減少染料在薄膜上的聚集，以提高元件的短路電流密度(Short-circuit current density (Jsc))，若能同時抑制電荷再結合，也可一併增加元件的開路電壓(Open-circuit voltage (Voc))與填充因子(Fill factor (FF))。本研究是針對本實驗室所開發的新型染料(包含釕錯合物CYC-21、CYC-53、CYC-55，與鋨錯合物CYC-45I、CYC-45Cl、CYC-33O )，進行元件條件的優化以提高其光電轉換效率，其調整項目除了使用不同的共吸附劑(包含Chenodeoxycholic acid (CDCA)與2-(4-Butoxyphenyl)-N-hydroxyacetamide (BPHA))與染料分子進行共吸附，以有效減少染料分子的聚集現象並填補裸露的TiO2表面外，也另外改變I-/I3-氧化還原對電解液的組成(包含不同濃度的LiI、4-tert-Butylpyridine (tBP)、Guanidinium thiocyanate (GuSCN)、Lithium carbonate (Li2CO3)等)、調整染料分子的吸附溫度和時間、以及嘗試使用不同有機小分子進行染料吸附之二氧化鈦表面的後處理等。在標準測試條件下(AM 1.5G，25 °C)，CYC-21與CYC-45I染料敏化元件經上述優化後的最高光電轉換效率分別為9.10%和6.17%，值得強調的是，本研究證實CYC-45I染料敏化元件性能可優於本實驗室先前已發表之CYC-33O染料(敏化元件效率為5.7%)，此部分結果可對高效能鋨錯合物染料的元件優化提供明確方向。

摘要(英)

Dye-sensitized solar cells (DSCs) have many advantages, such as easy fabrication. In this type of photovoltaic technology, dye molecules adsorbed onto porous titanium dioxide (TiO2) films are critical for influencing the device′s power conversion efficiency. To achieve optimal device performance, the thickness of the TiO2 film should be adjusted according to the light-harvesting and adsorption properties of the dye molecules. Co-adsorbents should be added to reduce dye aggregation on the film, aiming to increase the short-circuit current density (Jsc). Additionally, inhibiting charge recombination can enhance the open-circuit voltage (Voc) and fill factor (FF). This study focuses on optimizing the device fabrication conditions for newly developed dyes from our laboratory, including ruthenium complexes CYC-21, CYC-53, and CYC-55, and osmium complexes CYC-45I, CYC-45Cl, and CYC-33O, to enhance their performance. Adjustments include the use of different co-adsorbents such as chenodeoxycholic acid (CDCA) and 2-(4-butoxyphenyl)-N-hydroxyacetamide (BPHA), to effectively reduce dye aggregation and cover the bare TiO2 surface. Additionally, changes in the composition of the I-/I3- redox couple electrolyte (including various concentrations of LiI, 4-tert-butylpyridine (tBP), guanidinium thiocyanate (GuSCN), lithium carbonate (Li2CO3), etc.), modification of the TiO2 film thickness, adjustment of the dye molecules’ adsorption temperature and time, and exploration of different organic small molecules for post-staining surface treatment of the dye-adsorbed TiO2 were conducted. Under standard testing conditions (AM 1.5G, 25 °C), the highest power conversion efficiencies of the optimized CYC-21 and CYC-45I dye-sensitized devices were 9.10% and 6.17%, respectively. Notably, this study confirms that the performance of the CYC-45I dye-sensitized device surpasses that of the previously published CYC-33O dye (with an efficiency of 5.7%). These findings provide a clear index for the molecular design and the device optimization of high-efficiency osmium complex dyes.

關鍵字(中)

★ 染料敏化太陽能電池
★ 鋨錯合物
★ 釕錯合物

關鍵字(英)

論文目次

中文摘要 I
Abstract II
謝誌 IV
目錄 V
圖目錄 XI
表目錄 XXI
附錄 XXV
第一章、緒論 1
1.1. 前言 1
1.2. 太陽光譜的介紹 2
1.3. 太陽能電池光伏參數的影響 5
1.4. 染料敏化太陽能電池的工作原理 7
1.5. 染料敏化太陽能電池構造及影響效率的因素 10
1.5.1. 光電極 10
1.5.2. 染料分子 16
1.5.3. 電解質作用 21
1.5.4. 電解質中所使用的添加劑 23
1.6. 染料添中所使用的添加劑 29
1.6.1. 共吸附劑 29
1.6.2. 共吸附劑之種類 31
1.6.3. 預吸附劑 35
1.6.4. 表面後處理 37
1.7. 研究動機 40
第二章、實驗方法 41
2.1. 實驗藥品、材料與儀器 41
2.1.1. 實驗藥品 41
2.1.2. 實驗材料 44
2.1.3. 實驗儀器 44
2.2. 二氧化鈦球珠(TiO2 bead)之合成與漿料製備 46
2.2.1. 二氧化鈦球珠(TiO2 bead)的合成 46
2.2.2. 製備用於網印機(Screen Printing)塗布之二氧化鈦漿料 48
2.3. 染料溶液配製 49
2.4. 電解液配製 49
2.5. TiO2光電極製備過程 50
2.5.1. 預吸附、共吸附、後吸附的光電極製備程序 53
2.6. Pt對電極製備 54
2.7. 染料敏化太陽能電池元件的組裝和光伏參數的量測 55
2.8. 儀器分析與樣品製備 56
2.8.1. 太陽光模擬器與光電轉換效率量測 56
2.8.2. 太陽能電池外部量子效率量測系統 57
2.8.3. 紫外光/可見光/近紅外光吸收光譜 58
2.8.4. 光強度調制光電流/光電壓分析儀；電荷萃取 60
第三章、結果與討論 62
3.1. 自製TiO2球珠漿料(自製層)應用於Black dye染料元件效率和分析 62
3.2. 應用於本實驗之釕與鋨錯合物與有機共吸附染料簡介 67
3.3. CYC-21、CYC-53、CYC-55釕系染料敏化元件組裝條件的優化 70
3.3.1. 改變吸附時間對CYC-21、CYC-53敏化電池光伏參數之影響 70
3.3.2. 調整TiO2薄膜厚與比例對CYC-21與CYC-53敏化元件光伏參數的影響 74
3.3.3. 導入BPHA及改變共吸附濃度與種類對CYC-21敏化元件光伏參數的影響 81
3.3.4. 電解液組成變化對於CYC-21敏化元件光伏參數的影響 89
3.3.4-1. 電解液中添加不同濃度LiI對CYC-21敏化元件光伏參數的影響 89
3.3.4-2. 電解液中添加不同濃度BMII對CYC-21敏化元件光伏參數影響 92
3.3.4-3. 電解液中添加不同濃度I2對CYC-21元件光伏參數的影響 95
3.3.4-4. 電解液中添加不同濃度tBP對CYC-21敏化元件光伏參數的影響 98
3.4. 釕錯合物CYC-21系列染料與N719染料敏化元件之光伏性質比較 101
3.5. CYC-21系列敏化TiO2薄膜之光物理及元件電荷轉移性質探討 104
3.5.1. CYC-21系列及N719染料的UV/Vis吸收光譜圖 104
3.5.2. CYC-21系列染料元件電荷再結合現象與Voc值的關聯性 111
3.5.3. CYC-21系列染料元件的TiO2電子有效擴散係數 114
3.5.4. CYC-21系列染料元件TiO2薄膜上的電子擴散長度及電子收集率 116
3.5.5. 影響CYC-21系列染料元件填充因子的因素 117
3.5.6. CYC-21系列染料的長時間穩定性 118
3.6. CYC-33O、CYC-45Cl、CYC-45I鋨系染料敏化元件組裝條件的優化 120
3.6.1. 添加共吸附劑對CYC-45I敏化元件光伏參數之影響 122
3.6.2. 添加共吸附劑TBA-BPH對CYC-45I敏化元件光伏參數的影響 125
3.6.3. 導入後吸附劑對CYC-45I敏化元件光伏參數的影響 127
3.6.4. 改變吸附溫度對CYC-45I敏化元件光伏參數之影響 132
3.6.5. 調整TiO2薄膜層數對CYC-45I敏化元件光伏參數的影響 135
3.6.6. 電解液組成變化對於CYC-45I敏化元件光伏參數的影響 139
3.6.6-1. 電解液中添加不同濃度BMII對CYC-45I敏化元件光伏參數的影響 139
3.6.6-2. 電解液中添加不同濃度LiI對CYC-45I敏化元件光伏參數的影響 142
3.6.6-3. 電解液中添加不同濃度I2對CYC-45I敏化元件光伏參數的影響 145
3.6.6-4. 電解液中添加不同濃度tBP和GuSCN對CYC-45I敏化元件光伏參數的影響 148
3.6.6-5. 電解液中添加不同濃度Li2CO3對CYC-45I敏化元件光伏參數的影響 150
3.6.7. 調整浸泡時間對CYC-45I敏化元件光伏參數的影響 153
3.7. 鋨錯合物CYC-45系列染料與BD染料敏化元件之光伏性質比較 156
3.8. CYC-45系列元件之光物理及電荷轉移性質探討 159
3.8.1. CYC-45系列及BD染料的UV/Vis吸收光譜圖 159
3.8.2. CYC-45系列染料元件電荷再結合現象與Voc值的關聯性 166
3.8.3. CYC-45系列染料元件電子在TiO2薄膜上的有效擴散係數 168
3.8.4. CYC-45系列染料元件TiO2薄膜上的電子擴散長度及電子收集率 170
3.8.5. 影響CYC-45系列染料元件填充因子的因素 172
3.8.6. CYC-45系列染料的長時間穩定性 173
3.8.7. CYC-45Cl與CYC-45I與碘離子之作用 175
第四章、結論 177
參考文獻 180
附錄 193

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指導教授

陳家原(Chia-Yuan Chen)

審核日期

2024-8-19

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