應用於染料敏化太陽能電池之釕金屬錯合物合成與其性質探討

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劉毓琪(Yu-Chi Liu) 查詢紙本館藏

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化學學系

論文名稱

應用於染料敏化太陽能電池之釕金屬錯合物合成與其性質探討

相關論文

★ 含3,4-乙烯二氧噻吩輔助配位基之鋨、釕金屬錯合物合成與其在染料敏化太陽能電池的應用	★ 含共軛配位基之釕錯合物合成與其在染料敏化太陽能電池的應用
★ 新型三吡啶釕錯合物光敏化染料的合成與性質探討	★ 釕錯合物敏化太陽能電池元件優化與光伏特性探討
★ 金屬錯合物染料敏化太陽能電池的元件優化	★ 新型三吡啶鋨錯合物染料合成與配位基效應之探討
★ 含高度共軛芳香雜環之釕錯合物的合成以應用於染料敏化太陽能電池	★ 多聯吡啶釕錯合物光敏化染料的合成與性質探討
★ 有機共吸附染料的合成與性質探討

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摘要(中)

本研究主要針對染料敏化太陽能電池(Dye-sensitized solar cells (DSCs))設計合成出兩個新型釕金屬錯合物染料(代號CYC-37與CYC-39)，兩者的設計概念源自於Black dye (N749)，我們在其三吡啶(Terpyridine)固著配位基減少一個羧酸，並藉由四號位延伸配位基之共軛長度以拓展染料的吸光波長範圍和提高吸收係數，同時，兩染料共軛雜環(Conjugated heterocycle)末端均接上正己基以期能提高染料分子吸附之穩定性。在共軛雜環的選擇上，CYC-37是使用有推電子能力的3,4-乙烯二氧噻吩(3,4-ethylene-dioxythiophene (EDOT))單元，而CYC-39則史無前例地引入具拉電子效應的噻唑(Thiazole)，以詳細探討比較推拉電子效應對於染料分子性質與其敏化之電池元件的影響；在DMF溶劑下，CYC-37與CYC-39的最大吸收波長分別為615 nm與616 nm，相較於Black dye不僅紅移了10 nm以上，兩新穎染料的整體吸光強度亦高於Black dye，此外，CYC-39搭配碘電解液的電池元件初步測試效能可達9.0% (優於Black dye元件(8.8%))，此結果顯示由三吡啶固著配位基四號位連接具拉電子效果之共軛雜環，確實有機會提高釕金屬錯合物敏化太陽能電池的光電轉換效率。

摘要(英)

In this research, we designed and synthesized two new ruthenium complexes, coded CYC-37 and CYC-39, respectively for the application in dye-sensitized solar cells (DSCs). The concept of molecular engineering is originated from the Black dye (N749). We replaced one carboxyl group at the fourth position of terpyridine ligand with a conjugated moiety to expand the light absorption range and to enhance the molar absorption coefficient. A hexyl substituent was attached at the terminal of the anchoring ligands to improve adsorption stability of dye molecules. With the attempts to investigate the electron donating and withdrawing effects on the properties of dye molecules and the device performance, the conjugated heterocycle used in CYC-37 and CYC-39 is 3,4-ethylene-dioxythiophene (EDOT) and thiazole, respectively. The maximum absorption wavelength (λmax) of CYC-37 and CYC-39 in DMF is 615 nm and 616 nm, respectively. Compared to the Black dye, CYC-37 and CYC-39 both show superior light harvesting capability. The preliminary test shows that the device sensitized with CYC-39 in conjunction with an iodide-based electrolyte has the good efficiency of 9.0%, which surpasses that of Black dye (8.8%) measured under the same conditions. These results exhibit that the terpyridine ligand bearing unprecedentedly the electron withdrawing heterocycle, thiazole, at the fourth binding position is promising to boost the power conversion efficiency of ruthenium complex sensitized solar cells.

關鍵字(中)

★ 染料敏化太陽能電池
★ 釕金屬錯合物
★ 固著配位基

關鍵字(英)

論文目次

中文摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 x
第一章緒論 1
1-1前言 1
1-2太陽光譜與太陽能電池的光伏參數 1
1-3太陽能電池的發展歷史簡介 4
1-4染料敏化太陽能電池的工作原理 6
1-5染料分子設計相關文獻探討 9
1-5-1釕金屬錯合物之結構設計 10
1-5-2含噻唑單元之染料 27
1-6研究動機 36
第二章實驗部分 39
2-1實驗藥品 39
2-2中間產物之結構與簡稱 41
2-3合成流程及實驗步驟 45
2-3-1在四號位置帶有溴的三牙酯基之合成 45
2-3-2 Ligand-37-ester的合成 50
2-3-3 Ligand-39-ester的合成 53
2-3-4釕金屬錯合物CYC-37的合成 57
2-3-5釕金屬錯合物CYC-39的合成 59
2-4儀器分析與樣品製備 61
2-5 元件組裝與光電轉換效率量測 71
2-5-1 DSCs元件組裝流程 71
2-5-2 光電轉換效率量測系統 72
第三章結果與討論 74
3-1 合成反應之探討 74
3-1-1三吡啶配位基合成 74
3-1-2釕金屬錯合物合成遭遇之問題與解決方法 76
3-2 結構鑑定與光物理性質探討 82
3-2-1 染料官能基鑑定 82
3-2-2 釕金屬錯合物光物理性質探討 83
3-3 釕金屬錯合物電化學性質與前置軌域位能計算 86
3-4 CYC-37、CYC-39及Black dye敏化電池元件性能探討 90
第四章結論 95
參考文獻 96
附錄 101

參考文獻

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指導教授

陳家原(Chia-Yuan Chen)

審核日期

2018-1-31

推文