探索多功能有機分子與多過渡金屬化合物應用於染料敏化太陽能電池

Abstract

本研究涉及多個方面的研究成果，主要集中在染料敏化太陽能電池（DSSCs）領域。首先，研究提出了一系列新型無金屬有機染料，這些染料基於3,3'-二硫代烷基-2,2'-二噻吩（SBT），通過結構改造和使用不同的烷基鏈和共軛噻吩單元，成功抑制了染料的聚集和界面電荷重組，並提高了光電轉換效率（η）。優化的染料與共吸附劑鵝去氧膽酸 (CDCA)結合，在1個太陽光強度下實現了9.46％的高轉換效率。因此，使用該染料和CDCA共吸附劑的DSSC的長期穩定性顯著優於傳統的N719染料。其中，引入了一種新型多功能聚合物離子液體，即聚（氧乙烯）-酰亞胺-2,2,6,6-四甲基-1-哌啶基氧基（POEI-TEMPO），作為准固態DSSCs的添加劑。電解質中的POEI段提供了機械強度，而TEMPO有機自由基則具有良好的氧化還原性能。含有POEI-TEMPO /碘化物電解質的DSSC在1個太陽光強度下表現出9.83％的高效率，室內條件下更達到了令人印象深刻的25.99％。此外，使用POEI-TEMPO作為添加劑的DSSC的長期穩定性非常優秀，表明它在收集周圍光能方面具有實際應用的潛力。此外，探討了以星狀分子3,6-雙(5-(4,4′-雙(3-偶氮丙基)-[1,1′:3′,1′-三聯苯]-5′-基)-噻吩-2-基)-2,5-雙(2-乙基己基)吡咯[3,4-c]吡咯-1,4(2H,5H)-二酮（DPPTPTA）結合電紡法製備的雙金屬銅-鈷磷化物修飾的碳奈米纖維（CuCoP/CNF）進行鉑（Pt）鍍層對電極（CE）的改性。DPPTPTA@CuCoP/CNF修飾的CE在CE/電解質界面上實現了高效的電荷傳遞，低電荷傳遞電阻和良好的電荷分離能力，使得光電轉換效率（η）在1個太陽光強度下達到9.50％，在室內條件下更達到了令人印象深刻的25.44％。改性層的多孔三維奈米纖維結構還確保了長期穩定性，凸顯了其在可再生能源應用中的潛力。最後，探討了有機染料的結構修飾和雙金屬鈷-釩硒化物（CoVSe2）作為DSSCs對電極（CE）的合成。有機染料中引入不同的烷基鏈和共軛噻吩單元抑制了染料聚集和界面電荷再結合。在CE中使用CoVSe2作為活性材料增強了電子傳輸動力學。優化的元件在1個太陽光強度下實現了10.57％的高效率，室內條件下更達到了令人印象深刻的25.89％。該元件還展示出優異的穩定性，在4000小時的測試後保持了大約88％的效率。總結來說，這些研究結果突出了各種修飾、材料和添加劑對於不同照明條件下提高DSSCs效率、穩定性和光收集能力的潛力。這些章節的整合提供了對影響DSSC性能的因素的全面了解，並為高效穩定的太陽能電池元件的開發提供了有價值的見解。

This study encompasses various research findings primarily focused on the field of dye-sensitized solar cells (DSSCs). Firstly, a series of novel metal-free organic dyes based on 3,3'-disulfanyl-2,2'-bithiophene (SBT) were proposed. By modifying the structure and utilizing different alkyl chains and conjugated thiophene units, the aggregation and interfacial charge recombination of the dyes were successfully suppressed, leading to enhanced photoelectric conversion efficiency (η). The optimized dyes, in combination with the co-adsorbent chenodeoxycholic acid (CDCA), achieved a high conversion efficiency of 9.46% under 1 sun illumination. As a result, DSSCs utilizing this dye and CDCA co-adsorbent exhibited significantly improved long-term stability compared to traditional N719 dyes. Among them, a novel multifunctional polymer ionic liquid, poly(oxyethylene)-imide-2,2,6,6-tetramethyl-1-piperidinyloxyl (POEI-TEMPO), was introduced as Additives for quasi-solid-state DSSCs (QSS-DSSCs). The POEI segment in the electrolyte provided mechanical strength, while the TEMPO organic radical acted as a superior mediator with favorable redox properties. The DSSCs incorporating the POEI-TEMPO/iodide electrolyte exhibited a high efficiency of 9.83% under 1 sun and an impressive 25.99% under indoor conditions. Furthermore, the long-term stability of the DSSC with POEI-TEMPO as an additive was promising, indicating its potential for practical application in harvesting ambient light energy. In addition, the modification of the platinum (Pt) coated counter electrode (CE) was explored using a star-shaped molecule, 3,6-bis(5-(4,4′-bis(3-azidopropyl)-[1,1′:3′,1′-terphenyl]-5′-yl)-thien-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPPTPTA), in combination with electrospun bimetallic copper-cobalt phosphide decorated on carbon nanofibers (CuCoP/CNF). The DPPTPTA@CuCoP/CNF modified CE exhibited efficient charge transfer at the CE/electrolyte interface, low charge transfer resistance, and good charge separation ability, resulting in a photoelectric conversion efficiency (η) of 9.50% under 1 sun conditions and an impressive 25.44% under indoor conditions. The porous three-dimensional nanofiber structure of the modified layer also ensured long-term stability, highlighting its potential for renewable energy applications. Finally, explored the structural modification of organic dyes and the synthesis of bimetallic cobalt vanadium diselenide (CoVSe2) for the counter electrode (CE) in DSSCs. The introduction of different alkyl chains and conjugated thiophene units in the organic dyes suppressed significant dye aggregation and interfacial charge recombination. The use of CoVSe2 as an active material in the CE enhanced the electron transport dynamics. The optimized device achieved a high efficiency of 10.57% under 1 sun conditions and an impressive 25.89% under indoor conditions. The device also demonstrated excellent stability, retaining approximately 88% of its efficiency after 4000 h of testing. Overall, these findings highlight the potential of various modifications, materials, and additives for enhancing the efficiency, stability, and light-harvesting capabilities of DSSCs in different lighting conditions. The integration of these chapters provides a comprehensive understanding of the factors influencing DSSC performance and offers valuable insights for the development of efficient and stable solar cell devices.