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標題: | 雙金屬超分子高分子或N-甲基吩噻嗪離子液體應用於電致色變元件 Electrochromic Devices Based on Heterometallo-supramolecular Polymer or N-methylphenothiazine Derived Ionic Liquid |
作者: | Li-Yin Hsiao 蕭力尹 |
指導教授: | 何國川(Kuo-Chuan Ho) |
關鍵字: | 電致色變元件,全波段吸收,金屬超分子高分子,N-甲基吩??離子液體,多壁奈米碳管, Electrochromic device,Panchromatic,Metallo-supramolecular polymer,N-methylphenothiazine,Ionic liquid,Multi-walled carbon nanotube, |
出版年 : | 2018 |
學位: | 碩士 |
摘要: | 在本論文中,本研究主要製備了兩種電致色變元件並加以探討其電化學性質,組成第一種電致色變元件的變色材料為釕鐵雙金屬超分子高分子和普魯士藍,第二種電致色變元件則由N-甲基吩噻嗪離子液體和苯基紫精所製備而成。
在本研究第三章,首先製備出釕鐵雙金屬超分子高分子,並對其單膜電化學性質仔細探討。另外,由於普魯士藍是廣為人知非常穩定的電變色材料,且在光學表現上在600至800 nm處有不錯的吸收強度,而釕鐵雙金屬超分子高分子具有400到600 nm之強烈吸收峰,因此我們提出藉由此兩種材料之搭配,製備出能吸收全波段可見光的電致色變元件。為了防止漏液,此元件的電解質採用高分子電解質,當操作電位在1.3 V和-2.2 V之間,此元件在分別503、580和690 nm之波長下具有52.7%、46.9%和28.0%穿透度變化,在503 nm、580 nm波長下有小於0.5 s的快速著去色時間,還發現此元件具有特殊的三段式著色效率變化,而最大著色效率為525.1 cm2/C。另一方面,本研究還探討了記憶效應與長期穩定性相關性,藉由添加酸化過後的多壁奈米碳管,其表面所具有酸化官能基可以吸附過氯酸根離子,因此當釕鐵雙金屬超分子高分子加入些許多壁奈米碳管,在經過200秒之後,在相較記憶效應不好的503奈米波段,此薄膜仍可以維持42%原來之最高去色穿透度。 在本研究第四章,藉由五種步驟反應成功合成出全新之帶有N-甲基吩噻嗪的離子液體,分別為硫化、脘基化、取代反應、離子化和陰離子製換。且每步驟之中間產物和最終產物之結構皆用核磁共振和質譜儀確認。首先,在三級式之電解槽中對N-甲基吩噻嗪的離子液體做電化學分析,發現接上離子液體後,因為分子結構由原本平面分子(N-甲基吩噻嗪)改變為非平面分子,導致N-甲基吩噻嗪離子液體之吸收波長從520奈米偏移到575 nm之位置,顏色從紅色變為紫色。為了進一步確認N-甲基吩噻嗪離子液體在元件中電化學表現,我們使用穩定度很高的苯基紫精與之作為搭配來組成電致色變元件,此元件0 V與1.2 V的操作下,在575 nm波段下具有69.2%之光學穿透度化,小於4 s的著去色響應時間、高著色效率(531 cm2/C),在10,000圈操作後仍保持其最初97.8%之光學度穿透度變化。由此可知,本研究所合成出來的新型氧化著色材料:N-甲基吩噻嗪的離子液體同時保有N-甲基吩噻嗪的高吸收度變化和離子液體的高穩定性。 In this thesis, the electrochromic (EC) performance of two electrochromic devices (ECDs), Ru(II)/Fe(II)-based heterometallo-supramolecular polymer/Prussian blue (PolyRuFe/PB) and N-methylphenothiazine-based ionic liquid/phenyl viologen (NMP-IL/PV) was carefully investigated. Firstly, Ru(II)/Fe(II)-based heterometallo-supramolecular polymer (PolyRuFe) has been successfully synthesized and the electrochromic properties are carefully investigated. Also, Prussian blue (PB) is selected as counter electrode owing to its good stability and large absorbance change of UV-visible spectra from 600 to 800 nm, which is cooperated with main absorbance change of PolyRuFe from 400 to 600 nm. The PolyRuFe/PB ECD has been successfully fabricated with panchromatic characteristic and the mechanism is proposed. Switching between -1.3 and 2.2 V, the proposed ECD utilizing the gel-typed electrolyte based on PMMA preventing the leakage problem exhibits the transmittance changes of 52.7%, 46.9%, and 28.0% at 503, 580, and 690 nm, respectively. Moreover, the fast response time of less than 0.5 s could be observed at 503 and 580 nm for both coloring and bleaching. The PolyRuFe/PB ECD also exhibits three-step coloration efficiency and the highest values are 525.1 cm2/C at 503 nm. Furthermore, we proposed the relationship between the long-term stability and the memory effect of PolyRuFe/PB ECD. It was found that PolyRuFe incorporated with multi-walled carbon nanotubes (PolyRuFe-MWCNT) exhibits longer memory effect than bare PolyRuFe thin film. PolyRuFe-MWCNT remained 75%, 59% and 42% of their initial saturated bleaching state at 503 nm after 50, 100 and 200 s, respectively. In the second part, we synthesized the novel NMP-based IL via five-step reaction, including thionation, methylation, substitution, ionization and anion exchange that no one demonstrated before. Each structure of intermediates was confirmed by 1H-NMR, 13C-NMR and mass spectra. When the functional groups graft on the benzene, the obvious absorbance change to 575 nm is found. It is explained that molecular structures changes from open ion-radical to hindered ion-radical. Namely, the planar structure of NMP convert into NMP-IL which belongs to hindered system. In order to investigate the EC performance of NMP-IL in ECD, the complementary ECD was fabricated incorporating the cathodically coloring material, PV, which is well-known for its high optical contrast and good stability. The NMP-IL/PV ECD exhibits largest transimittance change of 69.2% and desirable coloration efficiency of 531 cm2/C at 575 nm, which is contributed to the additive absorbance change of both coloring material. Moreover, the short switching times of less 4 s and good long-term stability (remained 92%, 96.2% and 97.8% of its original ΔT after 10,000 cycles at 430, 575 and 710 nm respectively) is obtained. These evidences reveal that the new potential anodically coloring material, NMP-IL, combining both the advantages of NMP and ionic liquid have successfully synthesized. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/76411 |
DOI: | 10.6342/NTU201802607 |
全文授權: | 同意授權(全球公開) |
電子全文公開日期: | 2023-08-08 |
顯示於系所單位: | 化學工程學系 |
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