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  • 學位論文

導電高分子PDMICA薄膜之光電性質及其電致色變元件應用

On the Electro-Optical Properties of PDMICA Thin Film and Its Application to Electrochromic Devices

指導教授 : 何國川

摘要


本研究主要針對一新穎導電高分子材料, poly(5,6-dimethoxyindole-2-carboxylic acid) (PDMICA) 之電化學性質及其與 poly(3,4-ethylenedioxythiophene) (PEDOT) 搭配之電致色變元件進行探討。   在第一部份 (第四章) 中,利用電化學微量石英震盪天平 (EQCM) 探討 PDMICA 薄膜在四種不同電解質:LiTFSI、LiNO3、LiI、NaNO3 中,陰、陽離子以及水分子進出 PDMICA 薄膜的情形。實驗結果顯示陰離子比陽離子在 PDMICA 薄膜進行氧化還原的過程中扮演更重要的角色,因此,後續針對陰離子以及水分子進出 PDMICA 薄膜的情形做更詳細的探討,並量化出陰離子以及水分子的進出通量,計算出每個 TFSI- 離子會平均攜帶約 14.7 個水分子,而在每個 NO3- 離子會平均攜帶約 3.4 個水分子。   本論文之第二部份 (第四章與第五章) 中,藉由電聚合方法製備 PDMICA 薄膜,並利用循環伏安分析與紫外與可見光譜進行探討。 PDMICA 薄膜在添加 1.0 mM HCl 的 0.1 M LiTFSI 電解質中具有可逆的電致色變行為,其安全操作電位窗範圍為 -0.5 至 0.5 V (vs. Ag/AgCl) 之間,可由 -0.5 V 的透明無色變化至 0.5 V 的綠色,該薄膜在波長為 520 nm 下之最大的穿透度變化及著色效率分別可達到 15% 及 73 cm2/C。此全新之互補式薄膜型電致色變元件由 PDMICA 與 PEDOT 所組成,並達到高對比之效果,其穿透度變化可達 39%。該元件在波長為 583 nm 下之著色效率達到約 372 cm2/C。

並列摘要


In this research, the main objective is to analyze the electrochemical properties of a novel conducting polymer, poly(5,6-dimethoxyindole-2-carboxylic acid) (PDMICA), and its electrochromic device assembled with poly(3,4-ethylenedioxythiophene) (PEDOT). In the first part (Chapter 4), the transport phenomena of anions, cations, and water molecules through the film of PDMICA was studied in the electrolytes of LiTFSI, LiNO3, LiI, and NaNO3, by means of electrochemical quartz crystal microbalance (EQCM), intending to throw more light on its electrochromic behavior. Cations do not affect the ion transport, but anions play an important role during the reduction and oxidation of the film. The molar fluxes of anions and water molecules in the film of PDMICA were estimated for LiTFSI and LiNO3. Besides, the number of accompanying water molecules with TFSI- and NO3-, during the redox switching of PDMICA in LiTFSI and LiNO3 were calculated to be 14.7 and 3.4 per TFSI- and NO3-, respectively. In the second part (Chapter 4 and Chapter 5), PDMICA is prepared by electro-polymerization and investigated using in situ spectro-electrochemical analyses, including cyclic voltammertry (CV) and UV-visible (UV-vis) spectroscopy. A significant change from transparent (-0.5 V vs. Ag/AgCl) to green (0.5 V vs. Ag/AgCl) and a reversible electrochromic behavior of PDMICA film are observed when the film is performed in an aqueous solution consisting of 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1.0 mM hydrochloric acid (HCl). The maximum transmittance change (∆T) and the coloration efficiency (η) of PDMICA film are 15% and 73 cm2/C, respectively, at 520 nm. The PDMICA thin film and a thin film of PEDOT are chosen as an anode and a cathode, respectively, in a complementary manner to form a film-type electrochromic device (ECD). A remarkable absorbance attenuation of this ECD is observed in the visible region. The maximum ∆T of the ECD gives a value of 39% (@583 nm) when the applied potential for the device is switched between -0.5 and 1.0 V (PDMICA vs. PEDOT); the η of this ECD is estimated to be 372 cm2/C at 583 nm.

參考文獻


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