用于电致变发射率器件工作电极的聚苯胺薄膜修饰电极的制备及性能研究
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摘要
本文针对反射式电致变发射率器件对其面电极和背电极的要求,以PAn作为实现红外发射率调节的功能材料,分别采用Au/PET、Au/PES电极为基底,通过恒电流方法制备了可用于电致变发射率器件面电极和背电极的PAn/Au/PET、PAn/Au/PES。研究了制备过程中电流密度、聚合时间、单体浓度、支持电解质浓度等制备工艺条件对面电极和背电极电化学制备及性能的影响,确定了可用于制备面电极和背电极的电化学制备条件,得到了各制备工艺参数对PAn/Au/PET循环伏安特性及PAn/Au/PES电致变发射率性能的影响规律。以面电极和背电极组成了原理性电致变发射率目标组件,对其电致变色、电致变发射率、响应时间等性能进行了考察。
对面电极和背电极电化学制备的研究结果表明,制备循环可逆性良好的PAn/Au/PET的较佳聚合溶液组成为1:0.730min。
对PAn/Au/PES电致变发射率性能的研究表明,PAn/Au/PES初始ε曲线的位置将随电流密度的增加而降低,随聚合时间的延长或单体浓度的增加移向高发射率方向,约在C_(An):C_(H_2SO_4)为1:2时有最小值。外加负电压下PAn/Au/PESε曲线有明显下降,相比初始状态的ε曲线△ε在0.2以上,外加正电压对ε曲线的影响不大;PAn/Au/PES的△ε因电流密度改变引起的变化不大,随聚合时间延长或单体浓度的增加有所提高,但随支持电解质浓度的增加将减小。
以面电极和背电极组成的电致变发射率目标组件在工作状态下可弯折,具有一定的颜色记忆效应,红外发射率变化从0.4-0.9,最大红外发射率变化范围约为0.27,响应时间为秒级,循环使用寿命约50次。
Aiming at the requirements of the reflective mode IR-electrochromic device and considering the dynamic changes in IR region of polyaniline, this work focuses on preparing the polyaniline-modified electrodes which can be used as the top electrode and the bottom electrode of the IR-electrochromic device. Au/PET was used as the substrate of the bottom electrode, and Au/PES was used as the substrate of the top electrode. The top electrode (PAn/Au/PET) and the bottom electrode (PAn/Au/PES) were both obtained in the sulfuric solution using galvanostatic method. The interrelation between the electrochemical preparation of polyaniline-modified electrodes and conditions in the electropolymerization process, such as current density, polymerization time, monomer concentration and sulfuric acid concentration, had been analyzed. The electrochemical conditions which can be used toprepare PAn/Au/PET and PAn/Au/PES were confirmed. The prototypal IR-electrochromic devices were fabricated with the top electrodes and the bottom electrodes we prepared. It's properties, such as electrochromic , IR-electrochromic, switching time and cyclability, were investigated.
It was showed that, to prepare the bottom electrodes with the good cycle reversibility, the ideal electrochemical condition was 1:0.730min.
The emissivity property of the top electrodes was deeply effected by polymeric conditions. The s of the top electrodes without applied potential increased when current density decreased or polymeric time extended, and had the lowest value when C_(An):C_(H_2SO_4) was1:2.The s of the top electrodes with applied minus potential was lower thanεwithout applied potential. The effect of positive potential to the e of the top electrode was indistinctive. Monomer concentration increasing or polymeric time extending would lead to the increase ofΔε,but the increase of the sulfuric acid concentration would cause the decrease of As.
The prototypal IR-electrochromic devices exhibit an extreme durability, allowing them to be bent and twisted while in active operation without detriment, an optical memory, emittance value from 0.4 to 0.9, the maximum emittance vibration nearly 0.27, switching time at second level and cyclabilities of at least 50 cycles.
对面电极和背电极电化学制备的研究结果表明,制备循环可逆性良好的PAn/Au/PET的较佳聚合溶液组成为1:0.7
对PAn/Au/PES电致变发射率性能的研究表明,PAn/Au/PES初始ε曲线的位置将随电流密度的增加而降低,随聚合时间的延长或单体浓度的增加移向高发射率方向,约在C_(An):C_(H_2SO_4)为1:2时有最小值。外加负电压下PAn/Au/PESε曲线有明显下降,相比初始状态的ε曲线△ε在0.2以上,外加正电压对ε曲线的影响不大;PAn/Au/PES的△ε因电流密度改变引起的变化不大,随聚合时间延长或单体浓度的增加有所提高,但随支持电解质浓度的增加将减小。
以面电极和背电极组成的电致变发射率目标组件在工作状态下可弯折,具有一定的颜色记忆效应,红外发射率变化从0.4-0.9,最大红外发射率变化范围约为0.27,响应时间为秒级,循环使用寿命约50次。
Aiming at the requirements of the reflective mode IR-electrochromic device and considering the dynamic changes in IR region of polyaniline, this work focuses on preparing the polyaniline-modified electrodes which can be used as the top electrode and the bottom electrode of the IR-electrochromic device. Au/PET was used as the substrate of the bottom electrode, and Au/PES was used as the substrate of the top electrode. The top electrode (PAn/Au/PET) and the bottom electrode (PAn/Au/PES) were both obtained in the sulfuric solution using galvanostatic method. The interrelation between the electrochemical preparation of polyaniline-modified electrodes and conditions in the electropolymerization process, such as current density, polymerization time, monomer concentration and sulfuric acid concentration, had been analyzed. The electrochemical conditions which can be used toprepare PAn/Au/PET and PAn/Au/PES were confirmed. The prototypal IR-electrochromic devices were fabricated with the top electrodes and the bottom electrodes we prepared. It's properties, such as electrochromic , IR-electrochromic, switching time and cyclability, were investigated.
It was showed that, to prepare the bottom electrodes with the good cycle reversibility, the ideal electrochemical condition was 1:0.7
The emissivity property of the top electrodes was deeply effected by polymeric conditions. The s of the top electrodes without applied potential increased when current density decreased or polymeric time extended, and had the lowest value when C_(An):C_(H_2SO_4) was1:2.The s of the top electrodes with applied minus potential was lower thanεwithout applied potential. The effect of positive potential to the e of the top electrode was indistinctive. Monomer concentration increasing or polymeric time extending would lead to the increase ofΔε,but the increase of the sulfuric acid concentration would cause the decrease of As.
The prototypal IR-electrochromic devices exhibit an extreme durability, allowing them to be bent and twisted while in active operation without detriment, an optical memory, emittance value from 0.4 to 0.9, the maximum emittance vibration nearly 0.27, switching time at second level and cyclabilities of at least 50 cycles.
引文
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[3] Gentex Corporation. Web site: http://www.gentex.com.
[4] Lawrence Berckley National laboratory. Web site:http://windows.lbl.gov/comm_perf/electroSys.htm.
[5] F. Carpi, D. De Rossi.Colours from electroactive polymers: Electrochromic,electroluminescent and laser devices based on organic materials. Optics & Laser Technology 2006, 38: 29.
[6] P. Chandrasekhar, et al. Conducting polymer(CP) infrared electrochromics in spacecraft thermal control and military applications. Synthetic Metals, 2003 (135-136):23.
[7] 张吉东．有机近红外电致变色器件：[博士论文]．长春：中国科学院长春应用化学研究所，2004．
[8] R.B.Goldner, et al. Some lessons learned from research on a thin film electrochromic window. Solid State Ionics,1994(70/71): 613.
[9] Stuart F. Cogan, et al. Variable Transmittance Coatings Using Electrochromic Lithium Chromate and Amorphous WO_3 Thin Films. Journal of The Electrochemical Society,1997,144(3): 956.
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[11] Jeffrey S. Hale, John A. Woollam. Prospects for IR emissivity control using electrochromic structures. Thin Solid Films, 1999(339): 174.
[12] A.Azen,G.Gustavsson, et al. Electrochromic devices on polyester foil. Solid StateIonics. 2003, 165(1-4):1.
[13] Dynam IR Corporation. Web site: http://www.dynamircorp.com.
[14] C. G. Granqvist. Electrochromic devices. Journal of the European Ceramic Society 2005,25:2907.
[15] E. B. Franke, et al.All-solid-state electrochromic reflectance device for emittance modulation in the far-infrared spectral region. Applied physics letters, 2000,77(7): 930.
[16] Prasanna Chandrasekhar, et al. Large, Switchable Electrochromism in the Visible Through Far-Infrared in Conducting Polymer Devices. Adv. Funct. Mater. 2002, 12(2):95.
[17] 江燕．新盛世计划的第血颗卫星ST-5——“纳卫星星座计划开拓者”．国际太空.2003．4：19．
[18] 郭宁．可变发射率热控器件的研究进展．真空与低温．2003，9(4)：187
[19] A.Bessiere, et al. Optical properties of an all-plastic WO_3·H_2O-based infrared modulator. Journal of Applied Physics, 2004(95): 7701.
[20] N.Kislov, Electrochromic Variable Emittance Devices on Silicon Wafer for Spacecraft Thermal Control, Space Technology and Applications International Forum-STAIF 2004.
[21] P.Topart, P.Hourquebie. Infrared switching electroemissive devices based on highly conducting polymers. Thin Solid Films, 1999, 352:243.
[22] Prasanna Chandrasekhar, et al. Variable emittance materials based on conducting polymers for spacecraft thermal control. In: Space Technology Applications International Forum 2003. AIP Conference Proceedings. Albuquerque, NM: American institude of physics, 2003, 157.
[23] 周琴．聚苯胺类导电聚合物的电化学现场ESR研究：[博士论文]．武汉：武汉大学，2004．
[24] 李永舫．导电聚合物的电化学制备和电化学性质研究．电化学，2004，10(4)：369．
[25] Roncali, J. Synthetic principles for bandgap control in linear π-conjugated systems.Chemical Reviews, 1997, 97:173.
[26] Irina Schwendeman. Optical and transport properties of conjugated polymers and their application to electrochromic devices:[Dissertation]. Florida: The Graduate school of the university of of Florida, 2002.
[27] L.Groenendaal, et al.Poly(3,4-ethylenedioxythiophene) and Its Derivatives: Past,Present, and Future. Advanced Materials, 2000, 12(7): 481.
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