基于导电聚合物的电致变色器件的制备与性能研究
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摘要
电致变色器件(electrochromic device, ECD)通过电化学的氧化还原反应,展现出可逆的颜色改变,由于其在各种光学装置上的潜在应用而吸引了研究者的广泛兴趣。本课题以全固态电致变色器件的制备为目的,系统研究了各层材料的制备及性能,并将各层材料组装得到了全固态电致变色器件,对其性能进行了优化。
以苯胺为原料,水为反应溶剂,使用十二烷基苯磺酸为掺杂剂和乳化剂,过硫酸铵作为氧化剂,采用乳液聚合法合成了聚苯胺乳液,用于涂敷制膜。通过改变聚乙烯醇的种类和用量,来调节聚苯胺的成膜性,结果表明以PVA1750+50作为成膜助剂,质量分数为2.8%时,可得到成膜效果好,变色性能优异的聚苯胺薄膜。
使用溶胶凝胶法以钛酸丁酯为前驱体制备了二氧化钛溶胶,并通过提拉法制备了不同层数的二氧化钛薄膜。使用XRD、SEM、UV和循环伏安等多种手段对所制备的薄膜进行表征,结果表明:提拉法制备的二氧化钛薄膜提拉层在30～60层时效果良好;经500℃热处理后,可形成明显的锐钛矿型二氧化钛晶体,薄膜均匀平整,厚度大约为200nm,薄膜表面颗粒大小均匀,直径大约10-20nm;所得薄膜具有较强的离子储存能力,锂离子的抽出和嵌入速率稳定,适合作为离子储存层。
使用PMMA为基体制备了电导率为10-3S/cm的凝胶电解质,且平均光学透过率大于85%,适合作为电致变色器件的电解质。将制备得到的聚苯胺、二氧化钛和电解质根据不同的结构,组装成对称结构的电致变色器件(SSECD)和非对称结构的电致变色器件(ASECD)。现场电化学-紫外光谱检测发现,ASECD的最大透射率差ΔTmax=43.3%,比SSECD约增大一倍,显示出黄(-1.4V)、绿(0V)、蓝(1.4V)三色变化,且具有更快的着、褪色响应速度(0.8s),但其使用寿命较SSECD稍差,需进一步改进。
此外还进行了柔性电致变色器件的探索研究,得到了一些初步的结果。
The electrochromic devices (ECDs), which exhibit reversible color change through electrochemical redox reaction, have attracted considerable research interests because of their potential applications in various electronic and optical devices. In this thesis, the preparation technologies about the corresponding materials for the ECDs were investigated.
We used aniline as the electronic material, water as solvent, dodecylbenzenesulfonic acid as dopant and emulsifier, ammonium persulfate as oxidant through in-situ emulsion polymerization to prepare polyaniline-based emulsion, which was used to prepare the polyaniline film by spin-coating. The film-forming property of PANI was adjusted by using different types and content of polyvinyl alcohol during the in-situ emulsion polymerization process. It was found that PVA1750+50 was a good film-forming additive with an addition of 2.8%, resultly a polyaniline film present a well film-forming properties and good electrochromic properties.
Titanium dioxide sol was prepared by using tetrabutyl titanate as the precursor via sol-gel method. The different layers of titanium dioxide films were prepared by dip-coating method, and the resulted films were characterized by XRD, SEM, UV, cyclic voltammetry and so on. Results show that the number of titanium dioxide films is in 30 to 60 layer. Besides, the typical anatase titanium dioxide crystal was formed after heat-treated at 500℃, which had the thickness of about 200 nm with the uniform particle size diameter of about 10-20 nm. The films had strong ion storage capacity, steady extraction and embedding rates of lithium-ion, suitably used as the ion storage layer.
The gel electrolyte with PMMA-based system with a conductivity of 10-3S/cm and the optical transmittance more than 85% was prepared, which was suitable used as the electrolyte of electrochromic device. In addition, the symmetrical structure electrochromic device (SSECD) and the asymmetric structure electrochromic device (ASECD) were assembled with the as-prepared polyaniline, titanium dioxide and electrolytes. The in-situ electrochemical UV-visible spectroscopy investigation found that the maximum transmission rate difference of ASECD was 43.3%, nearly about twice of SSECD. Meanwhile, ASECD took on reversible color variation among yellow (-1.4 V), green (0 V) and blue (1.4 V), and had faster coloring/fading response time (0.8 s), but its lifetime was little less than that of the SSECD, and need a further improvement.
Moreover, a flexible electrochromic device was explorated and studied, and some preliminary results were obtained.
以苯胺为原料,水为反应溶剂,使用十二烷基苯磺酸为掺杂剂和乳化剂,过硫酸铵作为氧化剂,采用乳液聚合法合成了聚苯胺乳液,用于涂敷制膜。通过改变聚乙烯醇的种类和用量,来调节聚苯胺的成膜性,结果表明以PVA1750+50作为成膜助剂,质量分数为2.8%时,可得到成膜效果好,变色性能优异的聚苯胺薄膜。
使用溶胶凝胶法以钛酸丁酯为前驱体制备了二氧化钛溶胶,并通过提拉法制备了不同层数的二氧化钛薄膜。使用XRD、SEM、UV和循环伏安等多种手段对所制备的薄膜进行表征,结果表明:提拉法制备的二氧化钛薄膜提拉层在30～60层时效果良好;经500℃热处理后,可形成明显的锐钛矿型二氧化钛晶体,薄膜均匀平整,厚度大约为200nm,薄膜表面颗粒大小均匀,直径大约10-20nm;所得薄膜具有较强的离子储存能力,锂离子的抽出和嵌入速率稳定,适合作为离子储存层。
使用PMMA为基体制备了电导率为10-3S/cm的凝胶电解质,且平均光学透过率大于85%,适合作为电致变色器件的电解质。将制备得到的聚苯胺、二氧化钛和电解质根据不同的结构,组装成对称结构的电致变色器件(SSECD)和非对称结构的电致变色器件(ASECD)。现场电化学-紫外光谱检测发现,ASECD的最大透射率差ΔTmax=43.3%,比SSECD约增大一倍,显示出黄(-1.4V)、绿(0V)、蓝(1.4V)三色变化,且具有更快的着、褪色响应速度(0.8s),但其使用寿命较SSECD稍差,需进一步改进。
此外还进行了柔性电致变色器件的探索研究,得到了一些初步的结果。
The electrochromic devices (ECDs), which exhibit reversible color change through electrochemical redox reaction, have attracted considerable research interests because of their potential applications in various electronic and optical devices. In this thesis, the preparation technologies about the corresponding materials for the ECDs were investigated.
We used aniline as the electronic material, water as solvent, dodecylbenzenesulfonic acid as dopant and emulsifier, ammonium persulfate as oxidant through in-situ emulsion polymerization to prepare polyaniline-based emulsion, which was used to prepare the polyaniline film by spin-coating. The film-forming property of PANI was adjusted by using different types and content of polyvinyl alcohol during the in-situ emulsion polymerization process. It was found that PVA1750+50 was a good film-forming additive with an addition of 2.8%, resultly a polyaniline film present a well film-forming properties and good electrochromic properties.
Titanium dioxide sol was prepared by using tetrabutyl titanate as the precursor via sol-gel method. The different layers of titanium dioxide films were prepared by dip-coating method, and the resulted films were characterized by XRD, SEM, UV, cyclic voltammetry and so on. Results show that the number of titanium dioxide films is in 30 to 60 layer. Besides, the typical anatase titanium dioxide crystal was formed after heat-treated at 500℃, which had the thickness of about 200 nm with the uniform particle size diameter of about 10-20 nm. The films had strong ion storage capacity, steady extraction and embedding rates of lithium-ion, suitably used as the ion storage layer.
The gel electrolyte with PMMA-based system with a conductivity of 10-3S/cm and the optical transmittance more than 85% was prepared, which was suitable used as the electrolyte of electrochromic device. In addition, the symmetrical structure electrochromic device (SSECD) and the asymmetric structure electrochromic device (ASECD) were assembled with the as-prepared polyaniline, titanium dioxide and electrolytes. The in-situ electrochemical UV-visible spectroscopy investigation found that the maximum transmission rate difference of ASECD was 43.3%, nearly about twice of SSECD. Meanwhile, ASECD took on reversible color variation among yellow (-1.4 V), green (0 V) and blue (1.4 V), and had faster coloring/fading response time (0.8 s), but its lifetime was little less than that of the SSECD, and need a further improvement.
Moreover, a flexible electrochromic device was explorated and studied, and some preliminary results were obtained.
引文
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