导电聚合物基电致变色器件的制备及机理研究
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摘要
电致变色器件由于其独特的光-电特性,在新型显示器件、电子墨镜和信息存储器件、军事伪装、可调反射率汽车后视镜,以及可自动调光节能的智能窗等诸多领域都有着巨大的应用前景。本文对组成电致变色器件的几层材料分别进行了研究,制备了PDBrTh变色薄膜、TiO_2-CeO_2复合薄膜、PMMA基复合凝胶电解质,成功的组装了对称与非对称型大面积电致变色器件、侧面平行结构电致变色器件、双变色层电致变色器件以及柔性电致变色器件。
我们分别利用恒电流、恒电压法,以三氟化硼乙醚溶液(BFEE)为电解质,聚合得到了高性能的聚(3,4-二溴噻吩) (PDBrTh)薄膜,能够在亮红色和蓝色之间实现可逆变化,最快响应时间达到1.21s,循环寿命可达到1800圈。
以PMMA为聚合物基底,PC为溶剂,以纳米稀土氧化物为无机填料,制备了PMMA-PC-LiClO4-χwt%稀土氧化物的电解质薄膜。通过SEM、XRD、红外等分析方法研究电导率、结晶形态,化学结构,发现添加1.3wt% Y2O3后电导率达到最大,为7.4×10-4S/cm,比未添加时提高了近3倍,且有效地减少了气泡的产生。
使用凝胶-溶胶法合成了TiO_2-CeO_2复合薄膜,对其进行了电化学、光学等方面的测试,得到循环可逆值K为95.6%。,电荷储存量为9.46 mC·cm-2的离子储存薄膜。
利用上述制备的各层材料,我们组装了对称型与非对称型大面积电致变色器件,得到了对比度为23%,响应时间为0.9s的器件,并分析了其变色机理;组装了侧面平行结构的电致变色器件,证明了离子是平行于电致变色层材料传输的,测试了其开路记忆为9h,并将此结构应用在变色锂离子电池中进行了初步摸索;组装了双变色层器件,结果显示其对比度、响应时间均有所提高,而且还出现了颜色的层层叠加效应;除此之外,我们还尝试了聚苯胺基的柔性电致变色器件的制备,得到了绿色-蓝色可逆变化的柔性器件,为进一步研究制备柔性显示器件做出了贡献。
Due to their unique optical-electronic properties, electrochromic materials and devices have applications in various fields, such as novel display, electro-ink, information storage device, military camouflage, smart window and so on. In this dissertation, each layer material of electrochromic device is studied, and we prepare poly(3,4-dibromothiophene) (PDBrTh) electrochromic film,TiO_2-CeO_2 composite films, PMMA-based composite gel electrolytes. Finally we assemble the symmetric and asymmetric large-area ECD, the parallel structure ECD, double-color-layer ECD and flexible ECD.
High-quality poly(3,4-dibromothiophene)(PDBrTh) film is prepared electrochemically in boron trifluoride diethyl etherate. The resulted PDBrTh film can change between vivid red and blue reversiblly, and the fastest response time is 1.21 seconds, cycle life up to 1800 laps.
Using nanosized rare earth oxides as fillers, and Propylene Carbonate (PC) as organic solvent, the composite polymer electrolyte films PMMA-PC-LiClO4-χwt% was prepared by sol-gel technique. We research conductivity, crystal morphology, chemical structure by SEM, XRD, IR, et al.It is found that the highest ionic conductivity of 7.4×10-4S/cm is achieved with the Y2O3 content of 1.3wt%, approximately 3 times than before. In addition, it can effectively prevent formation of air bubbles.
TiO_2-CeO_2 composite films on ITO glass substrate were successfully prepared by sol-gel process. The structure and properties of the films were characterized by XRD, SEM, UV-vis transmitted spectrum and Cyclic voltammetry, respectively. The results show that TiO_2-CeO_2 thin films with the capacity of charge storage of 9.46 mC·cm-2 and the cycle of reversible K of 95%.
Using the above materials, we assemble the symmetric and asymmetric large area electrochromic devices, with a contrast ratio of 23%, response time of 0.9s, and analyze the mechanism of its color. We assemble a parallel structured ECD that the ion is transferd parallelly to the electrochromic material. Its' open memory is above 9h, used in colored lithium-ion batteries. Besides, a double layer ECD is assembled, the results show the contrast, response time has been enhanced, and the color superimposition is found also. In addition, we also try to prepare a polyaniline-based flexible electrochromic devices, and obtain a green-blue reversible flexible ECD, and the results in useful for the further study of flexible display devices.
我们分别利用恒电流、恒电压法,以三氟化硼乙醚溶液(BFEE)为电解质,聚合得到了高性能的聚(3,4-二溴噻吩) (PDBrTh)薄膜,能够在亮红色和蓝色之间实现可逆变化,最快响应时间达到1.21s,循环寿命可达到1800圈。
以PMMA为聚合物基底,PC为溶剂,以纳米稀土氧化物为无机填料,制备了PMMA-PC-LiClO4-χwt%稀土氧化物的电解质薄膜。通过SEM、XRD、红外等分析方法研究电导率、结晶形态,化学结构,发现添加1.3wt% Y2O3后电导率达到最大,为7.4×10-4S/cm,比未添加时提高了近3倍,且有效地减少了气泡的产生。
使用凝胶-溶胶法合成了TiO_2-CeO_2复合薄膜,对其进行了电化学、光学等方面的测试,得到循环可逆值K为95.6%。,电荷储存量为9.46 mC·cm-2的离子储存薄膜。
利用上述制备的各层材料,我们组装了对称型与非对称型大面积电致变色器件,得到了对比度为23%,响应时间为0.9s的器件,并分析了其变色机理;组装了侧面平行结构的电致变色器件,证明了离子是平行于电致变色层材料传输的,测试了其开路记忆为9h,并将此结构应用在变色锂离子电池中进行了初步摸索;组装了双变色层器件,结果显示其对比度、响应时间均有所提高,而且还出现了颜色的层层叠加效应;除此之外,我们还尝试了聚苯胺基的柔性电致变色器件的制备,得到了绿色-蓝色可逆变化的柔性器件,为进一步研究制备柔性显示器件做出了贡献。
Due to their unique optical-electronic properties, electrochromic materials and devices have applications in various fields, such as novel display, electro-ink, information storage device, military camouflage, smart window and so on. In this dissertation, each layer material of electrochromic device is studied, and we prepare poly(3,4-dibromothiophene) (PDBrTh) electrochromic film,TiO_2-CeO_2 composite films, PMMA-based composite gel electrolytes. Finally we assemble the symmetric and asymmetric large-area ECD, the parallel structure ECD, double-color-layer ECD and flexible ECD.
High-quality poly(3,4-dibromothiophene)(PDBrTh) film is prepared electrochemically in boron trifluoride diethyl etherate. The resulted PDBrTh film can change between vivid red and blue reversiblly, and the fastest response time is 1.21 seconds, cycle life up to 1800 laps.
Using nanosized rare earth oxides as fillers, and Propylene Carbonate (PC) as organic solvent, the composite polymer electrolyte films PMMA-PC-LiClO4-χwt% was prepared by sol-gel technique. We research conductivity, crystal morphology, chemical structure by SEM, XRD, IR, et al.It is found that the highest ionic conductivity of 7.4×10-4S/cm is achieved with the Y2O3 content of 1.3wt%, approximately 3 times than before. In addition, it can effectively prevent formation of air bubbles.
TiO_2-CeO_2 composite films on ITO glass substrate were successfully prepared by sol-gel process. The structure and properties of the films were characterized by XRD, SEM, UV-vis transmitted spectrum and Cyclic voltammetry, respectively. The results show that TiO_2-CeO_2 thin films with the capacity of charge storage of 9.46 mC·cm-2 and the cycle of reversible K of 95%.
Using the above materials, we assemble the symmetric and asymmetric large area electrochromic devices, with a contrast ratio of 23%, response time of 0.9s, and analyze the mechanism of its color. We assemble a parallel structured ECD that the ion is transferd parallelly to the electrochromic material. Its' open memory is above 9h, used in colored lithium-ion batteries. Besides, a double layer ECD is assembled, the results show the contrast, response time has been enhanced, and the color superimposition is found also. In addition, we also try to prepare a polyaniline-based flexible electrochromic devices, and obtain a green-blue reversible flexible ECD, and the results in useful for the further study of flexible display devices.
引文
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