CN116643435A - 基于无盐聚丙烯酸凝胶的电致变色器件及其制备方法 - Google Patents
基于无盐聚丙烯酸凝胶的电致变色器件及其制备方法 Download PDFInfo
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Abstract
本发明涉及材料技术领域，特别是涉及一种基于无盐聚丙烯酸凝胶的电致变色器件及其制备方法；本发明首先将交联剂N,N‑亚甲基双丙烯酰胺、引发剂过硫酸铵与去离子水混合溶解，磁力搅拌溶解均匀后，加入丙烯酸单体，得到前驱体溶液；再将前驱体溶液注入到普鲁士蓝/氧化钨电致变色器件空腔中，在设定温度下进行聚合反应；反应结束后，自然冷却至室温，即可得到含有原位聚合的无盐聚丙烯酸凝胶电解质的普鲁士蓝/氧化钨电致变色器件；本发明制备的凝胶电解质具有20～80μm的孔径、良好的离子电导率、高透过率，可以应用于电致变色器件及其相关领域。
Description
技术领域
本发明涉及材料技术领域，特别是涉及一种基于无盐聚丙烯酸凝胶的电致变色器件及其制备方法。
背景技术
在节能环保日益重要的今天，电致变色智能窗可以通过动态调节光学特性来调节建筑与环境之间的光热流动，是一个非常重要的研究方向。电解质是电致变色智能窗的主要组成部分之一。从功能上看，电解质层起到提供和输送离子的作用，从结构上看，它防止不同电极之间的直接电接触，从性能上看，电解质主要决定电致变色智能窗的电导率、电阻率和电压窗口。目前对电解质的研究主要集中在液体电解质、固体电解质和凝胶电解质。液体电解质导电性高，但也有较窄的电解质电压窗口和泄漏风险。即便使用有机溶剂增加电解液的电压窗口，仍然存在高电阻率、低比电容、毒性和可燃性等问题。固体电解质解决了液体电解质的泄漏、毒性和可燃性问题，但存在电导率降低、成本增加和界面接触问题。聚合物凝胶电解质结合了固态电解质易加工封装与液态电解质高离子电导率的优势，此外还表现出质量轻和黏弹性好等优点，为电致变色器件向轻、薄、柔韧、可穿戴和大面积化发展提供了有力保障，成为一类最具应用潜力的电解质材料。电致变色过程伴随着电子和离子的嵌入和抽出，所以电解质离子的传输动力学对电致变色性能起着极其关键的作用，电致变色器件已经从最初有限的电解质离子驱动(H+、Li+)发展到各种电解质离子驱动(H+、Li+、Na+、K+、Mg2+、Ca2+、Zn2+、Al3+)。例如Li等人用羟丙基甲基纤维素的化学交联剂和CaCl2的离子交联剂合成了一种聚丙烯酸水凝胶，将其浸入2mol·L-1的Li2SO4溶液，用于单层氧化钨电致变色器件中(A Self-Healing Polyacrylic Acid-Based Hydrogel Electrolyte forFlexible Quasi-Solid-State Electrochromic Device,Solar Energy Materials andSolar Cells,2023,250)。吕等人将LiClO4电解质加入含有聚乙烯醇与聚丙烯酸混合溶剂中，用于噻吩类聚合物/聚(3,4-乙烯二氧噻吩)电致变色器件中(一种基于聚乙烯醇-聚丙烯酸水凝胶电解质的电致变色器件及其制备方法与应用，CN202110018875.4)。这些方法通过在聚合物基体中添加不同的无机盐来增加离子导电性，这不仅会增加电解质的制造成本，还会降低电解质本身的透过率。在溶液中添加无机盐会影响溶液的浓度，而溶液浓度的变化会直接影响透过率；当溶解度较低时，溶液中会出现结晶体，这些结晶体会阻挡光线，也会降低透过率。
发明内容
为了克服现有技术的不足，本发明提供一种基于无盐聚丙烯酸凝胶电解质、电沉积的普鲁士蓝、电沉积的氧化钨的电致变色器件及其制备方法。
本发明第一个方面公开一种电致变色器件，包括无盐聚丙烯酸凝胶电解质和电致变色材料。
优选地，所述电致变色材料为电沉积的普鲁士蓝和/或电沉积的氧化钨。
本发明第二个方面公开了上述电致变色器件的制备方法，包括以下步骤：
S1：将N,N-亚甲基双丙烯酰胺、过硫酸铵、丙烯酸和去离子水混合溶解得到反应前驱体溶液；
S2：普鲁士蓝薄膜的电沉积制备：在三电极体系中，以设定浓度的铁氰化钾、三氯化铁和氯化钾为电解液，以FTO玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极，采用恒电流电沉积法制备普鲁士蓝薄膜，得到带有普鲁士蓝薄膜的FTO玻璃；
S3：氧化钨薄膜的电沉积制备：在三电极体系中，以设定浓度的二水合钨酸钠、硝酸、双氧水为电解液，以透明导电基底FTO玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极，采用恒电压电沉积法制备得到带有氧化钨薄膜的FTO玻璃；
S4：将S2制得的普鲁士蓝薄膜的FTO玻璃与S3制得的氧化钨薄膜的FTO玻璃用1mm厚双面胶贴合在一起，得到含有空腔的普鲁士蓝/氧化钨电致变色器件；
S5：将S1得到的反应前驱体溶液注入到S4所述普鲁士蓝/氧化钨电致变色器件的空腔中，在设定温度下进行聚合反应，反应结束后，自然冷却至室温，得到含有原位聚合的无盐聚丙烯酸凝胶电解质的普鲁士蓝/氧化钨电致变色器件。
优选地，S1反应前驱体溶液中，丙烯酸与去离子水的质量比为1:2～10。
优选地，S1反应前驱体溶液中，丙烯酸、N,N-亚甲基双丙烯酰胺和过硫酸铵的质量比为400:1～4:2～10。
更优选地，S1所述的去离子水为至少去除Cl-、SO4 2-、NO3 -、NO2 -、PO4 3-、HPO4 2-、Mg2+、Ca2+、Fe3+和Fe2+的水。
优选地，S2中铁氰化钾、三氯化铁和氯化钾的浓度比为1:1:5。
更优选地，以10mmol·L-1铁氰化钾、10mmol·L-1三氯化铁、50mmol·L-1氯化钾为电解液。
优选地，S2中所述恒电流电沉积法具体为在-40～-60μA·cm-2恒电流密度下电沉积280～320s。
更优选地，采用恒电流电沉积法在-50μAcm-2恒电流密度下电沉积300s。
优选地，S5所述聚合反应的温度为60～80℃，聚合反应时间为1～4h。
优选地，S5得到的聚丙烯酸凝胶具有20～80μm的孔径。表面微观为孔状结构，且具有良好的离子电导率和高透过率。
本发明第三个方面公开了上述无盐聚丙烯酸凝胶电解质在电致变色器件中的应用。所述电致变色器件包括智能玻璃、显示器等领域中所使用变色器件。
与现有技术相比，本发明的有益效果：
(1)本发明提供一种基于无盐聚丙烯酸凝胶电解质、电沉积的普鲁士蓝、电沉积的氧化钨的电致变色器件及其制备方法，形成了一种制造简单、价格低廉、高度透明和由羧基提供自由移动的H+离子的无盐聚丙烯酸凝胶电解质。当这种凝胶电解质与电沉积普鲁士蓝和电沉积氧化钨组装成电致变色器件时，可得到光调制幅度大，响应时间快的电致变色器件。通过调整实验参数，实现高离子电导率、高透过率聚丙烯酸凝胶的可控制备。
(2)本发明的制备方法控制聚合时间，控制凝胶的聚合度以及孔径大小；制备的聚丙烯酸凝胶离子导电率好、透过率高；制备的聚丙烯酸凝胶稳定性好，和普鲁士蓝/氧化钨电致变色器件的贴合度高；制备的含有聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件，具有较快的响应速度；同时凝胶制备工艺简单，无需添加无机盐，原材料价格低廉，容易得到，成本较低，对实验环境要求低，对人体无害。
附图说明
图1采用本发明实施例1制备的无盐聚丙烯酸凝胶的扫描电子显微镜照片。
图2采用本发明实施例1制备的无盐聚丙烯酸凝胶的透过率曲线。
图3采用本发明实施例1制备的无盐聚丙烯酸凝胶的傅里叶变换红外光谱。
图4采用本发明实施例1制备的含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件的循环伏安曲线。
图5采用本发明实施例1制备的含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件的褪色态(a)、着色态(b)效果图。
图6采用本发明实施例1制备的含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件的透过率曲线。
图7采用本发明实施例1制备的含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件的响应时间曲线。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1
(1)在三电极体系中，以10mmol·L-1铁氰化钾、10mmol·L-1三氯化铁、50mmol·L-1氯化钾为电解液；以FTO玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极；采用恒电流电沉积法在-50μA·cm-2恒电流密度下电沉积300s得到带有普鲁士蓝薄膜的FTO玻璃。
(2)在三电极体系中，以50mmol·L-1二水合钨酸钠、每升溶液体系中加入0.6mL双氧水、用硝酸将溶液pH调为1为电解液，以透明导电基底FTO玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极，采用恒电压电沉积法制备得到带有氧化钨薄膜的FTO玻璃；采用恒电流电沉积法为在-0.7V恒电压下电沉积400s得到带有氧化钨薄膜的FTO玻璃。与(1)得到带有普鲁士蓝薄膜的FTO玻璃双面贴合得到普鲁士蓝/氧化钨电致变色器件。
(3)将0.0125gN,N-亚甲基双丙烯酰胺和0.025g过硫酸铵溶解于10mL去离子水中。
(4)向(3)所得溶液加入2.5g丙烯酸，再注入到(2)中得到的双面胶贴合的普鲁士蓝/氧化钨电致变色器件空腔中，置于烘箱中70℃聚合2h，自然冷却至室温，即得到待测性能的含有聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件。
本实施例制备的无盐聚丙烯酸凝胶的扫描电子显微镜照片如图1所示，为微米孔洞结构；离子的自由移动较容易，适合电致变色电解质等领域。图2为本实施例制备的无盐聚丙烯酸凝胶的透过率曲线。本实施例得到的含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件扫描循环伏安曲线(CV)如图4所示，选择0.9V为着色电压，-2.4V为褪色电压，电化学工作站与紫外-可见分光光度计连用，在400～1100nm波长范围进行测试，透过率在660nm波长下调至幅度达到最大，电致变色器件在0.9V和-2.4V之间每隔20s跃迁一次形成的光响应曲线，所有数据在660nm处测得。图5为本实施例制备的含有聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件褪色(a)着色(b)变化图。图7为响应时间曲线，从图中可以看出，在0.9V电压下迅速转变为蓝色，当施加-2.4V正电压时，器件由蓝色转变为无色。着色态和褪色态在660nm处透过率的变化量最大，约为72.7％。经计算得到达到光调制幅度改变值90％时含有无盐聚丙烯酸凝胶的普鲁士蓝/氧化钨电致变色器件的着色时间约为2.6s，褪色时间约为2.2s。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种电致变色器件，其特征在于，包括无盐聚丙烯酸凝胶电解质和电致变色材料。
2.根据权利要求1所述的一种电致变色器件，其特征在于，所述电致变色材料为电沉积的普鲁士蓝和/或电沉积的氧化钨。
3.如权利要求2所述电致变色器件的制备方法，其特征在于，包括以下步骤：
S1：将N,N-亚甲基双丙烯酰胺、过硫酸铵、丙烯酸和去离子水混合溶解得到反应前驱体溶液；
S2：普鲁士蓝薄膜的电沉积制备：在三电极体系中，以设定浓度的铁氰化钾、三氯化铁和氯化钾为电解液，以氟掺杂氧化锡(FTO)透明导电玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极，采用恒电流电沉积法制备普鲁士蓝薄膜，得到带有普鲁士蓝薄膜的FTO玻璃；
S3：氧化钨薄膜的电沉积制备：在三电极体系中，以设定浓度的二水合钨酸钠、硝酸、双氧水为电解液，以透明导电基底FTO玻璃为工作电极，铂片为对电极，Ag/AgCl电极为参比电极，采用恒电压电沉积法制备得到带有氧化钨薄膜的FTO玻璃；
S4：将S2制得的普鲁士蓝薄膜的FTO玻璃与S3制得的氧化钨薄膜的FTO玻璃贴合在一起，得到普鲁士蓝/氧化钨电致变色器件；
S5：将S1得到的反应前驱体溶液注入到S4所述普鲁士蓝/氧化钨电致变色器件的空腔中，在设定温度下进行聚合反应，反应结束后，自然冷却至室温，得到含有原位聚合的无盐聚丙烯酸凝胶电解质的普鲁士蓝/氧化钨电致变色器件。
4.根据权利要求3所述的制备方法，其特征在于，S1反应前驱体溶液中，丙烯酸与去离子水的质量比为1:2～10。
5.根据权利要求3所述的制备方法，其特征在于，S1反应前驱体溶液中，丙烯酸、N,N-亚甲基双丙烯酰胺和过硫酸铵的质量比为400:1～4:2～10。
6.根据权利要求3所述的制备方法，其特征在于，S2中铁氰化钾、三氯化铁和氯化钾的浓度比为1:1:5；S2中所述恒电流电沉积法具体为在-40～-60μA·cm-2恒电流密度下电沉积280～320s。
7.根据权利要求3所述的制备方法，其特征在于，S3中二水合钨酸钠浓度为50mmol·L-1、双氧水为0.6mL、用硝酸将溶液pH调为1，S3中所述恒电压电沉积法具体为在-0.6V～-0.8V恒电压下电沉积380～420s。
8.根据权利要求3所述的制备方法，其特征在于，S5所述聚合反应的温度为60～80℃，聚合反应时间为1～4h。
9.根据权利要求3所述的制备方法，其特征在于，S5得到的聚丙烯酸凝胶具有20～80μm的孔径。
10.如权利要求1所述无盐聚丙烯酸凝胶电解质在电致变色器件中的应用。
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