CN115160544A - 电致变色聚合物、电致变色器件及其制备方法 - Google Patents
电致变色聚合物、电致变色器件及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种电致变色聚合物，该聚合物以3，4‑丙撑二氧噻吩高分子链为主链，3，4‑丙撑二氧噻吩单体含聚乙二醇单乙醚支链。电致变色聚合物对极性溶剂具有优良的亲和性，利于极性电解液对电致变色材料充分、快速、均匀地浸润。本发明还公开了电致变色聚合物的制备方法，以及基于电致变色聚合物的电致变色器件及其制备方法。该器件变色均匀、响应速率快、着色效率高，适用于制备大面积、快速响应、高稳定性的电致变色器件。
Description
技术领域
本发明涉及电致变色技术领域，具体涉及电致变色聚合物、电致变色器件及其制备方法。
背景技术
电致变色技术的应用载体是电致变色器件，其结构一般为典型的“三明治”夹层结构，包括两个透明电极、电致变色层、电解质层以及离子储存层(对电极层)，而电致变色技术的原理是电解质层中离子在外电场作用下，会可逆地嵌入/脱出电致变色膜层，从而使膜层发生可逆的氧化还原反应实现变色。电解质与变色膜间的界面离子传输对变色性能具有重要影响。常规的液态电解质体系，因与变色膜具有良好的界面浸润效果，使器件的变色均匀性、快速响应特性均较好，但液态电解质易泄露、安全性低等问题，使其难以大面积应用。
相比于液态电致变色器件，全固态器件采用固态电解质体系，应用安全性和封装简便性均优良。但现有的电解质前驱体溶液与电致变色聚合物涂层的亲和性较差，即电解质前驱体溶液无法充分浸润电致变色聚合物涂层，进一步导致电致变色器件响应速度慢、着色效率低、变色不均匀等劣化问题。
发明内容
本发明的目的之一在于克服现有技术中存在的缺陷，提供一种电致变色聚合物，通过在丙撑二氧噻吩杂环引入两个聚乙二醇单乙醚链取代基，优化极性的溶剂以及电解质对于电致变色聚合物亲和性和浸润均匀程度。
为了实现上述目的，本发明的技术方案为：一种电致变色聚合物，结构式如下：
式1中，R各自独立为
m为2～5的自然数；
n表示聚合度，n为8～100的自然数。进一步的，m为3或4；更进一步的，m为3，R为
进一步的，结构式中两个R为相同的官能团。
本发明的目的之二在于提供一种电致变色聚合物的制备方法，包括以下步骤：
式2所示化合物、式3所示化合物、无机弱碱、钯类催化剂和有机酸混合，聚合反应，聚合反应产物经后处理得电致变色聚合物；
式2和式3中R各自独立为
m为2～5的自然数。进一步的，m为3或4，更进一步的，m为3；进一步的，结构式中两个R为相同的官能团。
优选的技术方案为，式2所示化合物与式3所示化合物的摩尔比为(0.9～1.1)：1；和/或无机弱碱与式3所示化合物的摩尔比为(1～1.3)：1；和/或有机酸与式3所示化合物的摩尔比为(0.09～0.15)：1；和/或钯类催化剂与式3所示化合物的摩尔比为(0.02～0.04)：1。
优选的技术方案为，所述聚合反应的温度为130～145℃，反应时间为36～72h。
本发明的目的之二在于提供一种电致变色器件，包括层叠的电致变色材料层、复合电解质层、对电极层；所述电致变色材料层的材质为上述的电致变色聚合物。进一步的，复合电解质层为原位聚合电解质。该原位聚合电解质可选为紫外光聚合和/或热聚合的电解质。更近一步的，对电极层为PEDOT:PSS或NiO。
优选的技术方案为，复合电解质层为带PVDF-HFP多孔隔膜的原位热聚合电解质；
所述原位热聚合电解质由电解质前驱体溶液在器件组装过程加热原位聚合制得，所述电解质前驱体溶液的主要组成为热聚合单体、聚乙二醇、引发剂、离子液体。进一步的，聚乙二醇的分子量为500～20000，优选为500～10000，更优选为500～5000。聚乙二醇的分子量过大将导致离子电导率降低，过小则经热聚合获得的电解质可能仍为液态，不能获得固态的。PVDF-HFP多孔隔膜可避免电致变色器件出现短路现象，提高器件成功率。
优选的技术方案为，所述热聚合单体与聚乙二醇的质量比为(3～5)：1；
进一步的，所述离子盐为离子液体或锂盐与离子液体的混合物；所述离子盐的质量占电解质前驱体溶液质量的30％～80％，进一步优选为40％～60％。
优选的技术方案为，所述热聚合单体为丙烯酸单体，所述引发剂的质量为热聚合单体质量的1％～2％；
进一步的，所述热聚合单体为选自甲基丙烯甲酯、丙烯酸、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸肉桂酯和丙烯酸肉桂酯中的至少一种；
进一步的，所述引发剂为偶氮二异丁腈。更进一步的，原位热聚合电解质中聚合物含量为20％～40％，优选为25～35％，更优选为30％。
优选的技术方案为，锂盐与离子液体的混合物中锂盐浓度为0.5～1mol/L；
进一步的，所述离子液体为选自1-丁基-3-甲基双三氟甲磺酰亚胺盐、1-乙基-3-甲基双三氟甲磺酰亚胺盐、1-丁基-3-甲基四氟硼酸盐、1-丁基-1-甲基吡咯烷双三氟甲磺酰亚胺盐、1-乙基-3-甲基四氟硼酸盐、1-丁基-3-甲基四氟硼酸盐中的至少一种；
进一步的，锂盐为LiTFSI和LiClO4中的至少一种。
本发明的目的之四在于提供一种电致变色器件的制备方法，基于上述的电致变色器件，包括以下步骤：
S1：将电致变色聚合物溶液喷涂于透明导电基底表面，烘干；
S2：在另一透明导电基底的导电面覆设对电极层，在电极层表面制备PVDF-HFP多孔膜；
S3：S2透明导电基底的第二表面与多孔膜相背，将S1所得电致变色聚合物涂层与第二表面叠合，密封叠合件四周，在叠合间隔中注入所述电解质前驱体溶液；
S4：升温至热聚合温度，保温至前驱体溶液充分聚合，得目标电致变色器件。
本发明的优点和有益效果在于：
本发明电致变色材料基于3，4-丙撑二氧噻吩高分子链，通过向3，4-丙撑二氧噻吩杂环的同一碳原子引入两个聚乙二醇单乙醚支链，提高电致变色聚合物对极性溶剂的亲和性，利于极性电解液对电致变色材料充分、快速、均匀地浸润，同时该电致变色材料具有较优的着色褪色时间；
采用含有聚乙二醇单乙醚支链的3，4-丙撑二氧噻吩，2，5-二溴代-3，4-丙撑二氧噻吩作为反应物，在无机弱碱、钯类催化剂和有机酸的反应体系中，反应步骤简单、条件温和，适于制备预定聚合度的电致变色聚合物；
电致变色器件中采用包含聚乙二醇单乙醚支链的3，4-丙撑二氧噻吩聚合物作为电致变色材料，进一步的采用原位聚合电解质，充分利用电致变色材料可快速均匀浸润的特点；通过优化电解质的组成，使其与电致变色聚合物更趋适配，进一步改善电致变色聚合物与电解质的界面亲和性；以上因素均有助于改善器件的变色均匀性、响应速率和着色效率，适用于制备大面积、快速响应、高稳定性的电致变色器件。
附图说明
图1是实施例电致变色聚合物的核磁谱图；
图2是实施例电致变色聚合物的GPC谱图；
图3是实施例电致变色聚合物的热重曲线；
图4是实施例电致变色聚合物表面水、二碘甲烷和离子液体接触角照片；
图5是不同电压下电致变色聚合物的吸收光谱；
图6是电致变色聚合物薄膜的循环稳定性曲线和变色速率曲线；
图7是不同聚合物含量原位热聚合电解质的透射比；
图8是不同聚合物含量原位热聚合电解质的离子电导率；
图9是电致变色器件的响应变色曲线与颜色变换照片；
图10是电致变色器件的响应稳定性曲线；
图11是电致变色器件的着色效率图，测试波长为535nm。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
实施例
一、制备电致变色聚合物
1、电致变色聚合物的制备方法包括以下步骤：
S11：将包含四聚乙二醇单乙醚链取代基(发明内容部分式2化合物和式3化合物中的-O-R)的3，4-丙撑二氧噻吩(式2化合物)以及2，5-二溴代-3，4-丙撑二氧噻吩(式3化合物)加入至单口瓶中，加入乙酸钯(Pd(OAc)2)、特戊酸(PvAc)及碳酸钾，加热至140℃反应48h；
式2化合物和式3化合物的摩尔比为1:1，乙酸钯与式3反应物的摩尔比为1:50，特戊酸与式3反应物的摩尔比为1:10、碳酸钾与式3反应物的摩尔比为1:1；反应式如下：
S12：将前述反应产物滴入甲醇中进行沉淀，再采用索氏提取装置依次用甲醇、正已烷、氯仿提取24小时，收集并浓缩氯仿提取液，再滴入甲醇中进行沉淀，收集并干燥沉淀物即为电致变色聚合物，经检测，电致变色聚合物的重均分子量为22276，数均分子量为14404，聚合物分散指数(PDI)为1.55。
2、电致变色聚合物的性能检测
①核磁表征电致变色聚合物，见图1；
②电致变色聚合物的GPC谱图，见图2；
③热分析电致变色聚合物，图3为电致变色聚合物的热重曲线；热重测试表明聚合物在300℃以内具有良好的热稳定性。
④考察水、二碘甲烷和离子液体(1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐，BMIMTFSI)在电致变色聚合物涂层表面的接触角，见图4；图中水的接触角为34.66°，二碘甲烷的接触角为5.2°，离子液体的接触角为48.18°；
⑤将实施例电致变色聚合物溶于氯仿中，配制5mg/ml的溶液，在导电玻璃上进行喷涂、烘干得0.6μm的电致变色聚合物薄膜。采用聚合物薄膜为工作电极、铂丝为对电极、标定过的银丝为参比电极的三电极体系，支持电解质为高氯酸锂/丙烯碳酸酯。检测不同电压下电致变色聚合物的吸收光谱，见图5，聚合物表现出紫色至高透明的变换，在535nm处的对比度达到55％以上，响应时间均在2秒以内，且循环变色200次，完全没有衰减；
⑥电致变色聚合物薄膜的循环稳定性曲线图，见图6，着色和褪色时间分别为0.6s和1.1s，循环变色240次仅衰减0.6％的透过率对比度。以上电致变色聚合物性能参数中，着色时间表现较为突出，表现为着色响应速度快。
二、配置电解质前驱体溶液
1、电解质前驱体溶液的配置包括以下步骤：
S21：将甲基丙烯酸甲酯(MMA)与聚乙二醇(PEG，分子量1000)以质量比为3：1的比例进行混合，在40℃下搅拌30min，使PEG充分溶解，然后再继续超声20min；
S22：将含锂盐离子液体溶液(1mol/l LiTFSI/[BMIM][TFSI]，占电解质前驱体溶液质量的70％)加入到S21所得混合体系中，超声30min充分混合；后向混合体系中加入偶氮二异丁腈(AIBN，MMA质量的2％)，充分混合得电解质前驱体溶液。
2、热聚合电解质的性能检测
①80℃下加热30min进行固化成膜，膜厚为20μm；
②原位热聚合电解质的光学照片，考察不同聚合物含量原位热聚合电解质的透射比，见图7；
③考察不同聚合物含量原位热聚合电解质的离子电导率，见图8；
由图7和图8可知，膜层具有良好的光学透过率及离子电导率，其中原位热聚合电解质中聚合物含量为30％时，透射比和离子电导率较优。
三、配置电解质前驱体溶液
1、以上述实施例所制备的电致变色聚合物和电解质前驱体溶液为原料，组装电致变色器件，具体步骤为：
S31：将电致变色聚合物溶于氯仿，配制5mg/ml的溶液，采用喷涂的方式在ITO玻璃表面喷涂成膜后烘干作为工作电极；
S32：取另一块ITO玻璃，在其表面喷涂PEDOT:PSS作为对电极，再将2mM的PVDF-HFP的丙酮与水混合溶液喷涂于对电极上，60℃真空烘箱烘3h，使PVDF-HFP形成多孔膜；
S33：将S31工作电极的电致变色聚合物涂层与对电极的多孔膜面对面叠层，取环氧树脂密封叠合件四周，并保持工作电极与对电极间有一定的间隙，向间隙中注入电解质前驱体溶液，制得初始器件；
S34：将S33初始器件放入烘箱中，缓慢升温至80℃后，保温加热30min，使电解质前驱体溶液充分聚合，得电致变色器件。
2、电致变色器件的性能检测
①电致变色器件的响应变色曲线与颜色变换照片见图9；
②电致变色器件的响应稳定性曲线见图10；
③电致变色器件的着色效率见图11。
实施例电致变色器件具有均匀的变色特性，着色和褪色时间仅为3s和2s，循环变色300次仅衰减18％的透过率对比度，且着色效率达到918cm2/C，表现出优异的电致变色性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种电致变色聚合物，其特征在于，结构式如下：
式1中，R各自独立为
m为2～5的自然数；
n表示聚合度，n为8～100的自然数。
2.权利要求1所述的电致变色聚合物的制备方法，其特征在于，包括以下步骤：
式2所示化合物、式3所示化合物、无机弱碱、钯类催化剂和有机酸混合，聚合反应，聚合反应产物经后处理得电致变色聚合物；
式2和式3中R各自独立为
m为2～5的自然数。
3.根据权利要求2所述的电致变色聚合物的制备方法，其特征在于，式2所示化合物与式3所示化合物的摩尔比为(0.9～1.1)：1；和/或无机弱碱与式3所示化合物的摩尔比为(1～1.3)：1；和/或有机酸与式3所示化合物的摩尔比为(0.09～0.15)：1；和/或钯类催化剂与式3所示化合物的摩尔比为(0.02～0.04)：1。
4.根据权利要求2所述的电致变色聚合物的制备方法，其特征在于，所述聚合反应的温度为130～145℃，反应时间为36～72h。
5.一种电致变色器件，其特征在于，包括层叠的电致变色材料层、复合电解质层、对电极层；所述电致变色材料层的材质为权利要求1所述的电致变色聚合物。
6.根据权利要求5所述的电致变色器件，其特征在于，复合电解质层为带PVDF-HFP多孔隔膜的原位热聚合电解质；
所述原位热聚合电解质由电解质前驱体溶液在器件组装过程加热原位聚合制得，所述电解质前驱体溶液的主要组成为热聚合单体、聚乙二醇、引发剂、离子液体。
7.根据权利要求6所述的电致变色器件，其特征在于，所述热聚合单体与聚乙二醇的质量比为(3～5)：1；
进一步的，所述离子盐为离子液体或锂盐与离子液体的混合物，所述离子盐的质量占电解质前驱体溶液质量的30％～80％。
8.根据权利要求6所述的电致变色器件，其特征在于，所述热聚合单体为丙烯酸单体，所述引发剂的质量为热聚合单体质量的1％～2％；
进一步的，所述热聚合单体为选自甲基丙烯甲酯、丙烯酸、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸肉桂酯和丙烯酸肉桂酯中的至少一种；
进一步的，所述引发剂为偶氮二异丁腈。
9.根据权利要求7所述的电致变色器件，其特征在于，锂盐与离子液体的混合物中锂盐浓度为0.5～1mol/L；
进一步的，所述离子液体为选自1-丁基-3-甲基双三氟甲磺酰亚胺盐、1-乙基-3-甲基双三氟甲磺酰亚胺盐、1-丁基-3-甲基四氟硼酸盐、1-丁基-1-甲基吡咯烷双三氟甲磺酰亚胺盐、1-乙基-3-甲基四氟硼酸盐、1-丁基-3-甲基四氟硼酸盐中的至少一种；
进一步的，锂盐为LiTFSI和LiClO4中的至少一种。
10.一种电致变色器件的制备方法，其特征在于，基于权利要求5至9中任意一项所述的电致变色器件，包括以下步骤：
S1：将电致变色聚合物溶液喷涂于透明导电基底表面，烘干；
S2：在另一透明导电基底的导电面覆设对电极层，在电极层表面制备PVDF-HFP多孔膜；
S3：S2透明导电基底的第二表面与多孔膜相背，将S1所得电致变色聚合物涂层与第二表面叠合，密封叠合件四周，在叠合间隔中注入所述电解质前驱体溶液；
S4：升温至热聚合温度，保温至前驱体溶液充分聚合，得目标电致变色器件。
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