CN106633546B - 一种电致变色用准固态电解质薄膜及其制备和应用 - Google Patents

一种电致变色用准固态电解质薄膜及其制备和应用 Download PDF

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CN106633546B
CN106633546B CN201611160459.3A CN201611160459A CN106633546B CN 106633546 B CN106633546 B CN 106633546B CN 201611160459 A CN201611160459 A CN 201611160459A CN 106633546 B CN106633546 B CN 106633546B
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王宏志
刘学龙
李海增
辜为民
李耀刚
张青红
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Abstract

本发明涉及一种电致变色用准固态电解质薄膜及其制备和应用，原料混合浆料包括：高氯酸锂、溶剂、聚偏氟乙烯和二氧化硅。将高氯酸锂真空干燥去除水分，然后配制高氯酸锂溶液，取聚偏氟乙烯和二氧化硅溶于高氯酸锂溶液中，配制成可热压成膜的浆料，取出适量的浆料，涂覆于玻璃基底上，并热压成膜，冷却至室温即得，并用于电致变色器件中。本发明方法制备工艺简单、成本低；制得的准固态电解质膜电导率高，可用于电致变色器件中，并能有效的提高器件的电致变色性能，具有摆脱聚合物电解质薄膜难以大面积生产的限制，实现热压法制备电解质膜产业化的应用前景。

Description

一种电致变色用准固态电解质薄膜及其制备和应用
技术领域
本发明属于电致变色材料及其制备和应用领域，特别涉及一种电致变色用准固态电解质薄膜及其制备和应用。
背景技术
电致变色是指材料在外加电场或电流作用下所引起的颜色和透明度的可逆变化，这种变化是由于材料在紫外、可见光或近红外区域的光学属性(透射率、反射率或吸收率)在外加电场作用下产生了稳定的可逆变化而引起的。电致变色器件的基本结构是由玻璃或透明衬底、透明导电层、电致变色层、电解质层等多层薄膜组合而成，其中电解质层是在两电极之间起到传输离子的作用，也是电致变色器件最重要的部分之一。对于电致变色电解质需要满足高离子导电性和低电子导电性、高度透明性以及好的电化学稳定性。电致变色器件中最常用的为液态电解质，而液态电解质在实际使用中还存在很多问题，如：容易泄露、化学稳定性差且不易封装。
发明内容
本发明所要解决的技术问题是提供一种电致变色用准固态电解质薄膜及其制备和应用，本发明提供了一种热压法制备电致变色用准固态电解质薄膜的方法，利用本发明的方法所制得的准固态电解质膜应用到电致变色器件中展现了出色的电致变色性能，该方法制备工艺简单、成本低，具有产业应用的可能性。
本发明的一种电致变色用准固态电解质薄膜，将原料混合浆料热压成薄膜，其中原料混合浆料包括：高氯酸锂、溶剂、聚偏氟乙烯和二氧化硅，其中高氯酸锂、溶剂、聚偏氟乙烯和二氧化硅的质量比为4:62:33:1～8:54:33:5。
所述电致变色用准固态电解质薄膜的厚度为0.1～2mm。
所述溶剂为N,N-二甲基甲酰胺。
本发明的一种电致变色用准固态电解质薄膜的制备方法，包括：
(1)将干燥后的高氯酸锂加入溶剂中，得到高氯酸锂溶液；
(2)将聚偏氟乙烯和二氧化硅加入高氯酸锂溶液中，搅拌，静置，得到混合浆料；
(3)将上述混合浆料涂覆于玻璃基底上进行热压，冷却至室温，即得电致变色用准固态电解质薄膜。
步骤(1)中干燥后的高氯酸锂，其中干燥高氯酸锂的温度为20～80℃。
高氯酸锂的干燥具体为：室温下，将高氯酸锂置于真空烘箱中一定温度下干燥去除水分，备用，其中真空烘箱的温度为20～80℃。
所述步骤(1)中高氯酸锂溶液的浓度为0.5～2mol/L。
步骤(2)中聚偏氟乙烯和二氧化硅的质量配比是：聚偏氟乙烯：二氧化硅＝99:1～85:15；
步骤(2)中高氯酸锂溶液的体积为1-10mL。
所述步骤(2)中混合浆料量为1～10g。
所述步骤(3)中热压为：热压机进行热压，温度为80～150℃，时间为2～20min。
本发明的一种电致变色用准固态电解质薄膜的应用，电致变色用准固态电解质薄膜在电致变色器件、柔性器件中的应用。
有益效果
(1)本发明方法制备工艺简单、成本低，具有产业应用的可能性；
(2)本发明的准固态电解质薄膜具有高离子电导率，能够有效的提高电致变色器件的性能；
(3)本发明的电致变色准固态电解质是通过在玻璃基底上使用热压法，将电解质浆料热压成一定厚度的薄膜，具有厚度可控、可弯曲，能应用于柔性器件的前景。
附图说明
图1为实施例1制备准固态电解质薄膜的扫描电镜图；
图2为实施例1制备准固态电解质薄膜阻抗测试图；其中插图为本体阻抗放大图；
图3为实施例1中制备的电致变色器件的数码照片图；其中a为褪色态，b为着色态；
图4为实施例1中准固态电致变色器件分别在着色和褪色状态下的光透过率曲线；其中a为褪色态，b为着色态；
图5为实施例1中准固态电致变色器件的时间响应曲线；
图6为实施例2中准固态电解质膜的阻抗测试图；其中插图为本体阻抗放大图；
图7为实施例2制备准固态电解质器件的时间响应曲线。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
室温下，称取干燥后的高氯酸锂10.96g置于250mL烧杯中，加入100mL N,N-二甲基甲酰胺搅拌至高氯酸锂至完全溶解，配制成1mol/L高氯酸锂的N,N-二甲基甲酰胺溶液，称取0.97g聚偏氟乙烯和0.03g纳米二氧化硅加入到2ml的上述溶液中，搅拌均匀，之后静置半小时制备成浆料，然后将浆料取出涂覆与玻璃基底上置于热压机下，温度设置为120℃，时间为10min制得透明准固态电解质薄膜，并组装成电致变色器件。
图1为所制得准固态电解质薄膜的扫描电镜照片，可以看到薄膜具有多孔结构，具有一定的存储液态电解质的能力。
图2为电解质的阻抗测试图，结果表明该电解质膜的电导率为3.2*10-3S/cm。
为了了解上述实例所制得的准固态电解质薄膜的电致变色性能，将上述制备得到的电解质薄膜组装成如图3所示，器件用两电极系统结合电化学工作站和紫外分光光度计来测定制得器件的光透过率变化，结果表明，当对器件施加负压(-2.5V)后，器件变蓝；但对其施加正压时(-1.5V)，器件会发生褪色现象。
如图4所示该器件的透过率在300～800nm波段有着明显的变化，在λ＝632.8nm处达到32.5％；该器件的响应时间可以控制在70s以内，如图5所示；这种器件在未来电致变色智能窗领域具有非常好的应用前景。
实施例2
室温下，称取干燥后的高氯酸锂10.96g置于250mL烧杯中，加入100mL N,N-二甲基甲酰胺搅拌至高氯酸锂完全溶解，配制成1mol/L高氯酸锂的N,N-二甲基甲酰胺溶液，称取0.89g聚偏氟乙烯和0.11g纳米二氧化硅加入到2mL的上述溶液中，搅拌均匀，之后静置半小时制备成浆料，然后将浆料取出涂覆与玻璃基底上置于热压机下，温度设置为120℃，热压10min制得透明准固态电解质薄膜，并组装成电致变色器件。
图6为该电解质膜的阻抗测试图，结果表明该电解质膜的电导率为1.91*10‐3S/cm。
为了了解上述实例所制得的准固态电解质薄膜的电致变色性能，将上述制备得到的电解质薄膜组装成电致变色器件，该器件用两电极系统结合电化学工作站和紫外分光光度计来测定制得器件的光透过率变化，如图7所示，结果表明在施加电压在-2.5V～1.5V下器件的光透过率为10％，响应施加控制在96s以内。

Claims (9)

1.一种电致变色用准固态电解质薄膜，其特征在于：将原料混合浆料热压成薄膜，其中原料混合浆料组分为：高氯酸锂、溶剂、聚偏氟乙烯和二氧化硅，其中高氯酸锂、溶剂、聚偏氟乙烯和二氧化硅的质量比为4:62:33:1～8:54:33:5；电致变色用准固态电解质薄膜为多孔结构。
2.根据权利要求1所述的一种电致变色用准固态电解质薄膜，其特征在于：所述电致变色用准固态电解质薄膜的厚度为0.1～2mm。
3.根据权利要求1所述的一种电致变色用准固态电解质薄膜，其特征在于：所述溶剂为N,N-二甲基甲酰胺。
4.一种如权利要求1-3任一所述的电致变色用准固态电解质薄膜的制备方法，包括：
(1)将干燥后的高氯酸锂加入溶剂中，得到高氯酸锂溶液；
(2)将聚偏氟乙烯和二氧化硅加入高氯酸锂溶液中，搅拌，静置，得到混合浆料；
(3)将上述混合浆料涂覆于玻璃基底上进行热压，冷却至室温，即得电致变色用准固态电解质薄膜。
5.根据权利要求4所述的一种电致变色用准固态电解质薄膜的制备方法，其特征在于：步骤(1)中干燥后的高氯酸锂，其中干燥高氯酸锂的温度为20～80℃。
6.根据权利要求4所述的一种电致变色用准固态电解质薄膜的制备方法，其特征在于：所述步骤(1)中高氯酸锂溶液的浓度为0.5～2mol/L。
7.根据权利要求4所述的一种电致变色用准固态电解质薄膜的制备方法，其特征在于：所述步骤(2)中混合浆料量为1～10g。
8.根据权利要求4所述的一种电致变色用准固态电解质薄膜的制备方法，其特征在于：所述步骤(3)中热压为：热压机进行热压，温度为80～150℃，时间为2～20min。
9.一种如权利要求1-3任一所述的电致变色用准固态电解质薄膜的应用，其特征在于：电致变色用准固态电解质薄膜在电致变色器件、柔性器件中的应用。
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CN105680092B (zh) * 2016-01-25 2018-08-31 山东玉皇新能源科技有限公司 一种固态聚合物电解质及其制备方法

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