CN113787795A - 一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜及其制备方法 - Google Patents

一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜及其制备方法 Download PDF

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CN113787795A
CN113787795A CN202110919482.0A CN202110919482A CN113787795A CN 113787795 A CN113787795 A CN 113787795A CN 202110919482 A CN202110919482 A CN 202110919482A CN 113787795 A CN113787795 A CN 113787795A
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翁凌
邱金月
关丽珠
王小明
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Harbin University of Science and Technology
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Abstract

本发明公开了一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜的制备方法;属于高储能密度电介质电容器应用领域。本发明解决了掺杂填料导致击穿强度过低的问题。本发明复合薄膜分为三层,上层和下层为聚偏氟乙烯薄膜,中间层为掺杂态聚吡咯/聚偏氟乙烯复合薄膜。上层和下层采用流延法制得;采用静电纺丝法制备中间层;在通过热压法获得三明治结构复合薄膜。本发明三明治结构的引入大大提高了复合薄膜的击穿强度,且具有较低的损耗。三明治结构聚吡咯/聚偏氟乙烯复合薄膜的储能性能优异,设计方案简单,安全,在储能领域将具有很好的潜力,特别是在电气和电子设备的小型化,轻量化和集成方面有更明显的作用。

Description

一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜及其制备方法
技术领域
本发明属于高储能密度电介质电容器应用领域;具体涉及一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜及其制备方法。
背景技术
当今,人类对能源的消耗和依赖日益增加。如何有效储存能源,减少能源损失,已成为研究的热点问题。由于充电速度快、放电率高,电介质电容器具有很高的应用价值。然而,电介质电容器的主要缺点是能量密度低,不能满足先进应用日益增长的需求。电介质电容器的介电层是聚合物,因此有必要通过开发具有优良介电特性的聚合物基质复合材料来提高储能密度。通常,它可以通过在聚合物基质中添加铁电或导电填充剂来实现。例如,常见的铁电陶瓷填料和导电填充物包括BaTiO3、TiO2、金属、碳等。
发明内容
提高介电电容器的储能密度已成为储能领域广泛关注的焦点。然而,为了缓解添加填料造成的击穿强度下降的问题,有必要设计具有三明治结构的复合薄膜。
本发明要解决掺杂填料导致击穿强度过低的技术问题;而提供一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜及其制备方法。
通过以下技术方案解决上述技术问题:
本发明的三明治结构聚吡咯/聚偏氟乙烯复合薄膜。复合薄膜分为三层,上层和下层为聚偏氟乙烯薄膜,中间层为掺杂态聚吡咯/聚偏氟乙烯复合薄膜。
进一步地限定,中间层掺杂的掺杂态聚吡咯含量占中间层聚偏氟乙烯质量的10%-40%。
进一步地限定,上层和下层的聚偏氟乙烯薄膜的厚度为15μm-25μm。
进一步地限定,所述掺杂态聚吡咯为二氧化钛掺杂态聚吡咯,其中聚吡咯含量5wt.%,二氧化钛含量95wt.%。
上述复合薄膜制备方法是按下述步骤进行的:
步骤一、上层和下层的聚偏氟乙烯薄膜通过流延铺膜后烘干;
步骤二、采用静电纺丝法制备中间层的掺杂态聚吡咯/聚偏氟乙烯复合薄膜;
步骤三、将上层、中间层和下层按照顺序放置后热压,冷却后获得三明治结构复合薄膜。
进一步地限定,步骤一在烘箱70℃-90℃烘干2h-4h。
进一步地限定,步骤二静电纺丝法的步骤如下:
步骤1、将的聚吡咯和N,N二甲基甲酰胺混合,在超声波分散1-3小时后,添加聚偏氟乙烯,在40-80℃加热和搅拌1-3h得到聚吡咯/聚偏氟乙烯胶液;
步骤2、然后静电纺丝,参数如下:纺丝电压为15kV-16kV,纺丝距离为15cm-25cm,滚轴转速为130r/min-150r/min。
进一步地限定,步骤三热压是在平板硫化机上进行的,具体是通过下述步骤完成的:先在180℃-190℃下预热10min-30min,然后施加3MPa-8MPa压力,热压3min-8min,然后施加10MPa-15MPa压力,热压8min-15min,最后保持水冷却3min-8min,获得三明治结构复合薄膜。
聚吡咯作为一种导电高分子,具有高导电性、生物相容性和高稳定性[6],与非导电纳米填料相比,在低浓度下可以非常容易地获得更高的介电常数。通过添加导电填料制备聚偏氟乙烯基复合材料,获得优异的极化强度、较大的能量存储密度复合介质。
本发明制备的三明治结构聚吡咯/聚偏氟乙烯复合薄膜相比于单层复合薄膜,三明治结构的引入大大提高了复合薄膜的击穿强度,且具有较低的损耗。
掺杂态聚吡咯的加入,提高了复合薄膜的介电性能,且方法简单,便于实施,安全系数高。
三明治结构聚吡咯/聚偏氟乙烯复合薄膜的储能性能优异,可应用于储能电介质电容器中,在储能领域将具有很好的潜力。
本发明制备的三明治结构聚吡咯/聚偏氟乙烯复合薄膜特别是在电气和电子设备的小型化,轻量化和集成方面有更明显的作用。
附图说明
图1为(a)掺杂态聚吡咯粒子(b)聚吡咯/聚偏氟乙烯静电纺丝纤维(c)聚吡咯/聚偏氟乙烯单层复合薄膜(d)三明治结构聚吡咯/聚偏氟复合薄膜的扫描电镜图;
图2是(a)聚吡咯/聚偏氟乙烯单层复合薄膜和(b)三明治结构复合薄膜的介电常数随频率变化曲线图;
图3(a)聚吡咯/聚偏氟乙烯单层复合薄膜和(b)三明治结构复合薄膜的介电损耗随频率变化曲线图;
图4(a)聚吡咯/聚偏氟乙烯单层复合薄膜和(b)三明治结构复合薄膜的介电损耗随频率变化曲线图;
图5为三明治结构聚吡咯/聚偏氟乙烯复合薄膜的(a)储能密度和(b)充放电效率;
图6为聚吡咯/聚偏氟乙烯单层复合薄膜和三明治结构聚吡咯/聚偏氟乙烯复合薄膜的威布尔击穿强度。
具体实施方式
实施例1、本实施中三明治结构聚吡咯/聚偏氟乙烯复合薄膜,分为三层,上层和下层为聚偏氟乙烯薄膜,中间层为掺杂态聚吡咯/聚偏氟乙烯复合薄膜。
其中,中间层掺杂的掺杂态聚吡咯含量分别占中间层聚偏氟乙烯质量为10wt%,20wt%,30wt%,40wt%;
所述掺杂态聚吡咯为二氧化钛掺杂态聚吡咯,其中聚吡咯含量5wt.%,二氧化钛含量95wt.%
上层和下层的聚偏氟乙烯薄膜是采用流延铺膜的方式制得,将20g聚偏氟乙烯和120mL N,N二甲基甲酰胺置于三口瓶中,50℃加热搅拌2h,将所得胶液放入真空干燥箱内抽真空,除去气泡,再将胶液在铺膜机上铺膜,在80℃下烘干3h。
中间层掺杂态聚吡咯/聚偏氟乙烯复合薄膜的制备是将一定量的掺杂态聚吡咯和N,N二甲基甲酰胺放入三口烧瓶中,在超声波分散1h后,添加聚偏氟乙烯。在50℃加热和搅拌2h得到聚吡咯/聚偏氟乙烯胶液。将聚吡咯/聚偏氟乙烯胶液置于注射器中,放入纺丝机中,纺丝电压为15-16kV,纺丝距离为20cm,滚轴转速为140r/min。
三明治结构聚吡咯/聚偏氟乙烯复合薄膜的制备是将上层、中间层和下层按照顺序放置在平板硫化机上,然后在180℃下预热20min。将预热好的薄膜在平板硫化机上,施加5MPa压力和热压5min,然后施加12MPa压力和热压10min,最后保持水冷却4min,获得三明治结构聚吡咯/聚偏氟乙烯复合薄膜。
对比例:掺杂态聚吡咯/聚偏氟乙烯单层复合薄膜是将静电纺丝的掺杂态聚吡咯/聚偏氟乙烯复合纤维膜置于平板硫化机上,在180℃下预热20min。将预热好的薄膜在平板硫化机上,施加5MPa压力和热压5min,然后施加12MPa压力和热压10min,最后保持水冷却4min。
由图1可知,聚吡咯颗粒很好地嵌入在纤维中,三明治结构每层之间的分界线比较明显,中间层为聚吡咯/聚偏氟乙烯,外层为聚偏氟乙烯。
由图2可知,两种复合薄膜的介电常数均随着掺杂量的增加而逐渐增加,三明治结构复合薄膜的介电常数最高为20.6@133Hz,聚偏氟乙烯介电常数为9.4@133Hz。
由图3可知,两种复合薄膜的介电损耗均处于较低水平,且三明治结构复合薄膜介电损耗略低于单层复合薄膜。
由图4可知,两种复合薄膜的导电率随填充物的增加而增加。
由图5可知,当添加量为30wt%时,三明治结构复合薄膜的放电能量密度在1300kV/cm时为9.38J/cm3,是纯PVDF(2.43J/cm3)的3.8倍,放电效率为79%。
由图6可知,三明治结构复合薄膜的击穿强度明显高于单层薄膜,当填充量为10wt%时,三明治结构复合薄膜的击穿强度为161kV/mm。

Claims (8)

1.一种三明治结构聚吡咯/聚偏氟乙烯复合薄膜,其特征在于,所述复合薄膜分为三层,上层和下层为聚偏氟乙烯薄膜,中间层为掺杂态聚吡咯/聚偏氟乙烯复合薄膜。
2.根据权利要求1所述的复合薄膜,其特征在于,中间层掺杂的掺杂态聚吡咯含量占中间层聚偏氟乙烯质量的10%-40%。
3.根据权利要求1所述的复合薄膜,其特征在于,上层和下层的聚偏氟乙烯薄膜的厚度为15μm-25μm。
4.根据权利要求1所述的复合薄膜,其特征在于,所述掺杂态聚吡咯为二氧化钛掺杂态聚吡咯,其中聚吡咯含量5wt.%,二氧化钛含量95wt.%。
5.如权利要求1-4任意一项所述复合薄膜制备方法,其特征在于,所述制备方法是按下述步骤进行的:
步骤一、上层和下层的聚偏氟乙烯薄膜通过流延铺膜后烘干;
步骤二、采用静电纺丝法制备中间层的掺杂态聚吡咯/聚偏氟乙烯复合薄膜;
步骤三、将上层、中间层和下层按照顺序放置后热压,冷却后获得三明治结构复合薄膜。
6.根据权利要求5所述的制备方法,其特征在于步骤一在烘箱70℃-90℃烘干2h-4h。
7.根据权利要求5所述的制备方法,其特征在于,步骤二静电纺丝法的步骤如下:
步骤1、将聚吡咯和N,N二甲基甲酰胺混合,在超声波分散1h-3h后,添加聚偏氟乙烯,在40℃-80℃加热和搅拌1h-3h得到聚吡咯/聚偏氟乙烯胶液;
步骤2、然后静电纺丝,参数如下:纺丝电压为15kV-16kV,纺丝距离为15cm-25cm,滚轴转速为130r/min-150r/min。
8.根据权利要求5所述的制备方法,其特征在于,步骤三热压是在平板硫化机上进行的,具体是通过下述步骤完成的:
先在180℃-190℃下预热10min-30min,然后施加3MPa-8 MPa压力,热压3min-8min,然后施加10MPa-15 MPa压力,热压8min-15min,最后保持水冷却3min-8min,获得三明治结构复合薄膜。
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