CN111472055A - 一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及其制备方法 - Google Patents

一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及其制备方法 Download PDF

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CN111472055A
CN111472055A CN202010259298.3A CN202010259298A CN111472055A CN 111472055 A CN111472055 A CN 111472055A CN 202010259298 A CN202010259298 A CN 202010259298A CN 111472055 A CN111472055 A CN 111472055A
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胡艳霞
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Beijing Yucheng Technology Co ltd
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Abstract

一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及其制备方法。对于聚酰亚胺纳米纤维膜或聚酰亚胺为壳层的同轴纳米纤维膜，首先使用碱液刻蚀的方法，使其发生表层碱解开环形成聚酰胺酸盐，然后置于锆盐溶液中进行络合反应，再在去离子水中水解，超声清洗，最后再经过高温热处理，得到最终产物。对于其他类聚合物纳米纤维膜则采用臭氧进行表面活化处理，然后与锆盐进行络合，再经过水解、高温处理的方法，得到最终产物。本发明工艺过程简单易行，包覆层致密均匀，包覆程度高，应用前景良好。

Description

一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及 其制备方法
技术领域
本发明属于纳米纤维膜技术领域，尤其是涉及一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及其制备方法。
背景技术
锂离子电池由于其具有体积小，重量轻，功率密度高，使用寿命长和环境友好性等众多传统电池无法比拟的优点，已广泛应用于笔记本电脑，数码相机，手机等便携式电子设备供电。目前，国内外对锂离子电池在电子、医学、汽车、航天、军事等领域的研究也已经不断开展，锂离子电池正向着能量密度更高，安全性更强，更加轻便化的方向发展。这对锂离子电池关键组分之一的隔膜提出了更高的要求。传统的聚烯烃隔膜由于其耐温性和电解液浸润性较差，难以满足高温安全性和高倍率充放电的需求。因此，开发一种具有高耐温性、高浸润性的新型锂离子电池隔膜成为了一个越来越热门的课题。
静电纺丝法是一种制备纳米纤维膜简单有效的办法，而且该方法制备的纤维直径在纳米级，具有比表面积大、孔隙率高、孔径小而均匀吸液性能好等特点。基于静电纺丝法制备的耐高温类聚合物纳米纤维膜，不仅具备上述纳米纤维膜的优点，还兼具此类聚合物与生俱来的耐温性和化学稳定性，在锂离子电池隔膜的应用方面有很大的前景。在聚合物纳米纤维表面包覆无机粒子，不仅可以实现纤维膜孔结构的调控和力学性能的提高，而且可以结合表面无机层的亲水性和高温稳定性，赋予聚合物纳米纤维膜高强度、高浸润性、高耐温性等特性，已经成为近年来人们关注的焦点。例如专利CN105442301A采用原子层沉积法制备得到一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜，该工艺过程简单，包覆效率高，对基体无损伤，且二氧化钛纳米层的厚度可调可控，应用前景良好。
发明内容
本发明提供了一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜及其制备方法。该复合纳米纤维膜兼具聚合物纳米纤维膜和二氧化锆的优点，具有较高的孔隙率，优异的化学稳定性、热尺寸稳定性和机械性能。其制备的具体过程是，对于聚酰亚胺纳米纤维膜或聚酰亚胺为壳层的同轴纳米纤维膜，首先使用氢氧化钾溶液对其进行表面刻蚀处理，接着将其置于锆盐溶液中进行充分反应，在纤维表面形成一层致密的锆的络合物层。反应结束再置于去离子水中进行超声清洗以去除纤维膜表面残留的溶液。最后经过热处理，使锆的络合物层转化为二氧化锆，得到最终产物；对于其他类聚合物纳米纤维膜则采用臭氧进行表面活化处理，然后与锆盐络合，再经过水解、高温处理的方法，得到最终产物。
1.一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，其特征在于该复合膜中纳米纤维是由直径50～1000nm的聚合物纤维表面包覆厚度为5～80nm的二氧化锆纳米层构成，复合膜的孔隙率为50～85％，拉伸强度为20～100MPa。
2.如权利要求1所述的一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，其特征在于：所述聚合物纳米纤维膜包括聚酰亚胺纳米纤维膜、P84纳米纤维膜、芳纶纳米纤维膜、聚丙烯腈纳米纤维膜、聚酰亚胺为壳层聚丙烯腈为芯层的同轴纳米纤维膜、P84为壳层聚丙烯腈为芯层的同轴纳米纤维膜一种或者多种混合物。
3.一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜的制备方法，其特征在于包括以下两种方法：
方法一
A：将锆盐溶于醇和去离子水的混合溶剂中，并加入一定量的过氧化氢；
B：采用静电纺丝法制备聚酰胺酸纳米纤维膜或者聚酰胺酸同轴纳米纤维膜，并进行热酰亚胺化处理，处理温度为250～350℃，保温时间为2～5h，得到聚酰亚胺纳米纤维膜或者聚酰亚胺同轴纳米纤维膜；
C：将经B步骤得到的纳米纤维膜置于碱性溶液中进行表面处理，使聚酰亚胺纳米纤维表层的酰亚胺开环形成酰胺酸盐；
D：将经C步骤得到的纳米纤维膜置于A步骤所得的锆盐溶液中10～60min，随后置于去离子水中5～20min进行水解，然后用去离子水超声清洗；
E：将经过D步骤处理得到的纳米纤维膜在300℃下进行热处理，处理时间为1～3h，得到表面二氧化锆层致密包覆的聚酰亚胺纳米纤维膜或聚酰亚胺同轴纳米纤维膜。
方法二
A：将锆盐溶于醇和去离子水的混合溶剂中，并加入一定量的过氧化氢；
B：采用静电纺丝法制备聚合物纳米纤维膜或者聚合物同轴纳米纤维膜；
C：将经B步骤得到的纳米纤维膜置于去离子水中连续通入臭氧进行表面处理，臭氧的通入量为0.2-8g/h/L，处理时间为1-30min；
D：将C步骤制得的纳米纤维膜置于A步骤所得的锆盐溶液中10～60min，随后置于去离子水中5～20min进行水解，然后用去离子水超声清洗；
E：将经过D步骤处理得到的聚合物纳米纤维膜在300℃下进行热处理，处理时间为1～3h，得到表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜。
4.按照权利要求1和3所述，其特征在于，聚酰亚胺纳米纤维膜、聚酰亚胺/聚丙烯腈同轴纳米纤维膜应用方法一制备；P84纳米纤维膜、芳纶纳米纤维膜、聚丙烯腈纳米纤维、P84/聚丙烯腈同轴纳米纤维膜应用方法二制备。
5.按照权利要求3所述的方法，其特征在于，方法一和方法二步骤A中所述的锆盐为硝酸锆、柠檬酸锆、四氯化锆和氧氯化锆，溶液中锆离子的浓度为0.1～2mol/L；过氧化氢与锆盐的摩尔比为0.1～1。
6.按照权利要求3所述的方法，其特征在于，方法一和方法二步骤A中所述的醇为甲醇、乙醇、丙醇、丁醇、戊醇、苯甲醇、乙二醇和丙三醇，醇和水的质量比为0.5:1～2:1。
7.按照权利要求3所述的方法，其特征在于，方法一步骤C中的碱性溶液为氢氧化钠和氢氧化钾的水溶液，浓度为0.5～2mol/L，处理时间为5～10min。
与现有技术相比，本方法具有以下优良效果：
1.本发明原料获取途径方便，制备过程简单且易操作，工艺参数易于调节，可实现二氧化锆层包覆厚度的调控。
2.本发明制备的表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，具有孔隙率高、浸润性好、化学稳定性、热尺寸稳定性和机械性能优异的特点。
3.本发明制备表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，基于化学键结合的作用，附着力高，可实现二氧化锆层致密均匀的包覆。
附图说明
图1是按照实施例1制备的表面二氧化锆层致密包覆的聚酰亚胺纳米纤维膜的扫描电镜图，放大倍数20000倍。
图2是按照实施例2制备的表面二氧化锆层致密包覆的聚酰亚胺/聚丙烯腈纳米纤维膜的扫描电镜图，放大倍数20000倍。
图3是按照实施例3制备的表面二氧化锆层致密包覆的聚酰亚胺/聚丙烯腈纳米纤维膜的扫描电镜图，放大倍数20000倍。
图4是按照实施例4制备的表面二氧化锆层致密包覆的聚丙烯腈纳米纤维膜的扫描电镜图，放大倍数20000倍。
图5是按照实施例5制备的表面二氧化锆层致密包覆的芳纶纳米纤维膜的扫描电镜图，放大倍数20000倍。
具体实施方式
下面结合具体实施例，进一步阐述发明。应该说明的是：以下实施例仅用以说明本发明而并非限制本发明所描述的技术方案。因此，尽管本说明书参照下述的实施例对本发明已进行了详细的说明，但是，本领域的技术人员应当理解，仍然可以对本发明进行修改或等同替换；而一切不脱离本发明的精神和范围的技术方案及其改进，其均应涵盖在本发明的权利要求范围当中。
实施例1
(1)采用静电纺丝技术制备聚酰胺酸纤维膜。静电纺丝具体参数为纺丝电压：20kV；纺丝温度：室温；纺丝湿度：20％；接收辊转速：400r/min；接收距离：20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h；将所得聚酰胺酸纤维膜置于热炉中，以2℃/min的升温速度逐步升温至300℃，并保持2h，从而制得聚酰亚胺纳米纤维膜。(2)量取20ml去离子水，25ml无水乙醇，在烧杯中混合均匀。称取14g氧氯化锆，加入到乙醇和去离子水的混合溶剂中，并搅拌使其充分溶解。量取0.8ml H2O2加入其中，充分反应20min，得到锆盐溶液。(3)将聚酰亚胺纳米纤维膜浸泡在1mol/L的氢氧化钾溶液中，刻蚀处理5min，取出晾干。(4)将上一步处理得到的聚酰亚胺纳米纤维膜置于锆盐溶液中10min进行络合反应，然后再置于去离子水中超声清洗10min，取出晾干。(5)将上一步处理得到的纳米纤维膜置于300℃烘箱中进行热处理，处理时间为2h，所得纤维膜形貌如附图1所示。
实施例2
(1)采用静电纺丝技术制备聚酰胺酸为壳聚丙烯腈为核的同轴纳米纤维膜。静电纺丝具体参数为纺丝电压：20kV；纺丝温度：室温；纺丝湿度：20％；接收辊转速：400r/min；接收距离：20cm。将制备出的聚酰胺酸/聚丙烯腈同轴纳米纤维膜置于超净台中12h；将所得聚酰胺酸/聚丙烯腈同轴纳米纤维膜置于热炉中，以2℃/min的升温速度逐步升温至300℃，并保持2h，从而制得聚酰亚胺/聚丙烯腈同轴纳米纤维膜。(2)量取20ml去离子水，25ml无水乙醇，在烧杯中混合均匀。称取14g氧氯化锆，加入到乙醇和去离子水的混合溶剂中，并搅拌使其充分溶解。量取0.8ml H2O2加入其中，充分反应20min，得到锆盐溶液。(3)将聚酰亚胺/聚丙烯腈同轴纳米纤维膜浸泡在1mol/L的氢氧化钾溶液中，刻蚀处理5min，取出晾干。(4)将上一步处理得到的聚酰亚胺纳米纤维膜置于锆盐溶液中10min进行络合反应，然后再置于去离子水中超声清洗10min，取出晾干。(5)将上一步处理得到的纳米纤维膜置于300℃烘箱中进行热处理，处理时间为2h，所得纤维膜形貌如附图2所示。
实施例3
(1)采用静电纺丝技术制备聚酰胺酸为壳聚丙烯腈为核的同轴纳米纤维膜。静电纺丝具体参数为纺丝电压：20kV；纺丝温度：室温；纺丝湿度：20％；接收辊转速：400r/min；接收距离：20cm。将制备出的聚酰胺酸/聚丙烯腈同轴纳米纤维膜置于超净台中12h；将所得聚酰胺酸/聚丙烯腈同轴纳米纤维膜置于热炉中，以2℃/min的升温速度逐步升温至300℃，并保持2h，从而制得聚酰亚胺/聚丙烯腈同轴纳米纤维膜。(2)量取20ml去离子水，25ml无水乙醇，在烧杯中混合均匀。称取20g氧氯化锆，加入到乙醇和去离子水的混合溶剂中，并搅拌使其充分溶解。量取0.8ml H2O2加入其中，充分反应20min，得到锆盐溶液。(3)将聚酰亚胺/聚丙烯腈同轴纳米纤维膜浸泡在1mol/L的氢氧化钾溶液中，刻蚀处理5min，取出晾干。(4)将上一步处理得到的聚酰亚胺纳米纤维膜置于锆盐溶液中10min进行络合反应，然后再置于去离子水中超声清洗10min，取出晾干。(5)将上一步处理得到的纳米纤维膜置于300℃烘箱中进行热处理，处理时间为2h，所得纤维膜形貌如附图3所示。
实施例4
(1)采用静电纺丝技术制备聚丙烯腈纳米纤维膜。静电纺丝具体参数为纺丝电压：20kV；纺丝温度：室温；纺丝湿度：20％；接收辊转速：400r/min；接收距离：20cm。将制备出的聚丙烯腈纳米纤维膜置于超净台中12h；(2)量取20ml去离子水，25ml无水乙醇，在烧杯中混合均匀。称取14g氧氯化锆，加入到乙醇和去离子水的混合溶剂中，并搅拌使其充分溶解。量取0.8ml H2O2加入其中，充分反应20min，得到锆盐溶液。(3)将聚丙烯腈纳米纤维膜置于去离子水中，并以2g/h/L通入量的连续通入臭氧进行表面处理，处理过程持续30min。(4)将上一步处理过后的聚丙烯腈纳米纤维膜置于锆盐溶液中10min进行络合反应，然后再置于去离子水中超声清洗10min，取出晾干。(5)将上一步处理得到的纳米纤维膜置于300℃烘箱中进行热处理，处理时间为2h，所得纤维膜形貌如附图4所示。
实施例5
(1)采用静电纺丝技术制备芳纶纳米纤维膜。静电纺丝具体参数为纺丝电压：20kV；纺丝温度：室温；纺丝湿度：20％；接收辊转速：400r/min；接收距离：20cm。将制备出的芳纶纳米纤维膜置于超净台中12h；(2)量取20ml去离子水，25ml无水乙醇，在烧杯中混合均匀。称取14g氧氯化锆，加入到乙醇和去离子水的混合溶剂中，并搅拌使其充分溶解。量取0.8ml H2O2加入其中，充分反应20min，得到锆盐溶液。(3)将芳纶纳米纤维膜置于去离子水中，并以2g/h/L通入量的连续通入臭氧进行表面处理，处理过程持续30min。(4)将上一步处理得到的芳纶纳米纤维膜置于锆盐溶液中10min进行络合反应，然后再置于去离子水中超声清洗10min，取出晾干。(5)将上一步处理得到的纳米纤维膜置于300℃烘箱中进行热处理，处理时间为2h，所得纤维膜形貌如附图5所示。

Claims (7)

1.一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，其特征在于该复合膜中纳米纤维是由直径50～1000nm的聚合物纤维和表面包覆厚度为5～80nm的二氧化锆纳米层构成，复合膜的孔隙率为50～85％，拉伸强度为20～100MPa。
2.按照权利要求1所述的一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜，其特征在于：所述聚合物纳米纤维膜包括聚酰亚胺纳米纤维膜、P84纳米纤维膜、芳纶纳米纤维膜、聚丙烯腈纳米纤维膜、聚酰亚胺为壳层聚丙烯腈为芯层的同轴纳米纤维膜、P84为壳层聚丙烯腈为芯层的同轴纳米纤维膜一种或者多种混合。
3.一种表面二氧化锆层致密包覆的耐高温聚合物纳米纤维膜的制备方法，其特征在于包括以下两种方法：
方法一
A：将锆盐溶于醇和去离子水的混合溶剂中，并加入一定量的过氧化氢；
B：采用静电纺丝法制备聚酰胺酸纳米纤维膜或者聚酰胺酸同轴纳米纤维膜，并进行热酰亚胺化处理，处理温度为250～350℃，保温时间为2～5h，得到聚酰亚胺纳米纤维膜或者聚酰亚胺同轴纳米纤维膜；
C：将经B步骤得到的纳米纤维膜置于碱性溶液中进行表面处理，使聚酰亚胺纳米纤维表层的酰亚胺开环形成酰胺酸盐；
D：将经C步骤得到的纳米纤维膜置于A步骤所得的锆盐溶液中10～60min，随后置于去离子水中5～20min进行水解，然后用去离子水超声清洗；
E：将经过D步骤处理得到的纳米纤维膜在300℃下进行热处理，处理时间为1～3h，得到表面二氧化锆层致密包覆的聚酰亚胺纳米纤维膜或聚酰亚胺同轴纳米纤维膜。
方法二
A：将锆盐溶于醇和去离子水的混合溶剂中，并加入一定量的过氧化氢；
B：采用静电纺丝法制备聚合物纳米纤维膜或者聚合物同轴纳米纤维膜；
C：将经B步骤得到的纳米纤维膜置于去离子水中连续通入臭氧进行表面处理，臭氧的通入量为0.2-8g/h/L，处理时间为1-30min；
D：将C步骤制得的纳米纤维膜置于A步骤所得的锆盐溶液中10～60min，随后置于去离子水中5～20min进行水解，然后用去离子水超声清洗；
E：将经过D步骤处理得到的聚合物纳米纤维膜在300℃下进行热处理，处理时间为1～3h，得到表面二氧化锆层致密包覆的聚合物纳米纤维膜。
4.按照权利要求1和3所述，其特征在于，聚酰亚胺纳米纤维膜、聚酰亚胺/聚丙烯腈同轴纳米纤维膜应用方法一制备；P84纳米纤维膜、芳纶纳米纤维膜、聚丙烯腈纳米纤维、P84/聚丙烯腈同轴纳米纤维膜应用方法二制备。
5.按照权利要求3所述的方法，其特征在于，方法一和方法二步骤A中所述的锆盐为硝酸锆、柠檬酸锆、四氯化锆和氧氯化锆，溶液中锆离子的浓度为0.1～2mol/L；过氧化氢与锆盐的摩尔比为0.1～1。
6.按照权利要求3所述的方法，其特征在于，方法一和方法二步骤A中所述的醇为甲醇、乙醇、丙醇、丁醇、戊醇、苯甲醇、乙二醇和丙三醇，醇和水的质量比为0.5:1～2:1。
7.按照权利要求3所述的方法，其特征在于，方法一步骤C中的碱性溶液为氢氧化钠和氢氧化钾的水溶液，浓度为0.5～2mol/L，处理时间为5～10min。
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