CN105330287A - 一种电卡材料及其制备方法 - Google Patents

一种电卡材料及其制备方法 Download PDF

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CN105330287A
CN105330287A CN201510736091.XA CN201510736091A CN105330287A CN 105330287 A CN105330287 A CN 105330287A CN 201510736091 A CN201510736091 A CN 201510736091A CN 105330287 A CN105330287 A CN 105330287A
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张光祖
陈墨
王庆
沈孟
刘品
姜胜林
曾亦可
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Huazhong University of Science and Technology
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Abstract

本发明公开了一种电卡材料及其制备方法。电卡材料由覆盖在柔性衬底上的BST陶瓷纳米线阵列构成，所述BST陶瓷纳米线阵列中，Ba和Sr的摩尔比为(1～3):1。本发明首次将BST陶瓷纳米线阵列用作电卡材料，通过将BST陶瓷纳米线阵列转移到柔性衬底上，充分利用铁电陶瓷良好的电卡效应和纳米线阵列特殊微结构具有的柔韧性，制得具有良好柔韧性和理想电卡效应的电卡材料，实现了无机柔性电卡材料的制备。

Description

一种电卡材料及其制备方法
技术领域
本发明属于电子材料技术领域，更具体地，涉及一种电卡材料及其制备方法。
背景技术
在各种材料中，电卡材料利用外加电场来激发其体内的相变，并借助相变引起的吸热作用实现制冷。基于电卡材料的制冷器无需使用对环境具有严重危害的氟利昂等制冷剂，并拥有理想的制冷效率。电卡效应的应用是实现下一代高效环保型制冷器件的重要途径，高性能电卡材料与器件的研制将为未来固态集成制冷技术的发展奠定良好的基础，还可被应用于新型柔性电子与信息器件的导热和控温，并有望全面取代现有的空调、冰箱等对环境有严重危害的高能耗制冷设备。
电卡材料可分为无机电卡材料与有机电卡材料两大类。无机电卡材料，如钛酸钡、锆钛酸铅等陶瓷和单晶等，具有较高的电卡强度，但其介电击穿场强较低，且不具柔性，无法应用于可穿戴设备中。有机电卡材料，如聚偏氟乙烯(PVDF)基铁电共聚物，虽具有理想的柔韧性，但其电卡强度低，必须通过较大的外加电场来激发较强的电卡效应。因此，研究与开发具有柔性的高性能电卡材料具有重要的意义。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种电卡材料及其制备方法，其目的在于获得具有良好柔韧性和理想电卡效应的电卡材料，由此解决柔韧性和电卡强度不能兼备的技术问题。
为实现上述目的，按照本发明的一个方面，提供了一种电卡材料，其特征在于，由覆盖在柔性衬底上的BST陶瓷纳米线阵列构成，所述BST陶瓷纳米线阵列中，Ba和Sr的摩尔比为(1～3):1。
优选地，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
按照本发明的另一方面，提供了一种电卡材料的制备方法，其特征在于，包括如下步骤：(1)将表面镀有氟掺杂氧化锡的玻璃置于钛酸四丁酯的盐酸溶液中，在100℃～200℃下进行第一次水热反应，在玻璃表面生成二氧化钛纳米线阵列；(2)将表面长有二氧化钛纳米线阵列的玻璃放入含Ba2+和Sr2+的溶液中，其中，Ba2+和Sr2+的摩尔浓度比为(1～3):1，在150℃～230℃下进行第二次水热反应，在玻璃表面生成BST陶瓷纳米线阵列；(3)将BST陶瓷纳米线阵列从玻璃表面剥离并转移到柔性衬底上，得到BST陶瓷纳米线阵列电卡材料。
优选地，所述步骤(3)具体为：在柔性衬底上涂覆电极浆料，将柔性衬底覆盖BST陶瓷纳米线阵列，其中，电极浆料与BST陶瓷纳米线阵列接触；待电极浆料干燥后将柔性衬底从玻璃表面剥离完成BST陶瓷纳米线阵列的转移。
优选地，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
按照本发明的另一方面，提供了一种覆盖在柔性衬底上的BST陶瓷纳米线阵列作为电卡材料的应用。
优选地，所述BST陶瓷纳米线阵列中，Ba和Sr的摩尔比为(1～3):1。
优选地，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，具有以下有益效果：首次将BST陶瓷纳米线阵列用作电卡材料，通过将BST陶瓷纳米线阵列转移到柔性衬底上，充分利用铁电陶瓷良好的电卡效应和纳米线阵列特殊微结构具有的柔韧性，制得具有良好柔韧性和理想电卡效应的电卡材料，实现了无机柔性电卡材料的制备。
附图说明
图1是本发明实施例的电卡材料的制备方法流程图；
图2是实施例1制得的电卡材料的表面SEM图；
图3是实施例1制得的电卡材料的截面SEM图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
如图1所示，本发明实施例的电卡材料的制备方法包括如下步骤：
(1)将表面镀有氟掺杂氧化锡的玻璃置于钛酸四丁酯的盐酸溶液中，在100℃～200℃下进行第一次水热反应，在玻璃表面生成二氧化钛纳米线阵列。
(2)将表面长有二氧化钛纳米线阵列的玻璃放入含Ba2+和Sr2+的溶液中，其中，Ba2+和Sr2+的摩尔浓度比为(1～3):1，在150℃～230℃下进行第二次水热反应，在玻璃表面生成BST陶瓷纳米线阵列。
(3)将BST陶瓷纳米线阵列从玻璃表面剥离并转移到柔性衬底上，得到BST陶瓷纳米线阵列电卡材料。
具体操作为：在柔性衬底上涂覆电极浆料，将柔性衬底覆盖BST陶瓷纳米线阵列，其中，电极浆料与BST陶瓷纳米线阵列接触；待电极浆料干燥后将柔性衬底从玻璃表面剥离完成BST陶瓷纳米线阵列的转移。
具体地，柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
步骤(2)得到的在玻璃表面的陶瓷纳米线阵列是不具有柔性的，因为玻璃衬底不具有柔性，上述通过步骤(3)将陶瓷纳米线阵列从非柔性的玻璃表面剥离并转移到柔性衬底上，得到柔性陶瓷纳米线阵列电卡材料，利用这种阵列的柔性解决高性能无机电卡材料不具有柔性的问题。
为使本领域技术人员更好地理解本发明，下面结合具体实施例对本发明的电卡材料的制备方法进行详细说明。
实施例1
取质量分数为37％的盐酸与去离子水按照体积比1:1混合，得到盐酸溶液；在盐酸溶液中加入钛酸四丁酯，钛酸四丁酯与盐酸溶液的体积比为1.5:100，得到钛酸四丁酯的盐酸溶液；将表面镀有氟掺杂氧化锡的玻璃置于钛酸四丁酯的盐酸溶液中，放入水热反应釜，进行第一次水热反应，反应温度为150℃，反应时间为20小时；此后清洗反应后得到的二氧化钛纳米线阵列；将氢氧化钡和氢氧化锶溶于去离子水中，得到的混合液中氢氧化钡的浓度为0.015mol/L，氢氧化锶的浓度为0.005mol/L，将表面长有二氧化钛纳米线阵列的玻璃放入混合液中，进行第二次水热反应，反应温度为210℃，反应时间为8小时；对反应后的纳米线阵列进行清洗，得到BST陶瓷纳米线阵列，如图2和图3所示。将BST陶瓷纳米线阵列从玻璃表面剥离并转移到聚二甲基硅氧烷柔性衬底上，得到具有柔性的BST陶瓷纳米线阵列电卡材料。
实施例2和3
取质量分数为37％的盐酸分别与去离子水按照体积比1:2和2:1混合，其余同实施例1。
实施例4和5
钛酸四丁酯与盐酸溶液的体积比分别为1:100和10:100，其余同实施例1。
实施例6和7
第一次水热反应的反应温度分别为100℃和200℃，其余同实施例1。
实施例8、9和10
在第二次水热反应中，氢氧化钡和氢氧化锶在混合液中的浓度分别为0.012mol/L和0.005mol/L、0.01mol/L和0.005mol/L以及0.005mol/L和0.005mol/L，其余同实施例1。
实施例11和12
第二次水热反应的反应温度分别为150℃和230℃，其余同实施例1。
实施例13
第二次水热反应的反应时间为12小时，其余同实施例1。
实施例14和15
分别以聚酰亚胺薄膜和透明胶带为柔性衬底，其余同实施例1。
对上述实施例制得的电卡材料进行性能测试，结果如下表所示。
通过上表可以看出，实施例1的反应条件得到的电卡材料具有最好的性能。通过和其它实施例的对比我们可以看出两次水热反应的温度、盐酸溶液的浓度、钛酸四丁酯与盐酸溶液的比例、氢氧化钡和氢氧化锶溶液的浓度以及第二次水热反应的时间都会影响到材料的性能。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种电卡材料，其特征在于，由覆盖在柔性衬底上的BST陶瓷纳米线阵列构成，所述BST陶瓷纳米线阵列中，Ba和Sr的摩尔比为(1～3):1。
2.如权利要求1所述的电卡材料，其特征在于，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
3.一种电卡材料的制备方法，其特征在于，包括如下步骤：
(1)将表面镀有氟掺杂氧化锡的玻璃置于钛酸四丁酯的盐酸溶液中，在100℃～200℃下进行第一次水热反应，在玻璃表面生成二氧化钛纳米线阵列；
(2)将表面长有二氧化钛纳米线阵列的玻璃放入含Ba2+和Sr2+的溶液中，其中，Ba2+和Sr2+的摩尔浓度比为(1～3):1，在150℃～230℃下进行第二次水热反应，在玻璃表面生成BST陶瓷纳米线阵列；
(3)将BST陶瓷纳米线阵列从玻璃表面剥离并转移到柔性衬底上，得到BST陶瓷纳米线阵列电卡材料。
4.如权利要求3所述的电卡材料的制备方法，其特征在于，所述步骤(3)具体为：在柔性衬底上涂覆电极浆料，将柔性衬底覆盖BST陶瓷纳米线阵列，其中，电极浆料与BST陶瓷纳米线阵列接触；待电极浆料干燥后将柔性衬底从玻璃表面剥离完成BST陶瓷纳米线阵列的转移。
5.如权利要求3或4所述的电卡材料的制备方法，其特征在于，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
6.一种覆盖在柔性衬底上的BST陶瓷纳米线阵列作为电卡材料的应用。
7.如权利要求6所述的覆盖在柔性衬底上的BST陶瓷纳米线阵列作为电卡材料的应用，其特征在于，所述BST陶瓷纳米线阵列中，Ba和Sr的摩尔比为(1～3):1。
8.如权利要求6或7所述的覆盖在柔性衬底上的BST陶瓷纳米线阵列作为电卡材料的应用，其特征在于，所述柔性衬底为聚二甲基硅氧烷、聚酰亚胺薄膜或透明胶带。
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CN108573940A (zh) * 2018-04-09 2018-09-25 南京理工大学 一种柔性电卡制冷器件

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