CN108192247B - 一种铁电聚合物电卡材料及其制备方法 - Google Patents

一种铁电聚合物电卡材料及其制备方法 Download PDF

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CN108192247B
CN108192247B CN201810134566.1A CN201810134566A CN108192247B CN 108192247 B CN108192247 B CN 108192247B CN 201810134566 A CN201810134566 A CN 201810134566A CN 108192247 B CN108192247 B CN 108192247B
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ferroelectric polymers
electric card
aluminium oxide
porous anodic
card material
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CN108192247A (zh
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张光祖
胡昭耀
翁灵兮
姜胜林
李明钰
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

本发明公开了一种铁电聚合物电卡材料及其制备方法，其中铁电聚合物电卡材料为聚偏氟乙烯(PVDF)基铁电聚合物电卡纳米线阵列，该聚偏氟乙烯基铁电聚合物电卡纳米线阵列还内嵌于多孔阳极氧化铝AAO模板中。本发明是将聚偏氟乙烯基铁电聚合物电卡材料控制形成纳米线阵列，并将该纳米线阵列还内嵌于多孔阳极氧化铝AAO模板中，通过溶液浸润法在多孔阳极氧化铝AAO模板中制备该铁电聚合物纳米线阵列，通过对关键的铁电聚合物的形貌、结构、内部微观连接构造等进行改进，与现有技术相比能够有效解决铁电聚合物电卡强度低、电卡材料内的热传导困难、电卡器件的制冷功率密度低等问题。

Description

一种铁电聚合物电卡材料及其制备方法
技术领域
本发明属于制冷技术领域，更具体地，涉及一种铁电聚合物电卡材料及其制备方法，制得的电卡材料可用于新型固态制冷技术，尤其涉及铁电聚合物电卡纳米线阵列及其制备方法。
背景技术
制冷技术被广泛用于工业、军事、医疗和日常生活中。目前绝大多数制冷设备使用传统压缩制冷技术，而这种制冷方式存在制冷效率低、设备难以小型化等问题，并且压缩制冷所使用的制冷剂对环境造成了严重破坏，人们亟待寻找新型的制冷方式。
电卡制冷是一种新型制冷方式。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。电卡制冷属于固态制冷、无需对环境有危害的制冷剂，且具有制冷效率高、能耗低、易于小型化等特点，在制冷技术领域受到了广泛关注。近年来，铁电聚合物展现出较强的电卡效应，且易成型、重量轻，是电卡制冷器件和技术的重要材料之一。
然而，铁电聚合物电卡强度较低(即较强的电卡效应须要较高的电场来激发)，这给电卡制冷器件的设计带来了极大的难度，并使器件的稳定性和可靠性降低；与此同时，铁电聚合物的热导率低，电卡材料内的热传导困难，严重制约了电卡器件的制冷功率密度。因此，开发在低电场下具有强电卡效应和良好导热能力的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，本发明的目的在于提供一种铁电聚合物电卡材料及其制备方法，其中通过对关键的铁电聚合物的形貌、结构、内部微观连接构造(尤其是相对应的热传导微观机制)，以及对应制备方法的整体流程设计及各个关键步骤的条件与参数等进行改进，与现有技术相比能够有效解决铁电聚合物电卡强度低、电卡材料内的热传导困难、电卡器件的制冷功率密度低等问题，本发明是将聚偏氟乙烯基铁电聚合物电卡材料控制形成纳米线阵列，并将该纳米线阵列还内嵌于多孔阳极氧化铝AAO模板中，通过溶液浸润法在多孔阳极氧化铝AAO模板中制备该铁电聚合物纳米线阵列，一方面利用AAO多孔模板的纳米应力限制效应诱导铁电聚合物结晶行为的改变从而提升其电卡效应，另一方面将热导率高的AAO管壁作为高速导热通道，加速电卡材料与冷热端的热传递、提高电卡材料在工作中的制冷功率密度，使得铁电聚合物电卡材料在较低的电场下具有较强的电卡效应和良好的热传导能力，是一种尤其适用于新型固体制冷的铁电聚合物电卡材料。并且，本方法的制备工艺简单、易于实施，在电卡制冷领域有着重要的使用价值和良好的应用前景。
为实现上述目的，按照本发明的一个方面，提供了一种铁电聚合物电卡材料，其特征在于，该铁电聚合物电卡材料为聚偏氟乙烯(PVDF)基铁电聚合物电卡纳米线阵列，该聚偏氟乙烯基铁电聚合物电卡纳米线阵列还内嵌于多孔阳极氧化铝AAO模板中。
作为本发明的进一步优选，所述聚偏氟乙烯基铁电聚合物为聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))，或聚偏氟乙烯-三氟乙烯-氯代偏氟乙烯(P(VDF-TrFE-CFE))；
优选的，所述多孔阳极氧化铝AAO模板的孔径为30纳米～450纳米，厚度为10微米～500微米。
按照本发明的另一方面，本发明提供了一种铁电聚合物电卡材料的制备方法，其特征在于，包括以下步骤：
A、对多孔阳极氧化铝AAO模板进行退火处理；
B、以聚偏氟乙烯(PVDF)基铁电聚合物为原料，将该原料溶于溶剂，得到均匀混合的铁电聚合物溶液；
C、将所述铁电聚合物溶液浸润并贯穿于所述步骤A得到的所述多孔阳极氧化铝AAO模板的通孔；
D、在真空加热条件下使位于所述多孔阳极氧化铝AAO模板中的铁电聚合物溶液中的溶剂挥发；
E、将所述步骤D得到的所述多孔阳极氧化铝AAO模板置于烘箱中进行退火处理，即可得到位于所述多孔阳极氧化铝AAO模板中的铁电聚合物电卡材料。
作为本发明的进一步优选，所述铁电聚合物电卡材料的制备方法，还包括步骤：
F、在所述步骤E处理得到的所述多孔阳极氧化铝AAO模板的上表面和下表面分别制备电极，该多孔阳极氧化铝AAO模板任一孔隙内的铁电聚合物电卡材料则用于连接分别位于所述上表面和所述下表面上的电极。
作为本发明的进一步优选，所述步骤A中，所述多孔阳极氧化铝AAO模板是采用电化学方法制备得到的，其孔径为30纳米～450纳米，厚度为10微米～500微米。
作为本发明的进一步优选，所述步骤A中，所述退火处理的温度为600摄氏度～1300摄氏度。
作为本发明的进一步优选，所述步骤B中，所述聚偏氟乙烯基铁电聚合物为聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))，或聚偏氟乙烯-三氟乙烯-氯代偏氟乙烯(P(VDF-TrFE-CFE))；
优选的，所述步骤B中，所述溶剂为有机溶剂，优选为N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、磷酸三乙酯(TEP)和二甲基硫(DMS)中任意一种或任意几种的混合物；
所述步骤B得到的所述铁电聚合物溶液的浓度为5wt％～40wt％。
作为本发明的进一步优选，所述步骤C是将所述铁电聚合物溶液滴涂于所述多孔阳极氧化铝AAO模板的表面，使该溶液浸润并贯穿于所述多孔阳极氧化铝AAO模板的通孔。
作为本发明的进一步优选，所述步骤D中，所述挥发是在30摄氏度～100摄氏度的温度下保温2小时～24小时。
作为本发明的进一步优选，所述步骤E中，所述退火处理是在60摄氏度～160摄氏度的温度下处理5小时～28小时。
通过本发明所构思的以上技术方案，与现有技术相比，由于将聚偏氟乙烯基铁电聚合物电卡材料控制形成纳米线阵列，与传统模板法在制备纳米线后去掉多孔阳极氧化铝AAO模板不同，本发明先通过对多孔阳极氧化铝AAO模板进行退火处理(并对退火温度进行优选)以提升其热导率，并且还保留了多孔阳极氧化铝AAO模板，使纳米线阵列内嵌于多孔阳极氧化铝AAO模板中，以多孔阳极氧化铝AAO模板作为该电卡材料的内部微观连接构造，形成相对应的热传导微观机制，并进一步对聚偏氟乙烯基铁电聚合物纳米线阵列的形貌、结构(如纳米线的长度及直径)，也即多孔阳极氧化铝AAO模板的通孔形貌、结构(如孔径、厚度)进行优选，能够：(1)提高铁电聚合物电卡材料的电卡强度，使其在较低的外加电场下获得较强的电卡效应；(2)解决铁电聚合物中热传导困难的问题。
本发明与传统的铁电聚合物薄膜电卡材料相比，首次将铁电聚合物的电卡强度提高了3倍(表1，该表1所针对的铁电聚合物纳米线阵列对应本发明后续实施例1)；另外，本发明通过退火处理提升多孔阳极氧化铝AAO模板的热导率，也能有效提高电卡材料的制冷功率密度，例如，当传统的铁电聚合物薄膜与内嵌于AAO中的纳米线阵列的厚度均为100微米时，材料充分传热的时间由500毫秒缩短至30毫秒，电卡材料在25赫兹的工作频率下的制冷功率密度提高了5倍(表1)。
表1铁电聚合物纳米线阵列与薄膜的电卡性能对比
此外，本发明还通过对制备方法中关键的退火处理工艺进行优选，其中所使用的多孔阳极氧化铝AAO模板的退火处理温度优选为600摄氏度～1300摄氏度，后续形成的多孔阳极氧化铝AAO模板内嵌有聚偏氟乙烯基铁电聚合物电卡纳米线阵列的电卡材料整体的退火处理温度优选为60摄氏度～160摄氏度，通过控制各项参数，可有效降低该电卡材料整体的组织缺陷，提高电卡强度及制冷功率密度。
附图说明
图1为本发明流程步骤示意图。
图2为内嵌在AAO模板中的聚合物纳米线阵列表面电子扫描显微镜片。
图3为去除AAO模板后铁电聚合物纳米线阵列的电子扫描显微镜照片。
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。
本发明中的电卡材料，由PVDF基铁电聚合物电卡纳米线阵列内嵌于多孔阳极氧化铝(AAO)模板中构成；PVDF基铁电聚合物纳米线阵列中，聚合物的种类可优选包括聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))和聚偏氟乙烯-三氟乙烯-氯代偏氟乙烯(P(VDF-TrFE-CFE))中的至少一种；多孔AAO模板的通孔孔径优选为30纳米～450纳米，厚度优选为10微米～500微米。该电卡材料可以按以下步骤制备：
A、采用电化学法制备AAO模板，AAO模板的孔径为30纳米～450纳米，厚度为10微米～500微米；
B、在600摄氏度～1300摄氏度对AAO模板进行退火处理；
C、以P(VDF-TrFE)或P(VDF-TrFE-CFE)为原料，溶于溶剂，所得溶液浓度为5wt％～40wt％；
D、将上述溶液滴涂于退火后的AAO模板表面，使溶液浸润并贯穿于AAO模板的通孔；
E、将样品置于30摄氏度～100摄氏度的真空箱内干燥2小时～24小时使铁电聚合物溶液中的溶剂挥发；
F、将样品置于60摄氏度～160摄氏度的烘箱中退火处理5小时～28小时；
G、在材料上下表面制备电极。
其中步骤G为可选步骤。
以下为具体实施例：
实施例1
A、制备多孔AAO模板，具体步骤如下：
a、将铝箔在400摄氏度下退火处理，保温时间为2小时，有利于后续形成规则的孔洞结构；
b、铝箔先后在甲苯和乙醇中超声清洗10分钟；
c、以钢板为阴极、铝箔为阳极，在高氯酸与乙醇体积比为1：4的溶液中进行电化学抛光，电压为20V；
d、以抛光后的铝箔为阳极、钢板为阴极在0.3mol/L草酸中进行一次氧化，电压为60V，时间1小时；
e、将一次氧化后的铝箔浸泡在6wt％的磷酸和1.8wt％的铬酸的混合溶液中，置于80摄氏度的烘箱中去除一次氧化形成的表层氧化铝，反应时间为0.5小时；
f、将经上述处理过的铝箔作为阳极、钢板为阴极在0.3mol/L草酸中进行第二次氧化，反应电压为60V，反应时间3小时；
g、将二次氧化生成的AAO置于饱和硫酸铜溶液中去除剩余铝基底，并在5wt％磷酸溶液中浸泡30分钟去除阻挡层并扩孔，得到孔洞排列高度有序的AAO模板；
B、将A步骤中制作的AAO模板在850摄氏度下进行高温退火处理，保温时间为2小时；
C、将P(VDF-TrFE-CFE)铁电聚合物溶解于DMF中，配置浓度为30wt％的P(VDF-TrFE-CFE)-DMF溶液。使用磁力搅拌器搅拌24小时，使P(VDF-TrFE-CFE)充分溶解；
D、将上述溶液滴涂于退火后的AAO模板表面，使溶液浸润并贯穿于AAO模板的通孔；
E、将样品置于在60摄氏度的真空烘箱内干燥24小时，使DMF挥发；
F、将样品置于100摄氏度的烘箱中退火处理22小时；
G、使用离子溅射法在材料上下表面制备电极。
实施例2
步骤A中一次氧化电压为25V，反应时间为6小时；二次氧化电压为25V，反应时间为20小时，其余同实施例1。
实施例3
步骤A中电化学反应溶液为0.3mol/L磷酸溶液，一次氧化电压为195V，反应时间为6小时；二次氧化电压为195V，反应时间为20小时，其余同实施例1。
实施例4和5
步骤A中二次氧化反应时间分别为0.3小时和15小时，其余同实施例1。
实施例6和7
步骤B中AAO模板退火温度分别为600摄氏度和1300摄氏度，其余同实施例1。
实施例8
步骤B中AAO模板退火时间为6小时，其余同实施例1。
实施例9
步骤C中溶剂为DMAc，其余同实施例1。
实施例10和11
步骤C中溶液浓度分别为5wt％和40wt％，其余同实施例1。
实施例12和13
步骤E中将样品分别置于30摄氏度和100摄氏度的真空箱内干燥，其余同实施例1；
实施例14
步骤E中将样品置于100摄氏度的真空箱内干燥2小时，其余同实施例1；
实施例15
步骤F中样品退火温度为60摄氏度，其余同实施例1。
实施例16和17
步骤F中样品退火时间分别为5小时和28小时，其余同实施例1。
实施例18
步骤C中铁电聚合物为P(VDF-TrFE)，步骤F中退火温度为160摄氏度，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，在50MV/m的电场下测试结果如表2所示。
表2各实施例的电卡性能对比
[1]工作频率为25Hz。
根据上表可以看出，通过实施例的对比我们可以看出AAO模板的孔径和厚度、AAO模板退火温度和时间、聚合物和溶剂种类、溶液浓度、烘干温度和时间、退火温度和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 (10)

1.一种铁电聚合物电卡材料，其特征在于，该电卡材料为聚偏氟乙烯(PVDF)基铁电聚合物和多孔阳极氧化铝AAO的混合材料，该混合材料包括多孔阳极氧化铝AAO模板和内嵌于其中的PVDF基铁电聚合物纳米线阵列；所述多孔阳极氧化铝AAO模板经过温度为600摄氏度～1300摄氏度的退火处理。
2.如权利要求1所述铁电聚合物电卡材料，其特征在于，所述聚偏氟乙烯基铁电聚合物为聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))，或聚偏氟乙烯-三氟乙烯-氯代偏氟乙烯(P(VDF-TrFE-CFE))。
3.如权利要求1所述铁电聚合物电卡材料，其特征在于，所述多孔阳极氧化铝AAO模板的孔径为30纳米～450纳米，厚度为10微米～500微米。
4.制备如权利要求1－3任意一项所述铁电聚合物电卡材料的制备方法，其特征在于，包括以下步骤：
A、对多孔阳极氧化铝AAO模板进行退火处理；所述退火处理的温度为600摄氏度～1300摄氏度；
B、以聚偏氟乙烯(PVDF)基铁电聚合物为原料，将该原料溶于溶剂，得到均匀混合的铁电聚合物溶液；
C、将所述铁电聚合物溶液浸润并贯穿于所述步骤A得到的所述多孔阳极氧化铝AAO模板的通孔；
D、在真空加热条件下使位于所述多孔阳极氧化铝AAO模板中的铁电聚合物溶液中的溶剂挥发；
E、将所述步骤D得到的所述多孔阳极氧化铝AAO模板置于烘箱中进行退火处理，即可得到位于所述多孔阳极氧化铝AAO模板中的铁电聚合物电卡材料。
5.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述铁电聚合物电卡材料的制备方法，还包括步骤：
F、在所述步骤E处理得到的所述多孔阳极氧化铝AAO模板的上表面和下表面分别制备电极，该多孔阳极氧化铝AAO模板任一孔隙内的铁电聚合物电卡材料则用于连接分别位于所述上表面和所述下表面上的电极。
6.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述步骤A中，所述多孔阳极氧化铝AAO模板是采用电化学方法制备得到的，其孔径为30纳米～450纳米，厚度为10微米～500微米。
7.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述步骤B中，所述聚偏氟乙烯基铁电聚合物为聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))，或聚偏氟乙烯-三氟乙烯-氯代偏氟乙烯(P(VDF-TrFE-CFE))；
所述步骤B中，所述溶剂为有机溶剂，具体为N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、磷酸三乙酯(TEP)和二甲基硫(DMS)中任意一种或任意几种的混合物；
所述步骤B得到的所述铁电聚合物溶液的浓度为5wt％～40wt％。
8.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述步骤C是将所述铁电聚合物溶液滴涂于所述多孔阳极氧化铝AAO模板的表面，使该溶液浸润并贯穿于所述多孔阳极氧化铝AAO模板的通孔。
9.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述步骤D中，所述挥发是在30摄氏度～100摄氏度的温度下保温2小时～24小时。
10.如权利要求4所述铁电聚合物电卡材料的制备方法，其特征在于，所述步骤E中，所述退火处理是在60摄氏度～160摄氏度的温度下处理5小时～28小时。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539956A (zh) * 2013-10-10 2014-01-29 中国科学院上海技术物理研究所 一种pvdf基有机铁电聚合物纳米线的制备方法
CN103881119A (zh) * 2014-01-17 2014-06-25 中国科学院上海技术物理研究所 一种pvdf基有机铁电聚合物纳米管的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102317625B (zh) * 2007-06-08 2014-08-13 卡弗科技公司 将热能转化为电能的设备和方法
US20090056094A1 (en) * 2007-08-21 2009-03-05 Yong Shi Piezoelectric composite nanofibers, nanotubes, nanojunctions and nanotrees
KR101769459B1 (ko) * 2011-08-10 2017-08-21 삼성전자주식회사 나노 발전 소자 및 그 제조 방법
CN105540535B (zh) * 2015-12-29 2017-01-25 陕西科技大学 一种制备多尺度高γ相聚偏氟乙烯中空纳米线的方法
WO2018156079A1 (en) * 2017-02-21 2018-08-30 Agency For Science, Technology And Research Ultrasonic transducers and methods for producing an ultrasonic transducer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539956A (zh) * 2013-10-10 2014-01-29 中国科学院上海技术物理研究所 一种pvdf基有机铁电聚合物纳米线的制备方法
CN103881119A (zh) * 2014-01-17 2014-06-25 中国科学院上海技术物理研究所 一种pvdf基有机铁电聚合物纳米管的制备方法

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