CN112373162A - 一种具有三层结构的复合介电材料及其制备方法 - Google Patents
一种具有三层结构的复合介电材料及其制备方法 Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 32
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- 239000004408 titanium dioxide Substances 0.000 claims description 13
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 9
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- 229910002113 barium titanate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 7
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Abstract
本发明公开一种具有三层结构的复合介电材料,包括介电增强层、夹设于介电增强层的耐压增强层,所述介电增强层的材料为铁电聚合物/介电陶瓷填料复合物,所述耐压增强层为线性电介质高分子聚合物,还提供其制备方法,包括如下步骤:S1.将铁电聚合物溶解于N,N‑二甲基甲酰胺后,加入介电陶瓷填料并超声分散,得混合液,将所述混合液涂覆于石英玻璃板上,烘干后刮下,得介电增强薄膜;S2.将线性电介质高分子聚合物的N,N‑二甲基甲酰胺溶液涂覆于,石英玻璃板上,烘干后刮下,得耐压增强薄膜;S3.将所述耐压增强薄膜夹设于所述介电增强薄膜之间,热压成型后冷却,即得具有三层结构的复合介电材料,储能效率及储能密度高。
Description
技术领域
本发明涉及介电储能材料技术领域,具体涉及一种具有三层结构的复合介电材料及其制备方法。
背景技术
薄膜电容器具有功率密度大、充放电效率高、循环性能稳定等特点,在当代电子电力系统中发挥着重要作用。薄膜电容器的性能指标的优劣取决于电介质薄膜材料的关键性能参数如储能密度、充放电效率等。聚合物电介质材料具有柔性、质轻、易加工的特点且耐高压性能优异,是制备薄膜电容器的主要原材料。然而聚合物电介质材料的储能密度较低,限制了薄膜电容器的进一步发展,开发高效稳定的高储能密度新型电介质材料具有极强的理论意义与现实价值。
通过制备聚合物/介电陶瓷复合材料,是实现高储能密度电介质材料的有效手段。例如,Li等将聚乙烯吡络烷酮包覆的钛酸钡(BaTiO3)填料与聚偏氟乙烯(PVDF)复合,当改性钛酸钡纳米线的含量达到3 vol.%时,复合材料在300 MV/m的条件下,储能密度达到8.55J/cm3,较聚合物基体提升效果明显,然而,介电陶瓷的引入导致复合材料的击穿强度降低,储能效率下降,进而限制了储能性能的提升。
发明内容
为解决上述问题,本发明提供一种具有三层结构的复合介电材料,储能效率及储能密度高。
本发明的解决的技术方案是,一种具有三层结构的复合介电材料,包括介电增强层、夹设于介电增强层的耐压增强层,所述介电增强层的材料为铁电聚合物/介电陶瓷填料复合物,所述耐压增强层为线性电介质高分子聚合物。
优选地,所述铁电聚合物/介电陶瓷填料复合物中,铁电聚合物包括聚偏氟乙烯、聚偏氟乙烯-六氟丙烯、聚偏氟乙烯-三氟氯乙烯,聚偏氟乙烯-三氟乙烯中的一种,所述介电陶瓷填料包括钛酸钡、钛酸锶钡、二氧化钛中的一种。
优选地,所述线性电介质高分子聚合物包括聚甲基丙烯酸甲酯甲酯、聚碳酸酯、聚丙烯、聚苯乙烯中的一种。
优选地,所述介电增强层与所述耐压增强层的厚度相等。
优选地,所述介电陶瓷填料与所述铁电聚合物的质量之比为1:9-19。。
还提供一种具有三层结构的复合介电材料的制备方法,包括以下步骤:
S1.将铁电聚合物溶解于N,N-二甲基甲酰胺后,加入介电陶瓷填料并超声分散,得混合液,将所述混合液涂覆于石英玻璃板上,烘干后刮下,得介电增强薄膜;
S2.将线性电介质高分子聚合物的N,N-二甲基甲酰胺溶液涂覆于,石英玻璃板上,烘干后刮下,得耐压增强薄膜;
S3.将所述耐压增强薄膜夹设于所述介电增强薄膜之间,热压成型后冷却,即得具有三层结构的复合介电材料。
优选地,所述步骤S1及步骤S2中,烘干温度为60-70 ℃,烘干时间为24-48 h。
优选地,所述热压定型温度为180-200 ℃,热压压力为15-20 Mpa,热压时间为20-30 min。
优选地,所述耐压增强薄膜及介电增强薄膜的厚度均为5-8 μm。
优选地,所述铁电聚合物包括聚偏氟乙烯、聚偏氟乙烯-六氟丙烯、聚偏氟乙烯-三氟氯乙烯,聚偏氟乙烯-三氟乙烯中的一种,所述介电陶瓷填料包括钛酸钡、钛酸锶钡、二氧化钛中的一种,其中,所述介电陶瓷填料与所述铁电聚合物的质量之比为1:9-19。,所述线性电介质高分子聚合物包括聚甲基丙烯酸甲酯甲酯、聚碳酸酯、聚丙烯、聚苯乙烯中的一种。
本方案中,以铁电聚合物/介电陶瓷填料复合物为外层,即介电增强层,以提高复合材料整体的介电性能,将铁电聚合物与介电陶瓷填料按照一定比例,溶于N,N-二甲基甲酰胺中,利用溶液流延的成型方法,制备介电增强层薄膜,介电增强层选用铁电聚合物/介电陶瓷填料复合物的原因在于,铁电聚合物为含非对称极性基团,本身具有固定偶极矩的聚合物,可提高复合材料整体的介电性能,优选的介电陶瓷填料比可避免对复合介电材料受到的整体击穿电压与储能效率造成的明显影响;以线性电介质高分子聚合物为中间层,即耐压增强层,以提高复合材料整体的击穿性能与充放电效率。选用纯线性电介质高分子聚合物为材料的原因在于线性电介质聚合物是无非对称极性基团,正负电荷重心重合,为无固定偶极矩的聚合物电介质,低介电常数低,低电导损耗与高击穿电压,一方面可有效调控复合材料内的电场分布,阻碍电击穿行为的发生,提高材料的击穿性能,另一方面可有效限制载流子跃迁行为,降低电导损耗,提高复合材料的整体储能效率;结合复合介电材料内外层的功能,储能性能,击穿性能,储能效率,储能密度以及循环性能显著提升。
本发明的有益效果在于:
1.将铁电聚合物/介电陶瓷填料复合物作为介电增强层包覆耐压增强层,能提高复合介电材料的介电性能,且避免整体击穿电压对复合介电材料的造成的储能效率的影响;
2.将线性电介质聚合物作为耐压增强层夹设于介电增强层之间,一方面可有效调控复合介电材料内的电场分布,阻碍电击穿行为的发生,提高复合介电材料的击穿性能;另一方面可有效限制载流子跃迁行为,降低电导损耗,提高复合介电材料的整体储能效率;
3. 结合复合介电材料内外层的功能,各层之间相互协同,储能性能,击穿性能,储能效率,储能密度以及循环性能显著提升。
附图说明
图1为实例1中制备三层结构的复合介电材料的示意图片;
图2为实例1中制备三层结构的复合介电材料的SEM图片;
图3为实例1中制备三层结构的复合介电材料的电场分布模拟图;
图4 为实例1中制备的三层结构的复合介电材料在所承受电场下的电滞回线;
图5为实施例2中制备的三层结构的复合介电材料在所承受电场下的电滞回线;
图6为实施例3中制备的三层结构的复合介电材料在所承受电场下的电滞回线;
图7为实施例4中制备的三层结构的复合介电材料在所承受电场下的电滞回线;图8为对比例1中制备的三层结构的复合介电材料在所承受电场下的电滞回线;
图9为对比例2中制备的三层结构的复合介电材料在所承受电场下的电滞回线;
图10为对比例3中制备的三层结构的复合介电材料在所承受电场下的电滞回线。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
将0.45 g的聚偏氟乙烯-六氟丙烯粉末溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,然后在上述溶液加入0.05 g的钛酸钡纳米颗粒,继续搅拌1 h后超声处理30min直至钛酸钡纳米颗粒完全分散,将上述制备的混合溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到外层为聚偏氟乙烯-六氟丙烯/钛酸钡的薄膜即介电增强薄膜,薄膜厚度为5 μm;
将0.5 g的聚甲基丙烯酸甲酯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到内层为聚甲基丙烯酸甲酯的薄膜,即耐压增强薄膜,薄膜厚度为5 μm;
将耐压增强薄膜夹设于所述介电增强薄膜之间,如图1所示,利用热压机在180 ℃,20Mpa的条件下热压20 min后自然冷却,得到具有三层结构的复合介电材料,SEM图见图2,本实施例所制备的具有三层结构的复合介电材料,界面清晰,结构没有明显缺陷。
图3为利用计算机辅助方法得到的本实施例所制备的具有三层结构的复合介电材料在外加电场下内部的电场分布情况,可以看到聚甲基丙烯酸甲酯分担了更高的电压,由于聚甲基丙烯酸甲酯自身的耐高压性能优异,因此保证了复合介电材料体系的优异耐高压性能;图4为该复合材料在最高耐压电场下的电滞回线,可以看出该材料损耗较低,在560MV/m的电场强度下,储能效率为82%,储能密度为17.05 J/cm3。
实施例2
将0.95 g的聚偏氟乙烯粉末溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,然后在上述溶液加入0.05 g的钛酸锶钡纳米颗粒,继续搅拌1 h后超声处理30 min直至钛酸锶钡纳米颗粒完全分散,将上述制备的混合溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到外层为聚偏氟乙烯/钛酸锶钡的薄膜即介电增强薄膜,薄膜厚度为6 μm;
将0.5 g的聚碳酸酯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入70 ℃的烘箱中干燥24 h,得到内层为聚碳酸酯的薄膜,即耐压增强薄膜,薄膜厚度控制为6 μm;
将耐压增强薄膜夹设于所述介电增强薄膜之间,如图1所示,利用热压机在200 ℃,15Mpa的条件下热压30 min后自然冷却,得到具有三层结构的复合介电材料,对本实施例所制备的复合介电材料施加500 MV/m的电场强度,电滞回线如图5所示,得本实施例所制备的复合介电材料的储能效率为78%,储能密度为15.65 J/cm3。
实施例3
将0.9 g的聚偏氟乙烯-三氟氯乙烯粉末溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,然后在上述溶液加入0.1 g的二氧化钛纳米颗粒,继续搅拌1 h后超声处理30 min直至二氧化钛纳米颗粒完全分散,将上述制备的混合溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到外层为聚偏氟乙烯-三氟氯乙烯/二氧化钛的薄膜即介电增强薄膜,薄膜厚度为8 μm;
将1 g的聚丙烯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入65 ℃的烘箱中干燥48h,得到内层为聚丙烯的薄膜,即耐压增强薄膜,薄膜厚度为8 μm;
将耐压增强薄膜夹设于所述介电增强薄膜之间,如图1所示,利用热压机在190 ℃,18Mpa的条件下热压25 min后自然冷却,得到具有三层结构的复合介电材料,对本实施例所制备的复合介电材料施加500 MV/m的电场强度,电滞回线如图6所示,得本实施例所制备的复合介电材料的储能效率为80%,储能密度为16.13 J/cm3。
实施例4
将0.9 g的聚偏氟乙烯-三氟乙烯粉末溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,然后在上述溶液加入0.1 g的二氧化钛纳米颗粒,继续搅拌1 h后超声处理30min直至二氧化钛纳米颗粒完全分散,将上述制备的混合溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到外层为聚偏氟乙烯-三氟氯乙烯/二氧化钛的薄膜即介电增强薄膜,薄膜厚度为8 μm;
将1 g的聚苯乙烯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到内层为聚丙烯的薄膜,即耐压增强薄膜,薄膜厚度控制为8 μm;
将耐压增强薄膜夹设于所述介电增强薄膜之间,如图1所示,利用热压机在200℃,20Mpa的条件下热压20 min后自然冷却,得到具有三层结构的复合介电材料,对本实施例所制备的复合介电材料施加500 MV/m的电场强度,电滞回线如图7所示,得本实施例所制备的复合介电材料的储能效率为76%,储能密度为15.26 J/cm3。
对比例1
将0.9 g的聚偏氟乙烯-三氟乙烯粉末溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,然后在上述溶液加入0.1 g的二氧化钛纳米颗粒,继续搅拌1h后超声处理30min直至二氧化钛纳米颗粒完全分散,将上述制备的混合溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到聚偏氟乙烯-三氟氯乙烯/二氧化钛的薄膜,薄膜厚度为8 μm;
对本实施例所制备的复合介电材料施加500 MV/m的电场强度,电滞回线如图8所示,得本实施例所制备的复合介电材料的储能效率为72%,储能密度为13.52 J/cm3。
对比例2
将0.5 g的聚偏氟乙烯-六氟丙烯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到聚偏氟乙烯-六氟丙烯的薄膜,薄膜厚度为8 μm;
将1 g的聚苯乙烯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到聚丙烯的薄膜,薄膜厚度控制为8 μm;
利用热压机将聚偏氟乙烯-六氟丙烯的薄膜及聚苯乙烯的薄膜在200 ℃,20 Mpa的条件下热压20 min后自然冷却,得到复合介电材料,对本实施例所制备的复合介电材料施加500 MV/m的电场强度,电滞回线如图9所示,得本实施例所制备的复合介电材料的储能效率为80%,储能密度为6.47 J/cm3。
对比例3
将1 g的聚甲基丙烯酸甲酯溶于10 mL N,N-二甲基甲酰胺溶液中,隔夜搅拌至完全溶解,将上述制备的溶液利用刮刀均匀涂覆在干净平整的石英玻璃板上,迅速放入60 ℃的烘箱中干燥24 h,得到聚甲基丙烯酸甲酯的薄膜,薄膜厚度控制为10 μm;对本实施例所制备的介电材料施加500 MV/m的电场强度,电滞回线如图10所示,得本实施例所制备的复合介电材料的储能效率为92%,储能密度为5.15 J/cm3。
以上详细描述了本发明的具体实施例。
应当理解,本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此,凡本技术领域的技术人员以本发明构思在现有技术上通过逻辑分析、推理或者有限的实验可以得到的技术方案,都应在本权利要求书所确定的保护范围内。
Claims (10)
1.一种具有三层结构的复合介电材料,其特征在于,包括介电增强层、夹设于介电增强层的耐压增强层,所述介电增强层的材料为铁电聚合物/介电陶瓷填料复合物,所述耐压增强层为线性电介质高分子聚合物。
2.根据权利要求1所述的一种具有三层结构的复合介电材料,其特征在于,所述铁电聚合物/介电陶瓷填料复合物中,铁电聚合物包括聚偏氟乙烯、聚偏氟乙烯-六氟丙烯、聚偏氟乙烯-三氟氯乙烯,聚偏氟乙烯-三氟乙烯中的一种,所述介电陶瓷填料包括钛酸钡、钛酸锶钡、二氧化钛中的一种。
3.根据权利要求1所述的一种具有三层结构的复合介电材料,其特征在于,所述线性电介质高分子聚合物包括聚甲基丙烯酸甲酯、聚碳酸酯、聚丙烯、聚苯乙烯中的一种。
4.根据权利要求1所述的一种具有三层结构的复合介电材料,其特征在于,所述介电增强层与所述耐压增强层的厚度相等。
5.根据权利要求2所述的一种具有三层结构的复合介电材料,其特征在于,所述介电陶瓷填料与所述铁电聚合物的质量之比为1:9-19。
6.如权利要求1所述的一种具有三层结构的复合介电材料的制备方法,其特征在于,包括以下步骤:
S1.将铁电聚合物溶解于N,N-二甲基甲酰胺后,加入介电陶瓷填料并超声分散,得混合液,将所述混合液涂覆于石英玻璃板上,烘干后刮下,得介电增强薄膜;
S2.将线性电介质高分子聚合物的N,N-二甲基甲酰胺溶液涂覆于,石英玻璃板上,烘干后刮下,得耐压增强薄膜;
S3.将所述耐压增强薄膜夹设于所述介电增强薄膜之间,热压成型后冷却,即得具有三层结构的复合介电材料。
7.根据权利要求6所述的一种具有三层结构的复合介电材料的制备方法,其特征在于,所述步骤S1及步骤S2中,烘干温度为60-70 ℃,烘干时间为24-48 h。
8.根据权利要求6所述的一种具有三层结构的复合介电材料的制备方法,其特征在于,所述热压定型温度为180-200 ℃,热压压力为15-20 Mpa,热压时间为20-30 min。
9.根据权利要求6所述的一种具有三层结构的复合介电材料的制备方法,其特征在于,所述耐压增强薄膜及介电增强薄膜的厚度均为5-8 μm。
10.根据权利要求6所述的一种具有三层结构的复合介电材料的制备方法,其特征在于,所述铁电聚合物包括聚偏氟乙烯、聚偏氟乙烯-六氟丙烯、聚偏氟乙烯-三氟氯乙烯,聚偏氟乙烯-三氟乙烯中的一种,所述介电陶瓷填料包括钛酸钡、钛酸锶钡、二氧化钛中的一种,其中,所述介电陶瓷填料与所述铁电聚合物的质量之比为1:9-19,所述线性电介质高分子化合物包括聚甲基丙烯酸甲酯甲酯、聚碳酸酯、聚丙烯、聚苯乙烯中的一种。
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