CN110922618B - 一种提高储能密度的绝缘介质的制备方法 - Google Patents
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Abstract
本发明公开了一种提高储能密度的绝缘介质的制备方法,将1,4‑苯二异硫氰酸酯溶解于极性溶剂中,然后加入有机二胺,在氮气环境、室温条件下反应3‑6小时,然后加入4,4'‑二氨基二苯醚和均苯四甲酸二酐,在氮气环境、室温条件下反应12‑18小时,得到聚硫脲和聚酰胺酸的无规共聚物溶液;将聚硫脲和聚酰胺酸的无规共聚物溶液铺在铜板上,采用梯度升温,得到聚硫脲和聚酰亚胺无规共聚物。本发明通过改变聚酰亚胺单体在共聚物分子链中的排列方式,从而改变材料介电响应特性和陷阱参数来控制其介电常数和击穿场强,最终控制或者改善材料的储能密度,可以广泛应用于高压储能设备、脉冲功率源、航空航天、混合动力汽车等多个领域。
Description
技术领域
本发明属于高压绝缘材料领域,具体涉及一种提高储能密度的绝缘介质的制备方法。
背景技术
聚合物薄膜储能电容器因其具有较高功率密度和超长的循环使用寿命,能最大效率转化风能、潮汐能等间歇性可再生能源,是脉冲功率技术、电磁炮及激光等高能武器系统无可替代的核心储能器件,在航空航天、混合动力汽车等领域也得到了广泛的应用。然而,由于大多数聚合物的介电常数或者击穿场强较低,限制了其储存电能的能力。长期以来,国内外学者主要通过纳米掺杂来提升薄膜的电介质储能性能,但高体积分数纳米填料的引入却会增大材料的能量损耗。因此,开发具有高储能密度且可靠性良好的聚合物储能电容器,探索提高聚合物介质材料储能密度的方法,对实际工程应用具有十分重要的意义。
目前,国内外学者对储能聚合物材料的研究主要通过增大介电常数或者提高击穿场强来达到提高储能密度的目的。从介电常数角度考虑,在分子主链引入金属元素提高电子位移极化,或在分子主链、侧链引入极性基团提高转向极化,从而增大介电常数;从击穿场强角度考虑,引入强极性基团作为高能电子散射中心,或制备具有交联结构的聚合物,从而提高材料的击穿场强。但单一结构的聚合物难以同时增大介电常数和击穿场强,一种介电性能的提高往往会伴随着另一种介电性能的劣化。
通过制备共聚物,结合两种链段的优势,改变共聚物组成成分及其比例,以达到在保证击穿场强的基础上、提高介电常数的目的,已经吸引越来越多学者的注意。虽然共聚物中链段的排列方式也会对材料的宏观性能产生重要的影响,但是通过改变链段排列方式以改善共聚物介电响应特性、陷阱参数和储能密度的研究领域尚无人涉及。
发明内容
本发明的目的在于提供一种提高储能密度的绝缘介质的制备方法。
为达到上述目的,本发明采用了以下技术方案:
一种提高储能密度的绝缘介质的制备方法,包括以下步骤:
1)1,4-苯二异硫氰酸酯完全溶解于极性溶剂中,然后加入有机二胺,在氮气环境、室温条件下反应3-6小时,得到端胺基聚硫脲前驱体;
2)向步骤1)制备的端胺基聚硫脲前驱体中加入4,4'-二氨基二苯醚和均苯四甲酸二酐,在氮气环境、室温条件下反应12-18小时,得到聚硫脲和聚酰胺酸的无规共聚物溶液;
3)采用流延法,将聚硫脲和聚酰胺酸的无规共聚物溶液铺在铜板上,采用梯度升温,酰胺化成膜,得到聚硫脲和聚酰亚胺无规共聚物。
本发明进一步的改进在于,步骤1)中,1,4-苯二异硫氰酸酯与极性溶剂的比为0.96mmol:1-4mL。
本发明进一步的改进在于,步骤1)中,有机二胺为1,3-环己二胺。
本发明进一步的改进在于,均苯四甲酸二酐与1,4-苯二异硫氰酸酯的总的物质的量与1,3-环己二胺和4,4'-二氨基二苯醚的总的物质的量相同。
本发明进一步的改进在于,步骤1)中,1,4-苯二异硫氰酸酯与1,3-环己二胺的物质的量的比为0.96:1;
步骤2)中,4,4'-二氨基二苯醚与均苯四甲酸二酐的物质的量的比为0.96:1。
本发明进一步的改进在于,步骤1)中,极性溶剂为N,N-二甲基乙酰胺或N,N-二甲基甲酰胺。
本发明进一步的改进在于,步骤3)中,梯度升温具体过程为,在70℃下保温3小时,然后在100℃下保温1小时,在120℃下保温1小时,最后在150℃下保温3小时与现有技术相比,本发明的有益效果体现在:
本发明通过先制备端胺基聚硫脲前驱体,然后向端胺基聚硫脲前驱体中加入4,4'-二氨基二苯醚和均苯四甲酸二酐,反应过程中添加方式的不同能够改变聚硫脲和聚酰亚胺共聚物中链段的排列方式,制备出的PTU-b-PI嵌段共聚物和PTU-r-PI无规共聚物表现出明显不同的介电响应特性和陷阱特性。其中,链段之间的无规连接更有利于促进极性基团在外施电场作用下的转向和共聚物中陷阱能级深度的加深;这些变化有助于同时提高材料的介电常数、击穿场强和储能密度。与PTU-b-PI嵌段共聚物相比,PTU-r-PI无规共聚物的介电常数(20℃、0.1Hz)从4.55增大至6.85,室温条件下的直流击穿场强从350MV/m提高至507MV/m,储能密度从2.47J/cm3提高至7.79J/cm3。本发明提出的方法可以显著的提高绝缘介质材料的储能密度,且工艺难度低、可操作性强及可靠性高,能够广泛运用于高压绝缘材料领域。
进一步的,与1,3-苯二胺相比,1,3-环己二胺的脂环结构具有较强的空间位阻效应,使得分子链之间的距离增大,极性硫脲基团更容易在外施电场作用下定向,有利于增大极化强度和提高介电常数。与脂肪族二胺相比,1,3-环己二胺结构较为刚性,能够阻碍大分子链的运动,从而保持较低的介电损耗。因此,在本发明中,选用1,3-环己二胺作为反应单体。
附图说明
图1为PTU-b-PI的合成路线图。
图2为PTU-r-PI的合成路线图。
图3为PTU-r-PI和PTU-r-PI的红外谱图。其中,(a)为整体图,(b)为图(a)中局部放大图。
图4为PTU-r-PI和PTU-r-PI的AFM,其中,(a)为PTU-r-PI的高度图,(b)为PTU-r-PI的相位图,(c)为PTU-b-PI的高度图,(d)为PTU-b-PI的相位图。
具体实施方式
以下结合具体实施例对本发明作进一步的详细描述。
本发明的一种提高储能密度的绝缘介质制备方法,包括下述步骤:
1)1,4-苯二异硫氰酸酯完全溶解于极性溶剂中,然后加入1,3-环己二胺,在氮气环境、室温条件下反应3-6小时,得到端胺基聚硫脲前驱体。
其中,1,4-苯二异硫氰酸酯与极性溶剂的比为0.96mmol:1-4mL。
均苯四甲酸二酐与1,4-苯二异硫氰酸酯的总的物质的量与1,3-环己二胺和4,4'-二氨基二苯醚的总的物质的量相同。
1,4-苯二异硫氰酸酯与1,3-环己二胺的物质的量的比为0.96:1。
4,4'-二氨基二苯醚与均苯四甲酸二酐的物质的量的比为0.96:1。
极性溶剂为N,N-二甲基乙酰胺(DMAc)或N,N-二甲基甲酰胺(DMF)。
2)向步骤1)制备的端胺基聚硫脲前驱体中加入0.96mmol 4,4'-二氨基二苯醚和1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应12-18小时,得到聚硫脲和聚酰胺酸的无规共聚物(PTU-r-PAA)溶液。
3)采用流延法,将无规共聚物PTU-r-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺无规共聚物(PTU-r-PI)。
下面为具体实施例。
实施例1
参见图2,一种提高储能密度的绝缘介质制备方法,包括下述步骤;
1)将0.96mmol 1,4-苯二异硫氰酸酯完全溶解于2mL N,N-二甲基乙酰胺(DMAc)中,1mmol 1,3-环己二胺加入上述溶液中,在氮气环境、室温条件下反应6小时,反应得到端胺基聚硫脲前驱体。
2)根据步骤1)制备端胺基聚硫脲前驱体,在反应溶液中依次加入0.96mmol 4,4'-二氨基二苯醚和1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应18小时,得到聚硫脲和聚酰胺酸的无规共聚物(PTU-r-PAA)溶液。
3)采用流延法,将无规共聚物PTU-r-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺无规共聚物(PTU-r-PI)。
对比例
参见图1,聚硫脲和聚酰亚胺嵌段共聚物(PTU-b-PI)的制备方法包括以下步骤:
1)将0.96mmol 1,4-苯二异硫氰酸酯完全溶解于2mL N,N-二甲基乙酰胺(DMAc)中,然后加入1,3-环己二胺,在氮气环境、室温条件下反应6小时,得到端胺基聚硫脲前驱体;
2)将0.96mmol 4,4'-二氨基二苯醚完全溶解于4mL N,N-二甲基乙酰胺(DMAc)中,然后加入1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应6小时,得到端酐基聚酰胺酸前驱体。
3)将端胺基聚硫脲前驱体和端酐基聚酰胺酸前驱体混合,在氮气环境、室温条件下反应18小时,得到聚硫脲和聚酰胺酸的嵌段共聚物(PTU-b-PAA)溶液。
4)采用流延法,将嵌段共聚物PTU-b-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺嵌段共聚物(PTU-b-PI)。
参见图3中的(a)和(b),可以看出,PTU-r-PI中游离的极性硫脲键较多,因此更容易在外电场作用下转向,PTU-r-PI中极性硫脲基团引起的介电强度增大至0.96,如表1所示。
表1给出了PTU-b-PI和PTU-r-PI的介电响应特征参数,其中α’、β和γ分别是聚硫脲局部链段运动、酰胺极性基团和硫脲极性基团转向引起的松弛过程;表2给出了PTU-b-PI和PTU-r-PI试样的陷阱能级参数。
表1 PTU-b-PI和PTU-r-PI试样介电响应特征参数
表2 PTU-b-PTU和PI-r-PTU试样的陷阱能级
采用Novocontrol宽频介电谱测试系统测试PI-b-PTU和PI-r-PTU试样的介电响应特性。实验前,在试样两面溅射金电极,电极的直径均为12.8mm测试条件如下:频率范围为0.1—106Hz,温度范围为-150—120℃,测量介电温谱时升温间隔为10℃。测试过程中,试样两端施加交流电压,电压幅值为1V。
直流击穿实验测试中,试样厚度为20μm,实验时保证试样厚度的一致性。电极为不锈钢球-球电极,电极直径为25mm。试样和电极放在变压器油中进行实验,以消除试样边缘沿面闪络的影响。采用HJC-100kV击穿试验仪测试进行直流实验,采用连续升压法测试试样的击穿电压,升压速率为0.5kV/s。然后用击穿电压除以试样厚度计算试样的击穿场强。每种试样一次击穿实验至少测试10个击穿点,获得击穿点的击穿场强,采用两参数威布尔函数分析得到试样击穿场强。
聚硫脲和聚酰亚胺共聚物作为线性聚合物,其储能密度能够下列通过公式计算得到,
Ue=1/2ε0εrEb 2
式中,ε0为真空介电常数,εr为试样相对介电常数,Eb为试样直流击穿场强。
参见图4,可以看出,形貌差异表明PTU-b-PI中存在明显的相分离现象,而PTU-r-PI中结构均匀。PTU-b-PI中相界面的存在使得其内部存在更多的缺陷,导致其击穿场强明显低于PTU-r-PI,如表3所示。
表3给出了两种聚酰亚胺共聚物的介电常数、击穿场强和储能密度。
表3 PTU-b-PI和PTU-r-PI试样介电性能和储能密度
从表3中可以看到,聚硫脲和聚酰亚胺无规共聚物有利于同时增大介电常数和击穿场强,进而提高储能密度。相比于聚硫脲和聚酰亚胺嵌段共聚物,无规共聚物的介电常数、击穿场强、储能密度分别提高了50.5%、44.9%、215%。
实施例2
一种提高储能密度的绝缘介质制备方法,包括下述步骤;
1)将0.96mmol 1,4-苯二异硫氰酸酯完全溶解于1mL N,N-二甲基乙酰胺(DMAc)中,1mmol 1,3-环己二胺加入上述溶液中,在氮气环境、室温条件下反应3小时,反应得到端胺基聚硫脲前驱体。
2)根据步骤1)制备端胺基聚硫脲前驱体,在反应溶液中依次加入0.96mmol4,4'-二氨基二苯醚和1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应18小时,得到聚硫脲和聚酰胺酸的无规共聚物(PTU-r-PAA)溶液。
3)采用流延法,将无规共聚物PTU-r-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺无规共聚物(PTU-r-PI)。
实施例3
一种提高储能密度的绝缘介质制备方法,包括下述步骤;
1)将0.96mmol 1,4-苯二异硫氰酸酯完全溶解于4mL N,N-二甲基乙酰胺(DMAc)中,1mmol 1,3-环己二胺加入上述溶液中,在氮气环境、室温条件下反应4小时,反应得到端胺基聚硫脲前驱体。
2)根据步骤1)制备端胺基聚硫脲前驱体,在反应溶液中依次加入0.96mmol4,4'-二氨基二苯醚和1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应12小时,得到聚硫脲和聚酰胺酸的无规共聚物(PTU-r-PAA)溶液。
3)采用流延法,将无规共聚物PTU-r-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺无规共聚物(PTU-r-PI)。
实施例4
一种提高储能密度的绝缘介质制备方法,包括下述步骤;
1)将0.96mmol 1,4-苯二异硫氰酸酯完全溶解于3mL N,N-二甲基乙酰胺(DMAc)中,1mmol 1,3-环己二胺加入上述溶液中,在氮气环境、室温条件下反应6小时,反应得到端胺基聚硫脲前驱体。
2)根据步骤1)制备端胺基聚硫脲前驱体,在反应溶液中依次加入0.96mmol4,4'-二氨基二苯醚和1mmol均苯四甲酸二酐,在氮气环境、室温条件下反应15小时,得到聚硫脲和聚酰胺酸的无规共聚物(PTU-r-PAA)溶液。
3)采用流延法,将无规共聚物PTU-r-PAA溶液铺在清洗干净的铜板上,采用梯度升温(70℃,3小时;100℃,1小时;120℃,1小时;150℃,3小时),酰胺化成膜,最后100℃抽真空烘干处理24小时,得到聚硫脲和聚酰亚胺无规共聚物(PTU-r-PI)。
本发明提出的制备方法可以显著提高绝缘介质材料的储能密度。本发明通过改变聚酰亚胺单体在共聚物分子链中的排列方式,从而改变材料介电响应特性和陷阱参数来控制其介电常数和击穿场强,最终控制或者改善材料的储能密度。该方法可以广泛应用于高压储能设备、脉冲功率源、航空航天、混合动力汽车等多个领域。
Claims (6)
1.一种提高储能密度的绝缘介质的制备方法,其特征在于,包括以下步骤:
1)1,4-苯二异硫氰酸酯完全溶解于极性溶剂中,然后加入有机二胺,在氮气环境、室温条件下反应3-6小时,得到端胺基聚硫脲前驱体;其中,有机二胺为1,3-环己二胺;
2)向步骤1)制备的端胺基聚硫脲前驱体中加入4,4'-二氨基二苯醚和均苯四甲酸二酐,在氮气环境、室温条件下反应12-18小时,得到聚硫脲和聚酰胺酸的无规共聚物溶液;
3)采用流延法,将聚硫脲和聚酰胺酸的无规共聚物溶液铺在铜板上,采用梯度升温,酰胺化成膜,得到聚硫脲和聚酰亚胺无规共聚物。
2.根据权利要求1所述的一种提高储能密度的绝缘介质的制备方法,其特征在于,步骤1)中,1,4-苯二异硫氰酸酯与极性溶剂的比为0.96mmol:1-4mL。
3.根据权利要求1所述的一种提高储能密度的绝缘介质的制备方法,其特征在于,均苯四甲酸二酐与1,4-苯二异硫氰酸酯的总的物质的量与1,3-环己二胺和4,4'-二氨基二苯醚的总的物质的量相同。
4.根据权利要求1所述的一种提高储能密度的绝缘介质的制备方法,其特征在于,步骤1)中,1,4-苯二异硫氰酸酯与1,3-环己二胺的物质的量的比为0.96:1;
步骤2)中,4,4'-二氨基二苯醚与均苯四甲酸二酐的物质的量的比为0.96:1。
5.根据权利要求1所述的一种提高储能密度的绝缘介质的制备方法,其特征在于,步骤1)中,极性溶剂为N,N-二甲基乙酰胺或N,N-二甲基甲酰胺。
6.根据权利要求1所述的一种提高储能密度的绝缘介质的制备方法,其特征在于,步骤3)中,梯度升温具体过程为,在70℃下保温3小时,然后在100℃下保温1小时,在120℃下保温1小时,最后在150℃下保温3小时。
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