CN113527826A - 一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法 - Google Patents
一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法,特点是该复合薄膜由片状核壳结构Ni(OH)2@TiO2填充于聚偏氟乙烯共聚物复合而成,片状核壳结构为片状核层氢氧化镍外部包裹一层壳层二氧化钛,片状核壳结构在聚偏氟乙烯共聚物中的掺杂体积百分比为1‑4%,其制备方法包括以下步骤:首先采用水热法制备Ni(OH)2纳米片,然后对其进行二氧化钛包裹后,再与聚偏氟乙烯共聚物复合,应用刮刀涂布法制备得到片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜,优点是能够显著提高介电、击穿和储能性能,并维持了聚合物自身优异的电绝缘和机械性能。
Description
技术领域
本发明涉及属于介质电容器领域,尤其是涉及一种片状核壳结构掺杂聚偏氟乙烯共聚物PVDF-HFP复合薄膜及其制备方法。
背景技术
随着科学技术的进步,现代电子电力系统的发展对储能元件提出了更加全面多元的要求。其中介质电容器是通过物理电荷-位移机制储存能量的元件,具有电化学储能元件如蓄电池和电化学电容器等无法比拟的超高功率密度和高电压。在电力清洁能源和电动汽车系统以及脉冲功率技术等等方面,介质电容器都承担着至关重要的作用。然而,尽管介质电容器有着不可替代的作用,但较低的储能密度(商用的聚合物或陶瓷电容器的储能密度均小于2 J/cm3)已成为电子和电气系统进一步集成化、小型化和轻量化的瓶颈。对于介质电容器来讲,其储能密度是由两极板间的电介质材料决定的,因此,获得能够实现更高储能密度的新型电介质材料成为了科研工作者必须攻克的难关。介质材料的介电常数ε和击穿场强E b 是影响储能密度两个最关键的因素,无论是具有超高介电常数的陶瓷材料还是具有较高击穿场强的有机聚合物,单一的材料都无法同时具备这两种有利的性质。因此,研究人员设想出一种有机-无机复合材料,寄希望于这类复合材料能够兼具较高的介电常数和击穿性能。但早期大量研究显示,少量的陶瓷颗粒填充到有机聚合物基体无法显著提高基体的介电常数,大量的陶瓷颗粒填充(大于50 vol.%)会使基体产生大量的孔洞和缺陷,进而导致复合材料击穿性能和机械性能的显著下降。另外陶瓷材料(ε r >1k)和有机聚合物(ε r ~10)之间显著的介电差异还会引起有机-无机界面电场畸化,导致复合材料击穿场强的下降,无法获得令人满意的储能性能,因此选择合适的无机填料和有机聚合物成为优化复合电介质储能性能的关键。
近期的大量研究表明,一维(1D)纳米线、(2D)二维纳米片状材料在作为复合材料填料时,由于其各向异性相较于零维(0D)纳米颗粒具有以下优势:1、平行于电场方向排布:具有高长径比的1D、2D材料表现出较高的介电特性,少量的一维(1D)纳米线、(2D)二维纳米片材料的填充显著提升基体的介电常数;2、垂直于电场方向排布:1D、2D材料作为更有效的电子散射中心,阻碍载流子的运动,使载流子经过更曲折的击穿路径,提高抗击穿性能。此外,为了改善无机填料和有机基体之间的性能差异而引起的界面畸化,填料核壳结构的设计得到了广泛关注。在核心填料表面包覆适当的壳层材料,不仅提高了材料整体的极化性能,而且能够改善界面畸化,束缚核心内部电荷的扩散,降低材料的导电损耗,从提高材料的抗击穿性能和储能效率。然而对于复合电介质在提高极化的同时如何保持甚至优化聚合物基体本身具有的抗击穿性能是重要的难点。
发明内容
本发明所要解决的技术问题是提供一种能够显著提高介电、击穿和储能性能,并维持了聚合物自身优异的电绝缘和机械性能的片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法。
本发明解决上述技术问题所采用的技术方案为:一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜,所述的复合薄膜由片状核壳结构Ni(OH)2@TiO2填充于聚偏氟乙烯共聚物复合而成,所述的片状核壳结构为片状核层氢氧化镍(Ni(OH)2)外部包裹一层壳层二氧化钛(TiO2),所述的片状核壳结构在聚偏氟乙烯共聚物中的掺杂体积百分比为1-4%。
优选的,所述的片状核壳结构在聚偏氟乙烯共聚物的中的掺杂体积百分比为2%。
上述片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜的制备方法,包括以下步骤:首先采用水热法制备Ni(OH)2纳米片,然后对其进行二氧化钛包裹后,再与聚偏氟乙烯共聚物复合,应用刮刀涂布法制备得到片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜。
具体步骤如下:
(1)合成Ni(OH)2纳米片
将2.38 g NiCl2加入30 ml去离子水中,机械搅拌30 min至充分溶解后,加入1 g聚乙二醇2000,搅拌15 min至完全溶解,形成溶液A;将2.3 ml氨水滴入30 ml去离子水中,搅拌45 min形成溶液B;将溶液B缓慢倒入溶液A中,接着以400~600 r/min磁力搅拌反应2 h后,置于高温烘箱中,于200℃反应24 h后,将反应溶液用去离子水超声洗涤3次后,于5000~6000 r/min离心收集Ni(OH)2纳米片,再于80℃真空干燥12 h,研磨2 h即得到Ni(OH)2纳米片;
(2)合成Ni(OH)2@TiO2核壳结构
将0.1 g Ni(OH)2纳米片分散于50 ml异丙醇,超声分散1h,磁力搅拌1h,再滴加0.1 ml二乙烯三胺,继续搅拌1 h,形成溶液A;将2 ml钛酸异丙酯滴加到20 ml异丙醇内,搅拌1 h后用注射器缓慢滴入溶液A后,于600~800 r/min高速搅拌继续反应4 h后,置于高温烘箱,于200℃反应24 h后,将反应物用离心管洗涤离心,取沉淀分别用去离子水和无水乙醇洗涤3次后,于6000-8000 r/min离心收集Ni(OH)2@TiO2溶胶,80 ℃真空干燥12 h,研磨2h,即得到Ni(OH)2@TiO2核壳材料;加入二乙烯三胺是诱导TiO2壳层垂直生长,从而保持Ni(OH)2片状材料的特性;
(3)复合薄膜的制备
将0.0208-0.083 g的Ni(OH)2@TiO2核壳材料加入到由0.9 g PVDF-HFP(聚偏氟乙烯-六氟丙烯)溶于5 ml二甲基甲酰胺(DMF)得到的溶液中,超声分散1 h,用细胞破碎机1000 W处理30 min后继续磁力搅拌24-36 h,形成均匀分散的混合溶液,将混合溶液真空处理抽去气泡,取1~2 ml滴到导电玻璃的导电面并用刮刀铺平,置于100 ℃烘箱真空烘干6h,待完全蒸干多余溶剂二甲基甲酰胺后继续升温至210 ℃,保温10 min,将取出的复合薄膜迅速放入冰水中淬火,清洗烘干,即得到片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜。
与现有技术相比,本发明的优点在于:本发明一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法,选择PVDF-HFP为基体,相比于商用聚丙烯(BOPP介电常数约2.2)其介电常数为12,在具有优异击穿性能的同时具有较好的介电性能。以片状Ni(OH)2@TiO2核壳结构为无机填料,这两种材料的介电常数在20-200之间,在复合材料的界面不会由于巨大的介电差异而引起严重的电场畸化。首先,片状Ni(OH)2@TiO2核壳结构固有介电性质能够提高复合电介质的介电常数,而且由于聚合物和无机填料以及核壳之间具有不同的极性或电导率,在外电场的作用下电介质中的电子或离子在界面处聚集所引起的界面极化使复合电介质整体极化得到提高,进而提高复合材料的储能密度。其次,片状Ni(OH)2@TiO2核壳结构的核心是Ni(OH)2纳米片,在Ni(OH)2纳米片的表面诱导垂直生长TiO2壳层。这种整体的2D核壳结构在复合电介质材料中作为更有效的电子散射中心,阻碍击穿路径的形成,提高复合电介质的抗击穿性能。再次,片状Ni(OH)2@TiO2核壳结构的内核Ni(OH)2属于P型半导体,外壳TiO2是一种N型半导体,在Ni(OH)2@TiO2核壳结构的界面处形成类似于P-N结的结构,这个区域会形成内建电场,阻碍载流子的运动和扩散,抑制击穿路径的过早形成;此外,外壳TiO2本身的多子(电子)还会对聚合物中外电场加速的带负电的载流子(如电子)产生斥力,降低其动能从而抑制二次电离的产生,延缓材料的介电击穿,进一步提高复合电介质的抗击穿性能。而且,片状Ni(OH)2@TiO2核壳结构对载流子运动的阻碍显著降低了空间电荷的密度,从而降低复合材料的导电损耗,提高了复合介质的储能效率。因此,片状Ni(OH)2@TiO2核壳结构的填充不仅可以提高复合电介质的整体极化,对于其抗击穿性能以及储能效率也能够起到显著的优化作用,有望获得优异的储能性能。
综上所述,本发明是一种2D Ni(OH)2@TiO2核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜及其制备方法,实验结果表明2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜具有优异的介电和储能性能,这证明片状Ni(OH)2表面包裹TiO2这种核壳结构作为填料可以实现复合材料储能性能整体的大幅度提升,通过较低体积分数Ni(OH)2@TiO2核壳结构的填充不仅能够实现超高的储能密度,还保持了有机基体本身优异的机械性能,该制备流程绿色环保,工艺简便,可实现广泛适用。
附图说明
图1为Ni(OH)2@TiO2核壳结构的扫描电镜微观形貌图;
图2为Ni(OH)2和Ni(OH)2@TiO2的X射线衍射图谱;
图3为Ni(OH)2@TiO2/PVDF-HFP复合薄膜的介电常数随频率的变化曲线;
图4为Ni(OH)2@TiO2/PVDF-HFP复合薄膜的介电损耗随频率的变化曲线;
图5为Ni(OH)2@TiO2/PVDF-HFP复合薄膜击穿场强的威布尔分布图;
图6为Ni(OH)2@TiO2/PVDF-HFP复合薄膜储能性能的变化曲线。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
一、具体实施例
实施例1
一种2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜制备方法,步骤如下:
1、合成Ni(OH)2纳米片
将2.38 g NiCl2加入30 ml去离子水中,机械搅拌30 min至充分溶解后,加入1 g聚乙二醇2000,搅拌15 min至完全溶解,形成溶液A;将2.3 ml氨水滴入30 ml去离子水中,搅拌45 min形成溶液B;将溶液B缓慢倒入溶液A中,接着以400~600 r/min磁力搅拌反应2 h后,置于高温烘箱中,于200℃反应24 h后,将反应溶液用去离子水超声洗涤3次后,于5000~6000 r/min离心收集Ni(OH)2纳米片,再于80℃真空干燥12 h,研磨2 h即得到Ni(OH)2纳米片;
2、合成Ni(OH)2@TiO2核壳结构
将0.1 g Ni(OH)2纳米片分散于50 ml异丙醇,超声分散1h,磁力搅拌1h,再滴加0.1 ml二乙烯三胺,继续搅拌1 h,形成溶液A;将2 ml钛酸异丙酯滴加到20 ml异丙醇内,搅拌1 h后用注射器缓慢滴入溶液A后,于600~800 r/min高速搅拌继续反应4 h后,置于高温烘箱,于200℃反应24 h后,将反应物用离心管洗涤离心,取沉淀分别用去离子水和无水乙醇洗涤3次后,于6000-8000 r/min离心收集Ni(OH)2@TiO2溶胶,80 ℃真空干燥12 h,研磨2h,即得到Ni(OH)2@TiO2核壳材料;
3、复合薄膜的制备
首先将0.9 g PVDF-HFP(聚偏氟乙烯-六氟丙烯)溶于5 ml二甲基甲酰胺(DMF),搅拌至完全溶解得到溶液,然后分别将0.0208 gNi(OH)2@TiO2核壳材料(根据采用排水法测得PVDF-HFP密度,根据PVDF-HFP的密度计算出0.9 g PVDF-HFP的体积为0.5 cm3,将核壳材料质量除以核壳材料密度得到体积,将核壳材料体积除以PVDF-HFP的体积0.5 cm3得到核壳材料的体积百分数)加入溶液中,超声分散1 h,细胞破碎机1000 W处理30 min后继续磁力搅拌24-36 h,形成均匀分散的混合溶液后,将混合溶液真空处理抽去气泡,取1~2 ml滴到导电玻璃(FTO,面积3 cm*4 cm)的导电面并立刻用刮刀铺平,迅速放入100 ℃烘箱真空烘干6 h,待完全蒸干多余溶剂DMF后继续升温至210 ℃,保温10 min,将取出的复合薄膜迅速放入冰水中淬火,清洗烘干,即得到体积分数为1%的2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜。
实施例2
同上述实施例1,其区别在于:步骤(3)中将0.9 g PVDF-HFP(聚偏氟乙烯-六氟丙烯)溶于5 ml二甲基甲酰胺,搅拌至完全溶解得到溶液,然后将2 vol% (0.0415 g) Ni(OH)2@TiO2核壳材料加入溶液中,即得到体积分数为2%的2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜。
实施例3
同上述实施例1,其区别在于:步骤(3)中将0.9 g PVDF-HFP(聚偏氟乙烯-六氟丙烯)溶于5 ml二甲基甲酰胺,搅拌至完全溶解得到溶液,然后将3 vol% (0.06225 g) Ni(OH)2@TiO2核壳材料加入溶液中,即得到体积分数为3%的2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜。
实施例4
同上述实施例1,其区别在于:步骤(3)中将0.9 g PVDF-HFP(聚偏氟乙烯-六氟丙烯)溶于5 ml二甲基甲酰胺(DMF),搅拌至完全溶解得到溶液,然后将4 vol% (0.083 g)Ni(OH)2@TiO2核壳材料加入溶液中,即得到体积分数为4%的2D Ni(OH)2@TiO2核壳结构掺杂的PVDF-HFP复合薄膜。
二、结果分析
图1为Ni(OH)2@TiO2核壳结构的扫描电镜微观形貌图。从图1中可以非常清晰地看到在片状Ni(OH)2的表面生长了TiO2壳层,并且实现了垂直方向的诱导生长,这种垂直生长有利于进一步提高复合材料的界面极化。另外Ni(OH)2@TiO2这种2D核壳结构的直径大概在600 nm-1.5 um,拥有较大的长径比,在复合材料中作为散射中心,有效的阻碍击穿路径的形成。
图2为Ni(OH)2和Ni(OH)2@TiO2的X射线衍射图谱。在图2中,Ni(OH)2和Ni(OH)2@TiO2的X射线衍射图谱分别由不同颜色线形绘出,并且Ni(OH)2和TiO2两种物质的特征峰位置分别用不同符号标出。在Ni(OH)2@TiO2的X射线衍射图谱上可以看到Ni(OH)2和TiO2两种物质的特征峰,结合对应的微观形貌图证明实验室水热法成功制备出了Ni(OH)2@TiO2核壳结构填料。
图3为Ni(OH)2@TiO2/PVDF-HFP复合薄膜的介电常数随频率变化的曲线。本发明探究的复合薄膜的介电常数随频率的变化范围为0.5 kHz~1 MHz。从图3可以看出在频率为1kHz时,纯PVDF-HFP薄膜的介电常数约为12.2。填料Ni(OH)2@TiO2核壳结构的加入明显提升了复合薄膜的介电常数,并且随着填料体积分数的增加,介电常数也随之增大,当填料体积分数达到4 vol.%时,复合薄膜的介电常数增大到接近18,相比于纯的PVDF-HFP薄膜介电常数提高了50%。复合薄膜介电常数的显著改善不仅是由于填料本身较大的介电常数,更重要的是基体与填料之间以及核壳结构之间界面极化的作用。
图4为Ni(OH)2@TiO2/PVDF-HFP复合薄膜的介电损耗随频率变化的曲线,频率变化范围是0.5 kHz~1 MHz。从图4可以观察到损耗随着频率的增大先减小后增大,这是因为低频下界面极化占主导地位,这种极化产生的损耗也相应较高,但随着频率的增大,界面极化的影响逐渐下降,所以损耗表现为逐渐减小。在高频下由于材料中偶极子的反转跟不上电场的速度就会产生介电弛豫,进而产生较大的损耗,所以损耗曲线会随着频率的增加先减小后增大。但总的来讲,当频率为1 kHz的时候,复合薄膜的损耗基本保持在0.05以下,这也体现复合材料良好的绝缘性。
图5为Ni(OH)2@TiO2/PVDF-HFP复合薄膜击穿场强的威布尔分布图。本发明对每一个体积分数的复合薄膜分别选取50-100个点进行加压测试,并根据测试结果的离散程度选取10个点作为该组分复合薄膜击穿场强的威布尔分布,进行线性拟合如图5所示。从图5中可以清晰地看到,低填充量的复合薄膜的击穿场强要高于纯的PVDF-HFP薄膜,2 vol.% Ni(OH)2@TiO2/PVDF-HFP复合薄膜的击穿场强达到了525 MV/m,而随着填料体积分数的继续增加,复合薄膜的击穿场强在持续降低。首先,低填充量的复合薄膜击穿场强的增大可能归功于以下三个原因:a).片状的Ni(OH)2成为有效的电子散射中心,使得材料击穿路径的形成更加曲折和困难,延缓了复合薄膜的击穿;b). Ni(OH)2@TiO2核壳结构外壳TiO2是一种N型半导体,电场作用下在界面处形成负电荷区域,由于静电作用将会阻碍外部电子的运动,从而抑制二次电离的产生,延缓材料的击穿。c).内核Ni(OH)2属于P型半导体,在Ni(OH)2@TiO2核壳结构的界面处形成内建电场,阻碍载流子的运动和扩散, 进一步提高材料的抗击穿性能。然而,当填料的体积分数不断增加,由于分散不均填料之间不可避免地发生了团聚,填料和聚合物之间的缺陷也会越来越多,这些都会降低复合薄膜的抗击穿性能。另外在通常情况下,较高的β值代表复合薄膜击穿性能的稳定性和实验的可靠性。从图5中可以看出复合薄膜击穿性能的威布尔分布β值虽然略低于纯的PVDF-HFP复合薄膜,但仍然保持着较高的水平,这说明填料Ni(OH)2@TiO2核壳结构的加入没有对聚合物基体击穿性能的稳定性产生较大的影响。
图6为Ni(OH)2@TiO2/PVDF-HFP复合薄膜储能性能的曲线图。储能密度和效率是复合电介质薄膜储能性能的两大决定因素,较高的储能密度和效率意味着较高的有效放电密度和较低的能量损耗。从图6中可以看出2 vol.% Ni(OH)2@TiO2/PVDF-HFP复合薄膜表现出最高的放电密度20.1 J/cm3,而且储能效率也保持在约77.5%,这将意味着复合电介质薄膜中储存的能量接近80%的能量能够被有效的放出。这一数值相比于纯PVDF-HFP聚合物薄膜(10.5 J/cm3)提高了将近一倍。本发明为高储能高效率电介质材料的研究提供了一条行而有效的途径。
上述说明并非对本发明的限制,本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内,做出的变化、改型、添加或替换,也应属于本发明的保护范围。
Claims (4)
1.一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜,其特征在于:所述的复合薄膜由片状核壳结构Ni(OH)2@TiO2填充于聚偏氟乙烯共聚物复合而成,所述的片状核壳结构为片状核层氢氧化镍外部包裹一层壳层二氧化钛,所述的片状核壳结构在聚偏氟乙烯共聚物中的掺杂体积百分比为1-4%。
2.根据权利要求1所述的一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜,其特征在于:所述的片状核壳结构在聚偏氟乙烯共聚物P中的掺杂体积百分比为2%。
3.一种权利要求1所述的片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜的制备方法,其特征在于包括以下步骤:首先采用水热法制备Ni(OH)2纳米片,然后对其进行二氧化钛包裹后,再与聚偏氟乙烯共聚物复合,应用刮刀涂布法制备得到片状核壳结构掺杂聚偏氟乙烯共聚物复合薄膜。
4.根据权利要求3所述的一种片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜的制备方法,其特征在于具体步骤如下:
(1)合成Ni(OH)2纳米片
将2.38 g NiCl2加入30 ml去离子水中,机械搅拌30 min至充分溶解后,加入1 g聚乙二醇2000,搅拌15 min至完全溶解,形成溶液A;将2.3 ml氨水滴入30 ml去离子水中,搅拌45min形成溶液B;将溶液B缓慢倒入溶液A中,接着以400~600 r/min磁力搅拌反应2 h后,置于高温烘箱中,于200℃反应24 h后,将反应溶液用去离子水超声洗涤3次后,于5000~6000 r/min离心收集Ni(OH)2纳米片,再于80℃真空干燥12 h,研磨2 h即得到Ni(OH)2纳米片;
(2)合成Ni(OH)2@TiO2核壳结构
将0.1 g Ni(OH)2纳米片分散于50 ml异丙醇,超声分散1h,磁力搅拌1h,再滴加0.1 ml二乙烯三胺,继续搅拌1 h,形成溶液A;将2 ml钛酸异丙酯滴加到20 ml异丙醇内,搅拌1 h后用注射器缓慢滴入溶液A后,于600~800 r/min高速搅拌继续反应4 h后,置于高温烘箱,于200℃反应24 h后,将反应物用离心管洗涤离心,取沉淀分别用去离子水和无水乙醇洗涤3次后,于6000-8000 r/min离心收集Ni(OH)2@TiO2溶胶,80 ℃真空干燥12 h,研磨2 h,即得到Ni(OH)2@TiO2核壳材料;加入二乙烯三胺是诱导TiO2壳层垂直生长,从而保持Ni(OH)2片状材料的特性;
(3)复合薄膜的制备
将0.0208-0.083 g的Ni(OH)2@TiO2核壳材料加入到由0.9 g聚偏氟乙烯-六氟丙烯溶于5 ml二甲基甲酰胺得到的溶液中,超声分散1 h,用细胞破碎机1000 W处理30 min后继续磁力搅拌24-36 h,形成均匀分散的混合溶液,将混合溶液真空处理抽去气泡,取1~2 ml滴到导电玻璃的导电面并用刮刀铺平,置于100 ℃烘箱真空烘干6 h,待完全蒸干多余溶剂二甲基甲酰胺后继续升温至210 ℃,保温10 min,将取出的复合薄膜迅速放入冰水中淬火,清洗烘干,即得到片状核壳结构掺杂聚偏氟乙烯共聚物的复合薄膜。
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