Article(id=1210613543595021306, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.11.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1713369600000, receivedDateStr=2024-04-18, revisedDate=1716480000000, revisedDateStr=2024-05-24, acceptedDate=null, acceptedDateStr=null, onlineDate=1766562360904, onlineDateStr=2025-12-24, pubDate=1732032000000, pubDateStr=2024-11-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766562360904, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766562360904, creator=13701087609, updateTime=1766562360904, updator=13701087609, issue=Issue{id=1210613541111984320, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='11', pageStart='1', pageEnd='143', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766562360313, creator=13701087609, updateTime=1766564044072, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620603392987671, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620603392987672, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=40, endPage=50, ext={EN=ArticleExt(id=1210613543867651069, articleId=1210613543595021306, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research on energy storage performance of PVH based all-organic composite films, columnId=1210613542542241998, journalTitle=Insulating Materials, columnName=Special Issue on Key Materials and Technology for New Energy Vehicles, runingTitle=null, highlight=null, articleAbstract=

Excessive free electrons in thin film capacitors will increase the leakage current density, reduce the electric strength, and promote the breakdown of capacitors, thus preventing them from obtaining excellent energy storage performance. To mitigate the impact of free electrons and secondary impact ionization electrons (SIE) on energy storage performance, this study introduced perylene diimide (PDI), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDI), and 4-cyano-4′-pentylbiphenyl (5CB) into polyvinylidene-hexafluoropropylene (PVH) to construct an all-organic composite films, respectively, and the structure, thermal properties, and energy storage performance of three kinds of films were studied. The results show that PDI/PVH composite film with PDI mass fraction of 0.5% has the better thermal properties, smaller grain size, and tighter lattice structure, which is helpful to achieve higher electric strength and discharge energy density. Through comparison, it is found that PDI possesses a more suitable band structure and conductivity, which makes PDI/PVH composite film have better energy storage performance. The discharge energy density of 0.5%PDI/PVH composite film achieves 16.6 J/cm3 at 499.7 MV/m, and maintains a high charge-discharge efficiency of 80.5%.

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在薄膜电容器中自由电子过多会使得漏电流密度增加,电气强度降低,促使电容器击穿,从而阻碍了其获得优异的储能性能。为了减少自由电子和二次碰撞电离电子(SIE)对储能性能的影响,本文选择将苝酰亚胺(PDI)、1,4,5,8-萘四甲酸酐(NDI)和4-氰基-4′-戊基联苯(5CB)分别掺入聚偏氟乙烯-六氟丙烯(PVH)中构建全有机复合薄膜,对3种复合薄膜的结构、热学性能和储能性能等方面进行研究。结果表明:PDI质量分数为0.5%的PDI/PVH复合薄膜具有较好的热性能,更小的晶粒尺寸以及更紧密的晶格结构,有助于获得更高的电气强度和放电能量密度。通过对比发现PDI具有更合适的能带结构和电导率,使PDI/PVH复合薄膜具备更好的储能性能。0.5%PDI/PVH复合薄膜在499.7 MV/m的放电能量密度达到了16.6 J/cm3,并且保持了80.5%的高充放电效率。

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朱志彪(1998-),男(汉族),浙江温州人,硕士生,主要从事复合薄膜储能的研究;
侯亚飞(1987-),男(汉族),河北石家庄人,副教授,博士,主要从事绝缘材料与技术的研究。
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朱久军(1988-),男(汉族),黑龙江大庆市人,中级实验师,主要从事储能电介质薄膜的研究。

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朱久军(1988-),男(汉族),黑龙江大庆市人,中级实验师,主要从事储能电介质薄膜的研究。

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朱久军(1988-),男(汉族),黑龙江大庆市人,中级实验师,主要从事储能电介质薄膜的研究。

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PVH基全有机复合薄膜储能性能研究
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朱久军 , 朱志彪 , 付廷玉 , 侯亚飞
绝缘材料 | 新能源汽车用关键材料与技术专题 2024,57(11): 40-50
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绝缘材料 | 新能源汽车用关键材料与技术专题 2024, 57(11): 40-50
PVH基全有机复合薄膜储能性能研究
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朱久军, 朱志彪, 付廷玉, 侯亚飞
作者信息
  • 宁波大学 物理科学与技术学院,浙江 宁波 315211
  • 朱久军(1988-),男(汉族),黑龙江大庆市人,中级实验师,主要从事储能电介质薄膜的研究。

通讯作者:

朱志彪(1998-),男(汉族),浙江温州人,硕士生,主要从事复合薄膜储能的研究;
侯亚飞(1987-),男(汉族),河北石家庄人,副教授,博士,主要从事绝缘材料与技术的研究。
Research on energy storage performance of PVH based all-organic composite films
Jiujun ZHU, Zhibiao ZHU, Tingyu FU, Yafei HOU
Affiliations
  • School of Physical Science and Technology, Ningbo University, Ningbo 315211, China
出版时间: 2024-11-20 doi: 10.16790/j.cnki.1009-9239.im.2024.11.004
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在薄膜电容器中自由电子过多会使得漏电流密度增加,电气强度降低,促使电容器击穿,从而阻碍了其获得优异的储能性能。为了减少自由电子和二次碰撞电离电子(SIE)对储能性能的影响,本文选择将苝酰亚胺(PDI)、1,4,5,8-萘四甲酸酐(NDI)和4-氰基-4′-戊基联苯(5CB)分别掺入聚偏氟乙烯-六氟丙烯(PVH)中构建全有机复合薄膜,对3种复合薄膜的结构、热学性能和储能性能等方面进行研究。结果表明:PDI质量分数为0.5%的PDI/PVH复合薄膜具有较好的热性能,更小的晶粒尺寸以及更紧密的晶格结构,有助于获得更高的电气强度和放电能量密度。通过对比发现PDI具有更合适的能带结构和电导率,使PDI/PVH复合薄膜具备更好的储能性能。0.5%PDI/PVH复合薄膜在499.7 MV/m的放电能量密度达到了16.6 J/cm3,并且保持了80.5%的高充放电效率。

电子陷阱  /  全有机  /  复合材料  /  储能性能

Excessive free electrons in thin film capacitors will increase the leakage current density, reduce the electric strength, and promote the breakdown of capacitors, thus preventing them from obtaining excellent energy storage performance. To mitigate the impact of free electrons and secondary impact ionization electrons (SIE) on energy storage performance, this study introduced perylene diimide (PDI), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDI), and 4-cyano-4′-pentylbiphenyl (5CB) into polyvinylidene-hexafluoropropylene (PVH) to construct an all-organic composite films, respectively, and the structure, thermal properties, and energy storage performance of three kinds of films were studied. The results show that PDI/PVH composite film with PDI mass fraction of 0.5% has the better thermal properties, smaller grain size, and tighter lattice structure, which is helpful to achieve higher electric strength and discharge energy density. Through comparison, it is found that PDI possesses a more suitable band structure and conductivity, which makes PDI/PVH composite film have better energy storage performance. The discharge energy density of 0.5%PDI/PVH composite film achieves 16.6 J/cm3 at 499.7 MV/m, and maintains a high charge-discharge efficiency of 80.5%.

electron traps  /  all-organic  /  composite materials  /  energy storage performance
朱久军, 朱志彪, 付廷玉, 侯亚飞. PVH基全有机复合薄膜储能性能研究. 绝缘材料, 2024 , 57 (11) : 40 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2024.11.004
Jiujun ZHU, Zhibiao ZHU, Tingyu FU, Yafei HOU. Research on energy storage performance of PVH based all-organic composite films[J]. Insulating Materials, 2024 , 57 (11) : 40 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2024.11.004
当前,电子工业正在蓬勃发展,薄膜电容器作为一种基础器件,已被广泛应用于各个领域,特别是在电力传输系统、电子电路以及电动汽车领域[1-3]。随着越来越多的新能源汽车制造商采用800 V平台生产汽车,对电子元器件提出了更高的功率和耐压要求[4-5]。相比其他储能器件,薄膜电容器具有出色的放电功率密度和电气强度,在电子工业中得到了越来越广泛的应用[6-7]。然而,它们的放电能量密度和效率相对有限,这导致电子元器件必须增大体积以满足实际运行需求[8-9]。因此,提高薄膜电容器的储能性能成为当前研究的一个重要方向,而提高电容器的电气强度被认为是一种可行的方法。
聚合物由于其固有的高电气强度而受到广泛关注,例如聚甲基丙烯酸甲酯(PMMA)和已广泛商用的双向拉伸聚丙烯(BOPP)这类线性聚合物的电气强度可以达到600~800 MV/m,并且它们还拥有较低的介质损耗[10-11]。但是线性聚合物的介电常数普遍较低,这导致它们的放电能量密度相对较低 (2~4 J/cm3),阻碍了它们的进一步发展。与之不同的是以聚偏氟乙烯(PVDF)为代表的铁电聚合物,它们兼具高介电常数和较高的电气强度,从而获得了比线性聚合物更高的放电能量密度[1,12]。铁电聚合物较高的介电常数主要是得益于高极性的C-F键以及内部长程有序的铁电畴,但这也带来了更高的介质损耗和剩余极化,阻碍了其获得更高的储能性能[1]。研究者一般通过改变制备条件、拉伸、引入单体、电离辐射、引入结构缺陷、压折和接枝基团等方法,来降低聚合物电介质的剩余极化或者提升其介电常数[13-16]。研究发现,通过引入非晶相的六氟丙烯(HFP)制备聚偏氟乙烯-六氟丙烯(P(VDF-HFP),简称PVH),不仅可以限制大尺寸晶粒,而且可以减小剩余极化,获得的储能性能高于PVDF[17]。还有许多研究者将PVDF与PMMA进行共混,从而将PVDF的高介电常数和PMMA的高电气强度结合起来,这也是提升聚合物电介质放电能量密度和效率的有效方法[18]
在复合薄膜中自由电子在较短时间内聚集过多,导致大量二次碰撞电离电子(SIE)产生,促进了电树枝的发展,这也是导致其击穿的原因之一。近年来,通过非均相界面处的能级不匹配来构建电子陷阱也是一种提高聚合物电气强度的有效策略。与以往通过改变聚合物链的构象或界面处的排列来引入陷阱点位不同,通过能带结构构建的陷阱具有更深的陷阱深度[19-20],这对捕获电子特别是高能电子是非常有益的。深陷阱以及有机界面也被证实对聚合物储能性能的提升具有积极影响。LIU X X等[21]在铌酸钙(CNO)和聚酰亚胺(PI)之间通过金属有机框架构建了金属离子有机杂化界面(MOHI),这不仅能够降低复合材料的自由体积,而且可以在界面处引入深陷阱,从而抑制复合材料中的电场畸变。因此,含有MOHI的PI基电介质表现出优异的储能性能。
此前的研究并未比较不同的有机填料对复合薄膜储能性能的影响。本文选取具有高介电常数和低介质损耗的PVH作为基底,并且选择3种具有不同能带结构和电导率的有机填料,分别是苝酰亚胺(PDI)、1,4,5,8-萘四甲酸酐(NDI)和4-氰基-4′-戊基联苯(5CB),并分别掺入PVH中构建全有机复合薄膜,并对这3种复合薄膜的结构、热学性能和储能性能等进行研究。本文还将具有不同填料复合薄膜的储能性能进行比较,并结合能带结构与电导率分析复合薄膜储能性能改善的原因,为后续研究寻找更优秀的有机填料制备复合薄膜提供思路。
PVH型号为FR 904,购于上海华谊三爱富新材料有限公司;NDI购于上海麦克林生化科技股份有限公司;PDI、5CB和N,N-二甲基甲酰胺(DMF)均购于上海阿拉丁生化科技股份有限公司,材料纯度均为分析纯。
首先,将PDI加入到DMF中并破碎,之后加入PVH并加热搅拌5 h。然后,将上述混合溶液抽真空去除气泡并涂覆于氟掺杂氧化锡(FTO)导电玻璃上制备复合薄膜,再将复合薄膜真空烘干12 h。最后,将复合薄膜进行淬火并干燥,获得PDI质量分数为x的PDI/HFP复合薄膜。NDI/HFP和5CB/HFP复合薄膜的制备步骤与PDI/PVH复合薄膜相同;制备纯PVH薄膜时不加入有机填料即可。
使用扫描电子显微镜(SEM,型号为SU-70)获得复合薄膜的截面图;使用差示扫描量热仪(DSC,型号为耐驰DSC 214)在氩气氛围下获得复合薄膜的升降温曲线,测试温度为40~200℃;使用X射线衍射仪(XRD,型号为布鲁克D8 Advance)获得XRD图像,2θ为10°~40°;使用傅里叶变换红外光谱仪(FTIR,型号为尼高力6700)获得FTIR光谱,测量波长为500~2 000 cm-1;使用热重分析仪(TGA,型号为TA Q600)进行热重测试,升温速率为10℃/min,测试温度为50~700℃;使用阻抗分析仪(型号为安捷伦4294A)测试复合薄膜的介电性能,测试频率为103~106 Hz;使用铁电分析仪(型号为Radiant RT Premier)测试电滞回线、电气强度以及外加场强为-200~200 MV/m下的漏电流密度;使用Comsol Multiphysics 6.0模拟漏电流密度和空间电荷密度,电压设置为1 000 V,薄膜厚度为8 μm。基底和填料的介电常数分别设置为9.5和15,电导率分别为1×10-10 S/m和1×10-3 S/m,利用电势表达式对空间电荷密度模拟结果进行分析。
图1为PVH分别与3种有机填料之间的分子间作用力示意图以及各个复合薄膜的SEM图。从图1(a)(c)可以看出,3种有机填料与PVH都存在分子间作用力,分别存在于C=O键(PDI和NDI)与C-H键(PVH)之间和C≡N键(5CB)与C-H键(PVH)之间,分子间作用力有利于填料与基底之间构建较为匹配的有机界面,能够提升二者的相容性[22-23]
通过溶液浇铸法制备的PVH、0.5%PDI/PVH、0.5%NDI/PVH和0.5%5CB/PVH 4种电介质薄膜的SEM图如图1(d)(g)所示。从图1(d)(g)可以看出,所有薄膜的厚度都在8 μm左右,而且都非常均匀致密,也没有孔洞与空隙,这表明了制备工艺的可靠与稳定。特别是,PDI、NDI和5CB在加入PVH之后均匀分布,并未发生团聚,填料与基底表现出良好的相容性[9]
PVH中包含αβγδ 4种不同的晶相,其中α相和β相比较常见。α相属于非极性相,具有较小的偶极矩和较低的剩余极化;β相则与α相相反,属于极性相,具有较大的偶极矩与剩余极化[24]。本节通过DSC、FTIR、XRD和TGA测试,对各填料不同填充量下的复合薄膜和纯PVH的晶相结构和热性能进行研究。图2为纯PVH和各种复合薄膜的DSC测试结果,分别是第2次升温曲线和降温曲线。图中包含了各种电介质薄膜的熔融温度(Tm)、熔融焓(ΔHm)、结晶度(χc)和结晶温度(Tc)。从图2(a)可以看出,纯PVH薄膜的Tm为122.0℃,随着PDI的加入,Tm先降低后升高,0.5%PDI/PVH复合薄膜具有最小的Tm(116.8℃)。由图2(b)图2(c)可知,加入NDI和5CB的复合薄膜Tm变化趋势与PDI/PVH复合薄膜类似,并且所有复合薄膜的Tm都低于纯PVH薄膜。研究表明,Tm与晶粒尺寸有关,越小的Tm代表晶粒尺寸越小[25]。在铁电电介质中,更小的晶粒尺寸不仅可以增大电气强度,而且有助于打破大范围的铁电畴,从而降低剩余极化[26]。通过对升温曲线进行分析计算,可以发现PDI/PVH复合薄膜的χc整体呈现先增大后减小的趋势,其中0.5%PDI/PVH复合薄膜的χc最大(22.6%),值得注意的是,掺入PDI的复合薄膜χc都高于纯PVH薄膜(19.8%)。NDI/PVH与5CB/PVH复合薄膜的χc变化趋势与PDI/PVH复合薄膜的χc类似。从图2(d)可以看出,随着PDI含量的增加,PDI/PVH复合薄膜的Tc先从纯PVH薄膜的141.4℃升高到0.5%PDI/PVH复合薄膜的143.6℃,随后再次降低。另外两种复合薄膜Tc的变化趋势与之相似(如图2(e)图2(f)所示)。通过对比发现复合薄膜的χcTc变化趋势一致。在合适填充量下,3种填料可以诱导非均相成核,加速成核过程,使得χcTc都升高。但是当填充过量时,填料会阻碍结晶过程,导致χcTc降低[22]。对比0.5%PDI/PVH、0.5%NDI/PVH和0.5%5CB/PVH复合薄膜的TmχcTc可以看出,0.5%PDI/PVH复合薄膜具有最低的Tm和最高的χcTc,说明其具有更小的晶粒尺寸和更紧密的晶格结构,有助于复合薄膜得到更高的储能性能。
为了研究薄膜的晶相结构,对填料质量分数为0.5%的3种复合薄膜和纯PVH薄膜进行FTIR和XRD测试,结果如图3图4所示。从图3可以看出,3种复合薄膜均没有新的化学键产生,并且图中标注了α相和β相的波数,其中α相占比较多,其特征峰波数分别为614 cm-1(CF2弯曲)、762 cm-1(CF2弯曲)、795 cm-1(CF2振动)、854 cm-1(CF2对称伸缩)、975 cm-1(CF2扭曲)、1 148 cm-1(CF2对称伸缩)、1 207 cm-1(CF2不对称伸缩)、1 382 cm-1(CF2摇摆)、1 400 cm-1(CF2面外摇摆)和1 424 cm-1(CF2对称伸缩)。而极性β相的特征峰则较少,波数分别为840 cm-1(CH2振动)和1 275 cm-1(CH2弯曲)。从图4可以看出,α相的(020)、(110)和(021)晶面的特征峰分别在18.3°、19.9°和26.6°处。另外,20.3°处还存在β相的(110/200)晶面的一个较弱特征峰[22,27]。FTIR和XRD结果都表明,纯PVH薄膜及复合薄膜中存在大量的α相和少量的β相,这有助于复合薄膜获得高极化和低剩余极化。
图5为薄膜的TGA测试结果。从图5(a)可以看出,纯PVH薄膜经历了1次明显的失重过程,其失重温度为440℃左右,这主要是由PVH的热降解导致的[22];还可以看出PDI/PVH复合薄膜也经历了1次明显的失重过程,并且其失重温度也都在440℃左右,主要原因也是PVH在此温度下发生热降解。由于有机填料的填充量较少,PDI/PVH复合薄膜并未出现第2个明显的失重过程。
图5(b)图5(c)可以看出,NDI/PVH复合薄膜和5CB/PVH复合薄膜的TGA曲线与PDI/PVH复合薄膜相似,只出现了1次失重过程,并且失重温度也在440℃左右。对比0.5%PDI/PVH、0.5%NDI/PVH和0.5%5CB/PVH复合薄膜的TGA曲线可以看出,3种复合薄膜的失重过程几乎一致,失重温度也与纯PVH薄膜一致。
图6图7分别为各薄膜的介电常数和介质损耗因数测试结果。从图6可以看出,纯PVH薄膜在频率为103 Hz时,介电常数约为9.7,这主要得益于大偶极矩的C-F键。随着频率的增加,由于取向极化逐渐跟不上电场的变化,纯PVH薄膜的介电常数逐渐减小。随着填料的加入,复合薄膜中的非均相界面增多,更多的界面极化也带来了更大的介电常数[22-28]。但也由于界面极化的存在,当频率增加时,复合薄膜的介电常数减小的速率比纯PVH薄膜更快。频率越高,复合薄膜的介电常数越接近纯PVH薄膜。从图7可以看出,随着填料含量的增加,复合薄膜的介质损耗因数也随之增大,这主要得益于界面极化,而偶极子取向极化的德拜弛豫导致所有薄膜在高频电场下的介质损耗因数都进一步增大。虽然复合薄膜的介质损耗因数大于纯PVH薄膜,但所有复合薄膜的介质损耗因数仍控制在一个比较低的水平(<0.05)。对比0.5%PDI/PVH、0.5%NDI/ PVH和0.5%5CB/PVH复合薄膜的介电常数和介质损耗因数可以看出,3种复合薄膜的介电常数和介质损耗因数都比较接近,表明3种复合薄膜的介电性能相差不大。
810分别为薄膜的电滞回线、漏电流密度和电气强度威布尔分布结果。从图8可以看出,随着填料含量的增加,PDI/PVH、NDI/PVH和5CB/PVH复合薄膜电滞回线的斜率逐渐增大,这与介电常数的变化趋势一致。并且还发现,当填料质量分数为0.5%时,PDI/PVH、NDI/PVH和5CB/PVH复合薄膜的电气强度达到最大。从图9可以看出,填料质量分数为0.5%的复合薄膜具有比其他样品更低的漏电流密度。由于电子陷阱的存在,各复合薄膜的漏电流密度均控制在较低范围内,漏电流密度在10-7 A/cm2左右[29]。从图10可以看出,各种复合薄膜电气强度的β值(形状参数)都大于15,表明复合薄膜的电气强度(Eb)都具有高可靠性,这主要得益于有机填料与基底之间良好的相容性。当填料质量分数为0.5%时,PDI/PVH、NDI/PVH和5CB/PVH复合薄膜的电气强度最大,这与图8的结果一致。通过对比发现,随着填料含量的增加,复合薄膜的电气强度先增大后减小。从图10(a)可以看出,在PDI的填充量较低时,PDI通过构建的陷阱捕获电子,减少SIE数量,使得复合薄膜的漏电流密度减小和电气强度增大。但继续加入PDI后,可能会引入孔洞和空隙等缺陷,而且填充过多的PDI会导致各个PDI分子距离过近,在复合薄膜中形成电子导通路径,因此填料质量分数从0.5%增加到1.0%时,复合薄膜的漏电流密度随之增大,而电气强度逐渐减小。因此,PDI、NDI和5CB填充的复合薄膜的储能性能会有一些差别。
对比填料质量分数为0.5%的PDI/PVH、NDI/PVH和5CB/PVH复合薄膜电滞回线、漏电流密度和威布尔分布可以看出,3种复合薄膜的电滞回线的斜率相近,这与它们的介电常数大小情况相符;3种复合薄膜的电气强度可靠性都很高,β值都大于20,其中0.5%PDI/PVH复合薄膜具有最小的漏电流密度和最大的电气强度。
为了探究PDI、NDI和5CB填充复合薄膜的储能性能差异,图11图12给出了3种复合薄膜的能带和电荷转移示意图以及通过有限元模拟的PDI/PVH复合薄膜的空间电荷密度和漏电流密度,图12中颜色变化对应空间电荷密度的变化,而红色箭头的大小和方向则表示漏电流密度的大小和方向。从图11可以看出,由于PDI、NDI和5CB的能带结构与PVH不同,在填料与PVH界面处的能带发生弯曲,从而构建了电子陷阱,捕获电子。从图12可以看出,PDI在PVH中能够有效捕获电子、降低电子动能和减少SIE数量,从而为复合薄膜增大电气强度和降低漏电流密度做出贡献。图12中界面处颜色差异较大,主要是由于引入PDI后,正负电荷聚集在PDI与PVH界面处,这使得复合薄膜中的空间电荷密度分布不均匀,产生偶极矩,发生界面极化。虽然构建电子陷阱的方式相同,但是各种复合薄膜的电气强度、漏电流密度和储能密度等性能各不相同。由于PDI、NDI和5CB的导带位置不同,它们在PVH中构建的陷阱深度(Φe)不同,分别为3.81、5.41、2.81 eV。据报道,较大Φe的陷阱可以更有效地捕获电子,阻碍电子传输[30]。由于5CB具有最小的Φe,被5CB捕获的电子更容易在高外加电场下摆脱陷阱的束缚,进而继续在外加电场的作用下产生SIE,这导致0.5%5CB/PVH复合薄膜具有相对小的电气强度。有趣的是,虽然NDI具有最大的Φe,但是0.5%NDI/PVH复合薄膜的电气强度并不是3种复合薄膜中最大的。有研究表明,电介质的电导率(σ)过高会加速电子传输,使得SIE数量和漏电流密度增加,容易导致电介质击穿[19]。由于NDI的σ为1×10-2 S/m,比PDI的1×10-3 S/m大了1个数量级,NDI在复合薄膜中更容易形成电子导通路径,导致0.5%NDI/PVH复合薄膜的绝缘性较差[31-32]。这就是NDI具有最大的Φe,但0.5%NDI/PVH复合薄膜的电气强度却小于0.5%PDI/PVH复合薄膜的原因。
根据前文的电滞回线计算了各复合薄膜在不同电场下的放电能量密度和充放电效率,结果如图13所示。从图13可以看出,随着外加电场的增大,所有复合薄膜的放电能量密度随之增大,而充放电效率则先减小后增大,这主要是由铁电聚合物PVH导致的,当外加电场较低时,无法使所有铁电畴都朝着电场方向,导致损耗增加和充放电效率减小。而在高外加电场下,充放电效率增大主要是由于铁电畴方向逐渐一致,损耗相对较小[33-34]。从图13(a)可以看出,0.5%PDI/PVH复合薄膜在499.7 MV/m下的放电能量密度达到16.6 J/cm3,是纯PVH薄膜放电能量密度(8.7 J/cm3)的1.9倍。同时,0.5%PDI/PVH复合薄膜由于其低损耗具有80.5%的充放电效率。从图13(b)图13(c)可以看出,0.5%NDI/PVH复合薄膜和0.5%5CB/PVH复合薄膜分别在462.0 MV/m和452.3 MV/m放电能量密度14.5 J/cm3和13.4 J/cm3,并且充放电效率都在80%左右,分别为81.6%和78.2%。从图13可看出,0.5%PDI/PVH复合薄膜具有最大的放电能量密度和电气强度,并且在高外加电场下依然能保持高充放电效率。对比纯PVH薄膜、0.5%PDI/PVH、0.5%NDI/PVH和0.5%5CB/PVH复合薄膜的热性能和储能性能,可以看出3种复合薄膜的电气强度、放电能量密度、充放电效率、χcTc都明显高于PVH,并且0.5%PDI/PVH复合薄膜的热性能与储能性能都优于其他两种复合薄膜。本研究实验结果充分表明了利用有机填料与基底之间能带结构的不匹配来构建电子陷阱从而提升储能性能是行之有效的,并且为寻找合适的有机填料制备复合薄膜提供了思路。
本文将3种具有不同能带结构的有机填料PDI、NDI和5CB掺入PVH中,并对复合薄膜的结构、热性能和储能性能等进行了表征,主要得到以下结论:
(1)有机填料PDI、NDI和5CB与PVH之间具有良好的相容性,这主要得益于填料与基底间良好的分子间相互作用。
(2)复合薄膜的热性能都有一定提升,其中PDI质量分数为0.5%的PDI/PVH复合薄膜具有较好的热性能,这能够带来更小的晶粒尺寸和更紧密的晶格结构,有助于获得更高的电气强度和放电能量密度。复合薄膜较好的热性能得益于通过能带弯曲构建的电子陷阱,复合薄膜中的SIE数量减少,漏电流密度降低,电气强度得到提升。
(3)在有机填料带来的界面极化协同作用下,各复合薄膜的储能性能都有所提升,其中具有合适能带结构的PDI表现最好,0.5%PDI/PVH复合薄膜在499.7 MV/m下放电能量密度达到16.6 J/cm3,并且保持了80.5%的高充放电效率。
  • 宁波市自然科学基金资助项目(2023J130)
  • 省属高校基本科研业务费项目(理)(SJLY 2024009)
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2024年第57卷第11期
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doi: 10.16790/j.cnki.1009-9239.im.2024.11.004
  • 接收时间:2024-04-18
  • 首发时间:2025-12-24
  • 出版时间:2024-11-20
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  • 收稿日期:2024-04-18
  • 修回日期:2024-05-24
基金
宁波市自然科学基金资助项目(2023J130)
省属高校基本科研业务费项目(理)(SJLY 2024009)
作者信息
    宁波大学 物理科学与技术学院,浙江 宁波 315211

通讯作者:

朱志彪(1998-),男(汉族),浙江温州人,硕士生,主要从事复合薄膜储能的研究;
侯亚飞(1987-),男(汉族),河北石家庄人,副教授,博士,主要从事绝缘材料与技术的研究。
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2种不同金属材料的力学参数

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genus
种数
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Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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