Article(id=1251457065965793290, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, articleNumber=null, orderNo=null, doi=10.14106/j.cnki.1001-2028.2025.0036, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1737388800000, receivedDateStr=2025-01-21, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1776300215474, onlineDateStr=2026-04-16, pubDate=1759593600000, pubDateStr=2025-10-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1776300215474, onlineIssueDateStr=2026-04-16, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1776300215474, creator=13041195026, updateTime=1776300215474, updator=13041195026, issue=Issue{id=1251457062706820082, tenantId=1146029695717560320, journalId=1251194703438200922, year='2025', volume='44', issue='10', pageStart='1119', pageEnd='1244', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1776300214696, creator=13041195026, updateTime=1776300327814, updator=13041195026, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1251457537212629591, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1251457537212629592, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1145, endPage=1152, ext={EN=ArticleExt(id=1251457066158731280, articleId=1251457065965793290, tenantId=1146029695717560320, journalId=1251194703438200922, language=EN, title=Enhanced electrical properties of BOPP films by plasma treatment, columnId=1251457065399563262, journalTitle=Electronic Components and Materials, columnName=Research & Development, runingTitle=null, highlight=null, articleAbstract=

Biaxially oriented polypropylene(BOPP)exhibits superior energy conversion efficiency and remarkable power density. However,its inherently low dielectric constant fundamentally limits its energy storage capacity,thereby impeding its applications in power storage systems,smart manufacturing,and aerospace engineering. In this study,oxygen plasma treatment was systematically employed to modify the surface of BOPP films,which effectively increased the number of oxygen-containing functional groups on the film surface and enhanced its hydrophilicity. Subsequently,the electrical properties of the modified BOPP films were comprehensively characterized,and the influence of plasma treatment time on these properties was quantitatively investigated. The results indicate that with the extension of plasma treatment time,the dielectric constant of BOPP films increased monotonically from 2.20 to 2.37.When the treatment time was 5min,the breakdown strength and discharge energy density of the modified films reached 785.7MV·m-1 and 6.78J·cm-3,respectively. This work provides a feasible and novel strategy for the development of dielectric films with high energy storage performance,laying a foundation for their broader application in the advanced energy storage scenarios.

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双向拉伸聚丙烯(BOPP)具有极高的能量转换效率和超高的功率密度,但低介电常数制约了其储能性能,极大限制了BOPP电容器在能源存储、智能制造和航天航空等领域的进一步应用。采用氧等离子体处理工艺进行表面改性,显著提升了BOPP薄膜表面的含氧基团数量和亲水性。系统探究了等离子体处理时间对表面改性BOPP薄膜电性能的影响。结果表明:随着等离子体处理时间延长,薄膜相对介电常数由2.20提升至2.37;当处理时间为5min时,薄膜的击穿强度提升至785.7MV·m-1,放电能量密度提升至6.78J·cm-3。该工作为高储能性能电介质薄膜的研制提供了新思路。

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通信作者:张扬,高级实验师,博士,研究方向为聚合物电介质材料。E-mail:
通信作者:董丽杰,教授,博士,研究方向为先进复合材料。E-mail:
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figureFileSmall=M556Vmz6f3gfuRdPh8i/vA==, figureFileBig=62/MiyC6LIPxEuST/slaBQ==, tableContent=null), ArticleFig(id=1251457075130347911, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457065965793290, language=CN, label=图2, caption=不同等离子体处理时间BOPP薄膜含氧基团的含量, figureFileSmall=M556Vmz6f3gfuRdPh8i/vA==, figureFileBig=62/MiyC6LIPxEuST/slaBQ==, tableContent=null), ArticleFig(id=1251457075214233996, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457065965793290, language=EN, label=Fig. 3, caption=FTIR spectra of BOPP films with different plasma treatment time, figureFileSmall=PsJDyD5mQ/twbQRkme87Mw==, figureFileBig=bChgLgtIyNUusKjPo/FDbQ==, tableContent=null), ArticleFig(id=1251457075306508696, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457065965793290, language=CN, label=图3, caption=不同等离子体处理时间BOPP薄膜的红外光谱, figureFileSmall=PsJDyD5mQ/twbQRkme87Mw==, figureFileBig=bChgLgtIyNUusKjPo/FDbQ==, tableContent=null), 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等离子体处理技术增强BOPP薄膜的电性能
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周希 , 陈文雄 , 潘萌 , 张扬 , 董丽杰
电子元件与材料 | 研究与试制 2025,44(10): 1145-1152
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电子元件与材料 | 研究与试制 2025, 44(10): 1145-1152
等离子体处理技术增强BOPP薄膜的电性能
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周希, 陈文雄, 潘萌, 张扬 , 董丽杰
作者信息
  • 武汉理工大学 材料科学与工程学院,湖北 武汉 430070

通讯作者:

通信作者:张扬,高级实验师,博士,研究方向为聚合物电介质材料。E-mail:
通信作者:董丽杰,教授,博士,研究方向为先进复合材料。E-mail:
Enhanced electrical properties of BOPP films by plasma treatment
Xi ZHOU, Wenxiong CHEN, Meng PAN, Yang ZHANG , Lijie DONG
Affiliations
  • School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
出版时间: 2025-10-05 doi: 10.14106/j.cnki.1001-2028.2025.0036
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双向拉伸聚丙烯(BOPP)具有极高的能量转换效率和超高的功率密度,但低介电常数制约了其储能性能,极大限制了BOPP电容器在能源存储、智能制造和航天航空等领域的进一步应用。采用氧等离子体处理工艺进行表面改性,显著提升了BOPP薄膜表面的含氧基团数量和亲水性。系统探究了等离子体处理时间对表面改性BOPP薄膜电性能的影响。结果表明:随着等离子体处理时间延长,薄膜相对介电常数由2.20提升至2.37;当处理时间为5min时,薄膜的击穿强度提升至785.7MV·m-1,放电能量密度提升至6.78J·cm-3。该工作为高储能性能电介质薄膜的研制提供了新思路。

等离子体处理  /  聚丙烯  /  介电性能  /  击穿强度  /  储能密度

Biaxially oriented polypropylene(BOPP)exhibits superior energy conversion efficiency and remarkable power density. However,its inherently low dielectric constant fundamentally limits its energy storage capacity,thereby impeding its applications in power storage systems,smart manufacturing,and aerospace engineering. In this study,oxygen plasma treatment was systematically employed to modify the surface of BOPP films,which effectively increased the number of oxygen-containing functional groups on the film surface and enhanced its hydrophilicity. Subsequently,the electrical properties of the modified BOPP films were comprehensively characterized,and the influence of plasma treatment time on these properties was quantitatively investigated. The results indicate that with the extension of plasma treatment time,the dielectric constant of BOPP films increased monotonically from 2.20 to 2.37.When the treatment time was 5min,the breakdown strength and discharge energy density of the modified films reached 785.7MV·m-1 and 6.78J·cm-3,respectively. This work provides a feasible and novel strategy for the development of dielectric films with high energy storage performance,laying a foundation for their broader application in the advanced energy storage scenarios.

plasma treatment  /  polypropylene  /  dielectric properties  /  breakdown strength  /  energy density
周希, 陈文雄, 潘萌, 张扬, 董丽杰. 等离子体处理技术增强BOPP薄膜的电性能. 电子元件与材料, 2025 , 44 (10) : 1145 -1152 . DOI: 10.14106/j.cnki.1001-2028.2025.0036
Xi ZHOU, Wenxiong CHEN, Meng PAN, Yang ZHANG, Lijie DONG. Enhanced electrical properties of BOPP films by plasma treatment[J]. Electronic Components and Materials, 2025 , 44 (10) : 1145 -1152 . DOI: 10.14106/j.cnki.1001-2028.2025.0036
聚合物薄膜电容器具有极高的能量转换效率和超高的功率密度,在能源存储、智能制造和航天航空等领域发挥着至关重要的作用[1-4]。随着电子电力系统向智能化、集成化和小型化方向快速发展,薄膜电容器的功能化和多样化需求日益增加,对电介质材料提出了更高的要求[5-6]。双向拉伸聚丙烯(BOPP)凭借其低介电损耗、高击穿电场和高充放电效率等优异特性,成为目前应用最广泛的商业化电介质薄膜材料[7]。然而,商用BOPP的低介电常数严重限制了其储能性能,导致电容器体积增大,难以满足现代电子电力系统的发展需求[8]
为提升聚丙烯的介电储能性能,研究人员开展了大量探索性工作。使用功能填料填充聚合物基体是一种常见策略,通过填料与聚合物界面区域产生的深陷阱限制电荷传输,从而改善材料的介电储能性能[9]。例如,Zhu等[10]通过在聚丙烯中引入质量分数0.10%的镧系功能填料(WBG),复合膜在581.6MV·m-1电场下具有7.05J·cm-3的高储能密度和99.6%的超高能量转换效率。Zhang等[11]利用挤出成型工艺将聚丙烯与极性缺电子分子8-羟基喹啉(8-HQ)熔融共混制备了电介质材料。8-HQ分子能够捕获高电场下注入的电荷从而抑制漏电流,并促进晶粒生长,使所制备的电介质薄膜表现出9.87J·cm-3的高储能密度。此外,还可通过在聚合物分子链中引入极性基团来调控电介质材料的储能性能。例如,通过在聚丙烯上接枝具有含氟基团的甲基丙烯酸三氟乙酯(TFEMA)制备得到接枝聚合物PP-g-TFEMA,其在800MV·m-1电场下的放电能量密度高达8.20J·cm-3,能量转换效率超过90.0%[12]。然而,聚合物复合材料的制备通常涉及复杂的化学试剂和繁琐的工艺流程,高性能电介质薄膜的制备难以通过当前薄膜材料的制造工艺实现。因此,如何基于现有工艺,开发一种简单、高效且环境友好的改性方法,以进一步提升BOPP的介电储能性能,仍是当前该领域研究中的挑战[13-14]
等离子体处理工艺可以简单地通过控制等离子体处理条件(气体类型、处理功率、处理持续时间和工作压强)调控聚合物表面化学键,从而实现聚合物表面的可定制性[15]。因此,本文以商用BOPP薄膜为研究对象,通过氧等离子体处理工艺对其进行表面改性。通过控制处理时间,在薄膜表面引入含氧极性官能团,显著提升了其介电储能性能。实验结果表明,经氧等离子体处理的BOPP薄膜在保持高击穿电场和低介电损耗的同时,其放电能量密度得到显著提升。本工作采用的氧等离子体处理工艺具有步骤简单、无需化学试剂等优点,为高储能性能电介质薄膜的研究提供了新思路。
采用厚度为6.7 μm的BOPP薄膜,购自武汉欣申试化工科技有限公司。将薄膜裁剪为10cm×10cm尺寸,然后用乙醇洗涤并烘干。将烘干后的BOPP薄膜置于赛奥特科技有限公司YZD08-2C型等离子体清洗机中,选择氧气为处理气体,设置处理功率为50W,并将处理时间分别设置为0.5,1,3,5,10和20min。
(1)X射线光电子能谱(XPS)测试:采用美国Thermo,EscaLab 250Xi型X射线光电子能谱仪。
(2)傅里叶红外光谱(FTIR)测试:采用美国Thermo,Nicolet 6700型红外光谱仪,测试范围为4000~400cm-1
(3)X射线衍射(XRD)测试:采用德国Bruker,D8 Advance型X射线衍射分析仪,扫描速度为2(°)·min-1
(4)差示扫描量热(DSC)测试:采用美国TA,DSC 2500型差示扫描量热仪,采用N2为保护气,升温速率为5 ℃·min-1
(5)热重(TG)测试:采用德国NETZSCH,STA 449 F3 Jupiter型同步热分析仪,采用N2为保护气,升温速率为5 ℃·min-1
(6)原子力显微镜(AFM)测试:采用美国VEECO,Nanoscope Ⅳ型原子力显微镜,扫描面积为10 μm×10 μm。
采用北京格微仪器有限公司GVC-2000P型磁控离子溅射仪将薄膜双面喷金,电极面积为4.52mm2。介电常数和介电损耗采用精密数字LCR表(Agilent,E4980A)室温测试,测试频率范围为100Hz~2MHz。由LCR表得到电容C数据,再通过下列公式计算介电常数(εr):
式中:真空介电常数ε0 = 8.85×10-12 F·m-1C为薄膜样品测试所得电容值;d为薄膜样品厚度;S为样品电极面积。
采用华仪电子股份有限公司的7474型直流耐压测试系统测试击穿强度,电压上升速率为500V·s-1。使用双参数Weibull分布对薄膜的击穿性能进行评估,并通过下列公式计算出理论击穿场强:
式中:PE)表示累计击穿概率;E表示测试所得外加电场强度;Eb表示累计击穿概率为63.5%对应的击穿强度;β表示用于评估数据分散性的形状参数[16]
采用美国Radiant公司Premier II型铁电测试系统在室温下于硅油内测试样品在不同电场作用下的电位移-电场(D-E)回线,通过对D-E回线积分计算储能密度:
式中:E表示在两金属电极之间施加的电场强度;Dmax表示在电场下样品的最大电位移。
采用美国Instron Corporation公司Instron 5967型电子万能材料试验机以5mm·min-1的拉伸速率、搭配500 N传感器测试力学性能。
采用盛鼎精密仪器有限公司CSCDIC-100型接触角测量仪对等离子体处理薄膜进行亲疏水性测试。测量时,将去离子水水滴悬挂于针头,下移针头使其与薄膜接触,水接触角测量的结果取固液界面的平均角度。
不同等离子体处理时间BOPP膜的XPS谱图如图1所示。图1(a)中,在约532eV处的O1s峰强度随等离子体处理时间的增加先增强,后趋于稳定。由图1(b)图1(c)可知,等离子体处理会在BOPP薄膜表面诱导形成含氧极性基团,其中C-OH/C-O-C和O-C=O的含量随着等离子体处理时间的增加先增加,后趋于稳定,如图2所示。等离子体处理导致薄膜表面部分共价键断裂形成高化学活性的自由基,从而将氧原子引入分子链中,生成C-OH/C-O-C和O-C=O等极性官能团[13]
图3所示,在1715cm-1处检测到较弱吸收峰,表明在未经等离子体处理的BOPP薄膜中存在极少的C=O。随着等离子体处理时间的增加,C=O键对应的1715cm-1峰位吸收峰强度先增强,后减弱。不同等离子处理时间BOPP薄膜的XRD图谱对比如图4所示,等离子体处理时间少于5min时,BOPP膜的晶面特征峰强度与位置无明显变化,说明短时间的等离子体处理并未影响BOPP的结晶结构。然而,等离子体处理时间超过5min后,α晶的(040)晶面衍射峰强度明显降低。这是由于长时间的等离子体处理可能导致BOPP表面局部过热,使其发生热降解或热氧化,而热降解产生的低分子量物质可能干扰结晶过程[17-18]
图5(a)所示,DSC曲线表明BOPP薄膜经等离子体改性处理后,其熔融温度由172 ℃下降至168 ℃。这是因为等离子体高能粒子轰击导致BOPP薄膜表层部分共价键断裂,从而使分子量降低并导致链段迁移率提升,最终降低材料熔点[19]图5(b)的TG分析表明,不同等离子体处理时间BOPP薄膜的最大热失重温度稳定在360 ℃,说明经等离子体处理后,薄膜仍具有优异的热稳定性。
图6为不同等离子体处理时间下BOPP薄膜的AFM图。从图6(a)可以看出,未处理的BOPP薄膜表面形貌较为光滑平整,且无明显缺陷。经等离子体处理后(图6(b~d)),BOPP薄膜表面受到刻蚀而形成均匀的沟壑结构,且随着处理时间的增加逐渐加深,这是因为等离子体高能粒子轰击引发的表面降解。BOPP薄膜表面的平均粗糙度(Ra)随着处理时间的增加先增大后趋于稳定,如图7所示。等离子体放电技术能够均匀处理薄膜表面,不会对表面电荷分布产生较大影响,且有利于提升薄膜材料的粘附性能,进而提高金属层的附着力。然而,薄膜表面粗糙度过高可能促进电荷载流子的注入和空间电荷的积累而导致局部电场增强,从而增加其击穿风险,因此需要合理控制等离子体处理的时间[20]
图8所示,静态水接触角测试显示,BOPP薄膜表面的亲水性在等离子体处理后发生显著改变。随着等离子体处理时间的增加,BOPP薄膜表面润湿性发生显著变化,从BOPP的88.8°降低到处理时间20min时的28.2°,降幅达68.2%,表明薄膜亲水性增加。这种亲水性改变归因于等离子体处理在BOPP表面同时引入了含氧极性基团(-OH、C=O等)和纳米级沟壑结构。在一定范围内,聚合物表面亲水性的增加和表面附着力的提高,有利于提高金属层和聚合物之间的粘附强度[21-22]
等离子体处理时间对BOPP薄膜介电性能的影响如图9所示。从图9(a)可知,经等离子体处理后BOPP薄膜的介电常数有所提高,且介电损耗保持在较低水平。如图9(b)所示,当等离子体处理时间增加到20min时,在1kHz下的相对介电常数从2.20增加到2.37,增加了7.7%。这是由于C-OH/C-O-C和O-C=O在外加电场下促进了取向极化,从而增强了聚合物电介质的极性[23-24]。等离子体处理会使BOPP的介电损耗略有提高,这源于外加电场下偶极取向的摩擦,但在1kHz时,BOPP薄膜的介电损耗均低于0.002。等离子体处理后的BOPP薄膜介电常数和介电损耗随频率的升高未发生明显变化,表明薄膜具有良好的频率稳定性。
图10(a)为不同等离子体处理时间BOPP薄膜的电击穿强度Weibull分布。不同等离子体处理时间BOPP薄膜的形状参数β值均大于19,表明测试数据具有优异的可靠性。随着等离子体处理时间的增加,BOPP薄膜的击穿强度先增大后减小。在等离子体处理时间为5min时,击穿强度提升至785.7MV·m-1,较未处理的BOPP薄膜(708.1MV·m-1)提升了11%。
根据机电击穿机理,当外加电场引起的库仑力超过聚合物的屈服力时会发生击穿,因此,具有高杨氏模量的薄膜材料抵抗该库仑力的能力更强[25]。如图10(b)所示,随着等离子体处理时间的增加,BOPP薄膜的杨氏模量先增加后减小,从BOPP的1773MPa增加到等离子体处理时间5min的2169MPa,然后降低到等离子体处理时间20min的1525MPa。这是因为含氧极性基团的引入使聚丙烯分子链之间形成了一定的交联网络结构,从而提升了BOPP薄膜的杨氏模量[26-28]。较短时间的等离子体处理有助于提升BOPP薄膜的击穿性能,但是长时间的等离子体处理会使分子链降解而导致力学性能下降,从而影响薄膜的击穿性能[29-30]
图10(c)可知,在室温100MV·m-1下,BOPP薄膜经等离子体处理后漏电流密度从5.4×10-9A· cm-2降低至1.4×10-9A·cm-2,降低了约4倍。这可能是由于等离子体处理引入的含氧极性基团在BOPP薄膜中形成了深陷阱,从而阻碍了载流子的传输,这有利于提升薄膜的击穿强度[14]
图11为不同等离子体处理时间BOPP薄膜的储能性能。如图11(a)所示,等离子体处理后的BOPP薄膜表现出更高的电位移。例如,当等离子体处理时间为5min时,BOPP的最大电位移(Dmax)为1.79 μC·cm-2,是未处理BOPP膜(1.38 μC·cm-2)的1.3倍。值得注意的是,BOPP薄膜经等离子体处理后的剩余电位移(Dr)无明显增大,且η保持在95.0%以上。图11(b)总结了不同等离子体处理时间BOPP薄膜的储能密度和储能效率随电场强度的变化情况。在Weibull击穿强度下,等离子体处理时间为5min的BOPP薄膜的储能密度为6.78J·cm-3η为95.4%,相较于未经处理的BOPP薄膜的储能密度(4.92J·cm-3),提升约37.8%。
BOPP薄膜经等离子体处理后,其介电常数和击穿性能均得到了提高,并保持了较低的介电损耗。当等离子体处理时间为5min时,BOPP薄膜的击穿强度提升至785.7MV·m-1,并具有6.78J·cm-3的高能量密度和95.4%的充放电效率。等离子体处理在薄膜表面形成的含氧极性官能团提供了深陷阱,阻碍了电荷迁移。该方法不涉及化学溶剂,可直接应用于商用BOPP薄膜,为高储能性能电介质薄膜的研制提供了新途径。
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2025年第44卷第10期
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doi: 10.14106/j.cnki.1001-2028.2025.0036
  • 接收时间:2025-01-21
  • 首发时间:2026-04-16
  • 出版时间:2025-10-05
补充材料
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  • 收稿日期:2025-01-21
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    武汉理工大学 材料科学与工程学院,湖北 武汉 430070

通讯作者:

通信作者:张扬,高级实验师,博士,研究方向为聚合物电介质材料。E-mail:
通信作者:董丽杰,教授,博士,研究方向为先进复合材料。E-mail:
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https://castjournals.cast.org.cn/joweb/dzyjycl/CN/10.14106/j.cnki.1001-2028.2025.0036
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
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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