Article(id=1193556936206549395, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.04.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1716739200000, receivedDateStr=2024-05-27, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1762495748807, onlineDateStr=2025-11-07, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762495748807, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762495748806, creator=13701087609, updateTime=1762495748806, updator=13701087609, issue=Issue{id=1193556932167431095, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='4', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762495747843, creator=13701087609, updateTime=1762498255746, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567451108573868, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567451112768173, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1, endPage=8, ext={EN=ArticleExt(id=1193556936395293077, articleId=1193556936206549395, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Grafting technology and high temperature energy storage characteristics of polypropylene film by melt grafting, columnId=1193556932997903294, journalTitle=Insulating Materials, columnName=Advanced Energy Storage Dielectric Special Issue, runingTitle=null, highlight=null, articleAbstract=

Aiming at the problem that the energy storage characteristics of polypropylene (PP) capacitor films reduce greatly under high temperature and high electric field, the polypropylene was modified by melt grafting with maleic anhydride (MAH) at the molecular level, and the effects of grafting monomer content, initiator mass fraction, and reaction temperature on the high-temperature energy storage characteristics of the films were investigated. Then a maleic anhydride grafted polypropylene (PP-g-MAH) biaxially oriented capacitor film with superior high-temperature energy storage characteristics was prepared, and its structure and performances were characterized and tested. The results show that with the increase of monomer content, initiator mass fraction, and reaction temperature, the charge and discharge efficiency of the grafted sample increases at first and then decreases. The graft modification promotes the increase of crystal nuclei and the reduce of spherulite size in PP, which increases the trap depth and trap density of the film effectively, reduces the carrier mobility, and enhances the electric strength and energy storage characteristics at high temperature.

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针对聚丙烯(PP)电容器薄膜在高温高电场下储能特性大幅降低的问题,在分子层面对聚丙烯进行熔融接枝马来酸酐(MAH)改性,并研究熔融接枝的单体含量、引发剂质量分数、反应温度对薄膜样品高温储能特性的影响规律,制备具有优异高温储能特性的马来酸酐接枝聚丙烯(PP-g-MAH)双向拉伸电容器薄膜,并对其结构与性能进行表征和测试。结果表明:随着单体含量增加、引发剂质量分数和反应温度升高,接枝样品的充放电效率均大致呈现先增加后降低的趋势。接枝改性促使PP内部晶核增多,球晶尺寸减小,有效增大了薄膜陷阱深度和陷阱密度,降低了载流子迁移率,提升了其在高温下的电气强度和储能特性。

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李君洛(1998-),女(汉族),山东泰安人,博士生,主要从事高温储能电介质的研究;

李琦(1984-),男(汉族),湖北武汉人,副教授,主要从事聚合物电介质材料的研究。

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李君洛(1998-),女(汉族),山东泰安人,博士生,主要从事高温储能电介质的研究;

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李君洛(1998-),女(汉族),山东泰安人,博士生,主要从事高温储能电介质的研究;

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IEEE Transactions on Dielectrics and Electrical Insulation,1984,EI-19(3):227,33., articleTitle=Weibull statistics in dielectric breakdown; theoretical basis, applications and implications, refAbstract=null)], funds=[Fund(id=1195072498699083847, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556936206549395, awardId=92166203, language=CN, fundingSource=国家自然科学基金重大研究计划重点支持项目(92166203), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1195072493577839604, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556936206549395, xref=1, ext=[AuthorCompanyExt(id=1195072493586228213, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556936206549395, companyId=1195072493577839604, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 State Key Laboratory of Power System and Generation Equipment, Department of Electrical Engineering, Tsinghua 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编号 MAH单体质量分数/% 引发剂质量分数/% 反应温度/℃
PP 0 0 0
PP-g-2.5MAH0.3%-200℃ 2.5 0.3 200
PP-g-5.0MAH0.3%-200℃ 5.0 0.3 200
PP-g-7.5MAH0.3%-200℃ 7.5 0.3 200
PP-g-10.0MAH0.3%-200℃ 10.0 0.3 200
PP-g-5.0MAH0.2%-200℃ 5.0 0.2 200
PP-g-5.0MAH0.4%-200℃ 5.0 0.4 200
PP-g-5.0MAH0.5%-200℃ 5.0 0.5 200
PP-g-5.0MAH0.3%-180℃ 5.0 0.3 180
PP-g-5.0MAH0.3%-190℃ 5.0 0.3 190
PP-g-5.0MAH0.3%-210℃ 5.0 0.3 210
), ArticleFig(id=1195072498556477510, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556936206549395, language=CN, label=表1, caption=

不同配方及工艺下的接枝样品编号

, figureFileSmall=null, figureFileBig=null, tableContent=
编号 MAH单体质量分数/% 引发剂质量分数/% 反应温度/℃
PP 0 0 0
PP-g-2.5MAH0.3%-200℃ 2.5 0.3 200
PP-g-5.0MAH0.3%-200℃ 5.0 0.3 200
PP-g-7.5MAH0.3%-200℃ 7.5 0.3 200
PP-g-10.0MAH0.3%-200℃ 10.0 0.3 200
PP-g-5.0MAH0.2%-200℃ 5.0 0.2 200
PP-g-5.0MAH0.4%-200℃ 5.0 0.4 200
PP-g-5.0MAH0.5%-200℃ 5.0 0.5 200
PP-g-5.0MAH0.3%-180℃ 5.0 0.3 180
PP-g-5.0MAH0.3%-190℃ 5.0 0.3 190
PP-g-5.0MAH0.3%-210℃ 5.0 0.3 210
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熔融接枝聚丙烯薄膜的接枝工艺与高温储能特性
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李君洛 1 , 孟礼 1 , 刘雨杭 1 , 罗兵 2 , 徐永生 2 , 肖微 2 , 何金良 1 , 李琦 1
绝缘材料 | 先进储能电介质专题 2025,58(4): 1-8
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绝缘材料 | 先进储能电介质专题 2025, 58(4): 1-8
熔融接枝聚丙烯薄膜的接枝工艺与高温储能特性
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李君洛1, 孟礼1, 刘雨杭1, 罗兵2, 徐永生2, 肖微2, 何金良1, 李琦1
作者信息
  • 1 清华大学 电力系统及大型发电设备安全控制和仿真国家重点实验室,北京 100084
  • 2 特高压电力技术与新型电工装备基础国家工程研究中心,广东 广州 510080
  • 李君洛(1998-),女(汉族),山东泰安人,博士生,主要从事高温储能电介质的研究;

    李琦(1984-),男(汉族),湖北武汉人,副教授,主要从事聚合物电介质材料的研究。

Grafting technology and high temperature energy storage characteristics of polypropylene film by melt grafting
Junluo LI1, Li MENG1, Yuhang LIU1, Bing LUO2, Yongsheng XU2, Wei XIAO2, Jinliang HE1, Qi LI1
Affiliations
  • 1 State Key Laboratory of Power System and Generation Equipment, Department of Electrical Engineering, Tsinghua University, Beijing 100084, China
  • 2 National Engineering Research Center of UHV Technology and New Electrical Equipment, Guangzhou 510080, China
出版时间: 2025-04-20 doi: 10.16790/j.cnki.1009-9239.im.2025.04.001
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针对聚丙烯(PP)电容器薄膜在高温高电场下储能特性大幅降低的问题,在分子层面对聚丙烯进行熔融接枝马来酸酐(MAH)改性,并研究熔融接枝的单体含量、引发剂质量分数、反应温度对薄膜样品高温储能特性的影响规律,制备具有优异高温储能特性的马来酸酐接枝聚丙烯(PP-g-MAH)双向拉伸电容器薄膜,并对其结构与性能进行表征和测试。结果表明:随着单体含量增加、引发剂质量分数和反应温度升高,接枝样品的充放电效率均大致呈现先增加后降低的趋势。接枝改性促使PP内部晶核增多,球晶尺寸减小,有效增大了薄膜陷阱深度和陷阱密度,降低了载流子迁移率,提升了其在高温下的电气强度和储能特性。

马来酸酐  /  双向拉伸聚丙烯  /  熔融接枝  /  高温储能

Aiming at the problem that the energy storage characteristics of polypropylene (PP) capacitor films reduce greatly under high temperature and high electric field, the polypropylene was modified by melt grafting with maleic anhydride (MAH) at the molecular level, and the effects of grafting monomer content, initiator mass fraction, and reaction temperature on the high-temperature energy storage characteristics of the films were investigated. Then a maleic anhydride grafted polypropylene (PP-g-MAH) biaxially oriented capacitor film with superior high-temperature energy storage characteristics was prepared, and its structure and performances were characterized and tested. The results show that with the increase of monomer content, initiator mass fraction, and reaction temperature, the charge and discharge efficiency of the grafted sample increases at first and then decreases. The graft modification promotes the increase of crystal nuclei and the reduce of spherulite size in PP, which increases the trap depth and trap density of the film effectively, reduces the carrier mobility, and enhances the electric strength and energy storage characteristics at high temperature.

maleic anhydride  /  biaxially oriented polypropylene  /  melt grafting  /  high temperature energy storage
李君洛, 孟礼, 刘雨杭, 罗兵, 徐永生, 肖微, 何金良, 李琦. 熔融接枝聚丙烯薄膜的接枝工艺与高温储能特性. 绝缘材料, 2025 , 58 (4) : 1 -8 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.001
Junluo LI, Li MENG, Yuhang LIU, Bing LUO, Yongsheng XU, Wei XIAO, Jinliang HE, Qi LI. Grafting technology and high temperature energy storage characteristics of polypropylene film by melt grafting[J]. Insulating Materials, 2025 , 58 (4) : 1 -8 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.001
随着新能源需求的增加与化石燃料危机的迫近,全球进入多能源协同时代,加快新能源体系的建设成为能源转型的关键。电力电容器是海上风电、新能源汽车、智能电网等新能源产业发展所需要的一类极其重要的功率型器件[1-5]。聚合物薄膜电容器是电力电容器的一种,它具有耐压性能高、功率密度大、易加工、成本低等优势和独特的“自愈特性”,更适用于可再生能源的电能储存与电能转换需求,在新能源储能产业中发挥关键作用[6]。目前,商业化程度最高、应用最广泛的电容器薄膜材料为双向拉伸聚丙烯(biaxially oriented polypropy-lene,BOPP)薄膜,其综合性能优异、规模化制备工艺成熟,已广泛应用于多个新能源行业中[7-8]
然而,薄膜电容器现有性能与高温高电场下迅速增长的应用需求存在矛盾[9-10],例如,随着光伏发电与海上风电装机容量与规模的增大,发电功率不断增加,导致电容器内部发热严重。在高温条件下BOPP电容器薄膜介电储能特性会大幅下降,甚至可能导致器件过热损坏(热失控),无法满足电能储存与转换的应用需求。而引入冷却系统降低环境温度又会降低系统工作效率、增加生产和使用成本[11-12]。因此,寻找针对BOPP电容器薄膜高温应用的改性方法,使其在高温下具有优异的介电储能特性是亟需突破的技术瓶颈。
近年来,国内外学者针对PP电容器薄膜的改性开展了大量研究[13-16]。纳米复合是一种常见的材料改性方法,I RYTOLUOTO等[17]制备了BOPP/SiO2复合薄膜,结果表明纳米SiO2的引入减少了聚丙烯(PP)在直流电场下空间电荷的积累,使复合薄膜的体积电阻率降低,同时保持较低的介质损耗。但复合改性方法存在无机纳米颗粒与聚合物基体之间相容性较差且容易发生团聚的问题,难以实现高品质电容器薄膜的规模化制备[18]
化学接枝是一种从分子层面进行材料改性的方法,通过在PP分子链上引入具有高电子亲合能的基团,利用深陷阱限制载流子的输运,可提升PP的储能特性[19-20]。研究发现,马来酸酐、苯乙烯、甲基丙烯酸甲酯以及乙烯基三乙氧基硅烷等单体接枝的PP能够避免添加无机纳米颗粒可能带来的团聚问题,且具有较低的体积电导率和较高的电气强度[21-23]
PP接枝改性的方法包括熔融接枝、溶液接枝、固相接枝等。溶液接枝和固相接枝的反应时间较长,反应所需的溶剂后处理过程较复杂,且会污染环境[24-25]。熔融接枝是在PP熔点以上温度(190~230℃)下,将PP单体、接枝单体、引发剂和其他添加剂在少量分散剂的帮助下均匀混合,在一定条件下通过密炼或熔融挤出得到反应产物。熔融接枝的反应时间短,省去了聚合物分离和溶剂回收的时间,并且可以在现有的挤出机设备上实现工业化连续生产,因此熔融接枝是一种与BOPP工业化生产线兼容的改性方法,具有环保、经济、高效的优势。SHI D等[26]研究了熔融挤出法制备马来酸酐接枝聚丙烯(PP-g-MAH)的工艺,并通过电喷雾质谱和凝胶渗透色谱揭示了熔融接枝反应的机理,但是目前PP-g-MAH双向拉伸电容器薄膜的制备工艺鲜有探讨,接枝马来酸酐(MAH)对PP-g-MAH双向拉伸电容器薄膜结构和高温电性能的影响尚不明确。
本文利用熔融接枝的方法制备PP-g-MAH双向拉伸电容器薄膜,探索不同接枝工艺参数下薄膜高温储能特性的变化规律,筛选出在高温高电场下具有优异储能特性薄膜的熔融接枝工艺,并对接枝薄膜的结构和性能进行表征。该技术路线生产效率高,与现有熔融挤出生产线兼容,有望应用于电容器薄膜的批量化生产。
PP(熔体流动速率为4 g/10 min)、马来酸酐(MAH)、过氧化二异丙苯(DCP,引发剂)均购自上海阿拉丁生化科技股份有限公司。
将一定量的PP、MAH、DCP混合均匀后加入到预热后的双螺杆挤出机中进行熔融接枝反应,熔融挤出过程如图1所示。挤出机反应段温度分别为180、190、200、210℃,输出段温度为200℃,停留时间为300 s。熔融挤出得到PP-g-MAH片材,其厚度为108 μm。接枝MAH单体质量分数分别为2.5%、5.0%、7.5%、10.0%,引发剂DCP质量分数分别为0.2%、0.3%、0.4%、0.5%。不同配方及工艺下的接枝样品编号如表1所示。
将接枝样品在200℃和15 MPa条件下热压20 min,然后在20℃和10 MPa下水浴冷却5 min,再将处理后的样品采用广州市普同实验分析仪器有限公司生产的薄膜拉伸机(型号为POTOP FOCI-04S)双向拉伸成厚度为12 μm的薄膜。拉伸过程中,参数设置如下:①预热温度为160℃,预热时间为3 min;②拉伸温度为160℃,拉伸速率为200 mm/s,拉伸倍数为3×3,拉伸过程如图2所示。
采用Thermo Scientific iS10型傅里叶红外光谱(FTIR)测试样品的分子结构,采用全反射模式在波数为1 000~4 000 cm-1范围内进行扫描,为了消除接枝基团自聚的影响,在测试红外光谱之前将材料放入索氏抽提器中抽提24 h以去掉自聚物。采用Philips X’ Pert MPD型X射线衍射(XRD)测试样品的结晶结构,测试在室温下进行,2θ角为3°~35°。采用Nikon Eclipse LV100 NPOL型偏光显微镜(PLM)观察接枝前后样品等温结晶时的球晶形貌,观察过程中先将样品升温至200℃,再降温至120℃进行等温结晶,通过拍照记录样品形貌。采用TA Q2000型差示扫描量热仪(DSC)对PP-g-MAH薄膜的熔融和结晶行为进行研究,测试温度为30~200℃,采用氮气进行保护,测试时先将质量为3~5 mg的样品在30℃下保持3 min后,以10℃/min的速率升温至200℃后保持5 min,然后以相同的速率降温至30℃。
采用宽频介电谱仪(型号为Novocontrol Concept 80)测试接枝前后样品的相对介电常数和介质损耗因数,薄膜两端的交流电压有效值为1 V,测试频率为1 Hz~1 MHz,测试温度为120℃。采用静电计(型号为Keithley 6517B)对不同场强下样品的高温直流泄漏电流进行测试,测试温度为120℃,记录加压10 min后的电流值,获得稳态电流密度。测试样品表面用聚酰亚胺胶带粘贴,防止沿面闪络。高温电气强度试验采用Trek 610C型直流电压源,样品置于硅油中,测试温度为120℃,升压速率为500 V/s,逐渐加压直至样品击穿,测试20个点并记录击穿电压和样品厚度。采用具有Sawyer-Tower电路的高压测试系统(型号为K-CPe1901-AI-30 kV)进行电位移-电场电滞回线(D-E回路)测试,外施电压为频率为10 Hz的三角形单极波电压。
MAH是一种常见的接枝单体,其分子中带有氧孤对电子,反应活性较高。MAH接枝PP的反应机理已在前人研究中得到报道[27-28],引发剂分解产生的自由基可以同时引发PP大分子和MAH单体进行接枝反应,如图3所示。一般认为,三级自由基有断裂和接枝两种反应趋势,而二级自由基有接枝和交联两种反应趋势,图3所示MAH熔融接枝PP反应体系中主要为三级自由基,因此三级自由基的趋势决定了接枝产物的接枝率。
图4为PP和PP-g-MAH薄膜的红外光谱图。从图4可以看出,PP-g-MAH薄膜的红外光谱图较PP出现了1组新的吸收峰,即在波数为1 783 cm-1和1 858 cm-1处MAH的羰基吸收峰。因此,可以证明MAH成功接枝到PP上。
MAH单体含量对PP-g-MAH薄膜在120℃下储能特性的影响如图5所示。
图5可以看出,随着MAH单体含量的增加,PP-g-MAH薄膜的充放电效率呈现先升高后降低的趋势。MAH含量较少时,引发剂引发MAH产生自由基数量较少,导致发生β断裂的PP大分子自由基的数目较多,因此PP接枝率很低,同时大量PP分子长链被剪切,产生更多聚合物自由端的“缺陷位点”,减小了分子链的堆砌密度,使接枝后PP的充放电效率比接枝前低[29]。MAH含量增加时,引发剂引发MAH产生自由基数量增多,PP大分子自由基与MAH自由基碰撞的概率增大,PP接枝率显著提高。另外,MAH接枝到PP分子链上,抑制了PP分子链的降解[30],因此,由PP断裂产生的β大分子自由基数目的减少。此时接枝MAH可以引入大量深陷阱[31],使PP-g-MAH薄膜的充放电效率提升。进一步增加MAH含量时,引发剂引发MAH产生大量的MAH自由基会发生自聚,自聚相会导致电场分布不均匀、泄漏电流增加,从而导致PP-g-MAH薄膜充放电效率下降。
引发剂质量分数对PP-g-MAH薄膜在120℃下储能特性的影响如图6所示。
图6可以看出,引发剂质量分数的增加会使PP-g-MAH薄膜充放电效率先升高后降低。引发剂浓度较低时,产生的初始自由基数量较少,只有少部分MAH被成功接枝在PP分子链上,因此PP-g-MAH薄膜的储能特性较低。随着引发剂质量分数的增加,更多的MAH单体被成功接枝到PP分子链上,PP-g-MAH薄膜的充放电效率也随之提升。而引发剂过量不仅会导致MAH单体的均聚与PP主链的断裂,使PP接枝率大幅降低,同时引发剂作为杂质也会成为薄膜的电气弱点,因此PP-g-MAH薄膜的充放电效率下降。
接枝反应的温度指挤出机反应段的温度,对接枝反应的反应速率、引发剂活性等有显著影响[29]。本文分别测试了反应温度为180、190、200、210℃时PP-g-MAH薄膜的高温储能特性,结果如图7所示。从图7可以看出,随着反应温度升高,PP-g-MAH薄膜的储能效率呈现先升高后降低的趋势。这是因为在反应温度较低时,引发剂的分解速度较慢,分子链活动能力较低,反应存在“笼闭效应”。较少的MAH被接枝到PP分子链上,因此充放电效率较低,随着反应温度的升高,引发剂活性和分子链的活动能力随之提升,因此PP-g-MAH薄膜储能效率提升。而反应温度进一步升高后,PP分子链的热降解速率增大,聚丙烯分子链的降解会导致其性能劣化,因此PP-g-MAH薄膜的充放电效率略有下降。
基于上述接枝反应条件对薄膜样品高温储能特性的影响研究,可以得出,当单体质量分数为5.0%、引发剂质量分数为0.3%和反应温度为200℃时,双向拉伸电容器薄膜具有优异的高温储能特性,后续将对PP-g-5MAH0.3%-200℃薄膜进行进一步表征与测试。
PP常见的晶型包括α、β、γ 3种晶型,其中α晶型最为稳定,通过对衍射峰出现的位置可以分辨样品的不同晶型。图8为样品的XRD测试结果。从图8可以看出,PP和PP-g-5.0MAH0.3%-200℃薄膜的衍射峰位置基本相同,所对应的3个衍射峰的2θ为14.1°、16.9°、18.5°,分别对应α晶型的(110)、(040)、(130)晶面的标志性衍射峰,说明接枝并未影响PP的晶型和晶面间距。
采用PLM测得接枝前后样品的球晶形貌如图9所示。从图9可以看出,接枝前后均为α球晶的结构,这一点与XRD的测试结果相符合。PP薄膜的球晶尺寸为50~100 μm,PP-g-5MAH0.3%-200℃薄膜的球晶尺寸为20~60 μm,接枝前样品的球晶尺寸显著大于接枝后,这是由于MAH接枝链与PP分子链相容性较差,促进了冷却结晶过程中的非均相成核,使晶核数量增多、球晶尺寸减小。
图10为样品的DSC测试结果。从图10可以看出,接枝改性前后样品的DSC曲线均为单峰,表明接枝前后样品晶型不变。通过对曲线进行分析可以求得样品的熔点(T m)和结晶度(X c)。PP-g-0.5MAH0.3%-200℃薄膜的熔点和结晶度较PP薄膜的更低,说明接枝MAH使PP薄膜的熔程变短,影响了PP薄膜的结晶过程。接枝反应形成的接枝侧链破坏了PP分子链结构的规整性,扩大了分子链之间的距离,影响了PP结晶的完整度,同时使其分子量分布变窄。
电容器薄膜的介电常数和介质损耗因数反映其在电场作用下的极化特性。图11为接枝前后样品在120℃、1 Hz~1 MHz下的介电常数及介质损耗因数。从图11可以看出,接枝前后样品的介电常数随频率变化不大,接枝后样品的介电常数和介质损耗因数相对接枝前的样品略有提升。极性基团MAH的接入可以提升PP分子长链无定形区的极性,因此接枝后样品的介电常数略有提升。此外,接枝后样品的结晶度降低,分子链之间的距离扩大,使无定形区的范围扩大,因此分子链活动能力增强,使分子链弛豫损耗增大,因此介质损耗因数略有提升。
电介质在外加交变电场下的能量损耗主要分为弛豫损耗和漏导损耗,高温高电场下漏导损耗是能量损耗的主要来源,漏导损耗过高会使电容器内部发热并逐渐积累热量,严重影响电容器的使用寿命。因此,为进一步探索PP-g-5MAH0.3%-200℃薄膜中的电导损耗与电导机制,对高温高电场下接枝前后样品的泄漏电流进行测试,测试结果如图12(a)所示。从图12(a)可以看出,接枝后样品在高温高电场下的泄漏电流得到显著抑制。通过对J-E(泄漏电流密度-电场)进行拟合,可以获得接枝前后样品两段式变化的电荷传输机制。在低电场下,载流子传输主要以欧姆传导为主,电导电流密度与电场强度成正比关系。在高电场下,J-E曲线的特性可以用跳跃传导来解释。通过曲线拟合计算出PP和PP-g-5.0MAH0.3%-200℃薄膜的跳跃距离分别为0.58 nm、0.51 nm,接枝后样品的跳跃距离缩短,证明PP-g-5.0MAH0.3%-200℃薄膜中陷阱深度和陷阱密度更大[32]。因此MAH接枝基团的存在增大了陷阱深度和陷阱密度,从而减少了载流子迁移引起的电导损失。本文进一步对室温下(30℃)样品的泄漏电流进行测试,结果如图12(b)所示。从图12(b)可以看出,PP-g-5MAH0.3%-200℃薄膜的泄漏电流低于PP薄膜,说明接枝MAH在室温下也可以降低PP在高电场下的漏导损耗。
电容器薄膜的电气强度反映其在高电场下的耐压水平。本文对接枝前后的样品在120℃下的电气强度进行测试,并采用双参数Weibull分布提取特征电气强度[33],结果如图13所示。从图13可以看出,PP-g-5.0MAH0.3%-200℃薄膜的电气强度由纯PP薄膜的440 MV/m提高到529 MV/m,表现出优异的耐压性能。这是由于接枝增加的陷阱深度和陷阱密度可以使材料中的载流子入陷,减少在高温高电场下热电子对PP分子链的破坏,提升样品的电气强度[31]。同时,PP-g-5.0MAH0.3%-200℃薄膜的球晶相较于纯PP薄膜更小,小而密的球晶会延长击穿路径,同时大球晶在生长过程中会将较多的杂质排挤到无定形区,因此PP-g-5.0MAH0.3%-200℃薄膜无定形区的杂质相较纯PP薄膜较少,其电气强度在高温下得到了明显的提升。
充放电效率、放电能量密度是评价电容器性能的关键指标。PP薄膜在室温下具有较高的充放电效率,而在高温高电场下其放电能量效率会急剧下降,接枝MAH后PP-g-5.0MAH0.3%-200℃薄膜在高温下储能特性会有较大的提升。高温高电场下样品充放电效率的提升有助于减少发热问题,避免器件过热损坏,同时可以提升储能密度,使电容器更加小型化、轻量化。本文测试了30、70、120℃下PP薄膜和PP-g-5.0MAH0.3%-200℃薄膜在充放电效率为90%时的储能密度,结果如图14所示。从图14可以看出,在不同温度下,接枝MAH的方法对PP薄膜的储能密度均有一定提升,这归功于接枝MAH后薄膜的漏导损耗降低。同时,介电常数的提升和电气强度的提升也有助于薄膜获得更高的能量密度。
(1)增加MAH接枝单体含量、引发剂质量分数和升高反应温度,均使PP-g-MAH薄膜的充放电效率先升高后降低。其中,单体质量分数为5%,引发剂质量分数为0.3%,反应温度为200℃作为PP-g-MAH薄膜的优选接枝工艺。
(2)在接枝MAH前后PP的晶型和晶面间距不变,但接枝链的干扰使薄膜球晶细化,熔程变短,同时结晶度和熔点有所下降。
(3)接枝MAH后提升了PP薄膜在高温下的介电常数和电气强度,降低了漏导损耗,使其储能特性得到提升。
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2025年第58卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2025.04.001
  • 接收时间:2024-05-27
  • 首发时间:2025-11-07
  • 出版时间:2025-04-20
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  • 收稿日期:2024-05-27
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国家自然科学基金重大研究计划重点支持项目(92166203)
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    1 清华大学 电力系统及大型发电设备安全控制和仿真国家重点实验室,北京 100084
    2 特高压电力技术与新型电工装备基础国家工程研究中心,广东 广州 510080
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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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