Article(id=1210577665812197423, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.08.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1701187200000, receivedDateStr=2023-11-29, revisedDate=1711468800000, revisedDateStr=2024-03-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1766553806975, onlineDateStr=2025-12-24, pubDate=1724083200000, pubDateStr=2024-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766553806975, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766553806975, creator=13701087609, updateTime=1766553806975, updator=13701087609, issue=Issue{id=1210577662121209865, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='8', pageStart='1', pageEnd='147', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766553806095, creator=13701087609, updateTime=1766563971278, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620298043454173, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620298043454174, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=52, endPage=60, ext={EN=ArticleExt(id=1210577666894327872, articleId=1210577665812197423, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Charge transport characteristics of XLPE/SIR composite insulation under different ageing degree, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

Cross-linked polyethylene (XLPE) and silicone rubber (SIR) are commonly used insulation materials for high-voltage direct current cables and reinforced insulation materials for accessories at present. The composite insulation composed of the two will age under long-term thermal stress. To investigate the charge transport characteristics of XLPE/SIR composite insulation with different ageing degrees, XLPE/SIR samples with different ageing degrees were prepared and subjected to simultaneous measurement of space charge and isothermal relaxation current. At the same time, by combining Fourier transform infrared spectroscopy (FTIR) testing and quantum chemical computation (QCC), an energy band model of XLPE/SIR system before and after ageing was constructed, and the charge transport behavior of XLPE/SIR was explored. The results show that negative charges always accumulate at the XLPE/SIR interface, and the amount of charge increases with ageing time. There are always homopolar charges accumulating near the cathode and anode, and the distribution range decreases with ageing time. After ageing, the depth of charge traps in SIR does not change much, while deeper charge traps appear in XLPE. The negative charge accumulation at the interface between the unaged XLPE/SIR is mainly caused by Maxwell-Wagner polarization, while the increase of negative charge accumulation at the interface of the aged samples is mainly related to the introduction of shallow electron traps in SIR and deep electron traps in XLPE.

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交联聚乙烯(XLPE)与硅橡胶(SIR)是目前常用的高压直流电缆本体绝缘与附件增强绝缘材料,二者构成的复合绝缘在长期热应力作用下会发生老化。为探究不同老化程度XLPE/SIR复合绝缘的电荷输运特性,本研究制备了不同老化程度的XLPE/SIR试样,对其进行空间电荷与等温松弛电流联合测量。同时结合傅里叶红外光谱(FTIR)测试与量子化学计算(QCC),构建了老化前后XLPE/SIR体系的能带模型,基于此对XLPE/SIR的电荷输运行为进行探讨。结果表明:XLPE/SIR中间界面始终积聚负电荷,且电荷量随老化时间延长而增多。阴极与阳极附近始终存在同极性电荷积聚,且分布范围随老化时间延长而减小。材料发生老化后,SIR中的电荷陷阱深度变化不大,而XLPE中出现了更深的电荷陷阱。未老化XLPE/SIR中间界面处的负电荷积聚主要由Maxwell-Wagner极化导致,而老化后试样界面负电荷积聚增多主要与SIR中引入了电子浅陷阱以及XLPE中引入了电子深陷阱有关。

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杨兴武(1981-),男(汉族),河南南阳人,教授,主要研究方向为功率变换器高性能控制及新能源并网技术。
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王雅妮(1991-),女(汉族),陕西西安人,副教授,主要研究方向为电工绝缘材料与绝缘技术。

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王雅妮(1991-),女(汉族),陕西西安人,副教授,主要研究方向为电工绝缘材料与绝缘技术。

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王雅妮(1991-),女(汉族),陕西西安人,副教授,主要研究方向为电工绝缘材料与绝缘技术。

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figureFileBig=EDagnVUrl7TqlCDW+rO1Qg==, tableContent=null), ArticleFig(id=1218111691238326356, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577665812197423, language=EN, label=Table 1, caption=Electronic energy level parameters of SIR before and after ageing, figureFileSmall=null, figureFileBig=null, tableContent=
参数未老化老化后
ELUMO-0.23-0.28
EHOMO-6.76-6.80
Ec1.421.38
Ev-7.07-7.01
Ef-2.82-2.81
ϕg8.498.39
χ-1.42-1.38
), ArticleFig(id=1218111691326406741, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577665812197423, language=CN, label=表1, caption=

SIR老化前后的电子能级参数

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参数未老化老化后
ELUMO-0.23-0.28
EHOMO-6.76-6.80
Ec1.421.38
Ev-7.07-7.01
Ef-2.82-2.81
ϕg8.498.39
χ-1.42-1.38
), ArticleFig(id=1218111691414487128, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577665812197423, language=EN, label=Table 2, caption=Electronic energy level parameters of XLPE before and after ageing, figureFileSmall=null, figureFileBig=null, tableContent=
参数未老化XLPE老化后XLPE
ELUMO1.38-0.47
EHOMO-7.42-6.42
Ec1.961.00
Ev-7.60-7.49
Ef-3.02-3.24
ϕg9.568.49
χ-1.96-1.00
), ArticleFig(id=1218111691506761818, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577665812197423, language=CN, label=表2, caption=

XLPE老化前后的电子能级参数

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参数未老化XLPE老化后XLPE
ELUMO1.38-0.47
EHOMO-7.42-6.42
Ec1.961.00
Ev-7.60-7.49
Ef-3.02-3.24
ϕg9.568.49
χ-1.96-1.00
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不同老化程度XLPE/SIR复合绝缘的电荷输运特性
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王雅妮 , 齐寅山 , 王玉宁 , 李煜晨 , 杨兴武 , 刘春
绝缘材料 | 材料研究 2024,57(8): 52-60
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绝缘材料 | 材料研究 2024, 57(8): 52-60
不同老化程度XLPE/SIR复合绝缘的电荷输运特性
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王雅妮, 齐寅山, 王玉宁, 李煜晨, 杨兴武, 刘春
作者信息
  • 上海电力大学 电气工程学院,上海 200090
  • 王雅妮(1991-),女(汉族),陕西西安人,副教授,主要研究方向为电工绝缘材料与绝缘技术。

通讯作者:

杨兴武(1981-),男(汉族),河南南阳人,教授,主要研究方向为功率变换器高性能控制及新能源并网技术。
Charge transport characteristics of XLPE/SIR composite insulation under different ageing degree
Yani WANG, Yinshan QI, Yuning WANG, Yuchen LI, Xingwu YANG, Chun LIU
Affiliations
  • College of Electrical Engineering, Shanghai University of Electric Power, Shanghai 200090, China
出版时间: 2024-08-20 doi: 10.16790/j.cnki.1009-9239.im.2024.08.006
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交联聚乙烯(XLPE)与硅橡胶(SIR)是目前常用的高压直流电缆本体绝缘与附件增强绝缘材料,二者构成的复合绝缘在长期热应力作用下会发生老化。为探究不同老化程度XLPE/SIR复合绝缘的电荷输运特性,本研究制备了不同老化程度的XLPE/SIR试样,对其进行空间电荷与等温松弛电流联合测量。同时结合傅里叶红外光谱(FTIR)测试与量子化学计算(QCC),构建了老化前后XLPE/SIR体系的能带模型,基于此对XLPE/SIR的电荷输运行为进行探讨。结果表明:XLPE/SIR中间界面始终积聚负电荷,且电荷量随老化时间延长而增多。阴极与阳极附近始终存在同极性电荷积聚,且分布范围随老化时间延长而减小。材料发生老化后,SIR中的电荷陷阱深度变化不大,而XLPE中出现了更深的电荷陷阱。未老化XLPE/SIR中间界面处的负电荷积聚主要由Maxwell-Wagner极化导致,而老化后试样界面负电荷积聚增多主要与SIR中引入了电子浅陷阱以及XLPE中引入了电子深陷阱有关。

复合绝缘  /  热老化  /  电荷输运  /  量子化学计算  /  能带模型

Cross-linked polyethylene (XLPE) and silicone rubber (SIR) are commonly used insulation materials for high-voltage direct current cables and reinforced insulation materials for accessories at present. The composite insulation composed of the two will age under long-term thermal stress. To investigate the charge transport characteristics of XLPE/SIR composite insulation with different ageing degrees, XLPE/SIR samples with different ageing degrees were prepared and subjected to simultaneous measurement of space charge and isothermal relaxation current. At the same time, by combining Fourier transform infrared spectroscopy (FTIR) testing and quantum chemical computation (QCC), an energy band model of XLPE/SIR system before and after ageing was constructed, and the charge transport behavior of XLPE/SIR was explored. The results show that negative charges always accumulate at the XLPE/SIR interface, and the amount of charge increases with ageing time. There are always homopolar charges accumulating near the cathode and anode, and the distribution range decreases with ageing time. After ageing, the depth of charge traps in SIR does not change much, while deeper charge traps appear in XLPE. The negative charge accumulation at the interface between the unaged XLPE/SIR is mainly caused by Maxwell-Wagner polarization, while the increase of negative charge accumulation at the interface of the aged samples is mainly related to the introduction of shallow electron traps in SIR and deep electron traps in XLPE.

composite insulation  /  thermal ageing  /  charge transport  /  Quantum chemical computation  /  energy band models
王雅妮, 齐寅山, 王玉宁, 李煜晨, 杨兴武, 刘春. 不同老化程度XLPE/SIR复合绝缘的电荷输运特性. 绝缘材料, 2024 , 57 (8) : 52 -60 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.006
Yani WANG, Yinshan QI, Yuning WANG, Yuchen LI, Xingwu YANG, Chun LIU. Charge transport characteristics of XLPE/SIR composite insulation under different ageing degree[J]. Insulating Materials, 2024 , 57 (8) : 52 -60 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.006
高压直流输电(high voltage direct current transmission,HVDC)由于具有输送容量大、输送距离长、线路损耗小等优势而被广泛应用于远距离输电、海底输电、新能源接入等关键领域,HVDC电缆及其附件作为HVDC输电的重要载体,其绝缘性能的好坏对于直流输电可靠性具有重要影响[1-2]。目前,交联聚乙烯(cross-linked polyethylene,XLPE)和硅橡胶(silicon rubber,SIR)由于具有优异的绝缘性能,分别被广泛用作HVDC电缆的主绝缘和附件增强绝缘[3-5]。然而,在直流电场作用下,XLPE与SIR内部极易积聚空间电荷,造成电场畸变,这一问题一直制约着HVDC电缆电压等级的进一步提升[6-7]。在实际运行工况下,电缆本体绝缘XLPE及附件增强绝缘SIR不仅承受着直流电应力的作用,同时因电缆线芯通流发热,还承受着热应力的作用。已有研究表明,长期热应力影响会促进绝缘材料分子发生氧化反应,导致分子链断裂形成新的基团与自由基,进而向材料内部引入更多电荷陷阱,在一定程度上加剧绝缘材料的空间电荷积聚问题[8-10]
目前,国内外学者针对XLPE热老化过程中的理化特性转变及其对材料绝缘性能的影响做了大量研究[11-17],针对热老化对SIR的理化特性及绝缘性能的影响也有少量报道[18-20]。CHEN X R等[11]研究了热老化对320 kV直流XLPE电缆绝缘空间电荷特性、直流电导率和陷阱分布的影响,发现热老化会使样品中的陷阱密度增加,空间电荷积累增多。WANG S C等[12]研究了热老化对不同交联剂含量XLPE中的空间电荷积累和耗散的影响,发现热老化会同时增加XLPE电荷深陷阱和浅陷阱的密度。严玉婷等[20]针对SIR进行了加速热老化实验,发现在老化初期,SIR分子链段进一步交联,随着老化程度加深,SIR交联结构逐渐被破坏,交联密度减小,对电荷的束缚能力减弱,导致电荷迁移率增大,电气强度减小。然而,目前尚未见热老化对XLPE/SIR复合绝缘电荷输运特性影响的报道。
近年来,基于密度泛函理论(density functional theory,DFT)的量子化学计算(quantum chemical computation,QCC)被广泛应用于绝缘材料领域[21]。通过QCC可得到材料的能带结构、最高占据分子轨道-最低未占有分子轨道(HOMO-LUMO)能级及其分布位置,进一步分析可得到材料的电子/空穴陷阱深度,可基于此对材料的电荷输运行为进行解释。
本文制备了不同老化程度的XLPE/SIR复合绝缘试样,对其进行空间电荷与等温松弛电流联合测量,获得其电荷输运特性。同时对不同老化程度的XLPE与SIR进行傅里叶变换红外光谱(FTIR)测试,基于FTIR测试结果,构建老化前后XLPE与SIR的分子模型,并进行量子化学计算。基于QCC结果构建老化前后XLPE/SIR复合绝缘接触能带模型,在此基础上对不同老化程度的XLPE/SIR复合绝缘的电荷输运特性进行探讨。
XLPE试样选用某商用超净XLPE粒料制备。首先将粒料在10-2 Pa、70℃下干燥24 h,然后使用转矩流变仪在120℃下对粒料进行混炼,之后用平板硫化机将其逐渐加热至180℃,加压至20 MPa,热压15 min使其交联,最后自然冷却至室温,获得厚度为200 μm、边长为10 cm的XLPE试样。
SIR试样选用某商用双组分加成型SIR制备。首先将A、B两种成分以1∶1的质量比混合并充分搅拌,然后用真空烘箱在室温下对其脱气20 min,之后用平板硫化机在20 MPa、140℃下热压15 min,随后升温至180℃并保持2 h,最后自然冷却至室温,得到厚度为200 μm、边长为10 cm的SIR试样。
将制得的XLPE与SIR试样置于恒温鼓风烘箱中,在110℃下分别老化0、6、12 d。将相同老化天数的XLPE和SIR紧密贴合在一起,形成用于进行空间电荷与等温松弛电流测量所需的XLPE/SIR复合绝缘试样。
FTIR测试是进行聚合物官能团定性和结构分析的常用方法。采用美国THERMO FISHER公司生产的Nicolet 6700型红外光谱仪对不同老化时间的XLPE和SIR试样进行FTIR测试,扫描温度为室温,扫描波数范围为500~4 000 cm-1
空间电荷与等温松弛电流联合测量系统如图1所示。测试时,空间电荷测量和电流测量交替进行。测量空间电荷时,单刀双置开关接地,电荷信号经压电传感器和宽频放大器传输到示波器;测量电流时,单刀双置开关接电流表,电流可在无干扰的情况下被完整测量。测试数据最终由计算机记录。
在室温下,对不同老化程度的XLPE/SIR复合绝缘试样进行空间电荷与等温松弛电流联合测量,测试时将XLPE侧接高压,SIR侧接地。首先将试样在10 kV/mm电场下极化600 s,然后提高电场至20 kV/mm后极化1 800 s,最后进行短路1 800 s,记录整个测试过程中的空间电荷与电流信号。
对热老化前后的XLPE与SIR分子进行建模,使用量子化学计算软件基于密度泛函理论对其进行计算,设置B3LYP为交换相关泛函,6-31G(d)为基组。计算后得到XLPE与SIR的最高占据分子轨道、最低未占据分子轨道、费米能级和带隙等参数。
图2为XLPE和SIR的FTIR测试结果。由图2(a)可知,老化前后的XLPE在波数为2 915、2 847、1 463、729 cm-1处均出现了特征吸收峰,分别对应亚甲基的不对称伸缩振动、亚甲基的对称伸缩振动、碳-碳单键的骨架振动、碳-碳单键的伸缩振动。老化后的XLPE试样在1 720 cm-1处出现了明显的特征吸收峰,对应的官能团为羰基,且老化时间越长特征峰强度越大,说明XLPE老化过程中产生羰基,且其含量随老化时间延长而增加。由图2(b)可知,SIR在老化后并未出现新的特征吸收峰,这表明SIR在当前老化条件下没有产生新的官能团。
图3所示为不同老化时间下的XLPE/SIR的空间电荷分布。从图3可以看出,3组试样在极化过程中均存在空间电荷积累,且电荷积累量均随外施电场的升高而增大。中间界面处都存在不同程度的负电荷积累,老化后试样的界面电荷量要明显高于未老化试样,且界面电荷量随着老化程度的增加而增加。除此之外,在靠近电极附近的XLPE和SIR内部存在同极性电荷积累,即在XLPE中靠近阳极侧存在正电荷积累,在SIR中靠近阴极侧存在负电荷积累,同时发现未老化试样中的同极性电荷分布范围最广,随着试样老化程度加重,同极性电荷分布范围逐渐缩小。在去极化过程中,试样内部积聚的电荷表现出不同程度的衰减。
为进一步反映去极化阶段电荷的衰减情况,图4给出了不同老化时间下XLPE/SIR在20 kV/mm极化后短路过程中的空间电荷分布,0 μm处为阴极,400 μm处为阳极,200 μm处为XLPE与SIR界面。由图4可知,在短路0 s时未老化试样界面处积累的电荷量很少,电荷密度峰值仅为1.29 C/m³,老化6 d和12 d试样界面处积累的电荷明显增多,电荷密度峰值分别为2.08 C/m³和3.36 C/m³。当去极化阶段结束(短路1 800 s)时,相较于去极化阶段最初时刻(短路0 s),图4(a)中未老化试样界面处在短路过程中的界面电荷密度峰值下降幅度很小,而图4(b)(c)中老化6 d和12 d试样的界面电荷密度峰值下降幅度较大,其中老化12 d试样的界面电荷密度峰值下降幅度最大,意味着其界面电荷衰减速率最快。
基于联合测量记录的电流值得到不同老化时间的XLPE/SIR在10 kV/mm与20 kV/mm下的稳态电流密度,并进一步计算得到相应的复合电导率,具体结果如图5所示。由图5可知,未老化和老化6 d试样的复合电导率相差不大,而老化12 d试样的复合电导率明显增大。
SIR分子建模选择甲基乙烯基硅橡胶。未老化SIR分子模型由交替排列的Si原子和O原子、甲基(-CH3),以及分子链两端两个乙烯基(-CH=CH2)组成,分子式为C32H84Si12O10。通过FTIR测试发现,老化6 d和12 d的SIR并未产生新的官能团,意味着SIR老化并不严重,同时有学者研究发现SIR在老化初期会发生交联反应[20]。因此,本研究将老化后的SIR分子设置为侧链上甲基被氧化并与相邻主链发生交联反应,交联点设置为两个,如图6所示。
经过量子化学计算得到老化前后SIR分子的电子能级分布,如图7所示。由图7可知,未老化SIR分子的LUMO能级ELUMO为-0.23 eV,HOMO能级EHOMO为-6.76eV,导带底部能级Ec为1.42 eV,价带顶部能级Ev为-7.07 eV。老化后SIR分子的ELUMO为-0.28 eV,EHOMO为-6.80 eV,Ec为1.38 eV,Ev=-7.01 eV。计算费米能级Ef、带隙ϕg、电子亲合能χ由式(1)~(3)确定。具体计算结果如表1所示。
Ef=Ec+Ev2
ϕg=Ec-Ev
χ=VL-Ec
式(3)中,EVL为真空能级,取值0 eV。
图7可知,未老化SIR的LUMO能级和导带底部能级之间存在离散的局域态能级,这些能级和LUMO能级是电子陷阱,深度为0.45~1.65 eV;HOMO能级和价带顶部之间也存在离散的局域态能级,这些能级和HOMO能级是空穴陷阱,深度为0.11~0.43 eV。上述结果表明,未老化SIR分子的电子陷阱主要以深陷阱为主,空穴陷阱以浅陷阱为主,这意味着SIR中的正电荷更容易参与电荷传导,而由于电子深陷阱的作用负电荷在SIR中移动更为困难。老化后SIR的电子陷阱深度为0.13~1.66 eV,空穴陷阱的深度为0.21~0.52 eV。由此可见,老化后的SIR引入了更深的空穴陷阱和更浅的电子陷阱,但总体而言电荷陷阱深度变化很小。此外,未老化SIR分子的LUMO和HOMO主要分布在链两端的乙烯基及其相邻基团附近,而老化后SIR分子的LUMO和HOMO分布更集中于链端的乙烯基处。因此认为碳碳双键是SIR分子形成电子陷阱和空穴陷阱的化学位置。
未老化的XLPE分子模型由3个-[CH2-CH2]n-长链和链间3个交联点组成。基于FTIR测试结果,老化后的XLPE分子模型在未老化XLPE分子的基础上,设置侧链被氧化形成3个羰基,如图8所示。
通过量子化学计算得到老化前后XLPE分子电子能级分布如图9所示,具体参数和计算结果如表2所示。
未老化XLPE的电子陷阱深度为0.17~0.58 eV,空穴陷阱深度为0.18 eV,可见其电子陷阱和空穴陷阱都为浅陷阱。老化后XLPE的电子陷阱深度为1.23~1.47 eV,空穴陷阱深度为0.95~1.09 eV,表明老化后XLPE分子引入了更深的电子陷阱和空穴陷阱。此外,由图9可知,未老化XLPE分子的LUMO主要分布在交联点附近,而HOMO则沿分子链分布,因此推测分子链间形成新的化学键交联会形成电子浅陷阱,而链间相互作用会形成空穴浅陷阱。老化后XLPE分子的LUMO和HOMO分布在羰基附近且分布更为集中,因此可认为碳氧双键是形成深陷阱的主要原因。
本节基于上文QCC结果构建了老化前后XLPE/SIR与Al和SC电极在20 kV/mm电场下的能带模型,如图10所示。由图10(a)可知,SIR的电子陷阱主要为深陷阱(0.45~1.65 eV),XLPE中空穴陷阱主要为浅陷阱(0.18 eV),这意味着空穴在XLPE中的迁移相较于电子在SIR中的迁移更为容易。这解释了为什么在未老化XLPE/SIR中,XLPE靠近阳极时附近积累了大量分布范围较广的正电荷,而SIR靠近阴极侧时尽管也有负电荷积累,但分布范围较窄。此时XLPE/SIR中间界面电荷的形成主要受Maxwell-Wagner极化影响[23-25]。Maxwell-Wagner界面极化描述了直流电场作用下,双层介质界面电荷的极性和密度受两种介质介电常数和电导率的作用。图11为XLPE/SIR双层介质的Maxwell-Wagner极化示意图,左侧为SIR,右侧为XLPE,界面电荷的极性和密度如式(4)计算可得。
ψ(t)=εSσX-εXσSσXdS+σSdXV01-e-t/ττ=εSdX+εXdSσSdX+σXdS
式(4)中:V0为外加电压;Ψ为界面处的电荷密度;dXdS分别为XLPE和SIR的厚度;εXεS分别为XLPE和SIR的介电常数;σXσS分别为XLPE和SIR的电导率。界面电荷的极性由XLPE与SIR的介电常数和电导率决定,本文中,εX取值为2.3,εS为2.7,电导率取电场强度为20 kV/mm下的计算结果,得到σX为1.7×10-15 S/m,σS为1.26×10-14 S/m。经计算可得,XLPE/SIR界面在极化1 800 s时的界面电荷为-1.16 C/m³,这与空间电荷的测量结果接近。
图10(b)为老化后XLPE/SIR的能带模型,由前文QCC结果可知,老化后XLPE中的空穴陷阱深度有了显著增加,意味着空穴向XLPE内部的迁移变得困难,因此图3中观察到老化后试样的阳极附近空穴分布范围有所减小。与此同时,老化后的SIR中引入了电子浅陷阱,这有助于电子在SIR内部的迁移,降低了注入电子迁移至中间界面的难度。同时,老化后的XLPE中电子陷阱的深度显著增加,这对电子的输运产生了两方面的影响:一方面,此时XLPE中电子陷阱能级与SIR中电子陷阱能级的差距缩小,使界面对电子由SIR向XLPE中转移的阻碍作用减弱,可能导致SIR中迁移至界面的电子更易进入XLPE中;另一方面,进入XLPE中的电子容易被新产生的深陷阱捕获而难以脱陷,从而在界面处形成负电荷积聚,以上两方面因素共同导致XLPE/SIR界面处积聚的负电荷有所增加,因此图3中观察到老化6 d和老化12 d试样界面处的负电荷量比未老化试样更大。
此外,由QCC结果可知,XLPE中引入的电子深陷阱主要分布在羰基附近,而由FTIR可知,老化时间越长,XLPE中羰基含量越多,因此可以推测,老化12 d XLPE中的电子深陷阱比老化6 d中的多,老化12 d的XLPE/SIR界面处积聚的负电荷量更大,这与图3中观察到的现象一致。
基于前文2.3节计算得到的XLPE/SIR复合电导率可以发现,未老化试样和老化6 d试样的电导率相对较小,而老化12 d试样的复合电导率显著增大。推测这是因为老化12 d的SIR试样引入的电子浅陷阱降低了XLPE/SIR的界面势垒,注入电子更容易穿越中间界面,从而在宏观上表现出更高的复合电导率。
本文对不同老化程度的XLPE/SIR进行了空间电荷和松弛电流的联合测试,通过量子化学计算得到老化前后XLPE与SIR的能带结构,并基于此构建了老化前后XLPE/SIR体系的能带模型,在此基础上讨论了不同老化程度XLPE/SIR的电荷输运特性。主要结论如下:
(1)在本文测试条件下,XLPE/SIR的中间界面处始终存在负电荷积聚,且电荷量随老化时间延长而逐渐增多。阴极与阳极附近始终存在同极性电荷积聚,且分布范围随老化时间延长逐渐减小。
(2)当材料发生老化后,SIR中的电子及空穴陷阱深度变化不大,而XLPE中引入了更深的空穴陷阱和电子陷阱。碳碳双键是SIR分子形成电子陷阱和空穴陷阱的主要化学位置,而老化过程中引入的碳氧双键是XLPE分子形成深陷阱的主要化学位置。
(3)未老化XLPE/SIR中间界面处的负电荷积聚主要由Maxwell-Wagner极化导致,而老化后试样界面负电荷积聚增多主要与SIR中的电子浅陷阱以及XLPE中的电子深陷阱有关。
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doi: 10.16790/j.cnki.1009-9239.im.2024.08.006
  • 接收时间:2023-11-29
  • 首发时间:2025-12-24
  • 出版时间:2024-08-20
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  • 收稿日期:2023-11-29
  • 修回日期:2024-03-27
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国家自然科学基金资助项目(52207025)
作者信息
    上海电力大学 电气工程学院,上海 200090

通讯作者:

杨兴武(1981-),男(汉族),河南南阳人,教授,主要研究方向为功率变换器高性能控制及新能源并网技术。
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2种不同金属材料的力学参数

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种数
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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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