Article(id=1319973063114994457, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973019079000285, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230807, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1697731200000, receivedDateStr=2023-10-20, revisedDate=1699632000000, revisedDateStr=2023-11-11, acceptedDate=null, acceptedDateStr=null, onlineDate=1792635702160, onlineDateStr=2026-10-22, pubDate=1713542400000, pubDateStr=2024-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792635702160, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792635702160, creator=13701087609, updateTime=1792635702160, updator=13701087609, issue=Issue{id=1319973019079000285, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='4', pageStart='1171', pageEnd='1476', issueExtLink='null', onlineDate='null', pubDate='1713542400000', pubDateStr='2024-04-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792635691661, creator='13701087609', updateTime=1792641833008, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319998777822396474, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973019079000285, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319998777822396475, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973019079000285, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1355, endPage=1364, ext={EN=ArticleExt(id=1319973063337292570, articleId=1319973063114994457, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Effect of Rare-Earth Ce4+ Doping on Structure and Energy Storage Properties of BCT-BZNT Ceramics, columnId=1321894869182828764, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on Dielectric Energy Storage Materials—Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Dielectric ceramic capacitors are widely used in the field of high energy pulse because of their high power density, ultra-fast charge-discharge speed and good stability. However, compared with other capacitors, the low recoverable energy storage density (Wrec) affects its development in the field of energy storage. The typical ferroelectric BaTiO3 (BT) with good dielectric and insulation properties is restricted in the development of energy storage field due to the low breakdown strength and large residual polarization. It is indicated that the combination of multi-component solid solution and ion doping induces the polar nanoregions (PNRs) and the transformation of BaTiO3 ceramics from ferroelectrics to relaxation ferroelectrics due to the reduction of Pr and the improvement of energy storage performance. In addition, obtaining simutanously the high Wrec and energy storage efficiency (η) is a challenge. In this paper, (1-x){0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3}-xCeO2 (abbreviated as BCT-BZNT-xCe, x = 0, 0.010, 0.015, 0.020, 0.025) ceramics were prepared by a conventional solid-state reaction method. The structure and energy storage properties of the ceramics with differet Ce+4 doping contents were investigated.

Methods

High purity BaCO3, CaCO3, TiO2, Bi2O3, ZnO, Nb2O5, Ta2O5 and CeO2 were used as raw materials. The raw materials were weighted and mixed according to stoichometric ratio. The mixed raw materials were firstly ground in a ball mill, and then dried and calcined in air at 900 ℃ for 4 h. Afterwards, the calcined powder was further ground, dried and pressed into discs with 10 mm in diameter. The discs were sintered at 1 200 ℃ for 2 h to obtain the ceramic samples. The ceramic samples were thinned and polished to 0.05 mm, and sputtered with Au electrodes for the energy storage properties.

The phase structure of the samples was analyzed by a model SmartLab X-ray diffractometer (XRD, Rigaku Co., Japan) in the range of 20°-80°. The Raman spectra of the samples were analyzed by a model Renishaw inVia Laser Confocal Raman Microspectroscopy (Renishaw Co., UK). The microstructure and elemental analysis (EDS) were determined by a model Merlin Compact Field Emission Scanning Electron Microscope (FE-SEM, Zeiss Co., Germany). The dielectric properties were analyzed by a model HCT1821 High-Low Temperature Dielectric Testing System (Tongguo Technology Co., China). The unipolar P-E curves were measured by a model TF2000 ferroelectric tester (aixACCT Co., Germany) to investigate the ferroelectric performance. The pulsed performance of the samples was examined by a model CFD-003 plus high-voltage charge-discharge measuring instrument (Tongguo Technology Co., China).

Results and discussion

All the samples are a multiphase structure with a tetragonal phase BaTiO3 (BT) as a main phase and an orthorhombic phase CaTiO3 (CT) as a second phase. The excessive Ce4+ causes the appearance of the diffraction peak at 28.5° of 2θwhen x=0.025. Also, the diffraction peaks move to a low angle from the magnified (200). The minimum average grain size (AGS) of both coarse and fine grains is obtained when x=0.02. The BCT-BZNT-0.02Ce ceramic obtains a high breakdown strength. The EDS analysis indicates that the coarse grains contain more Ba, while the fine grains contain more Ca.

The dielectric permittivity of samples decreases with increasing the frequency. A large valence difference betweent the A-site and B-site ions induces PNRs, having a typical relaxation behavior. Besides, the diffuseness parameter (γ) as x=0.02 is the maximum value (i.e., 1.917), which is similar to that of the ideal relaxation ferroelectric. The unipolar P-E curves of all the samples are slender and exhibit good relaxation characteristics. The breakdown strength and maximum polarization strength (Pmax) increase with the increase of Ce content, and reach the maximum values as x=0.02. A high Wrec of 5.49 J/cm3 and a high η of 89.4% are obtained at 600 kV/cm in BCT-BZNT-0.02Ce ceramic, which is attributed to the increasse of breakdown strength and Pmax. Moreover, the superior charge-discharge performance is obtained in BCT-BZNT-0.02Ce ceramic. The ultra-high current density (i.e., CD=1 757.07 A/cm2) and power density (i.e., PD=237.20 MW/cm3) are obtained at 270 kV/cm. Besides, a discharge energy density (WD) of 1.55 J/cm3 and an ultra-fast charge-discharge speed (t0.9) of 23.8 ns are obtained simultaneously. The WD is smaller than the Wrec due to the unremarkable contribution of domain wall motion at higher frequencies from the perspective of dynamics. The BCT-BZNT-0.02Ce ceramic with ultra-high Wrec (5.49 J/cm3), η (89.4%), CD (1 757.07 A/cm2), PD (237.20 MW/cm3) and ultra-fast t0.9 (23.8 ns) can be used in pulsed capacitors.

Conclusions

The grains size of BCT-BZNT-xCe ceramics was refined via the introduction of rare-earth element Ce. The γ of the BCT-BZNT-xCe ceramics was improved, and the BCT-BZNT-0.02Ce ceramic showed a typical relaxation ferroelectric performance (i.e., γ =1.917). The superior energy storage performance (i.e., Wrec=5.49 J/cm3, η=89.4%) of BCT-BZNT-0.02Ce ceramic was achieved at 600 kV/cm at room temperature due to the breakdown strength and Pmax. Also, the BCT-BZNT-0.02Ce ceramic exhibited a superior charge-discharge performance (i.e., CD=1 757.07 A/cm2, PD=237.20 MW/cm3, and t0.9=23.8 ns). The BCT-BZNT-0.02Ce ceramic with the superior comprehensive properties could have a great application prospect in pulsed capacitors.

, authors=Xiang REN, Xiaoyang LI, Zhongqiu GUO, Peng LI, Jigong HAO, Wei LI, authorsList=Xiang REN, Xiaoyang LI, Zhongqiu GUO, Peng LI, Jigong HAO, Wei LI, authorCompany=null, correspAuthors=Wei LI, authorNote=

REN Xiang (1997-), female, Master candidate. E-mail:

, correspAuthorsNote=
LI Wei (1981-), male, Ph.D., Professor. E-mail:
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电介质电容器由于具有超高的功率密度、超快的充放电速率,被广泛应用于脉冲功率电子设备。利用传统固相反应法合成了(1-x){0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3}-xCeO2陶瓷(BCT-BZNT-xCe,x=0,0.010,0.015,0.020,0.025)。研究了稀土Ce对0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3陶瓷相结构、微观形貌、介电和储能性能的影响。结果表明:随着Ce含量的增加,陶瓷的晶粒得到细化,介电常数和介电损耗减小。此外,Ce的引入显著增强了样品的饱和极化和击穿电场强度。当x=0.02时,陶瓷在600 kV/cm的电场强度下获得了极高的可回收储能密度5.49 J/cm3和储能效率89.4%,同时具有超快的充放电速率(t0.9=23.8 ns)。样品BCT-BZNT-0.02Ce呈现出优异的综合性能,使其在脉冲功率领域具有很好的发展潜力。

, authors=任香, 李筱瑒, 郭中秋, 李朋, 郝继功, 李伟, authorsList=任香, 李筱瑒, 郭中秋, 李朋, 郝继功, 李伟, authorCompany=null, correspAuthors=李伟, authorNote=

任香(1997—),女,硕士研究生。

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李伟(1981—),男,博士,教授。
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稀土Ce4+掺杂对BCT-BZNT陶瓷结构和储能性能的影响
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任香 , 李筱瑒 , 郭中秋 , 李朋 , 郝继功 , 李伟
硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1355-1364
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硅酸盐学报 |电介质储能材料专刊—研究论文 2024 , 52 (4) : 1355 -1364
稀土Ce4+掺杂对BCT-BZNT陶瓷结构和储能性能的影响
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任香 , 李筱瑒, 郭中秋, 李朋, 郝继功, 李伟
作者信息
  • 聊城大学材料科学与工程学院,山东省教育厅敏感材料与器件实验室,山东 聊城 252059
通讯作者:
李伟(1981—),男,博士,教授。
作者简介:

任香(1997—),女,硕士研究生。

Effect of Rare-Earth Ce4+ Doping on Structure and Energy Storage Properties of BCT-BZNT Ceramics
Xiang REN , Xiaoyang LI, Zhongqiu GUO, Peng LI, Jigong HAO, Wei LI
Affiliations
  • School of Materials Science and Engineering, Laboratory of Sensitive Materials and Devices Shandong Department of Education, Liaocheng University, Liaocheng 252059, Shandong, China
  • Corresponding Author:
    LI Wei (1981-), male, Ph.D., Professor. E-mail:

    REN Xiang (1997-), female, Master candidate. E-mail:

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230807
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电介质电容器由于具有超高的功率密度、超快的充放电速率,被广泛应用于脉冲功率电子设备。利用传统固相反应法合成了(1-x){0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3}-xCeO2陶瓷(BCT-BZNT-xCe,x=0,0.010,0.015,0.020,0.025)。研究了稀土Ce对0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3陶瓷相结构、微观形貌、介电和储能性能的影响。结果表明:随着Ce含量的增加,陶瓷的晶粒得到细化,介电常数和介电损耗减小。此外,Ce的引入显著增强了样品的饱和极化和击穿电场强度。当x=0.02时,陶瓷在600 kV/cm的电场强度下获得了极高的可回收储能密度5.49 J/cm3和储能效率89.4%,同时具有超快的充放电速率(t0.9=23.8 ns)。样品BCT-BZNT-0.02Ce呈现出优异的综合性能,使其在脉冲功率领域具有很好的发展潜力。

钛酸钡  /  弛豫铁电体  /  储能性能  /  充放电速率
Introduction

Dielectric ceramic capacitors are widely used in the field of high energy pulse because of their high power density, ultra-fast charge-discharge speed and good stability. However, compared with other capacitors, the low recoverable energy storage density (Wrec) affects its development in the field of energy storage. The typical ferroelectric BaTiO3 (BT) with good dielectric and insulation properties is restricted in the development of energy storage field due to the low breakdown strength and large residual polarization. It is indicated that the combination of multi-component solid solution and ion doping induces the polar nanoregions (PNRs) and the transformation of BaTiO3 ceramics from ferroelectrics to relaxation ferroelectrics due to the reduction of Pr and the improvement of energy storage performance. In addition, obtaining simutanously the high Wrec and energy storage efficiency (η) is a challenge. In this paper, (1-x){0.88(Ba0.6Ca0.4)TiO3-0.12Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3}-xCeO2 (abbreviated as BCT-BZNT-xCe, x = 0, 0.010, 0.015, 0.020, 0.025) ceramics were prepared by a conventional solid-state reaction method. The structure and energy storage properties of the ceramics with differet Ce+4 doping contents were investigated.

Methods

High purity BaCO3, CaCO3, TiO2, Bi2O3, ZnO, Nb2O5, Ta2O5 and CeO2 were used as raw materials. The raw materials were weighted and mixed according to stoichometric ratio. The mixed raw materials were firstly ground in a ball mill, and then dried and calcined in air at 900 ℃ for 4 h. Afterwards, the calcined powder was further ground, dried and pressed into discs with 10 mm in diameter. The discs were sintered at 1 200 ℃ for 2 h to obtain the ceramic samples. The ceramic samples were thinned and polished to 0.05 mm, and sputtered with Au electrodes for the energy storage properties.

The phase structure of the samples was analyzed by a model SmartLab X-ray diffractometer (XRD, Rigaku Co., Japan) in the range of 20°-80°. The Raman spectra of the samples were analyzed by a model Renishaw inVia Laser Confocal Raman Microspectroscopy (Renishaw Co., UK). The microstructure and elemental analysis (EDS) were determined by a model Merlin Compact Field Emission Scanning Electron Microscope (FE-SEM, Zeiss Co., Germany). The dielectric properties were analyzed by a model HCT1821 High-Low Temperature Dielectric Testing System (Tongguo Technology Co., China). The unipolar P-E curves were measured by a model TF2000 ferroelectric tester (aixACCT Co., Germany) to investigate the ferroelectric performance. The pulsed performance of the samples was examined by a model CFD-003 plus high-voltage charge-discharge measuring instrument (Tongguo Technology Co., China).

Results and discussion

All the samples are a multiphase structure with a tetragonal phase BaTiO3 (BT) as a main phase and an orthorhombic phase CaTiO3 (CT) as a second phase. The excessive Ce4+ causes the appearance of the diffraction peak at 28.5° of 2θwhen x=0.025. Also, the diffraction peaks move to a low angle from the magnified (200). The minimum average grain size (AGS) of both coarse and fine grains is obtained when x=0.02. The BCT-BZNT-0.02Ce ceramic obtains a high breakdown strength. The EDS analysis indicates that the coarse grains contain more Ba, while the fine grains contain more Ca.

The dielectric permittivity of samples decreases with increasing the frequency. A large valence difference betweent the A-site and B-site ions induces PNRs, having a typical relaxation behavior. Besides, the diffuseness parameter (γ) as x=0.02 is the maximum value (i.e., 1.917), which is similar to that of the ideal relaxation ferroelectric. The unipolar P-E curves of all the samples are slender and exhibit good relaxation characteristics. The breakdown strength and maximum polarization strength (Pmax) increase with the increase of Ce content, and reach the maximum values as x=0.02. A high Wrec of 5.49 J/cm3 and a high η of 89.4% are obtained at 600 kV/cm in BCT-BZNT-0.02Ce ceramic, which is attributed to the increasse of breakdown strength and Pmax. Moreover, the superior charge-discharge performance is obtained in BCT-BZNT-0.02Ce ceramic. The ultra-high current density (i.e., CD=1 757.07 A/cm2) and power density (i.e., PD=237.20 MW/cm3) are obtained at 270 kV/cm. Besides, a discharge energy density (WD) of 1.55 J/cm3 and an ultra-fast charge-discharge speed (t0.9) of 23.8 ns are obtained simultaneously. The WD is smaller than the Wrec due to the unremarkable contribution of domain wall motion at higher frequencies from the perspective of dynamics. The BCT-BZNT-0.02Ce ceramic with ultra-high Wrec (5.49 J/cm3), η (89.4%), CD (1 757.07 A/cm2), PD (237.20 MW/cm3) and ultra-fast t0.9 (23.8 ns) can be used in pulsed capacitors.

Conclusions

The grains size of BCT-BZNT-xCe ceramics was refined via the introduction of rare-earth element Ce. The γ of the BCT-BZNT-xCe ceramics was improved, and the BCT-BZNT-0.02Ce ceramic showed a typical relaxation ferroelectric performance (i.e., γ =1.917). The superior energy storage performance (i.e., Wrec=5.49 J/cm3, η=89.4%) of BCT-BZNT-0.02Ce ceramic was achieved at 600 kV/cm at room temperature due to the breakdown strength and Pmax. Also, the BCT-BZNT-0.02Ce ceramic exhibited a superior charge-discharge performance (i.e., CD=1 757.07 A/cm2, PD=237.20 MW/cm3, and t0.9=23.8 ns). The BCT-BZNT-0.02Ce ceramic with the superior comprehensive properties could have a great application prospect in pulsed capacitors.

barium titanate  /  relaxor ferroelectrics  /  energy storage performance  /  charge-discharge speed
任香, 李筱瑒, 郭中秋, 李朋, 郝继功, 李伟. 稀土Ce4+掺杂对BCT-BZNT陶瓷结构和储能性能的影响. 硅酸盐学报, 2024 , 52 (4) : 1355 -1364 . DOI: 10.14062/j.issn.0454-5648.20230807
Xiang REN, Xiaoyang LI, Zhongqiu GUO, Peng LI, Jigong HAO, Wei LI. Effect of Rare-Earth Ce4+ Doping on Structure and Energy Storage Properties of BCT-BZNT Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1355 -1364 . DOI: 10.14062/j.issn.0454-5648.20230807
  • 国家自然科学基金(52102132)
  • 山东省自然科学基金(ZR2020ME031; ZR2020ME033)
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doi: 10.14062/j.issn.0454-5648.20230807
  • 接收时间:2023-10-20
  • 首发时间:2026-10-22
  • 出版时间:2024-04-20
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  • 收稿日期:2023-10-20
  • 修回日期:2023-11-11
基金
国家自然科学基金(52102132)
山东省自然科学基金(ZR2020ME031; ZR2020ME033)
作者信息
    聊城大学材料科学与工程学院,山东省教育厅敏感材料与器件实验室,山东 聊城 252059

通讯作者:

李伟(1981—),男,博士,教授。
参考文献
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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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