Article(id=1319973041107485054, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973019079000285, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230739, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1695571200000, receivedDateStr=2023-09-25, revisedDate=1696608000000, revisedDateStr=2023-10-07, acceptedDate=null, acceptedDateStr=null, onlineDate=1792635696912, onlineDateStr=2026-10-22, pubDate=1713542400000, pubDateStr=2024-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792635696912, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792635696912, creator=13701087609, updateTime=1792635696912, 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=1229, endPage=1239, ext={EN=ArticleExt(id=1319973041325588863, articleId=1319973041107485054, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Effect of Bi2O3 on Dielectric Energy Storage Performance of K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2 Glass-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

With the development of power electronic systems, energy storage capacitors have the advantages of large discharge power, fast charging and discharging speed and stable performance, and play an important role in power systems, electronic devices, pulse power supplies, etc.. They are widely used in civilian and military fields. Compared with fuel cells, the energy storage capacitors do not need to convert the Gibbs free energy of the chemical energy of the fuel into electrical energy through electrochemical reactions, but store the charge by pressurizing between the two plates of the capacitor with higher safety and reliability as well as environmentally friendness. The existing pulsed dielectric materials are mainly divided into ceramics, glass ceramics, thin films and other composite materials. Glass ceramics have energy storage advantages, compared with other materials. Increasing the dielectric constant of dielectric materials plays a crucial role in increasing the energy density.

Methods

A glass with the composition of 13K2O-21SrO-32Nb2O5-5B2O3-4Al2O3-25SiO2-xBi2O3 (x=0.0%, 1.0%, 2.0%, and 4.0%, in mole) was produced by a conventional melt annealing process. First, 40 g of raw materials were weighed and ground in a polypropylene ball mill in ethanol for 12 h. The resulting mixture was dried at 100 ℃ and subsequently melted in a corundum crucible in a resistance furnace at 1 500 ℃ for 2 h. The molten liquid was pressed into a sheet on a preheated copper plate and then annealed at 500 ℃ for 6 h to eliminate residual internal stresses. Finally, a niobate glass was obtained. The glass slices were crystallized at 850 ℃ and 950 ℃ for 2 h to obtain glass ceramics. The glass ceramic samples were ground, polished, and plated with electrodes for the structural and performance tests.

Results and discussion

The effect of Bi2O3 concentrations (x=0.0%, 1.0%, 2.0%, and 4.0% in mole) on the phase evolution, microstructure, dielectric and energy storage properties of K2O-SrO-Nb2O5-B2O3-Al2O3-SiO2 glass ceramics was investigated by a controlled crystallization process. Based on the XRD analysis, KSr2Nb5O15 is a main precipitated crystalline phase, and the crystallization promotes due to the addition of bismuth oxide. The A-site ions are adjusted by Bi3+ with a smaller radius (i.e., 1.03 Å) into the crystal lattice instead of Sr2+ with a larger radius (i.e., 1.18 Å), thus reducing the unit cell volume and increasing the lattice distortion. From the Raman spectra, the change of A-site occupancy leads to the distortion of the structure and enhances the spontaneous polarization. The microstructure shows that the grains are dense and evenly distributed, and the grain size is fine. The dielectric temperature spectroscopy indicates that the relaxation characteristics correspond to the polar nanoregion of the microstructure, and the DC breakdown strength firstly increases and then decreases, which is consistent with the change of the dielectric constant. The polarized electric field curve is slender with a large spontaneous polarization and a small residual polarization, improving the energy storage efficiency. The charge-discharge curve shows that the energy density firstly increases and then decreases with the addition of bismuth oxide, and the glass-ceramic sample B2-9 obtains the maximum energy density, discharge power density and fast discharge time, having a great application prospect in the field of dielectric energy storage.

Conclusions

Strontium niobate potassium glass ceramics were prepared by a conventional melting method and a controlled crystallization technology. At a crystallization temperature of 950 ℃, the unit cell volume of the crystalline phase decreased from 611.83 Å3 to 610.19 Å3 with the increase of Bi2O3 doping content. The grain size of the microstructure firstly decreased and then increased, and the optimal grain size of glass ceramic sample B2-9 was 57.72 nm. The dielectric and energy storage properties also firstly increased and then decreased, and the maximum dielectric constant of glass-ceramic sample B2-9 was 342 times greater than that of glass-ceramic sample B2-8, which was 1.9 times greater than that of glass-ceramic sample B2-8. According to the P-E curve, the glass ceramic sample B2-9 had the optimum performance (i.e., Pmax=9.33 μC/cm2, Pr=0.73 μC/cm2, Wrec=1.27 J/cm3, Wtotal=1.55 J/cm3, η=82% at 350 kV/cm). The energy density of the glass ceramic sample B2-9 was 1.33 J/cm3 at 400 kV/cm, the maximum discharge power density was 124.13 MW/cm3, and the fastest discharge time was 22 ns. The breakdown strength firstly increased and then decreased, which were 742, 886, 923 kV/cm and 622 kV/cm, respectively. Glass-ceramic materials could have great application prospects in the field of dielectric energy storage.

, authors=Xile GENG, Xianjie FENG, Fei SHANG, Guohua CHEN, authorsList=Xile GENG, Xianjie FENG, Fei SHANG, Guohua CHEN, authorCompany=null, correspAuthors=Fei SHANG, Guohua CHEN, authorNote=

GENG Xile (1998-), female, Master candidate. E-mail:

, correspAuthorsNote=
SHANG Fei (1981-), male, Ph.D., Associate Professor. E-mail: ;
CHEN Guohua (1962-), male, Ph.D., Professor.
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随着电力电子系统的不断发展,高功率脉冲电容器的需求增多。电介质电容器因具有放电功率大、充放电速度快及性能稳定等优点,在电力系统、电子器件、脉冲电源等方面发挥着重要作用,广泛应用于民用领域及军事领域。通过熔融压延制备玻璃基体,采用可控结晶工艺研究了不同含量的Bi2O3(x=0.0%、1.0%、2.0%、4.0%,摩尔分数)对K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2玻璃陶瓷物相演化、微观结构、介电和储能性能的影响。在该玻璃陶瓷中,KSr2Nb5O15为主要析出晶相,当Bi2O3的加入量为x=2.0%(摩尔分数)时,热处理温度为950 ℃时,玻璃陶瓷样品的储能密度最大可达到1.27 J/cm3,室温下介电常数可达342,是热处理温度为850 ℃时样品介电常数的1.9倍。在脉冲RLC电路测试中,当Bi2O3的加入量为x=2.0%(摩尔分数)且施加电场强度为400 kV/cm时,实测储能密度随着热处理温度的升高从1.02 J/cm3增加到1.33 J/cm3。

, authors=耿喜乐, 冯先杰, 尚飞, 陈国华, authorsList=耿喜乐, 冯先杰, 尚飞, 陈国华, authorCompany=null, correspAuthors=尚飞, 陈国华, authorNote=

耿喜乐(1998—),女,硕士研究生。

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尚飞(1981—),男,博士,副教授;
陈国华(1964—),男,博士,教授。
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Bi2O3对K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2玻璃陶瓷介电储能性能的影响
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耿喜乐 , 冯先杰 , 尚飞 , 陈国华
硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1229-1239
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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) : 1229 -1239
Bi2O3对K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2玻璃陶瓷介电储能性能的影响
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耿喜乐 , 冯先杰, 尚飞 , 陈国华
作者信息
  • 桂林电子科技大学电子信息材料与器件教育部工程中心,材料科学与工程学院,广西 桂林 541004
通讯作者:
尚飞(1981—),男,博士,副教授;
陈国华(1964—),男,博士,教授。
作者简介:

耿喜乐(1998—),女,硕士研究生。

Effect of Bi2O3 on Dielectric Energy Storage Performance of K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2 Glass-Ceramics
Xile GENG , Xianjie FENG, Fei SHANG , Guohua CHEN
Affiliations
  • School of Materials Science and Engineering, Engineering Center of Electronic Information Materials and Devices, Ministry of Education, Guilin University of Electronic Technology, Guilin, 541004, Guangxi, China
  • Corresponding Author:
    SHANG Fei (1981-), male, Ph.D., Associate Professor. E-mail: ;
    CHEN Guohua (1962-), male, Ph.D., Professor.

    GENG Xile (1998-), female, Master candidate. E-mail:

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230739
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随着电力电子系统的不断发展,高功率脉冲电容器的需求增多。电介质电容器因具有放电功率大、充放电速度快及性能稳定等优点,在电力系统、电子器件、脉冲电源等方面发挥着重要作用,广泛应用于民用领域及军事领域。通过熔融压延制备玻璃基体,采用可控结晶工艺研究了不同含量的Bi2O3(x=0.0%、1.0%、2.0%、4.0%,摩尔分数)对K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2玻璃陶瓷物相演化、微观结构、介电和储能性能的影响。在该玻璃陶瓷中,KSr2Nb5O15为主要析出晶相,当Bi2O3的加入量为x=2.0%(摩尔分数)时,热处理温度为950 ℃时,玻璃陶瓷样品的储能密度最大可达到1.27 J/cm3,室温下介电常数可达342,是热处理温度为850 ℃时样品介电常数的1.9倍。在脉冲RLC电路测试中,当Bi2O3的加入量为x=2.0%(摩尔分数)且施加电场强度为400 kV/cm时,实测储能密度随着热处理温度的升高从1.02 J/cm3增加到1.33 J/cm3。

玻璃陶瓷  /  相结构  /  介电性能  /  储能性能
Introduction

With the development of power electronic systems, energy storage capacitors have the advantages of large discharge power, fast charging and discharging speed and stable performance, and play an important role in power systems, electronic devices, pulse power supplies, etc.. They are widely used in civilian and military fields. Compared with fuel cells, the energy storage capacitors do not need to convert the Gibbs free energy of the chemical energy of the fuel into electrical energy through electrochemical reactions, but store the charge by pressurizing between the two plates of the capacitor with higher safety and reliability as well as environmentally friendness. The existing pulsed dielectric materials are mainly divided into ceramics, glass ceramics, thin films and other composite materials. Glass ceramics have energy storage advantages, compared with other materials. Increasing the dielectric constant of dielectric materials plays a crucial role in increasing the energy density.

Methods

A glass with the composition of 13K2O-21SrO-32Nb2O5-5B2O3-4Al2O3-25SiO2-xBi2O3 (x=0.0%, 1.0%, 2.0%, and 4.0%, in mole) was produced by a conventional melt annealing process. First, 40 g of raw materials were weighed and ground in a polypropylene ball mill in ethanol for 12 h. The resulting mixture was dried at 100 ℃ and subsequently melted in a corundum crucible in a resistance furnace at 1 500 ℃ for 2 h. The molten liquid was pressed into a sheet on a preheated copper plate and then annealed at 500 ℃ for 6 h to eliminate residual internal stresses. Finally, a niobate glass was obtained. The glass slices were crystallized at 850 ℃ and 950 ℃ for 2 h to obtain glass ceramics. The glass ceramic samples were ground, polished, and plated with electrodes for the structural and performance tests.

Results and discussion

The effect of Bi2O3 concentrations (x=0.0%, 1.0%, 2.0%, and 4.0% in mole) on the phase evolution, microstructure, dielectric and energy storage properties of K2O-SrO-Nb2O5-B2O3-Al2O3-SiO2 glass ceramics was investigated by a controlled crystallization process. Based on the XRD analysis, KSr2Nb5O15 is a main precipitated crystalline phase, and the crystallization promotes due to the addition of bismuth oxide. The A-site ions are adjusted by Bi3+ with a smaller radius (i.e., 1.03 Å) into the crystal lattice instead of Sr2+ with a larger radius (i.e., 1.18 Å), thus reducing the unit cell volume and increasing the lattice distortion. From the Raman spectra, the change of A-site occupancy leads to the distortion of the structure and enhances the spontaneous polarization. The microstructure shows that the grains are dense and evenly distributed, and the grain size is fine. The dielectric temperature spectroscopy indicates that the relaxation characteristics correspond to the polar nanoregion of the microstructure, and the DC breakdown strength firstly increases and then decreases, which is consistent with the change of the dielectric constant. The polarized electric field curve is slender with a large spontaneous polarization and a small residual polarization, improving the energy storage efficiency. The charge-discharge curve shows that the energy density firstly increases and then decreases with the addition of bismuth oxide, and the glass-ceramic sample B2-9 obtains the maximum energy density, discharge power density and fast discharge time, having a great application prospect in the field of dielectric energy storage.

Conclusions

Strontium niobate potassium glass ceramics were prepared by a conventional melting method and a controlled crystallization technology. At a crystallization temperature of 950 ℃, the unit cell volume of the crystalline phase decreased from 611.83 Å3 to 610.19 Å3 with the increase of Bi2O3 doping content. The grain size of the microstructure firstly decreased and then increased, and the optimal grain size of glass ceramic sample B2-9 was 57.72 nm. The dielectric and energy storage properties also firstly increased and then decreased, and the maximum dielectric constant of glass-ceramic sample B2-9 was 342 times greater than that of glass-ceramic sample B2-8, which was 1.9 times greater than that of glass-ceramic sample B2-8. According to the P-E curve, the glass ceramic sample B2-9 had the optimum performance (i.e., Pmax=9.33 μC/cm2, Pr=0.73 μC/cm2, Wrec=1.27 J/cm3, Wtotal=1.55 J/cm3, η=82% at 350 kV/cm). The energy density of the glass ceramic sample B2-9 was 1.33 J/cm3 at 400 kV/cm, the maximum discharge power density was 124.13 MW/cm3, and the fastest discharge time was 22 ns. The breakdown strength firstly increased and then decreased, which were 742, 886, 923 kV/cm and 622 kV/cm, respectively. Glass-ceramic materials could have great application prospects in the field of dielectric energy storage.

glass-ceramics  /  phase structure  /  dielectric properties  /  energy storage performance
耿喜乐, 冯先杰, 尚飞, 陈国华. Bi2O3对K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2玻璃陶瓷介电储能性能的影响. 硅酸盐学报, 2024 , 52 (4) : 1229 -1239 . DOI: 10.14062/j.issn.0454-5648.20230739
Xile GENG, Xianjie FENG, Fei SHANG, Guohua CHEN. Effect of Bi2O3 on Dielectric Energy Storage Performance of K2O-B2O3-SrO-Al2O3-Nb2O5-SiO2 Glass-Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1229 -1239 . DOI: 10.14062/j.issn.0454-5648.20230739
  • 广西科技基地和人才专项(桂科AD21220138)
  • 国家自然科学基金地区科学基金项目(52162001)
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doi: 10.14062/j.issn.0454-5648.20230739
  • 接收时间:2023-09-25
  • 首发时间:2026-10-22
  • 出版时间:2024-04-20
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  • 收稿日期:2023-09-25
  • 修回日期:2023-10-07
基金
广西科技基地和人才专项(桂科AD21220138)
国家自然科学基金地区科学基金项目(52162001)
作者信息
    桂林电子科技大学电子信息材料与器件教育部工程中心,材料科学与工程学院,广西 桂林 541004

通讯作者:

尚飞(1981—),男,博士,副教授;
陈国华(1964—),男,博士,教授。
参考文献
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2种不同金属材料的力学参数
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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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