CN113972068B - Glass glaze capacitor and preparation method thereof - Google Patents

Glass glaze capacitor and preparation method thereof Download PDF

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Publication number
CN113972068B
CN113972068B CN202111190286.0A CN202111190286A CN113972068B CN 113972068 B CN113972068 B CN 113972068B CN 202111190286 A CN202111190286 A CN 202111190286A CN 113972068 B CN113972068 B CN 113972068B
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maleic anhydride
methacrylic acid
glass
anhydride copolymer
capacitor
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CN113972068A (en
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朱少敏
刘春燕
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Sichuan Shengrongda Capacitive Resistance Technology Co ltd
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Sichuan Shengrongda Capacitive Resistance Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/003Apparatus or processes for encapsulating capacitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

The invention belongs to the technical field of capacitors, and particularly relates to a glass glaze capacitor and a preparation method thereof, wherein the glass glaze capacitor comprises a packaging medium and a sealing film layer, and the packaging medium is formed by mixing 50-100 parts of glass glaze powder, 1-6 parts of adhesive and 40-90 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:1-3:0.2-0.4, and copolymerizing under ultraviolet irradiation. In the technical scheme of the invention, in the methacrylic acid-maleic anhydride copolymer prepared by ultraviolet irradiation polymerization, two carbonyl groups formed after ring opening of maleic anhydride in the polymerization process can chelate noble metal ions, so that the noble metal ions are bound, and the phenomenon that the noble metal ions migrate and breakdown occurs to cause the damage of a capacitor is prevented.

Description

Glass glaze capacitor and preparation method thereof
Technical Field
The invention relates to the technical field of capacitors, in particular to a glass glaze capacitor and a preparation method thereof.
Background
The glass glaze capacitor is one kind of common capacitor device, and is used mainly in low frequency coupling, filtering and other fields, and the dielectric is glass glaze powder pressurized sheet with high dielectric coefficient, small volume and other features.
The glass glaze capacitor has the characteristics of large dielectric coefficient, small volume, small loss and the like, but noble metal ion migration phenomenon can be generated along with the increase of service years, so that breakdown occurs, and the capacitor is damaged.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a glass glaze capacitor and a preparation method thereof, and aims to solve the problem that noble metal ions in the glass glaze capacitor migrate to cause breakdown and damage to the capacitor.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions:
the glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 50-100 parts of glass glaze powder, 1-6 parts of adhesive and 40-90 parts of methacrylic acid-maleic anhydride copolymer powder.
Preferably, the sealing film layer is made of one of nickel, aluminum, copper and cobalt.
Preferably, the photoinitiator is photoinitiator-651.
Preferably, the preparation method of the glass glaze capacitor comprises the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, and after the copolymerization reaction is finished, the methacrylic acid-maleic anhydride copolymer powder is obtained through centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and performing vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection to obtain the finished product.
Preferably, the wavelength of ultraviolet light in the step (1) is 340-365nm.
Preferably, the conditions of the copolymerization reaction in the step (1) are that the reaction is carried out for 2 to 4 hours at the temperature of 110 to 130 ℃.
Preferably, the vacuum drying time in the step (3) is 8-12h, and the drying temperature is 100-120 ℃.
Preferably, in the step (3), the stirring speed is 70-90r/min, and the stirring time is 20-40min.
(III) beneficial technical effects
In the technical scheme of the invention, in the methacrylic acid-maleic anhydride copolymer prepared by ultraviolet irradiation polymerization, the methacrylic acid-maleic anhydride copolymer is mixed in glass glaze powder, noble metal ions participate in solid phase reaction on the surface of glass glaze medium, an interface layer is formed at the contact position of the glass glaze medium and the noble metal ions, two carbonyl groups formed after ring opening of maleic anhydride in the polymerization process can chelate the noble metal ions, so that the noble metal ions are bound, the noble metal ion migration phenomenon is prevented, breakdown occurs, and the capacitor is damaged.
In the technical scheme of the invention, methacrylic acid-maleic anhydride copolymer powder is prepared by ultraviolet copolymerization of methacrylic acid, maleic acid and a photoinitiator, is easy to polymerize at low temperature, and can obtain pure methacrylic acid-maleic anhydride copolymer without initiator residues in the polymerization process.
Detailed Description
To achieve the above object, the present invention provides the following examples and comparative examples:
example 1
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 50 parts of glass glaze powder, 1 part of adhesive and 40 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:1:0.2 and is formed by copolymerization under the irradiation of ultraviolet light.
The sealing film layer is made of aluminum, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 340nm, the copolymerization reaction condition is that the reaction is carried out for 2 hours at 110 ℃, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 8 hours, the drying temperature is 100 ℃, the stirring speed is 70r/min, and the stirring time is 20 minutes, thus obtaining the finished product.
Example 2
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 60 parts of glass glaze powder, 2 parts of adhesive and 50 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:2:0.3, and copolymerizing under ultraviolet irradiation.
The sealing film layer is made of aluminum, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 350nm, the copolymerization reaction condition is that the reaction is carried out for 3 hours at 120 ℃, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 10 hours, the drying temperature is 110 ℃, the stirring speed is 80r/min, and the stirring time is 30 minutes, thus obtaining the finished product.
Example 3
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 70 parts of glass glaze powder, 3 parts of adhesive and 60 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:3:0.4, and copolymerizing under ultraviolet irradiation.
The sealing film layer is made of nickel, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 365nm, the copolymerization reaction condition is 130 ℃ for 4 hours, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 12h, the drying temperature is 120 ℃, the stirring speed is 90r/min, and the stirring time is 40min, thus obtaining the finished product.
Example 4
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 80 parts of glass glaze powder, 4 parts of adhesive and 70 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:2:0.3, and copolymerizing under ultraviolet irradiation.
The sealing film layer is made of copper, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 350nm, the copolymerization reaction condition is that the reaction is carried out for 3 hours at 120 ℃, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 10 hours, the drying temperature is 110 ℃, the stirring speed is 80r/min, and the stirring time is 30 minutes, thus obtaining the finished product.
Example 5
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 90 parts of glass glaze powder, 5 parts of adhesive and 80 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:2:0.3, and copolymerizing under ultraviolet irradiation.
The sealing film layer is made of cobalt, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 350nm, the copolymerization reaction condition is that the reaction is carried out for 3 hours at 120 ℃, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 10 hours, the drying temperature is 110 ℃, the stirring speed is 80r/min, and the stirring time is 30 minutes, thus obtaining the finished product.
Example 6
A glass glaze capacitor comprises a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 100 parts of glass glaze powder, 6 parts of adhesive and 90 parts of methacrylic acid-maleic anhydride copolymer powder; methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:2:0.3, and copolymerizing under ultraviolet irradiation.
The sealing film layer is made of aluminum, and the photoinitiator is a photoinitiator-651.
In this embodiment, the preparation method of the glass-glazed capacitor includes the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, the wavelength of the ultraviolet light is 350nm, the copolymerization reaction condition is that the reaction is carried out for 3 hours at 120 ℃, and methacrylic acid-maleic anhydride copolymer powder is obtained after the copolymerization reaction is finished by centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain a packaging medium;
(3) Adding the methacrylic acid-maleic anhydride copolymer powder obtained in the step (1), the packaging medium obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and then carrying out vacuum drying, rolling, cutting, lamination, shell entering, sealing and liquid injection, wherein the vacuum drying time is 10 hours, the drying temperature is 110 ℃, the stirring speed is 80r/min, and the stirring time is 30 minutes, thus obtaining the finished product.
Comparative example 1
The comparative example is a glass glaze capacitor of a high voltage ceramic chip capacitor sold in the market.
The glass-glazed capacitors obtained in examples 1 to 6 and comparative example 1 were subjected to performance test:
after the glass glaze capacitors obtained in examples 1 to 6 and comparative example 1 were used for 3 months, the capacitance loss tangent values thereof were measured, and the glass glaze capacitors obtained in examples 1 to 6 and comparative example 1 were measured using an LCR tester, with a set frequency of 120HZ, and a gold film capacitance of 1KHZ, and the test results were shown in Table 1 below:
TABLE 1
Project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1
Loss tangent of capacitance 0.0013 0.0012 0.0010 0.0009 0.0008 0.0007 0.0015
As can be seen from examples 1-6 and comparative example 1 of Table 1 above, a glass-glazed capacitor prepared according to the present invention has a smaller capacitance loss tangent value after chelation of metal particles by methacrylic acid-maleic anhydride copolymer in glass-glazed medium, compared with comparative example 1, indicating that the capacitor prepared according to the technical scheme of the present invention has better performance.
To evaluate the specific capacitance of the glass enamel capacitors prepared in accordance with the invention, the specific capacitances of the glass enamel capacitors of examples 1 to 6 and comparative example 1 at a current of 5A were measured by cyclic voltammetry, and the measurement results are shown in Table 2:
TABLE 2
Project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1
Specific capacitance (F/g) 203.4 203.2 202.7 202.6 202.3 201.6 188.5
As can be seen from examples 1-6 and comparative example 1 of table 2 above, a glass-glazed capacitor prepared according to the present invention has a better specific capacitance at the same current than comparative example 1 by providing multiple layers of glass-glazed dielectric layers.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.

Claims (8)

1. The glass glaze capacitor is characterized by comprising a packaging medium and a sealing film layer, wherein the packaging medium is formed by mixing 50-100 parts of glass glaze powder, 1-6 parts of adhesive and 40-90 parts of methacrylic acid-maleic anhydride copolymer powder; the methacrylic acid-maleic anhydride copolymer powder is prepared from methacrylic acid, maleic anhydride and a photoinitiator in a mass ratio of 1:1-3:0.2-0.4, and copolymerizing under ultraviolet irradiation.
2. A glass-glazed capacitor according to claim 1, wherein: the sealing film layer is made of one of nickel, aluminum, copper and cobalt.
3. A glass-glazed capacitor according to claim 1, wherein: the photoinitiator is photoinitiator-651.
4. A method of manufacturing a glass-glazed capacitor as claimed in any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) Under the condition that a photoinitiator exists, methacrylic acid and maleic anhydride are subjected to copolymerization reaction under the irradiation of ultraviolet light, and after the copolymerization reaction is finished, the methacrylic acid-maleic anhydride copolymer powder is obtained through centrifugation and drying;
(2) Mixing and stirring the obtained methacrylic acid-maleic anhydride copolymer powder and glass glaze powder to obtain mixed powder;
(3) And (3) adding the mixed powder obtained in the step (2) and the adhesive into a stirring kettle, stirring to obtain slurry, coating the slurry on a sealing film layer, and performing vacuum drying, rolling, cutting, laminating, shell entering, sealing and liquid injection to obtain a finished product.
5. The method for manufacturing a glass-glazed capacitor according to claim 4, wherein: the wavelength of ultraviolet light in the step (1) is 340-365nm.
6. The method for manufacturing a glass-glazed capacitor according to claim 4, wherein: the condition of the copolymerization reaction in the step (1) is that the reaction is carried out for 2-4 hours at the temperature of 110-130 ℃.
7. The method for manufacturing a glass-glazed capacitor according to claim 4, wherein: and (3) performing vacuum drying for 8-12h at 100-120 ℃.
8. The method for manufacturing a glass-glazed capacitor according to claim 4, wherein: in the step (3), the stirring speed is 70-90r/min, and the stirring time is 20-40min.
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JPS57170839A (en) * 1981-04-15 1982-10-21 Matsushita Electric Works Ltd Glaze composition
CN1499545A (en) * 2002-10-30 2004-05-26 ������������ʽ���� Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor
CN1847183A (en) * 2005-04-11 2006-10-18 三星电机株式会社 Glass frit for dielectrics, multilayer ceramic capacitor, and method for manufacturing the same
CN105036557A (en) * 2015-07-29 2015-11-11 无锡隆傲电子有限公司 Ceramic glass glaze slurry and ceramic capacitor manufactured by using same
JP2015231924A (en) * 2014-06-10 2015-12-24 日油株式会社 Slurry composition for manufacturing laminate ceramic capacitor and ceramic green sheet
CN111269448A (en) * 2020-03-20 2020-06-12 清华大学 Dielectric film, preparation method thereof and film capacitor
CN111668024A (en) * 2020-06-05 2020-09-15 国家电网有限公司 Capacitor using modified polypropylene film medium
CN113488342A (en) * 2021-07-02 2021-10-08 鹏盛国能(深圳)新能源集团有限公司 Solid electrolyte material for tantalum capacitor lithium battery and preparation method thereof

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US7098525B2 (en) * 2003-05-08 2006-08-29 3M Innovative Properties Company Organic polymers, electronic devices, and methods
US7830644B2 (en) * 2007-03-05 2010-11-09 Northop Grumman Systems Corporation High dielectric capacitor materials and method of their production
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Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57170839A (en) * 1981-04-15 1982-10-21 Matsushita Electric Works Ltd Glaze composition
CN1499545A (en) * 2002-10-30 2004-05-26 ������������ʽ���� Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor
CN1847183A (en) * 2005-04-11 2006-10-18 三星电机株式会社 Glass frit for dielectrics, multilayer ceramic capacitor, and method for manufacturing the same
JP2015231924A (en) * 2014-06-10 2015-12-24 日油株式会社 Slurry composition for manufacturing laminate ceramic capacitor and ceramic green sheet
CN105036557A (en) * 2015-07-29 2015-11-11 无锡隆傲电子有限公司 Ceramic glass glaze slurry and ceramic capacitor manufactured by using same
CN111269448A (en) * 2020-03-20 2020-06-12 清华大学 Dielectric film, preparation method thereof and film capacitor
CN111668024A (en) * 2020-06-05 2020-09-15 国家电网有限公司 Capacitor using modified polypropylene film medium
CN113488342A (en) * 2021-07-02 2021-10-08 鹏盛国能(深圳)新能源集团有限公司 Solid electrolyte material for tantalum capacitor lithium battery and preparation method thereof

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