CN108962607A - A kind of impregnated graphite slurry and preparation method thereof - Google Patents

A kind of impregnated graphite slurry and preparation method thereof Download PDF

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Publication number
CN108962607A
CN108962607A CN201710369511.4A CN201710369511A CN108962607A CN 108962607 A CN108962607 A CN 108962607A CN 201710369511 A CN201710369511 A CN 201710369511A CN 108962607 A CN108962607 A CN 108962607A
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CN
China
Prior art keywords
slurry
impregnated graphite
graphite
solvent
impregnated
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CN201710369511.4A
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Chinese (zh)
Inventor
杨康
庞锦标
郭明亚
敬通国
韩玉成
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China Zhenhua Group Yunke Electronics Co Ltd
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China Zhenhua Group Yunke Electronics Co Ltd
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Priority to CN201710369511.4A priority Critical patent/CN108962607A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a kind of impregnated graphite slurry and preparation method thereof, the impregnated graphite slurry, by percentage to the quality, raw material includes following components: conducting particles 4~16%;Fluoropolymer resin carrier 6~20%;Solvent 71~89%;Auxiliary agent 1~5%.The preparation method comprises the following steps: (1) according to default proportion, each component is weighed, then the 1/3 of solvent total weight is used to dissolve fluoropolymer resin carrier, and it is gradually added into conducting particles under conditions of 100~300rpm/min stirring, primary black lead wash is made after being uniformly mixed;(2) primary black lead wash is rolled, so that remaining 2/3 solvent less than 5 μm, is finally diluted primary black lead wash by fineness, being diluted to viscosity is 300~1000cp, obtains the impregnated graphite slurry.That the invention enables silver layer and graphite linings overlap joints is good, contact interface resistance is small, so that the ESR of tantalum capacitor be greatly lowered.

Description

A kind of impregnated graphite slurry and preparation method thereof
Technical field
The invention belongs to technical field of electronic devices, and in particular to a kind of impregnated graphite slurry and preparation method thereof.
Background technique
Since tantalum capacitor is found, be always the basic device that is most widely used in electronics industry it One, it is widely applied in various types of electronic circuits.In nineteen fifty-five, the wheat Courlene of AT&T Labs of the U.S. (D.McLean) and Bauer (F.Power) successfully develops first solid electrolyte Ta capacitor of industry, is with manganese dioxide For electrolyte, the problem of not only overcoming liquid electrolyte " desiccation ", but also greatly improve its stability characteristic (quality) and frequency is special Property, solid foundation has been established for the business application of tantalum capacitor in the future.
Tantalum capacitor is good etc. excellent because itself having large capacity, low-leakage current, long-life, miniaturization, low-loss, stability Good feature, so that no matter it is in the civilian neck such as phone, colour TV, refrigerator, Video Camera, digital camera, programme-controlled exchange, computer Domain is still all widely applied in national defences such as Aeronautics and Astronautics, guided missile, satellite, radars, especially in national defence Using the development for accelerating tantalum capacitor, new step has been marched toward.
ESR (Equivalent series Resistance) i.e. equivalent series resistance, ESR=Ra+Rb+Rc, wherein RaIt is It is related with tantalum pentoxide dielectric oxide film that it is lost by the resistance and film and MnO of tantalum pentoxide film2Contact resistance, RbIt is MnO inside tantalum block2Resistance, RcIt is tantalum block appearance MnO2And Conductive graphite cream, polymer silver paste etc. resistance and mutually Between contact resistance.With the development of electronic technology and electronic component, low-power consumption and high speed processing are modern electronic equipments Developing direction, to tantalum capacitor performance, more stringent requirements are proposed, wherein low ESR tantalum capacitor is exactly a research hot topic.
The manufacturer of domestic external capacitive body has all been the ESR (equivalent series resistance) for reducing capacitor and has largely ground Study carefully, but compared to external capacitor producer, studies in China is later, development speed is slow, and the ESR value of the low ESR tantalum capacitor of manganese systems is basic More than 40m Ω.External low ESR tantalum capacitor then has reached preferable level, such as: AVX Corp. releases low ESR value Chip tantalum capacitor series " TPS Series III ";Vishay company also releases the chip of the low ESR value of 0603 type of minimum shell number Tantalum capacitor " MicroTan-TR8 " series, the ESR value of product is down to 25m Ω or so.But low ESR tantalum capacitor is reducing Still there is also many shortcomings in terms of ESR, still need to further perfect.So reducing the ESR of tantalum capacitor to greatest extent It is current one of tantalum capacitor manufacturing industry primary study project both at home and abroad, is of great significance.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of impregnated graphite slurry so that silver layer and graphite linings overlap joint it is good, Contact interface resistance is small, so that the ESR of tantalum capacitor be greatly lowered.
The technical solution of the present invention is as follows: a kind of impregnated graphite slurry, by percentage to the quality, raw material includes following components:
Preferably, the conducting particles includes graphite and carbon black, the mass ratio of the graphite and carbon black is 1:0.3~1: 0.7。
Preferably, the fluoropolymer resin carrier be one of acrylic resin, epoxy resin and fluorubber or It is a variety of.
Preferably, the solvent is tributyl citrate, butyl acetate, ethyl caprilate, ethyl acetate, acetic acid positive penta Ester, butyl glycol ether, 2-Butoxyethyl acetate, polyamide wax, tetraethyl titanate, terpinol, butyl carbitol acetate, second One of ethyl acetoacetic acid ethyl ester and methylimidazole are a variety of.
Preferably, the auxiliary agent include one of dispersing agent, sagging inhibitor, defoaming agent and adhesion promoter or It is a variety of.
The present invention also provides the preparation methods of above-mentioned impregnated graphite slurry, comprising the following steps:
(1) according to default proportion, each component has been weighed, has then been used to dissolve fluoropolymer resin for the 1/3 of solvent total weight Carrier, and it is gradually added into conducting particles under conditions of 100~300rpm/min stirring, primary stone is made after being uniformly mixed Ink slurry;
(2) primary black lead wash is rolled so that fineness is less than 5 μm, finally by remaining 2/3 solvent to primary black lead wash into Row dilution, being diluted to viscosity is 300~1000cp, obtains the impregnated graphite slurry.
The present invention also provides a kind of tantalum capacitors, including tantalum core and the graphite linings being covered on tantalum core, the graphite linings It is prepared by above-mentioned impregnated graphite slurry.
For tantalum capacitor, ESR mainly includes three parts, first is that related with tantalum pentoxide dielectric oxide film R is lost1, including the equivalent resistance and film that are generated by tantalum pentoxide film and MnO2Contact resistance, second is that tantalum block inside MnO2 Or the resistance R of conducting polymer2, third is that tantalum block appearance MnO2, electrically conductive graphite layer, conductive silver layer, cathodic metal piece etc. resistance with And mutual contact resistance R3.Reduction for ESR, wherein R1、R2ESR it is smaller and stablize, be gradually improved at present;And The ESR of cathode outlet is larger, and unstable, and be significantly improved space.Therefore, in R1And R2In the case where immobilizing, this hair The bright desired ESR for reducing tantalum capacitor, by reducing R3Mode realize, that is, reduce impregnated graphite slurry and impregnated silver pulp Between contact resistance, the contact interface both improved guarantees there is good overlap joint therebetween, between the two to reduce Contact resistance.
Compared with prior art, the beneficial effects of the present invention are embodied in:
The ESR value of manganese systems tantalum capacitor is reduced to by original 40mm Ω or more after impregnated graphite slurry application of the invention 27m Ω is hereinafter, be expected to be applied in the production of low ESR tantalum capacitor.Using the black lead wash preparation tantalum capacitor ESR compared with It is small, it has excellent performance, there is important practical value in the industrialized production of low ESR solid electrolytic tantalum capacitors.
Detailed description of the invention
Fig. 1 is impregnated graphite sizing process flow chart in the present invention.
Fig. 2 is the apparent figure of impregnated graphite slurry in the present invention.
Fig. 3 is the structural schematic diagram of slurry tantalum core impregnated graphite slurry and polymer silver paste in the present invention.
Fig. 4 is interface microscopic appearance figure between graphite linings and silver layer in the present invention.
Fig. 5 is 3D scanning figure in interface between graphite linings and silver layer in the present invention.
Fig. 6 is that Interface composition is analyzed between graphite linings and silver layer in the present invention.
Specific embodiment
Embodiment 1
(1) preparation of impregnated graphite slurry
In mass ratio by conducting particles, acrylic resin carrier, solvent and auxiliary agent, conducting particles: acrylic resin carrier: Solvent: auxiliary agent=6.5:8.5:83:2 carries out ingredient, and wherein conducting particles is made of graphite and conductive black, mass ratio 5:3; Solvent be butyl glycol ether, tributyl citrate and 2-Butoxyethyl acetate composition mixed solvent, mass ratio 45: 30:25, raw material specification are as shown in table 1.Suitable mixed solvent (one third for accounting for about total solvent) is weighed, by load weighted third Olefin(e) acid resin first dissolves, it is to be dissolved completely after, be gradually added into conducting particles under stirring conditions, after adding conducting particles, Other auxiliary agents are added, after stirring half an hour, until being uniformly mixed, primary black lead wash is made;Then primary black lead wash is passed through Three-high mill rolling adjusts roll spacing according to slurry fineness, repeats rolling until the fineness of conductive graphite paste is less than 5 μm;Finally Black lead wash is diluted with the solvent of residue 2/3rds, impregnated graphite slurry can be obtained.
1 experimental raw of table and specification
(2) tantalum core dipping, solidification
By the graphite slurry of complete tantalum fuse impregnation steps (1) preparation of envelope, first 3~5min at room temperature, from room temperature liter Temperature is solidified to heat preservation 45min at a temperature of 200~240 DEG C, and Fig. 3 is that tantalum core impregnated graphite slurry and the structure of polymer silver paste are shown It is intended to, wherein 1 is the tantalum anode block for having formed oxidation film in Fig. 3;2 (partially penetrate into tantalum anode block for manganese dioxide layer Portion);3 be graphite, silver slurry layer;4 be assembly scolding tin material;5 be copper shell;6 be anode tap;7 be negative wire;8 be insulator.
(3) performance test
10 tantalum capacitor sample measurement performance parameters of arbitrary extracting, test result are as shown in table 2:
The ESR and graphite linings adhesive force of the different samples of table 2
As can be found from Table 2, capacitor ESR value is small, and consistency is preferable, and adhesive force is good.Illustrate black lead wash with polymerize The contact of object silver paste is good, and overlap joint is good, and resistance is small between interface, significantly reduces the ESR of tantalum capacitor, and compressive property Good, adhesive force is stronger under high temperature.
Embodiment 2
In mass ratio by conducting particles, acrylic resin carrier, solvent and auxiliary agent, conducting particles: epoxy resin carrier: molten Agent: auxiliary agent=6:8:83.5:2.5 carries out ingredient, and wherein conducting particles is made of graphite and conductive black, mass ratio 3:2;It is molten Agent is DBE, and raw material specification is as shown in table 1.Other operating process are the same as embodiment 1.
10 tantalum capacitor sample measurement performance parameters of arbitrary extracting, test result are as shown in table 3:
The ESR of the different samples of table 3
As can be known from Table 3, capacitor ESR value is little, and consistency is preferable, and adhesive force is larger.Illustrate black lead wash with polymerize The contact of object silver paste is good, and overlap joint is good, and resistance is small between interface, significantly reduces the ESR of tantalum capacitor, and compressive property Good, adhesive force is stronger under high temperature.

Claims (7)

1. a kind of impregnated graphite slurry, which is characterized in that by percentage to the quality, raw material includes following components:
2. impregnated graphite as described in claim 1 slurry, which is characterized in that the conducting particles includes graphite and carbon black, described The mass ratio of graphite and carbon black is 1:0.3~1:0.7.
3. impregnated graphite as described in claim 1 slurry, which is characterized in that the fluoropolymer resin carrier be acrylic resin, One of epoxy resin and fluorubber are a variety of.
4. impregnated graphite as described in claim 1 slurry, which is characterized in that the solvent be tributyl citrate, butyl acetate, Ethyl caprilate, ethyl acetate, n-amyl acetate, butyl glycol ether, 2-Butoxyethyl acetate, polyamide wax, tetraethyl titanate, One of terpinol, butyl carbitol acetate, ethyl acetoacetate and methylimidazole are a variety of.
5. impregnated graphite slurry as described in claim 1, which is characterized in that the auxiliary agent includes dispersing agent, sagging inhibitor, defoaming One of agent and adhesion promoter are a variety of.
6. the preparation method that the impregnated graphite as described in Claims 1 to 5 is any is starched, which comprises the following steps:
(1) according to default proportion, each component has been weighed, has then been used to dissolve fluoropolymer resin carrier for the 1/3 of solvent total weight, And it is gradually added into conducting particles under conditions of 100~300rpm/min stirring, primary black lead wash is made after being uniformly mixed;
(2) primary black lead wash is rolled, so that fineness is less than 5 μm, it is finally that remaining 2/3 solvent is dilute to the progress of primary black lead wash It releases, being diluted to viscosity is 300~1000cp, obtains the impregnated graphite slurry.
7. a kind of tantalum capacitor, including tantalum core and the graphite linings being covered on tantalum core, which is characterized in that the graphite linings are by right It is required that 1~5 any impregnated graphite slurry is prepared.
CN201710369511.4A 2017-05-23 2017-05-23 A kind of impregnated graphite slurry and preparation method thereof Pending CN108962607A (en)

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CN108962607A true CN108962607A (en) 2018-12-07

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5825611A (en) * 1997-01-29 1998-10-20 Vishay Sprague, Inc. Doped sintered tantalum pellets with nitrogen in a capacitor
CN1614726A (en) * 2004-09-28 2005-05-11 宁夏星日电子股份有限公司 Producing method for solid electrolytic capacitor
CN102329496A (en) * 2011-06-30 2012-01-25 苏州新纶超净技术有限公司 High-conductivity carbon slurry and preparation method thereof
CN103915134A (en) * 2014-04-17 2014-07-09 江南石墨烯研究院 Method for preparing environment-friendly graphene-based conductive carbon paste

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5825611A (en) * 1997-01-29 1998-10-20 Vishay Sprague, Inc. Doped sintered tantalum pellets with nitrogen in a capacitor
CN1614726A (en) * 2004-09-28 2005-05-11 宁夏星日电子股份有限公司 Producing method for solid electrolytic capacitor
CN102329496A (en) * 2011-06-30 2012-01-25 苏州新纶超净技术有限公司 High-conductivity carbon slurry and preparation method thereof
CN103915134A (en) * 2014-04-17 2014-07-09 江南石墨烯研究院 Method for preparing environment-friendly graphene-based conductive carbon paste

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王军等: "钽电容器用石墨导电胶的研究", 《电子元件与材料》 *

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Application publication date: 20181207