CN115274180A - Conductive silver paste for solid fuel cell and preparation method thereof - Google Patents
Conductive silver paste for solid fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN115274180A CN115274180A CN202211046590.2A CN202211046590A CN115274180A CN 115274180 A CN115274180 A CN 115274180A CN 202211046590 A CN202211046590 A CN 202211046590A CN 115274180 A CN115274180 A CN 115274180A
- Authority
- CN
- China
- Prior art keywords
- parts
- silver
- solid fuel
- silver paste
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a conductive silver paste for a solid fuel cell and a preparation method thereof, wherein the conductive silver paste comprises the following components in parts by weight: 40 to 50 parts of nano water-based silver powder, 10 to 15 parts of silver chloride powder, 15 to 20 parts of modified methacrylic resin, 5 to 10 parts of polyurethane resin, 10 to 20 parts of dibasic ester, 5 to 10 parts of ethylene glycol monomethyl ether acetate, 2 to 5 parts of butyl acetate, 0.2 to 0.5 part of polytetrafluoroethylene, 0.2 to 0.5 part of dimethyl siloxane, 0.05 to 0.1 part of silane coupling agent, 1 to 1.5 parts of ethyl acetate, 0.2 to 0.5 part of fumed silica and 0.1 to 0.5 part of flake graphite. Fully mixing the raw materials in a mixer, then dispersing the raw materials at a high speed by using a high-speed dispersion machine, and finally grinding the raw materials on a three-high mill for multiple times to obtain the conductive silver paste for the solid fuel cell. Compared with the prior art, the conductive silver paste for the solid fuel cell has the advantages of good electrode potential stability, good adhesiveness and the like.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and relates to conductive silver paste for a solid fuel cell and a preparation method thereof.
Background
Achieving the "dual carbon" goal is the first conscious, step-by-step improvement of living environment, a multinational co-operation in human history. Since the industrial revolution, fossil energy such as coal, oil, natural gas and the like plays unprecedented roles in the development of global economy and society and the advancement of civilization, however, under the relevant technical conditions, production modes and consumption modes, the defect that human consumes a large amount of fossil energy is increasingly prominent. The carbon dioxide released by fossil fuel and the greenhouse gas emitted by human production and consumption activities are causing the global climate change, which not only brings serious challenges to the survival and development of human beings, but also seriously threatens the biological safety and ecological balance of the whole earth. In the climate change meeting of paris 12 months in 2015, nearly 200 contracting parties in the climate change frame convention of united nations reach paris climate change agreement, so that the climate change actions are uniformly arranged in the world after 2020, and all nations have to take substantial steps. This is an important milestone in human history.
Solid Oxide Fuel Cells (SOFCs) are a new type of green fuel, among which flat solid oxide fuel cells have the advantages of low cost, high power density, simple process, etc. In order to further reduce the cost, widen the material selection range and improve the stability of the SOFC system, a great deal of work is done in recent years to reduce the working temperature of the SOFC from the traditional 1000 ℃ to 600-800 ℃. The original nickel and ceramic composite electrode and YSZ electrolyte have larger ohmic resistance at medium and low temperature, which seriously affects the performance of the battery, and the silver and ceramic composite material can be used as a cathode material of high-performance medium and low temperature SOFC. Silver has high electronic conductivity, the material compounded with the silver is ceramic YSZ with oxygen ion conductivity and has good stability, and the doped cerium oxide not only has high ionic conductivity, but also has good catalytic activity on the redox reaction of the SOFC electrode. Composite materials of silver and gadolinium-doped ceria (GDC) are widely used on cathodes and anodes of solid oxide fuel cells because silver is relatively stable in high temperature oxidizing atmospheres and carbon-containing gases.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the conductive silver paste for the solid fuel cell and the preparation method thereof, wherein the conductive silver paste has good electrode potential stability and good adhesion.
The purpose of the invention can be realized by the following technical scheme: the conductive silver paste for the solid fuel cell comprises the following components in parts by weight: 40 to 50 parts of nano water-based silver powder, 10 to 15 parts of silver chloride powder, 15 to 20 parts of modified methacrylic resin, 5 to 10 parts of polyurethane resin, 10 to 20 parts of dibasic ester, 5 to 10 parts of glycol monomethyl ether acetate, 2 to 5 parts of butyl acetate, 0.2 to 0.5 part of polytetrafluoroethylene, 0.2 to 0.5 part of dimethyl siloxane, 0.05 to 0.1 part of silane coupling agent, 1 to 1.5 parts of ethyl acetate, 0.2 to 0.5 part of fumed silica and 0.1 to 0.5 part of flake graphite.
Further, the nano water-based silver powder is prepared by the following method:
(1) Weighing a proper amount of silver nitrate, dissolving the silver nitrate in deionized water to prepare a silver nitrate solution, preheating the silver nitrate solution in a water bath at 50 ℃ for 30min, then weighing sodium hypophosphite, sodium hexametaphosphate and PVP, mixing, dissolving the mixture in the deionized water, stirring, and completely dissolving to obtain a silver ion solution;
(2) Dripping the silver ion solution prepared in the step (1) into a reducing solution at the speed of 20-30 drops per minute, and stirring at a high speed for 30min after finishing dripping to obtain brown nano silver sol;
(3) Stirring the prepared nano silver sol at a high speed, placing the nano silver sol in an ultrasonic field, continuously stirring, dropwise adding a pH regulator, continuing to perform ultrasonic treatment and stirring for 30min after the dropwise adding is completed, standing, performing vacuum filtration, soaking the filtered nano silver powder in a passivator, treating for 30min, performing vacuum filtration again, finally cleaning for three times by using absolute ethyl alcohol, and completely drying by using a vacuum drying oven to obtain the nano water-based silver powder with the average particle size of 35-50 nm.
Further, the mass ratio of the silver nitrate, the sodium hypophosphite, the sodium hexametaphosphate and the PVP in the step (1) is 1-3.
Further, the volume ratio of the reducing solution to the silver ion solution in the step (2) is 1; the reducing solution is 1.0mol/L sulfuric acid.
Further, the pH regulator in the step (2) is sodium hydroxide solution, and the pH value of the nano silver sol is regulated to 6-7;
the passivator is a commercial trivalent chromium aluminum passivator solution.
Furthermore, the silver chloride powder is an auxiliary conductive phase, the purity of the silver chloride powder is analytically pure, and the average particle size of the silver chloride powder is less than 1 mu m.
Further, the modified methacrylic resin is prepared by the following method:
(1) Preparing materials according to the parts by weight: 5-10 parts of acrylic acid, 15-20 parts of acrylic acid monomer, 2-5 parts of initiator, 3-6 parts of ethyl acetate, 2-5 parts of dodecyl mercaptan, 1-3 parts of triethylamine, 15-20 parts of isophorone diisocyanate, 5-10 parts of hydroxyethyl methacrylate and 0.2-1 part of dibutyltin dilaurate;
(2) Evenly mixing acrylic acid, acrylic acid monomer, 2/3 initiator, 50 percent of ethyl acetate and dodecyl mercaptan to prepare a mixed solution A,
(3) Dissolving the rest initiator into 25 percent of ethyl acetate to prepare a mixed solution B;
(4) Adding 25% of ethyl acetate and the homogeneous mixed solution A into a reactor, slowly heating to 72 ℃, reacting for 30min, dropwise adding the mixed solution B at the speed of 1 drop/s, reacting for 3h after the dropwise adding is finished to obtain colorless transparent resin PAC, cooling to below 60 ℃, and then adding triethylamine under stirring to perform salt forming reaction to obtain an acrylate copolymer WPAC;
(5) Adding isophorone diisocyanate (IPDI) blown with nitrogen into a reactor, slowly heating to 50 ℃, dropwise adding hydroxyethyl methacrylate while stirring, continuously reacting for 2H at the temperature of 60-65 ℃ after dropwise adding, cooling to 50 ℃, adding dibutyltin dilaurate, dropwise adding WPAC blown with nitrogen while stirring, reacting for 2.5H at the temperature of 55 ℃ after dropwise adding, finally titrating the reaction end point by a di-n-butylamine method, adding absolute ethyl alcohol for blocking, and adding a polymerization inhibitor H-TEMPO to obtain the isocyanate modified acrylic resin.
The initiator is AIBN.
40-50 parts of nano aqueous silver powder, 10-15 parts of silver chloride powder, 15-20 parts of modified methacrylic resin, 5-10 parts of polyurethane resin, 10-20 parts of dibasic acid ester, 5-10 parts of ethylene glycol monomethyl ether acetate, 2-5 parts of butyl acetate, 0.2-0.5 part of polytetrafluoroethylene, 0.2-0.5 part of dimethyl siloxane, 0.05-0.1 part of silane coupling agent, 1-1.5 parts of ethyl acetate, 0.2-0.5 part of fumed silica and 0.1-0.5 part of flake graphite are fully mixed in a mixer, and then are dispersed at high speed by using a high-speed disperser, and finally are ground on a three-roll mill for multiple times, so that the conductive silver paste for the solid fuel cell is obtained.
The obtained silver paste has fineness below 10 μm and viscosity of 10-15Pa · S.
Compared with the prior art, the invention has the following beneficial effects:
1. the polymer resin is a bonding phase of the conductive silver paste, and can provide basic rheological adhesion, an anti-settling function, adhesive force, bending resistance and anti-discoloration performance. The mechanical property and bonding property of the conductive silver paste are mainly determined by the polymer resin. It must meet the following requirements: has chemical stability, certain suspension property, moderate rheological property and volatility, good adhesion property and the like. In the formula design, self-made modified acrylic resin is selected as a binding phase, the synthesis of the resin is mainly divided into two steps of acrylic monomer copolymerization and isocyanate modification, and the resin is endowed with special properties such as binding property by a soft monomer and cohesive force by a hard monomer in the monomer copolymerization process, so that the product performance is finally improved.
2. The silver powders are classified by particle size (average particle size), and roughly classified into nano silver powders (less than 0.1 μm), fine silver powders (0.1 μm < Dav < 10 μm), and coarse silver powders (more than 10 μm). The preparation method of silver powder is also various, and the liquid phase reduction method is mainly adopted at present. The principle of the silver-silver plating solution is mainly that silver salt is dissolved in water, a chemical reducing agent is added, silver powder is deposited, and the silver-silver plating solution is formed by washing and drying. Due to the selection of the reducing agent, the control of reaction conditions and the selection of interface additives, silver micro powder (tap density, apparent density, specific surface area, average particle size and particle size distribution, grain size, crystallinity and the like) with different characteristics can be prepared, and the reduced powder is ball-milled to obtain bright silver powder and flake silver powder. Silver powders for the electronics industry are now classified into seven categories according to their use in silver conductor pastes: (1) high sintering activity silver powder for high-temperature sintering of the silver conductive paste; (2) sintering the high-dispersion silver powder for the silver conductive silver paste at a high temperature; (3) highly conductive reduced silver powder; (4) bright silver powder; (5) flake silver powder; (6) nano silver powder; (7) and (4) coarse silver powder. (1) The silver powders of (2) and (3) are collectively called silver micro powder, the silver powder of (6) is applied to silver conductor slurry in the exploration process, and the silver powder of (7) is mainly used in the electrical aspects of silver alloy and the like. The morphology of silver powder also has an influence on the conductivity of silver paste. With the same silver content, the flake silver powder mainly forms surface-to-surface contact, the spherical silver powder mainly forms point-to-point contact, and the spherical silver powder can play good roles of supplement and connection when being added into the flake silver powder, so that the resistance is further reduced.
The formula adopts the nano silver powder as a main conductive phase, and the nano silver powder can form a compact point-reaching coating and is not easy to agglomerate. The coating can provide excellent conductive performance while covering the heating carbon paste. The coating is compact, so that the phenomenon of carbon slurry infiltration or penetration is not easy to occur. The silver chloride powder is an auxiliary conductive phase, and the conductive silver paste for the solid fuel cell, which has good electrode potential stability and good adhesiveness, is formed in the formula system.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
The invention adopts various raw materials, except that the nano water-based silver powder and the modified methacrylic resin are self-made products, and the other raw materials are all commercial products.
Example 1
1. The nano water-based silver powder is prepared by the following method:
(1) Weighing a proper amount of silver nitrate, dissolving the silver nitrate in deionized water to prepare a silver nitrate solution, preheating the silver nitrate solution in a water bath at 50 ℃ for 30min, then weighing sodium hypophosphite, sodium hexametaphosphate and PVP, mixing, dissolving the mixture in the deionized water, stirring, and completely dissolving to obtain a silver ion solution; the mass ratio of silver nitrate, sodium hypophosphite, sodium hexametaphosphate and PVP is 1.
(2) Dripping the silver ion solution prepared in the step (1) into the reducing solution at the speed of 20 drops per minute, and stirring at a high speed for 30min after finishing dripping to obtain brown nano silver sol; the volume ratio of the reducing solution to the silver ion solution is 1; the reducing solution is 1.0mol/L sulfuric acid.
(3) Stirring the prepared nano silver sol at a high speed, placing the nano silver sol in an ultrasonic field, continuously stirring, dropwise adding a pH regulator sodium hydroxide solution, regulating the pH value of the nano silver sol to 6-7, continuing to perform ultrasonic treatment and stirring for 30min after dropwise adding, standing, performing vacuum filtration, soaking the filtered nano silver powder in a commercially available trivalent chromium aluminum passivator solution, treating for 30min, performing vacuum filtration again, finally cleaning for three times by using absolute ethyl alcohol, and completely drying by using a vacuum drying oven to obtain the nano water-based silver powder with the average particle size of 35-50 nm.
2. The modified methacrylic resin is prepared by the following method:
(1) Preparing materials according to parts by weight: 8 parts of acrylic acid, 18 parts of acrylic acid monomer, 3 parts of initiator AIBN3, 5 parts of ethyl acetate, 3 parts of dodecyl mercaptan, 2 parts of triethylamine, 18 parts of isophorone diisocyanate, 6 parts of hydroxyethyl methacrylate and 0.5 part of dibutyltin dilaurate;
(2) Evenly mixing acrylic acid, acrylic acid monomer, 2/3 initiator, 50 percent of ethyl acetate and dodecyl mercaptan to prepare a mixed solution A,
(3) Dissolving the rest initiator in 25% of ethyl acetate to prepare a mixed solution B;
(4) Adding 25% of ethyl acetate and a homogeneous phase mixed solution A into a reactor, slowly heating to 72 ℃, reacting for 30min, dropwise adding the mixed solution B at the speed of 1 drop/s, reacting for 3h after dropwise adding to obtain colorless transparent resin PAC, cooling to below 60 ℃, and adding triethylamine under stirring to perform salt forming reaction to obtain an acrylate copolymer WPAC;
(5) Adding isophorone diisocyanate (IPDI) blown with nitrogen into a reactor, slowly heating to 50 ℃, dropwise adding hydroxyethyl methacrylate while stirring, continuously reacting for 2H at the temperature of 60-65 ℃ after dropwise adding, cooling to 50 ℃, adding dibutyltin dilaurate, dropwise adding WPAC blown with nitrogen while stirring, reacting for 2.5H at the temperature of 55 ℃ after dropwise adding, finally titrating the reaction end point by a di-n-butylamine method, adding absolute ethyl alcohol for blocking, and adding a polymerization inhibitor H-TEMPO to obtain the isocyanate modified acrylic resin.
3. 45 parts of nano aqueous silver powder, 12 parts of silver chloride powder, 18 parts of modified methacrylic resin, 6 parts of polyurethane resin, 15 parts of dibasic ester, 8 parts of ethylene glycol monomethyl ether acetate, 3 parts of butyl acetate, 0.3 part of polytetrafluoroethylene, 0.3 part of dimethyl siloxane, 0.08 part of silane coupling agent, 1.2 parts of ethyl acetate, 0.3 part of fumed silica and 0.3 part of flake graphite are fully mixed in a mixer, then a high-speed dispersion machine is used for high-speed dispersion, and finally grinding is carried out on a three-roll mill for multiple times, the fineness of the silver paste is controlled to be below 10 mu m, and the viscosity is 10-15 Pa.S, so that the conductive silver paste for the solid fuel cell is obtained.
Example 2
1. The nano water-based silver powder is prepared by the following method:
(1) Weighing a proper amount of silver nitrate, dissolving the silver nitrate in deionized water to prepare a silver nitrate solution, preheating the silver nitrate solution in a water bath at 50 ℃ for 30min, then weighing sodium hypophosphite, sodium hexametaphosphate and PVP, mixing, dissolving the mixture in the deionized water, stirring, and completely dissolving to obtain a silver ion solution; the mass ratio of silver nitrate, sodium hypophosphite, sodium hexametaphosphate and PVP is 1.
(2) Dripping the silver ion solution prepared in the step (1) into a reducing solution at the speed of 20-30 drops per minute, and stirring at a high speed for 30min after finishing dripping to obtain brown nano silver sol; the volume ratio of the reducing solution to the silver ion solution is 1; the reducing solution is 1.0mol/L sulfuric acid.
(3) Stirring the prepared nano silver sol at a high speed, placing the nano silver sol in an ultrasonic field, continuously stirring, dropwise adding a pH regulator sodium hydroxide solution, regulating the pH value of the nano silver sol to 6-7, continuing to perform ultrasonic treatment and stirring for 30min after dropwise adding is completed, standing, performing vacuum filtration, soaking the filtered nano silver powder in a commercially available trivalent chromium aluminum passivator solution, treating for 30min, performing vacuum filtration again, finally cleaning for three times by using absolute ethyl alcohol, and completely drying by using a vacuum drying oven to obtain the nano water-based silver powder with the average particle size of 35 nm.
2. The modified methacrylic resin is prepared by the following method:
(1) Preparing materials according to parts by weight: 5 parts of acrylic acid, 15 parts of acrylic acid monomer, 2 parts of initiator AIBN, 3 parts of ethyl acetate, 2 parts of dodecyl mercaptan, 1 part of triethylamine, 15 parts of isophorone diisocyanate, 5 parts of hydroxyethyl methacrylate and 0.2 part of dibutyltin dilaurate;
(2) Evenly mixing acrylic acid, acrylic acid monomer, 2/3 initiator, 50 percent of ethyl acetate and dodecyl mercaptan to prepare a mixed solution A,
(3) Dissolving the rest initiator in 25% of ethyl acetate to prepare a mixed solution B;
(4) Adding 25% of ethyl acetate and a homogeneous phase mixed solution A into a reactor, slowly heating to 72 ℃, reacting for 30min, dropwise adding the mixed solution B at the speed of 1 drop/s, reacting for 3h after dropwise adding to obtain colorless transparent resin PAC, cooling to below 60 ℃, and adding triethylamine under stirring to perform salt forming reaction to obtain an acrylate copolymer WPAC;
(5) Adding isophorone diisocyanate (IPDI) blown with nitrogen into a reactor, slowly heating to 50 ℃, dropwise adding hydroxyethyl methacrylate while stirring, continuously reacting for 2 hours at the temperature of 60-65 ℃ after dropwise adding, cooling to 50 ℃, adding dibutyltin dilaurate, dropwise adding WPAC blown with nitrogen while stirring, reacting for 2.5 hours at the temperature of 55 ℃ after dropwise adding, finally titrating the reaction end point by a di-n-butylamine method, adding absolute ethyl alcohol for blocking, and adding a polymerization inhibitor H-TEMPO to obtain the isocyanate modified acrylic resin.
3. 40 parts of nano aqueous silver powder, 10 parts of silver chloride powder, 15 parts of modified methacrylic resin, 5 parts of polyurethane resin, 10 parts of dibasic ester, 5 parts of ethylene glycol monomethyl ether acetate, 2 parts of butyl acetate, 0.2 part of polytetrafluoroethylene, 0.2 part of dimethyl siloxane, 0.05 part of silane coupling agent, 1 part of ethyl acetate, 0.2 part of fumed silica and 0.1 part of flake graphite are fully mixed in a mixer, then a high-speed dispersion machine is used for high-speed dispersion, and finally grinding is carried out on a three-roll mill for multiple times, wherein the fineness of the silver paste is controlled to be below 10 mu m, and the viscosity is 10-15 Pa.S, so that the conductive silver paste for the solid fuel cell is obtained.
Example 3
1. The nano water-based silver powder is prepared by the following method:
(1) Weighing a proper amount of silver nitrate, dissolving the silver nitrate in deionized water to prepare a silver nitrate solution, preheating the silver nitrate solution in a water bath at 50 ℃ for 30min, then weighing sodium hypophosphite, sodium hexametaphosphate and PVP, mixing, dissolving the mixture in the deionized water, stirring, and completely dissolving to obtain a silver ion solution; the mass ratio of silver nitrate, sodium hypophosphite, sodium hexametaphosphate and PVP is (1).
(2) Dripping the silver ion solution prepared in the step (1) into a reducing solution at the speed of 20-30 drops per minute, and stirring at a high speed for 30min after finishing dripping to obtain brown nano silver sol; the volume ratio of the reducing solution to the silver ion solution is 1; the reducing solution is 1.0mol/L sulfuric acid.
(3) Stirring the prepared nano silver sol at a high speed, placing the nano silver sol in an ultrasonic field, continuously stirring, dropwise adding a pH regulator sodium hydroxide solution, regulating the pH value of the nano silver sol to 6-7, continuing to perform ultrasonic treatment and stirring for 30min after dropwise adding, standing, performing vacuum filtration, soaking the filtered nano silver powder in a commercially available trivalent chromium aluminum passivator solution, treating for 30min, performing vacuum filtration again, finally cleaning for three times by using absolute ethyl alcohol, and completely drying by using a vacuum drying oven to obtain the nano water-based silver powder with the average particle size of 35-50 nm.
2. The modified methacrylic resin is prepared by the following method:
(1) Preparing materials according to the parts by weight: 10 parts of acrylic acid, 20 parts of acrylic acid monomer, 5 parts of initiator AIBN, 6 parts of ethyl acetate, 5 parts of dodecyl mercaptan, 3 parts of triethylamine, 20 parts of isophorone diisocyanate, 10 parts of hydroxyethyl methacrylate and 1 part of dibutyltin dilaurate;
(2) Evenly mixing acrylic acid, acrylic acid monomer, 2/3 initiator, 50 percent of ethyl acetate and dodecyl mercaptan to prepare a mixed solution A,
(3) Dissolving the rest initiator into 25 percent of ethyl acetate to prepare a mixed solution B;
(4) Adding 25% of ethyl acetate and a homogeneous phase mixed solution A into a reactor, slowly heating to 72 ℃, reacting for 30min, dropwise adding the mixed solution B at the speed of 1 drop/s, reacting for 3h after dropwise adding to obtain colorless transparent resin PAC, cooling to below 60 ℃, and adding triethylamine under stirring to perform salt forming reaction to obtain an acrylate copolymer WPAC;
(5) Adding isophorone diisocyanate (IPDI) blown with nitrogen into a reactor, slowly heating to 50 ℃, dropwise adding hydroxyethyl methacrylate while stirring, continuously reacting for 2H at the temperature of 60-65 ℃ after dropwise adding, cooling to 50 ℃, adding dibutyltin dilaurate, dropwise adding WPAC blown with nitrogen while stirring, reacting for 2.5H at the temperature of 55 ℃ after dropwise adding, finally titrating the reaction end point by a di-n-butylamine method, adding absolute ethyl alcohol for blocking, and adding a polymerization inhibitor H-TEMPO to obtain the isocyanate modified acrylic resin.
3. 50 parts of nano aqueous silver powder, 15 parts of silver chloride powder, 20 parts of modified methacrylic resin, 10 parts of polyurethane resin, 20 parts of dibasic ester, 10 parts of ethylene glycol monomethyl ether acetate, 5 parts of butyl acetate, 0.5 part of polytetrafluoroethylene, 0.5 part of dimethyl siloxane, 0.1 part of silane coupling agent, 1.5 parts of ethyl acetate, 0.5 part of fumed silica and 0.5 part of flake graphite are fully mixed in a mixer, then a high-speed dispersion machine is used for high-speed dispersion, and finally grinding is carried out on a three-roll mill for multiple times, the fineness of the silver paste is controlled to be below 10 mu m, and the viscosity is 10-15 Pa.S, so that the conductive silver paste for the solid fuel cell is obtained.
The product performance tests obtained in the above examples are shown in Table 1
Claims (10)
1. The conductive silver paste for the solid fuel cell is characterized by comprising the following components in parts by weight: 40 to 50 parts of nano water-based silver powder, 10 to 15 parts of silver chloride powder, 15 to 20 parts of modified methacrylic resin, 5 to 10 parts of polyurethane resin, 10 to 20 parts of dibasic ester, 5 to 10 parts of glycol monomethyl ether acetate, 2 to 5 parts of butyl acetate, 0.2 to 0.5 part of polytetrafluoroethylene, 0.2 to 0.5 part of dimethyl siloxane, 0.05 to 0.1 part of silane coupling agent, 1 to 1.5 parts of ethyl acetate, 0.2 to 0.5 part of fumed silica and 0.1 to 0.5 part of flake graphite.
2. The conductive silver paste for solid fuel cells according to claim 1, wherein the nano aqueous silver powder is prepared by the following method:
(1) Weighing a proper amount of silver nitrate, dissolving the silver nitrate in deionized water to prepare a silver nitrate solution, preheating the silver nitrate solution in a water bath at 50 ℃ for 30min, then weighing sodium hypophosphite, sodium hexametaphosphate and PVP, mixing, dissolving the mixture in the deionized water, stirring, and completely dissolving to obtain a silver ion solution;
(2) Dripping the silver ion solution prepared in the step (1) into the reducing solution at the speed of 20-30 drops per minute, and stirring at a high speed for 30min after finishing dripping to obtain brown nano silver sol;
(3) Stirring the prepared nano silver sol at a high speed, placing the nano silver sol in an ultrasonic field, continuously stirring, dropwise adding a pH regulator, continuing to perform ultrasonic treatment and stirring for 30min after the dropwise adding is completed, standing, performing vacuum filtration, soaking the filtered nano silver powder in a passivator, treating for 30min, performing vacuum filtration again, finally cleaning for three times by using absolute ethyl alcohol, and completely drying by using a vacuum drying oven to obtain the nano water-based silver powder with the average particle size of 35-50 nm.
3. The conductive silver paste for solid fuel cells according to claim 2, wherein the mass ratio of silver nitrate, sodium hypophosphite, sodium hexametaphosphate and PVP in step (1) is 1-3.
4. The conductive silver paste for a solid fuel cell according to claim 2, wherein the volume ratio of the reducing solution to the silver ion solution in the step (2) is 1; the reducing solution is 1.0mol/L sulfuric acid.
5. The conductive silver paste for solid fuel cells according to claim 2, wherein the pH regulator in step (2) is sodium hydroxide solution, and the pH value of the nano silver sol is regulated to 6-7;
the passivator is a commercial trivalent chromium aluminum passivator solution.
6. The conductive silver paste for solid fuel cell according to claim 1, wherein said silver chloride powder is an auxiliary conductive phase, and the purity thereof is analytical grade, and the average particle size thereof is less than 1 μm.
7. The conductive silver paste for solid fuel cells according to claim 1, wherein the modified methacrylic resin is prepared by the following method:
(1) Preparing materials according to parts by weight: 5-10 parts of acrylic acid, 15-20 parts of acrylic acid monomer, 2-5 parts of initiator, 3-6 parts of ethyl acetate, 2-5 parts of dodecyl mercaptan, 1-3 parts of triethylamine, 15-20 parts of isophorone diisocyanate, 5-10 parts of hydroxyethyl methacrylate and 0.2-1 part of dibutyltin dilaurate;
(2) Evenly mixing acrylic acid, acrylic acid monomer, 2/3 initiator, 50 percent of ethyl acetate and dodecyl mercaptan to prepare a mixed solution A,
(3) Dissolving the rest initiator in 25% of ethyl acetate to prepare a mixed solution B;
(4) Adding 25% of ethyl acetate and a homogeneous phase mixed solution A into a reactor, slowly heating to 72 ℃, reacting for 30min, dropwise adding the mixed solution B at the speed of 1 drop/s, reacting for 3h after dropwise adding to obtain colorless transparent resin PAC, cooling to below 60 ℃, and adding triethylamine under stirring to perform salt forming reaction to obtain an acrylate copolymer WPAC;
(5) Adding isophorone diisocyanate (IPDI) blown with nitrogen into a reactor, slowly heating to 50 ℃, dropwise adding hydroxyethyl methacrylate while stirring, continuously reacting for 2H at the temperature of 60-65 ℃ after dropwise adding, cooling to 50 ℃, adding dibutyltin dilaurate, dropwise adding WPAC blown with nitrogen while stirring, reacting for 2.5H at the temperature of 55 ℃ after dropwise adding, finally titrating the reaction end point by a di-n-butylamine method, adding absolute ethyl alcohol for blocking, and adding a polymerization inhibitor H-TEMPO to obtain the isocyanate modified acrylic resin.
8. The conductive silver paste for solid fuel cells according to claim 7, wherein the initiator is AIBN.
9. The preparation method of the conductive silver paste for the solid fuel cell according to claim 1, wherein 40 to 50 parts of nano aqueous silver powder, 10 to 15 parts of silver chloride powder, 15 to 20 parts of modified methacrylic resin, 5 to 10 parts of polyurethane resin, 10 to 20 parts of dibasic ester, 5 to 10 parts of ethylene glycol monomethyl ether acetate, 2 to 5 parts of butyl acetate, 0.2 to 0.5 part of polytetrafluoroethylene, 0.2 to 0.5 part of dimethyl siloxane, 0.05 to 0.1 part of silane coupling agent, 1 to 1.5 parts of ethyl acetate, 0.2 to 0.5 part of fumed silica and 0.1 to 0.5 part of flake graphite are fully mixed in a mixer, and then are dispersed at a high speed by using a high-speed disperser, and finally are ground on a three-roll mill for multiple times to obtain the conductive silver paste for the solid fuel cell.
10. The method for preparing conductive silver paste for solid fuel cell according to claim 9, wherein the fineness of the obtained silver paste is controlled below 10 μm and the viscosity is 10-15Pa · S.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046590.2A CN115274180A (en) | 2022-08-30 | 2022-08-30 | Conductive silver paste for solid fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046590.2A CN115274180A (en) | 2022-08-30 | 2022-08-30 | Conductive silver paste for solid fuel cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115274180A true CN115274180A (en) | 2022-11-01 |
Family
ID=83755631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211046590.2A Pending CN115274180A (en) | 2022-08-30 | 2022-08-30 | Conductive silver paste for solid fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115274180A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220306887A1 (en) * | 2021-03-24 | 2022-09-29 | Science Applications International Corporation | Self-Sintering Conductive Inks |
| CN116709667A (en) * | 2023-06-30 | 2023-09-05 | 常州海弘电子有限公司 | Silver paste hole filling process method for circuit board |
-
2022
- 2022-08-30 CN CN202211046590.2A patent/CN115274180A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220306887A1 (en) * | 2021-03-24 | 2022-09-29 | Science Applications International Corporation | Self-Sintering Conductive Inks |
| CN116709667A (en) * | 2023-06-30 | 2023-09-05 | 常州海弘电子有限公司 | Silver paste hole filling process method for circuit board |
| CN116709667B (en) * | 2023-06-30 | 2024-01-19 | 常州海弘电子有限公司 | Silver paste hole filling process method for circuit board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115274180A (en) | Conductive silver paste for solid fuel cell and preparation method thereof | |
| EP4310953A1 (en) | Iron-manganese-based positive electrode material, and preparation method therefor and use thereof | |
| CN113353909B (en) | Method for preparing lithium iron phosphate positive electrode material by utilizing recovered lithium | |
| CN109449429B (en) | Lithium iron phosphate/silicon carbide composite material and preparation method thereof | |
| CN111987313A (en) | Scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and preparation method thereof | |
| CN110247107A (en) | A kind of solid electrolyte, and its preparation method and application | |
| CN114229918B (en) | Method for regulating phase proportion in positive electrode material of sodium-ion battery, preparation and application thereof | |
| CN113078323A (en) | Preparation method of composite multi-element iron phosphate manganese vanadium lithium cathode material | |
| CN102810344B (en) | Silver-plated copper containing paste for solar cell back electrode and method for preparing silver-plated copper containing paste | |
| CN113258086B (en) | Three-phase conductor proton conductor composite cathode material and preparation method thereof | |
| CN106450346A (en) | Ca-doping medium-low-temperature solid oxide fuel battery cathode material | |
| CN115806281B (en) | Lithium iron manganese phosphate composite material, preparation method thereof and battery | |
| CN109755518B (en) | Preparation method of carbon-coated lithium iron phosphate material | |
| CN114695873B (en) | Ternary lithium ion battery positive electrode material uniformly coated with elements and preparation method thereof | |
| CN101615673A (en) | Natural iron disulfide lithiation positive electrode material and production method thereof | |
| CN111590086A (en) | Ultrathin flake silver powder with smooth surface and preparation method thereof | |
| CN116207269A (en) | High-conductivity nano-coating current collector, electrode, battery and preparation method of current collector | |
| EP4297128A1 (en) | Lithium iron phosphate, preparation method therefor, and application thereof | |
| CN113629258B (en) | Platinum-cobalt alloy catalyst with platinum-rich surface and preparation method and application thereof | |
| CN115304720A (en) | Slump-retaining concrete glue reducing agent and preparation method thereof | |
| CN115148981A (en) | Lithium ion battery positive electrode material and preparation method and application thereof | |
| CN111599507A (en) | Conductive silver paste based on smooth ultrathin flake silver powder and preparation method thereof | |
| CN112117447A (en) | Preparation process of composite lithium battery negative electrode material | |
| CN101901915B (en) | Preparation of sulfur-oxygen solid oxide fuel cell anode | |
| CN101916872B (en) | Method for preparing cell slice of sulfur-oxygen solid oxide fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |