CN113234360A - Preparation method of nano-silver conductive ink - Google Patents
Preparation method of nano-silver conductive ink Download PDFInfo
- Publication number
- CN113234360A CN113234360A CN202110725318.6A CN202110725318A CN113234360A CN 113234360 A CN113234360 A CN 113234360A CN 202110725318 A CN202110725318 A CN 202110725318A CN 113234360 A CN113234360 A CN 113234360A
- Authority
- CN
- China
- Prior art keywords
- nano
- conductive ink
- silver conductive
- silver
- agent
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000003223 protective agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 6
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000007767 bonding agent Substances 0.000 claims abstract 2
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 235000006708 antioxidants Nutrition 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 12
- 239000000976 ink Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012937 correction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of nano-silver conductive ink, which comprises the following steps: s1, adding a silver nitrate solution and a reducing agent solution into a protective agent solution at the same time for reaction to obtain a reaction solution, wherein the protective agent is one or more of ammonium citrate, sodium aluminate and sodium silicate; s2, centrifuging the reaction solution, and taking precipitate to obtain nano silver paste; s3, mixing the nano silver paste with a solvent, a bonding agent and a stabilizer to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink; low sintering temperature and good conductivity.
Description
Technical Field
The invention relates to the field of conductive ink, in particular to a preparation method of nano-silver conductive ink.
Background
As a functional material, the excellent conductivity of the nano metal conductive ink quickly draws high attention of a plurality of famous companies in Europe, America, Japan, Korean and other countries, invests and establishes a research and development center, and focuses on researching the low-temperature curing conductive ink represented by nano silver and nano copper. The conductive ink can be counted as one of electronic pastes, and is sometimes called as electronic ink, and the conductive ink is prepared by taking a solvent as a carrier, adding conductive particles (which can be micron-sized or nanometer-sized) as a conductive functional phase, adding other additives, improving the printing performance of the conductive ink, and having conductivity after sintering and curing.
Printed electronics require the use of various electronic materials, such as metal nanoparticles, semiconductor nanomaterials, polymers, carbon nanotubes, etc., which are widely used to fabricate conductive lines due to the lower cost of silver relative to gold and the chemical stability relative to copper. In the electronics industry, metallic silver is often processed into silver powder and then mixed into a polymer solution to form a high content dispersion, i.e., silver conductive ink.
The invention patent with the publication number of CN106147403A and the name of 'conductive ink and manufacturing method of conductive layer' discloses the matter and weight percentage contained in the nano-silver conductive ink, which needs to be sintered at the highest temperature of 200 ℃ to form the conductive layer; the conductive ink can generate a large amount of volatile substances in the sintering process due to excessively high organic matter content, so that the environment is seriously influenced, a conductive circuit can be formed only by sintering at a high temperature, the high sintering temperature not only can generate certain influence on a substrate, but also increases the process flow, so that the cost is correspondingly increased, and meanwhile, the conductive performance is poor.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of nano-silver conductive ink, which has low sintering temperature and good conductive performance.
The technical scheme of the invention is to provide a preparation method of nano-silver conductive ink, which comprises the following steps:
s1, adding a silver nitrate solution and a reducing agent solution into a protective agent solution at the same time for reaction to obtain a reaction solution, wherein the protective agent is one or more of ammonium citrate, sodium aluminate and sodium silicate;
s2, centrifuging the reaction solution, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with a solvent, an adhesive and a stabilizer to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink, wherein the fluorocarbon resin curing agent is DN980(HMDI polymer) or N-75(HDI biuret).
Preferably, the reducing agent is one or more of ascorbic acid, sodium borohydride and hydrazine hydrate.
Preferably, the solvent comprises at least one of ethylene glycol, butyl glycol ether, isopropyl alcohol, propylene glycol methyl ether, diethylene glycol butyl ether, glycerol, n-propanol, polyethylene glycol.
Preferably, the stabilizer comprises a surfactant, a dispersing agent, an antioxidant and a leveling agent, wherein the surfactant can be FS-3100, the dispersing agent can be BYK dispersing agent, the antioxidant can be antioxidant 1010 and the leveling agent can be GLP-333.
Preferably, the adhesive comprises one or more of phenolic resin and diethylene glycol butyl ether acetate.
Preferably, the reaction temperature of the step S1 is 30-100 ℃, the reaction pH value is 9-10, and the reaction time is 3-6 h.
Preferably, the molar ratio of the silver nitrate to the reducing agent is 2-8:1, and the molar ratio of the silver nitrate to the protective agent is 10-20: 1.
Preferably, the preparation method of the nanographene comprises the following steps:
k1, putting the expanded graphite into absolute ethyl alcohol, uniformly stirring, grinding and dispersing to obtain slurry, carrying out suction filtration, washing and freeze drying on the slurry to obtain pretreated expanded graphite;
k2, adding the pretreated expanded graphite into N-methyl pyrrolidone, stirring, ultrasonically treating, centrifuging, taking upper-layer liquid, carrying out vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preferably, the mass ratio of the pretreated expanded graphite to the N-methyl pyrrolidone is 3: 8-12.
In the scheme, the protective agent is one or more of ammonium citrate, sodium aluminate and sodium silicate, which are short chain molecules, the short chain molecules are used as dispersing agents, the nano silver particles are dispersed in the conductive ink by an electrostatic repulsion mechanism, in the prior art, most of the nano silver particles in the conductive ink are coated by long chain molecular dispersing agents such as polyvinylpyrrolidone, the long chain of the high molecule is fully extended in a solvent to form an adsorption layer of several nanometers to dozens of nanometers, the nano silver particles are dispersed by a steric hindrance mechanism, the nano silver particles are heated to 140-, the conductive circuit is formed, so that the temperature requirement for forming the sintering neck and the conductive channel is high, the nano-silver conductive ink in the scheme only needs to reach the volatilization temperature of the solvent when in use, the electrostatic repulsion type mechanism fails after the solvent is volatilized, the short-chain molecules cannot coat nano-silver particles like the long-chain molecules, the temperature requirement for forming the sintering neck and the conductive channel is low, and the applicable material range is wider;
meanwhile, the nano graphene is adopted to enhance the conductivity, and due to certain repulsion action among the nano silver pastes, the conductive particles are basically and independently dispersed in the ink matrix, so that the conductive particles are not in contact with each other, certain pores exist, and a conductive channel is not formed among part of the nano silver pastes during sintering; the expanded graphite is a loose and porous vermicular substance obtained by intercalating, washing, drying and high-temperature bulking natural graphite flakes, the nano graphene prepared by utilizing liquid phase stripping of the expanded graphite is of a three-layer flaky structure, graphene particles with smaller particle sizes can be distributed near nano silver slurry to fill gaps among the nano silver slurry, the connection among the nano silver particles is increased to form a conductive channel, and the graphene particles with larger particle sizes can form 'bridging' among the nano silver particles, so that the conductive performance of the ink is greatly improved; meanwhile, fluorine atoms in the fluorocarbon resin are combined on a C-C main chain in the resin molecules to densely surround the C-C main chain to form a spiral structure, so that a C-C bond is protected from being impacted and soaked by chemical substances, and the ink coating taking the fluorocarbon resin as a substrate has stronger corrosion resistance and weather resistance.
The invention has the beneficial effects that:
1. according to the scheme, the fluorocarbon resin is used as the printing ink matrix, so that the printing ink coating has strong corrosion resistance and weather resistance, and the nano graphene can enhance the conductive channels among nano silver particles through the compound conduction of the nano silver and the nano graphene, so that the conductive performance of the printing ink is greatly improved;
2. the obtained nano silver particles are uniform, the dispersibility is good, the nano silver particles can be stored for a long time, the temperature requirement for forming a sintering neck and a conductive channel is low, and the applicable material range is wider;
3. the nano silver particles obtained by the preparation method are uniform and good in dispersity, and can be stored for a long time.
Drawings
FIG. 1 shows resistivity results of copper sheet coated with different conductive nano-silver inks after sintering for 1 hour at different temperatures;
FIG. 2 shows the ratio of flocs obtained by applying different nano-silver conductive inks to a copper sheet and standing for different times;
fig. 3 shows whether the coatings coated on the copper plate paper with different nano silver conductive inks have swelling, roughness, and foaming and falling-off phenomena after the alkali resistance and acid resistance tests.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Preparing nano graphene:
k1, placing 100g of expanded graphite into 3000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 30 ℃ and 8000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 80g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 150r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 4000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 2mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.2mol of ammonium citrate, adjusting the pH to 9, and reacting at 30 ℃ for 3 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 4000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with ethylene glycol, phenolic resin, a surfactant, a dispersing agent, an antioxidant and a flatting agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Example 2
Preparing nano graphene:
k1, putting 100g of expanded graphite into 3000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 120g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 8mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of ammonium citrate, adjusting the pH to 10, and reacting at 100 ℃ for 6 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with ethylene glycol butyl ether, diethylene glycol butyl ether acetate, a surfactant, a dispersant, an antioxidant and a leveling agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Example 3
Preparing nano graphene:
k1, placing 100g of expanded graphite into 2000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 100g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 6mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of ammonium citrate, adjusting the pH to 9.5, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with isopropanol, diethylene glycol monobutyl ether acetate, a surfactant, a dispersant, an antioxidant and a leveling agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Example 4
Preparing nano graphene:
k1, placing 100g of expanded graphite into 2000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 80g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 5mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of sodium silicate, adjusting the pH to 9, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with propylene glycol methyl ether, phenolic resin, a surfactant, a dispersing agent, an antioxidant and a flatting agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Example 5
Preparing nano graphene:
k1, placing 100g of expanded graphite into 2000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 100g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 6mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of sodium aluminate, adjusting the pH value to 9.5, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with glycerol, n-propanol, polyethylene glycol, diethylene glycol butyl ether acetate, a surfactant, a dispersing agent, an antioxidant and a leveling agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Comparative example 1
Preparing nano silver conductive ink:
s1, simultaneously adding 5mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of ammonium citrate, adjusting the pH to 9, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
and S3, mixing the nano silver paste with propylene glycol methyl ether, phenolic resin, a surfactant, a dispersant, an antioxidant and a flatting agent to obtain a mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Comparative example 2
Preparing nano graphene:
k1, placing 100g of expanded graphite into 2000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 100g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 6mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of polyvinylpyrrolidone, adjusting the pH to 9.5, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with isopropanol, diethylene glycol monobutyl ether acetate, a surfactant, a dispersant, an antioxidant and a leveling agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Comparative example 3
Preparing nano graphene:
k1, placing 100g of expanded graphite into 3000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 30 ℃ and 8000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 80g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 150r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 4000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, mixing 2mol of silver nitrate and 1mol of ascorbic acid into distilled water, adjusting the pH to 9, and reacting at 30 ℃ for 3 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 4000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with ethylene glycol, phenolic resin, a surfactant, a dispersing agent, an antioxidant and a flatting agent to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Comparative example 4
Preparing nano silver conductive ink:
s1, mixing 6mol of silver nitrate and 1mol of ascorbic acid into distilled water, adjusting the pH to 9.5, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with isopropanol, diethylene glycol monobutyl ether acetate, a surfactant, a dispersant, an antioxidant and a flatting agent to obtain a mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
Comparative example 5
Preparing nano graphene:
k1, placing 100g of expanded graphite into 2000ml of absolute ethyl alcohol, uniformly stirring, dispersing and grinding for 1h at 40 ℃ and 9000r/min by using a high-shear grinding dispersion machine to obtain slurry, carrying out suction filtration and washing on the slurry, and carrying out freeze drying to obtain pretreated expanded graphite;
k2, adding 30g of the pretreated expanded graphite into 100g of N-methyl pyrrolidone, mechanically stirring for 30min at a speed of 200r/min, performing ultrasonic treatment for 5h, centrifuging at a speed of 5000r/min, taking the upper-layer liquid, performing vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
Preparing nano silver conductive ink:
s1, simultaneously adding 6mol of silver nitrate and 1mol of ascorbic acid into an aqueous solution containing 0.4mol of sodium aluminate, adjusting the pH value to 9.5, and reacting at 80 ℃ for 4 hours to obtain a reaction solution;
s2, centrifuging the reaction solution at 3000r/min, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with isopropanol, diethylene glycol monobutyl ether acetate, a surfactant, a dispersant, an antioxidant and a leveling agent to obtain a mixture, adding nano graphene into the mixture, and performing ultrasonic dispersion to obtain the nano silver conductive ink.
Effect testing
The nano silver conductive ink obtained in examples 1 to 5 and comparative examples 1 to 5 was coated on coated paper using a four-sided preparation machine, and sintered at 25 ℃, 70 ℃, 100 ℃, 130 ℃ and 160 ℃ for 1 hour to obtain a printed product.
Taking the obtained printed product for smoothnessObserving and testing the conductivity, wherein the thickness of the printed film can be measured by a surface roughness meter, the conductivity testing method is measuring by a KDY-1 four-probe instrument, the basic principle is that a constant current source provides stable measuring current for probe heads (1, 4), the probes of the probe heads (2, 3) measure a potential difference V, and the resistivity is measured according to a formula p = (V/I) WFsfF(W/S)F(S/D)FtWherein V is the voltage reading, I is the current reading, W is the film thickness,fF (W/S) is thickness correction coefficient (table look-up table), F (S/D) is diameter correction coefficient (table look-up table), FsfFor the probe pitch correction factor (look-up table), FtThe temperature correction coefficient (table lookup) is adopted, the detected result is shown in fig. 1, fig. 1 is a resistivity result measured by sintering different nano-silver conductive ink at different temperatures for 1 hour after the nano-silver conductive ink is coated on a copper sheet, and the nano-silver conductive ink prepared by the scheme can achieve good conductivity even when being sintered at a lower temperature.
The nano silver conductive inks obtained in examples 1 to 5 and comparative examples 1 to 5 were allowed to stand for different periods of time, and then the settling time was observed, which proved that the nano silver conductive ink obtained in this scheme had good dispersibility and long storage time, and the results are shown in fig. 2, which is a ratio of flocs obtained by allowing different nano silver conductive inks to stand for different periods of time after being coated on a copper sheet.
The nano silver conductive inks obtained in examples 1 to 5 and comparative examples 1 to 5 were subjected to chemical resistance experiments:
alkali resistance: immersing in 5% NaOH solution for 2 h; acid resistance: at 5% H2SO4Immersing the solution for 2 h; the evaluation criteria were: the phenomena of swelling, roughness, bubbling and falling off should not occur; the result is shown in fig. 3, fig. 3 shows whether the coating layer coated on the copper plate paper by different nano silver conductive inks has swelling, roughness, bubbling and falling phenomena after the alkali resistance and acid resistance test, and the nano silver conductive ink prepared by the scheme has good chemical resistance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. The preparation method of the nano-silver conductive ink is characterized by comprising the following steps of:
s1, adding silver nitrate and a reducing agent into a protective agent solution at the same time for reaction to obtain a reaction solution, wherein the protective agent is one or more of ammonium citrate, sodium aluminate and sodium silicate;
s2, centrifuging the reaction solution, and taking precipitate to obtain nano silver paste;
s3, mixing the nano silver paste with a solvent, a bonding agent and a stabilizer to obtain a mixture, adding nano graphene into the mixture, performing ultrasonic dispersion, and finally adding a fluorocarbon resin curing agent for ultrasonic dispersion to obtain the nano silver conductive ink.
2. The method for preparing nano-silver conductive ink according to claim 1, wherein the reducing agent is one or more of ascorbic acid, sodium borohydride and hydrazine hydrate.
3. The method for preparing nano-silver conductive ink according to claim 1, wherein the solvent comprises at least one of ethylene glycol, ethylene glycol butyl ether, isopropyl alcohol, propylene glycol methyl ether, diethylene glycol butyl ether, glycerol, n-propanol, and polyethylene glycol.
4. The method for preparing nano-silver conductive ink according to claim 1, wherein the stabilizer comprises a surfactant, a dispersant, an antioxidant and a leveling agent.
5. The method for preparing nano-silver conductive ink according to claim 1, wherein the binder comprises one or more of phenolic resin and diethylene glycol butyl ether acetate.
6. The method for preparing nano-silver conductive ink according to claim 1, wherein the reaction temperature of step S1 is 30-100 ℃, the reaction pH is 9-10, and the reaction time is 3-6 h.
7. The method for preparing nano-silver conductive ink according to claim 1, wherein the molar ratio of the silver nitrate to the reducing agent is 2-8:1, and the molar ratio of the silver nitrate to the protective agent is 10-20: 1.
8. The method for preparing nano-silver conductive ink according to claim 1, wherein the step of preparing nano-graphene comprises:
k1, putting the expanded graphite into absolute ethyl alcohol, uniformly stirring, grinding and dispersing to obtain slurry, carrying out suction filtration, washing and freeze drying on the slurry to obtain pretreated expanded graphite;
k2, adding the pretreated expanded graphite into N-methyl pyrrolidone, stirring, ultrasonically treating, centrifuging, taking upper-layer liquid, carrying out vacuum filtration to obtain a deposit, and freeze-drying the deposit to obtain the nano graphene.
9. The method for preparing nano-silver conductive ink according to claim 8, wherein the mass ratio of the pretreated expanded graphite to the N-methyl pyrrolidone is 3: 8-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110725318.6A CN113234360A (en) | 2021-06-29 | 2021-06-29 | Preparation method of nano-silver conductive ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110725318.6A CN113234360A (en) | 2021-06-29 | 2021-06-29 | Preparation method of nano-silver conductive ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113234360A true CN113234360A (en) | 2021-08-10 |
Family
ID=77141100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110725318.6A Pending CN113234360A (en) | 2021-06-29 | 2021-06-29 | Preparation method of nano-silver conductive ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234360A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649588A (en) * | 2021-08-12 | 2021-11-16 | 北京大华博科智能科技有限公司 | Nano metal powder, conductive ink and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102464A (en) * | 2018-01-05 | 2018-06-01 | 华南理工大学 | It is a kind of can the water nano silver electrically conductive ink of room temperature sintering and its preparation and application |
| CN109971257A (en) * | 2019-04-03 | 2019-07-05 | 长沙集智创新工业设计有限公司 | A kind of nano-graphene electrically conductive ink and preparation method thereof |
-
2021
- 2021-06-29 CN CN202110725318.6A patent/CN113234360A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102464A (en) * | 2018-01-05 | 2018-06-01 | 华南理工大学 | It is a kind of can the water nano silver electrically conductive ink of room temperature sintering and its preparation and application |
| CN109971257A (en) * | 2019-04-03 | 2019-07-05 | 长沙集智创新工业设计有限公司 | A kind of nano-graphene electrically conductive ink and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649588A (en) * | 2021-08-12 | 2021-11-16 | 北京大华博科智能科技有限公司 | Nano metal powder, conductive ink and preparation method thereof |
| CN113649588B (en) * | 2021-08-12 | 2023-08-22 | 北京大华博科智能科技有限公司 | Nano metal powder, conductive ink and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1514280B1 (en) | Electroconductive carbon fibril-based inks and coatings | |
| WO2018228407A1 (en) | Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof | |
| JP5954922B2 (en) | Silver-containing aqueous formulations and their use to produce conductive or reflective coatings | |
| KR101133466B1 (en) | Low temperature dryable conductive paste composite for solar cell and printing method using the same | |
| KR20180059490A (en) | Conductive paste and conductive film | |
| ZA200903196B (en) | Printable compositions containing silver nanoparticles,processes for producing electrically conductive coatings using the same,and coatings prepared thereby | |
| US4781980A (en) | Copper powder for use in conductive paste | |
| EP3029686B1 (en) | Conductive filler, method for producing same, conductive paste and method for producing conductive paste | |
| KR20090117827A (en) | Shielding based on metallic nanoparticle compositions and devices and methods thereof | |
| CN113808779B (en) | Low-temperature curing insulating medium slurry for chip resistor | |
| US8911821B2 (en) | Method for forming nanometer scale dot-shaped materials | |
| CN113234360A (en) | Preparation method of nano-silver conductive ink | |
| CN101908388B (en) | Forming method of nano-dotted materials | |
| TWI567756B (en) | A conductive paste composition for forming conductive thin film on a flexible substrate and a method for producing the same | |
| CN113402923B (en) | 3D laser photosensitive printing conductive ink for integrated circuit and preparation method thereof | |
| CN113284672B (en) | Preparation method of silver nanowire conductive paste | |
| CN110698925B (en) | Nano printing conductive ink composition and preparation method and application thereof | |
| CN106398398B (en) | Metal nano conductive ink and preparation method thereof | |
| CN115274213A (en) | Preparation method of bending-resistant resistance carbon paste | |
| CN114231092A (en) | Copper conductive ink, flexible substrate and preparation method of flexible substrate | |
| CN112723855B (en) | Laser engraving preparation method and application of graphene-ceramic composite electrode array | |
| Li et al. | Fabrication of flexible printed circuits on polyimide substrate by using Ag nanoparticle ink through 3D direct-writing and reliability of the printed circuits | |
| JP2012052043A (en) | Composite comprising metal particle and electroconductive polymer, and method of manufacturing the same | |
| KR20200062181A (en) | Silver particulate dispersion | |
| CN117877813B (en) | Preparation method and application of environment-friendly water-based conductive silver paste |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210810 |
|
| RJ01 | Rejection of invention patent application after publication |