CN111500121B - Conductive ink for flexible printed electronics and sonochemical synthesis method - Google Patents
Conductive ink for flexible printed electronics and sonochemical synthesis method Download PDFInfo
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- CN111500121B CN111500121B CN202010386209.1A CN202010386209A CN111500121B CN 111500121 B CN111500121 B CN 111500121B CN 202010386209 A CN202010386209 A CN 202010386209A CN 111500121 B CN111500121 B CN 111500121B
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000012990 sonochemical synthesis Methods 0.000 title claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052802 copper Inorganic materials 0.000 claims abstract description 93
- 239000010949 copper Substances 0.000 claims abstract description 93
- 239000002105 nanoparticle Substances 0.000 claims abstract description 74
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052709 silver Inorganic materials 0.000 claims abstract description 47
- 239000004332 silver Substances 0.000 claims abstract description 47
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 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 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- -1 amine nitrite Chemical class 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 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
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 36
- 239000002245 particle Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 239000003223 protective agent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 150000004008 N-nitroso compounds Chemical class 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Crystallography & Structural Chemistry (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a conductive ink for flexible printing electronics and a sonochemical synthesis method, wherein the preparation method comprises the following steps: firstly, a copper nanoparticle precursor is efficiently obtained by using a high-intensity ultrasonic field, and then a process of replacing copper atoms by silver is realized by using a low-energy uniformly-dispersed ultrasonic field, so that a silver-coated copper nanoparticle dispersion liquid is obtained; and secondly, separating the silver-coated copper nanoparticle dispersion liquid to obtain pure antioxidant silver-coated copper nanoparticles, repeatedly washing, and adding various organic solvents to mix to obtain the nano silver-coated copper conductive ink. The preparation method of the conductive ink is simple to operate, high in efficiency, high in yield, environment-friendly, low in cost and suitable for large-scale production, overcomes the defects of high-cost nano silver ink and easily-oxidized nano copper ink, and has a wide application prospect in the field of flexible printed electronics.
Description
Technical Field
The invention belongs to the preparation technology of conductive ink, relates to conductive ink for flexible printed electronics and a sonochemical synthesis method, and particularly relates to a preparation method taking nano silver-coated copper particles as conductive filler, which is mainly applied to processing and manufacturing various components in the flexible printed electronics.
Background
Human beings have entered the new century and a great deal of research progress has been made in developing the next generation of flexible, low-cost and environmentally friendly printed electronics. With the continuous and intensive research on printed electronics in recent years, people have found wide application in the fields of flexible electronic devices, printed circuit boards, light emitting diodes, radio frequency identification tags, electromagnetic shielding, chip packaging and the like. The printed electronic technology is an electronic preparation technology based on a printing principle, and mainly prints and patterns some liquid materials with good dispersibility or soluble materials so as to realize the preparation of electronic components. Compared with the traditional PCB manufacturing method, the printed electronic technology is more convenient, the traditional PCB manufacturing method needs 8 steps of film coating, gluing, baking and the like, and the printed electronic only needs two steps, namely printing and sintering. And the printed electronics also have the inherent advantages of independence on substrate materials, mass production, low cost, environmental protection and the like. One of the key technologies is to prepare novel conductive ink with environmental protection and low cost.
The conductive ink mainly comprises conductive filler, a regulator, a solvent and various auxiliaries, and can be divided into the following components according to different functional components: a metal-based conductive ink, a carbon-based conductive ink, and an organic polymer-based conductive ink. The selection of the conductive ink is very limited, the dispersibility of the organic conductive ink in the preparation process is difficult to solve, so that the printability of the organic conductive ink is poor in the use process, and the conductive performance of the organic conductive ink is inferior to that of the inorganic conductive ink, so that the use of the organic conductive ink is greatly challenged. Although the conductive performance of carbon-based conductive ink is slightly lower than that of metal conductive ink, the greatest difficulty is that the purification is difficult, so that the manufacturing cost is too high, and the application of the carbon-based conductive ink to printed electronics is limited. At present, the conductivity of silver is relatively good, the stability is also good, and the price is much cheaper than that of gold, platinum and the like. However, the silver content in conductive inks is low, and the overall cost of the ink is acceptable, but the conductivity is poor. The copper-based ink has the advantages of low cost and good conductivity, but the problems of instability and easy oxidation bring great trouble to researchers. Therefore, in the scheme of coating a stable substance on the surface of copper to improve the oxidation resistance, silver-shell-coated copper core-shell structure nanoparticles (Cu @ Ag NPs) formed by coating a copper core with a silver shell are most studied. Such as: chinese patent 201610154292.3 discloses a method for preparing silver-coated copper nanoparticle conductive ink, which is simple to operate, high in purity, low in cost, high in yield, environment-friendly and suitable for mass production. Chinese patent 201711241749.5 discloses a conductive nano silver-coated copper material for RFID antenna conductive patterns, which has simple preparation process, environment-friendly and renewable ink solvent, and has great application prospect in the field of conductive ink for RFID antennas.
At present, the preparation method of the conductive nano silver-coated copper ink which has the advantages of particle size within 100nm, simple process, no need of protective gas, greenness, no pollution and suitability for mass production is not disclosed.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a conductive ink for flexible printing electronics and a sonochemical preparation method. The method has the advantages of simple preparation process, low cost, environmental friendliness, high efficiency, energy conservation and suitability for large-scale production.
The technical scheme adopted by the invention is as follows:
a sonochemical synthesis method of conductive ink for flexible printed electronics, comprising the steps of:
step one, preparing copper nanoparticles: preparing copper nanoparticles under the action of ultrasonic sonochemistry by adopting a mixture of a copper source, a reducing agent, a dispersing agent and one or more solvents;
step two, preparing silver-coated copper nanoparticles: mixing the obtained copper nanoparticles, a silver source, a reducing agent, a dispersing agent and one or more solvents, quickly synthesizing silver-coated copper nanoparticle dispersion liquid under the efficient action of ultrasonic sonochemistry, separating the silver-coated copper nanoparticles from the silver-coated copper nanoparticle dispersion liquid, and washing to obtain pure antioxidant silver-coated copper nanoparticles;
step three, preparing the conductive ink: and adding a proper amount of various organic solvents, and uniformly mixing to obtain the nano silver-coated copper conductive ink.
More specifically, a sonochemical synthesis method of conductive ink for flexible printed electronics, comprising the steps of:
step one, preparing copper nanoparticles:
adding a copper source into the solvent A according to 0.1-1mol/L, uniformly stirring, and heating to 60-160 ℃ to obtain a solution a; adding a reducing agent into the solvent A according to 0.1-1mol/L, then adding a certain amount of dispersing agent, and uniformly stirring to obtain a solution b; putting the solution b into a customized ultrasonic device at 60-160 ℃, and quickly dissolving the solution b according to preset ultrasonic parameters; and after the solution b is uniformly mixed, quickly pouring the solution a into the solution b, carrying out ultrasonic treatment for 0.2-3h, cooling to room temperature, and repeatedly centrifuging for multiple times to obtain the precipitated copper nanoparticles.
The copper source is preferably at least one of copper hydroxide, copper nitrate, copper acetylacetonate, copper sulfate or copper chloride.
The solvent A is preferably one or a mixture of at least two of deionized water, ethanol, ethylene glycol, diethylene glycol, -dipropylene glycol and glycerol.
The reducing agent is preferably one or a mixture of at least two of hydrazine hydrate, potassium borohydride, sodium hypophosphite, ascorbic acid and methylamine.
The dispersing agent is preferably one or a mixture of at least two of lauryl sodium sulfate, polyacrylamide, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and span.
The ultrasonic parameters are preferably as follows: the ultrasonic power is 200-800W, the ultrasonic frequency is 20-80kHz, and the ultrasonic intermittent pulse ratio is 1: 1-4: 1.
preferably, the temperature of the solution a and the solution b is the same.
Preferably, the centrifugation condition is that the centrifugation washing is carried out at 3000-8000 r/min.
Preferably, the number of centrifugal washing times is 4.
Step two, preparing silver-coated copper nanoparticles:
adding a silver source into the solvent B according to 0.025-0.25mol/L, and uniformly stirring to obtain a solution c; adding the prepared fresh copper nanoparticles into a solvent B, and adding the fresh copper nanoparticles into the solvent B according to the mol/L of 0.05-0.5mol/L to be uniformly mixed to obtain a solution d; putting the solution d into a customized ultrasonic device at the temperature of 20-50 ℃, and quickly dissolving the solution d according to preset ultrasonic parameters; and after the solution d is uniformly mixed, slowly dripping the solution c into the solution d, carrying out ultrasonic treatment for 0.2-3h, cooling to room temperature, and repeatedly centrifuging for multiple times to obtain the precipitated silver-coated copper nanoparticles.
The silver source is preferably at least one of silver nitrate, silver sulfate and silver acetate.
The solvent B is preferably one or a mixture of at least two of deionized water, ethanol, glycol, diethylene glycol and glycerol.
The ultrasonic parameters are preferably as follows: the ultrasonic power is 20-100W, the ultrasonic frequency is 20-80kHz, and the ultrasonic intermittent pulse ratio is 1: 1-4: 1.
preferably, the temperature of the solution c is the same as that of the solution d.
Preferably, the centrifugation condition is centrifugation washing at 3000-.
Preferably, the centrifugal washing times are 3-6.
Step three, preparing the conductive ink:
mixing freshly prepared silver-coated copper nanoparticles, a solvent C, a binder D, a foaming agent E and the like according to a certain mass ratio, and then putting the mixture into a special paste mixing machine to stir uniformly, thereby finally obtaining the required nano-silver-coated copper conductive ink.
The solvent C is preferably one or a mixture of at least two of deionized water, ethanol, glycol and glycerol.
The binder D is preferably one or a mixture of at least two of glycerol, terpineol, ethyl cellulose, polyethylene, alcohol polyurethane and polyacrylate.
The foaming agent E is preferably one or a mixture of at least two of N-nitroso compound, azodicarbonamide, glycol and amine nitrite
The mass ratio of the nano particles to the solvent is 4: 1-8: 1.
the mass ratio of the nano particles to the binder is 10: 1-20: 1.
the mass ratio of the nano particles to the foaming agent is 20: 1-30: 1
Preferably, the rotating speed of the paste mixing machine is 200-1000 r/min.
Preferably, the paste mixing times are 3-6 times.
The invention provides conductive ink for flexible printed electronics, which is prepared by any one of the methods, wherein the particle size of silver-coated copper nanoparticles is less than 100nm, the average particle size is about 55-60 nm, and the solid content of the silver-coated copper nanoparticles is preferably 50-90%.
Compared with the prior art, the invention has the advantages that:
(1) the invention introduces the ultrasonic action, the ultrasonic chemical synthesis accelerates the collision and contact of reaction ions in the solution by means of special effects (acoustic flow, cavitation, acoustic gradient and the like) of ultrasonic waves in the liquid state, further improves the chemical reaction process, and greatly shortens the reaction time by utilizing the unique effect of an ultrasonic field in the liquid state, thereby obtaining nanoparticles with better dispersibility.
(2) The method is characterized in that the ultrasonic parameters of the silver-coated copper nanoparticles prepared by the two-step method are accurately regulated, wherein the copper nanoparticles are prepared by adopting high-power and high-frequency short pulse ultrasonic waves, and the generated high-energy ultrasonic field greatly accelerates the reaction process and shortens the reaction time; and the silver-copper replacement needs to adopt ultrasonic waves with small power, low frequency and long pulse, the uniform ultrasonic field generated by the ultrasonic waves is beneficial to the generation of a silver coating layer, and the silver layer thickness is controlled to realize the protection of copper nanoparticles.
(3) The silver-coated copper nanoparticles prepared by the method have good oxidation resistance and conductivity, and the double defects of high-price silver and easy-oxidation copper are overcome; the conductive ink prepared by the invention has the characteristics of about 55-60 nm of average particle size, low sintering temperature and excellent conductivity, and has wide application prospect in the field of printed electronics.
(4) The invention does not need protective gas, has easily obtained raw materials, simple process, environmental protection and ultrahigh efficiency, and is suitable for mass production.
Drawings
FIG. 1 is a schematic representation of an ultrasonic sonochemical reaction during example 1 of the present invention;
fig. 2 is an XRD pattern of nano silver-coated copper particles obtained in example 1 of the present invention;
FIGS. 3a-3b are SEM images and particle size distribution histograms of the nano-silver-coated copper particles obtained in example 1 of the present invention;
FIG. 4 is a comparative UV chart of the process of preparing nano silver-coated copper particles obtained in example 1 of the present invention;
FIG. 5 is a TEM image of nano-silver coated copper particles obtained in example 1 of the present invention;
FIG. 6 is a pictorial representation of a printed electronic circuit obtained in example 1 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the following figures and specific examples, but the invention is not limited thereto:
example 1
(1) Weighing 8g of copper sulfate, adding the copper sulfate into 80ml of glycerol solvent, uniformly mixing, continuously stirring, heating to 60 ℃, and completely dissolving to obtain a solution a; weighing 6g of sodium hypophosphite as a reducing agent, weighing 5g of polyvinylpyrrolidone (K-20) as a protective agent, uniformly mixing the sodium hypophosphite and the protective agent, adding the mixture into 100ml of glycerol for dissolving, continuously stirring, heating to 60 ℃, and obtaining a solution b after complete dissolution;
and placing the solution b in a pulse ultrasonic device which exerts direct downward action, heating to 60 ℃, quickly pouring the solution a into the solution b for reaction for 10min, and obtaining the copper nanoparticle solution after the solution is changed from light blue to reddish brown.
And cooling the obtained copper nanoparticle solution to room temperature, and centrifugally washing the copper nanoparticle solution for 4 times by using deionized water at 3000r/min to obtain pure copper nanoparticles.
(2) Weighing a certain amount of the copper nanoparticles obtained in the step (1), adding the copper nanoparticles into 100ml of glycol solvent, and carrying out ultrasonic treatment for 5min to uniformly mix the copper nanoparticles and the glycol solvent to obtain a solution d; weighing 2g of silver nitrate, adding the silver nitrate into 100ml of ethylene glycol solvent, continuously stirring, and obtaining a solution c after the silver nitrate is completely dissolved;
and (3) placing the solution d in a pulse ultrasonic device, heating the solution to 40 ℃, slowly dropping the solution c into the solution d for reaction for 30min until the solution is changed from reddish brown to light gray, and obtaining the silver-coated copper nanoparticle solution.
And cooling the obtained silver-coated copper nanoparticle solution to room temperature, and centrifugally washing the solution for 4 times by deionized water at the speed of 3000r/min to obtain pure silver-coated copper nanoparticles.
(3) And (3) mixing the freshly prepared silver-coated copper nanoparticles obtained in the step (2), ethylene glycol, glycerol, terpilenol and ethyl cellulose in a mass ratio of 6: 2: 1: 0.5: 0.5, mixing uniformly, and then placing the mixture into a special paste mixing machine with the rotating speed of 700r/min for mixing for 4 times to finally obtain the silver-coated copper nanoparticle conductive ink.
Wherein, FIG. 1 is a schematic diagram of an ultrasonic sonochemical reaction during example 1; fig. 2 is an XRD pattern of the nano silver-coated copper particles obtained in example 1; FIGS. 3a-3b are SEM photograph and particle size distribution bar chart of the nano-silver coated copper particles obtained in example 1; FIG. 4 is a comparative UV chart of the process of preparing nano silver-coated copper particles obtained in example 1; FIG. 5 is a TEM image of the nano-silver-coated copper particles obtained in example 1; FIG. 6 is a pictorial representation of a printed electronic circuit obtained in example 1.
Example 2
(1) Weighing 6g of copper sulfate, adding the copper sulfate into 70ml of glycerol solvent, uniformly mixing, continuously stirring, heating to 50 ℃, and obtaining a solution a after complete dissolution; weighing 8g of sodium hypophosphite as a reducing agent, weighing 5g of polyvinylpyrrolidone (K-30) as a protective agent, uniformly mixing the sodium hypophosphite and the protective agent, adding the mixture into 100ml of glycerol for dissolving, continuously stirring, heating to 50 ℃, and obtaining a solution b after the mixture is completely dissolved;
and placing the solution b in a pulse ultrasonic device which exerts direct downward action, heating to 50 ℃, quickly pouring the solution a into the solution b for reaction for 20min, and obtaining the copper nanoparticle solution after the solution is changed from light blue to reddish brown.
And cooling the obtained copper nanoparticle solution to room temperature, and centrifugally washing the copper nanoparticle solution for 4 times by using deionized water at 3000r/min to obtain pure copper nanoparticles.
(2) Weighing a certain amount of the copper nanoparticles obtained in the step (1), adding the copper nanoparticles into 100ml of glycol solvent, and carrying out ultrasonic treatment for 5min to uniformly mix the copper nanoparticles and the glycol solvent to obtain a solution d; then weighing 2g of silver nitrate, adding the silver nitrate into 100ml of ethylene glycol solvent, continuously stirring, and obtaining a solution c after the silver nitrate is completely dissolved;
and (3) placing the solution d in a pulse ultrasonic device, heating the solution to 40 ℃, slowly dropping the solution c into the solution d, and reacting for 30min until the solution is changed from reddish brown to light gray to obtain the silver-coated copper nanoparticle solution.
And cooling the obtained silver-coated copper nanoparticle solution to room temperature, and centrifugally washing the silver-coated copper nanoparticle solution for 4 times by using deionized water at 3000r/min to obtain pure silver-coated copper nanoparticles.
(3) And (3) mixing the freshly prepared silver-coated copper nanoparticles obtained in the step (2), ethylene glycol, glycerol, terpilenol and ethyl cellulose in a mass ratio of 6: 2: 1: 0.5: 0.5, then placing the mixture into a special paste mixing machine with the rotating speed of 700r/min for mixing for 4 times, and finally obtaining the silver-coated copper nanoparticle conductive ink.
Example 3
(1) Weighing 8g of copper sulfate, adding the copper sulfate into 80ml of glycerol solvent, uniformly mixing, continuously stirring, heating to 60 ℃, and obtaining a solution a after complete dissolution; weighing 6g of sodium hypophosphite as a reducing agent, weighing 5g of polyvinylpyrrolidone (K-20) as a protective agent, uniformly mixing the sodium hypophosphite and the protective agent, adding the mixture into 100ml of glycerol for dissolving, continuously stirring, heating to 60 ℃, and obtaining a solution b after the mixture is completely dissolved;
and (3) placing the solution b in a pulse ultrasonic device which exerts direct downward action, heating to 60 ℃, quickly pouring the solution a into the solution b for reaction for 15min, and obtaining the copper nanoparticle solution after the solution is changed from light blue to reddish brown.
And cooling the obtained copper nanoparticle solution to room temperature, and centrifugally washing the solution for 4 times by deionized water at the speed of 3000r/min to obtain pure copper nanoparticles.
(2) Weighing a certain amount of the copper nanoparticles obtained in the step (1), adding the copper nanoparticles into 150ml of glycol solvent, and carrying out ultrasonic treatment for 5min to uniformly mix the copper nanoparticles and the glycol solvent to obtain a solution d; weighing 4g of silver nitrate, adding the silver nitrate into 100ml of ethylene glycol solvent, continuously stirring, and obtaining a solution c after the silver nitrate is completely dissolved;
and (3) placing the solution d in a pulse ultrasonic device, heating the solution to 50 ℃, slowly dropping the solution c into the solution d, and reacting for 60min until the solution is changed from reddish brown to light gray to obtain the silver-coated copper nanoparticle solution.
And cooling the obtained silver-coated copper nanoparticle solution to room temperature, and centrifugally washing the solution for 4 times by deionized water at the speed of 3000r/min to obtain pure silver-coated copper nanoparticles.
(3) And (3) mixing the freshly prepared silver-coated copper nanoparticles obtained in the step (2), glycol, glycerol, terpineol and ethyl cellulose in a mass ratio of 5: 1: 1: 1: 1, uniformly mixing, and then placing the mixture in a special paste mixing machine with the rotating speed of 700r/min for mixing for 4 times to finally obtain the silver-coated copper nanoparticle conductive ink.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (1)
1. A sonochemical synthesis method of conductive ink for flexible printed electronics, characterized in that:
step one, preparing copper nanoparticles: adding a copper source into the solvent A according to 0.1-1mol/L, uniformly stirring, and heating to 60-160 ℃ to obtain a solution a; adding a reducing agent into the solvent A according to 0.1-1mol/L, then adding a certain amount of dispersing agent, and uniformly stirring to obtain a solution b; putting the solution b into an ultrasonic device which applies a pulse acting directly downwards at the temperature of 60-160 ℃, and quickly dissolving the solution b according to preset ultrasonic parameters; after the solution b is uniformly mixed, quickly pouring the solution a into the solution b, carrying out ultrasonic treatment for 0.2-3h, cooling to room temperature, repeatedly centrifuging for multiple times to obtain precipitated copper nanoparticles, wherein the ultrasonic parameters are as follows: the ultrasonic power is 200-800W, the ultrasonic frequency is 20-80kHz, and the ultrasonic intermittent pulse ratio is 1: 1-4: 1,
wherein, the solvent A is one or a mixture of at least two of deionized water, ethanol, glycol, diethylene glycol, dipropylene glycol and glycerol; the reducing agent is selected from one or a mixture of at least two of hydrazine hydrate, potassium borohydride, sodium hypophosphite, ascorbic acid and methylamine; the dispersing agent is selected from one or a mixture of at least two of sodium dodecyl sulfate, polyacrylamide, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and span;
step two, preparing silver-coated copper nanoparticles: adding a silver source into the solvent B according to the mol/L of 0.025-0.25, and uniformly stirring to obtain a solution c; adding the prepared fresh copper nanoparticles into a solvent B, adding the prepared fresh copper nanoparticles into the solvent B according to the mol/L of 0.05-0.5mol/L, uniformly mixing to obtain a solution d, placing the solution d into an ultrasonic device which applies a pulse acting downwards at 20-50 ℃, and quickly dissolving the solution d according to preset ultrasonic parameters; after the solution d is uniformly mixed, slowly dropping the solution c into the solution d, carrying out ultrasonic treatment for 0.2-3h, cooling to room temperature, repeatedly centrifuging for multiple times to obtain precipitated silver-coated copper nanoparticles, wherein the ultrasonic parameters are set as follows: the ultrasonic power is 20-100W, the ultrasonic frequency is 20-80kHz, and the ultrasonic intermittent pulse ratio is 1: 1-4: 1,
wherein the silver source is at least one selected from silver nitrate, silver sulfate and silver acetate; the solvent B is one or a mixture of at least two of deionized water, ethanol, glycol, diethylene glycol and glycerol;
step three, preparing the conductive ink: mixing the freshly prepared silver-coated copper nanoparticles, a solvent C, a binder D and a foaming agent E according to a certain mass ratio, then putting the mixture into a special paste mixing machine for stirring uniformly to finally obtain the required nano silver-coated copper conductive ink,
wherein, the solvent C is one or a mixture of at least two of deionized water, ethanol, glycol and glycerol; the binder D is one or a mixture of at least two of glycerol, terpineol, ethyl cellulose and polyacrylate; the foaming agent E is one or a mixture of at least two of azodicarbonamide, ethylene glycol and amine nitrite.
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