CN111496266A - Environment-friendly conductive nano copper ink and preparation method thereof - Google Patents
Environment-friendly conductive nano copper ink and preparation method thereof Download PDFInfo
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- CN111496266A CN111496266A CN202010385875.3A CN202010385875A CN111496266A CN 111496266 A CN111496266 A CN 111496266A CN 202010385875 A CN202010385875 A CN 202010385875A CN 111496266 A CN111496266 A CN 111496266A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 239000010949 copper Substances 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 39
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 10
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 10
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 8
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 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
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 3
- 229910001379 sodium hypophosphite Inorganic materials 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
- 150000004008 N-nitroso compounds Chemical class 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000008569 process Effects 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 abstract 1
- SBJKKFFYIZUCET-UHFFFAOYSA-N Dehydroascorbic acid Natural products OCC(O)C1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-UHFFFAOYSA-N 0.000 abstract 1
- 235000020960 dehydroascorbic acid Nutrition 0.000 abstract 1
- 239000011615 dehydroascorbic acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 54
- 239000000976 ink Substances 0.000 description 41
- 238000005303 weighing Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 9
- 239000003223 protective agent Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a green and environment-friendly conductive nano-copper ink and a preparation method thereof, wherein the preparation method utilizes cavitation and acoustic flow effect of high-energy ultrasonic waves in a liquid phase to change a chemical reaction mechanism so as to efficiently obtain nano-copper particles, and the specific contents of the preparation method comprise: firstly, adopting ascorbic acid as a reducing agent and copper hydroxide as a copper source, and then utilizing the dispersion effect of a product dehydroascorbic acid after ascorbic acid reaction and combining the special effect of ultrasonic waves in a liquid phase to efficiently synthesize a required copper nanoparticle solution; and then, separating the copper nanoparticle dispersion liquid to obtain pure copper nanoparticles, repeatedly washing, and adding various organic solvents to mix to obtain the nano copper conductive ink. The preparation method has the advantages of unique reaction mechanism, novel preparation means, simple process, low cost, high yield efficiency, environmental friendliness, easiness in formation of large-scale production and the like, and has wide application prospect in the field of printed electronics.
Description
The technical field is as follows:
the invention belongs to the technology of conductive ink preparation, and particularly relates to green and environment-friendly conductive nano copper ink and a preparation method thereof, which are widely applied to processing and manufacturing of components in printed electronics.
Background art:
compared with the traditional micro-nano processing, the biggest characteristic of the printed electronics is that the printed electronics does not depend on the conductor or semiconductor property of a substrate material and can be deposited on any material in a thin film form.
The conductive ink mainly comprises conductive filler and various additives, and can be divided into inorganic conductive ink and organic conductive ink according to the difference of conductive media. Among them, organic conductive inks have not been put to practical use, but have poor printability during use due to poor dispersibility during preparation, and have poor conductivity as compared with inorganic conductive inks; the inorganic conductive ink can be divided into metal conductive ink and carbon conductive ink, wherein the conductivity of the carbon conductive ink is slightly lower than that of the metal conductive ink, and the inorganic conductive ink is difficult to purify, so that the manufacturing cost is overhigh, and the application of the inorganic conductive ink in printed electronics is limited; the metal conductive ink mainly comprises conductive ink prepared by noble metal nano particles such as nano gold, silver, copper and the like, and in consideration of cost and conductivity, the copper conductive ink has the highest cost performance relatively and low cost but the conductivity is almost equivalent to that of silver.
For example, patent CN201010221315.0 discloses a method for preparing a nano-copper conductive ink, which comprises the steps of dissolving a copper salt and a protective agent in a solvent, heating and stirring, adding a small amount of alkaline solution to adjust the pH value to 7-10, dripping a reducing agent, continuously stirring for reaction for 30-60 minutes, cooling to room temperature to obtain a nano-copper dispersion liquid, centrifuging and washing the nano-copper dispersion liquid, drying in vacuum at room temperature to obtain nano-copper particles, dispersing the nano-copper particles in an organic solvent, performing ultrasonic treatment to obtain the nano-copper conductive ink, and patent CN201410778114.9 discloses a conductive nano-copper ink and a preparation method thereof, wherein the preparation method comprises the steps of mixing and reacting freshly prepared copper hydroxide and the protective agent in a first solvent, adding L-ascorbic acid to obtain a copper nano-particle dispersion liquid, separating the copper nano-particles from the copper nano-particle dispersion liquid to obtain the copper nano-particles, and adding a second solvent after washing to obtain the nano-copper conductive ink.
In addition, CN201910191510.4 discloses a preparation method and application of a nano-copper ink-jet printing ink, wherein the preparation method comprises the steps of preparing polyvinylpyrrolidone precursor liquid, replacing polyvinylpyrrolidone with different average molecular weights to obtain copper nanoparticles with different particle sizes, preparing copper source precursor liquid and reducing agent precursor liquid, dropwise adding the copper source precursor liquid and the reducing agent precursor liquid into the polyvinylpyrrolidone precursor liquid together, stirring the mixture in an oil bath, centrifugally washing the obtained product, drying the product in vacuum to obtain copper nanoparticles, mixing the copper nanoparticles with different particle sizes, dissolving the mixture in a mixed solution of deionized water, ethylene glycol and glycerol, and ultrasonically dispersing the mixture to obtain the nano-copper ink-jet printing ink, CN200810201967.0 discloses a method of preparing nano-copper conductive ink with stable performance at 120-160 ℃ by using sodium hypophosphite as a precursor, adding L D and polyvinylpyrrolidone (PVP) as a surfactant and a dispersant, using a liquid phase reduction method of organic diethylene glycol (DEG) to remove impurity ions in black water, and enabling the content of the copper nanoparticles to be uniform in distilled water (the electrodialysis water, and enabling the content of the copper nanoparticles to be 20-50 nm).
At present, the preparation method of the copper nanoparticles is various, but the preparation method of quickly obtaining the copper nanoparticles by utilizing the efficient ultrasonic sonochemical effect is not reported yet, and the copper nanoparticles prepared by the method have the advantages of simple process, low cost, environmental protection, high yield, good oxidation resistance, excellent dispersibility and easiness in large-scale production.
The invention content is as follows:
the invention aims to provide environment-friendly conductive nano-copper ink and an efficient preparation method thereof. The method has the advantages that the cavitation and acoustic flow effect formed in the liquid phase by utilizing high-power ultrasonic waves is firstly proposed, and the basic chemical reduction process is changed by the phonochemical effect. In high-energy sonochemical processes, radicals or high-energy species generated by acoustic cavitation diffuse into the liquid phase, initiating a series of chemical reactions, thereby forming nanoparticles. In addition, the product of the reducing agent in the method has excellent dispersion effect, so the prepared copper nanoparticles have good dispersibility, simple process, low cost and no pollution to the environment, the large-scale production is easy to form, and the synthesized conductive ink has stable performance and low cost and is suitable for the wide requirements of printed electronics.
Specifically, the technical scheme adopted by the invention is as follows:
first, the present invention provides a method for preparing copper nanoparticles for green and environmentally friendly conductive ink, the method comprising:
adding a copper source into a solvent A according to the proportion of 0.2-2 mol/L, uniformly stirring, heating to 50-90 ℃ to obtain a solution a, adding a reducing agent into the solvent A according to the proportion of 2-10 mol/L, then adding a certain amount of dispersing agent, uniformly stirring to obtain a solution b, placing the solution b into a customized ultrasonic device at 50-90 ℃, rapidly dissolving the solution b according to preset ultrasonic parameters, rapidly pouring the solution a into the solution b after the solution b is uniformly mixed, carrying out ultrasonic treatment for 0.1-1h, cooling to room temperature, and repeatedly centrifuging for multiple times to obtain precipitated copper nanoparticles.
The method utilizes the unique chemical reaction characteristic of copper hydroxide and ascorbic acid, and dehydrogenated ascorbic acid molecules generated by the reaction are adsorbed on the surface of the nano-particles to further prevent the nucleation and growth process of atoms, so that the copper nano-particles with uniform dispersion and uniform particle size are realized. Secondly, the byproduct generated by the reaction is water, the reaction process is mild and pollution-free, so that the necessary conditions of safety, reliability and environmental protection are provided for realizing large-scale production of the reaction, which is completely different from the two patents; finally, the invention introduces ultrasonic waves to accelerate the reaction, thereby realizing better reaction effect and dispersion, which determine the adaptability and printability of the copper-based conductive ink in the process of printing electrons.
The copper source is preferably at least one of copper nitrate, copper sulfate, copper hydroxide or copper chloride.
The solvent A is preferably one or a mixture of at least two of diethylene glycol, ethanol, ethylene glycol and glycerol.
The reducing agent is preferably one or a mixture of at least two of sodium hypophosphite, ascorbic acid, hydrazine hydrate, potassium borohydride and methylamine.
The dispersing agent is preferably one or a mixture of at least two of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyacrylamide and span.
The ultrasonic parameters are preferably as follows: the ultrasonic power is 1000-3000W, the ultrasonic frequency is 20-200kHz, and the ultrasonic intermittent pulse ratio is 1: 1-10: 1.
preferably, the temperature of the solution a and the solution b is the same.
Preferably, the centrifugation condition is centrifugation washing at 5000-.
Preferably, the number of centrifugal washing times is 4.
The material selected in the process of preparing the copper nanoparticles by the method has the advantages that no pollutant or complex by-product is generated in the chemical synthesis process, and the reagents have the characteristics of environmental protection, no toxicity and the like; in addition, the ultrasonic parameters and the reagent proportion selected by the method are obtained by optimizing a large number of experimental explorations, and the method has the advantages of high repeatability, good process stability, suitability for large-scale generation and the like.
Secondly, the invention provides a preparation method of green and environment-friendly conductive nano-copper ink on the basis of the method, which is characterized by comprising the following steps: the preparation method comprises the following steps: mixing the copper nanoparticles prepared by the preparation method, a third solvent, a binder, a foaming agent and the like according to a certain mass ratio, and then putting the mixture into a special paste mixing machine for stirring uniformly to finally obtain the required nano-copper conductive ink
Specifically, the prepared copper nanoparticles, the third solvent B, the binder C, the foaming agent D and the like are mixed according to a certain mass ratio, and then the mixture is put into a special paste mixing machine to be uniformly stirred, so that the required nano-copper conductive ink is finally obtained.
The third solvent B is preferably one or a mixture of at least two of ethylene glycol, glycerol, deionized water and ethanol.
The binder C is preferably one or a mixture of at least two of ethyl cellulose, polyethylene, alcohol polyurethane, glycerol, terpineol and polyacrylate.
The foaming agent D is preferably one or a mixture of at least two of azodicarbonamide, ethylene glycol, N-nitroso compound and amine nitrite
Preferably, the mass ratio of the nanoparticles to the solvent is 2: 1-6: 1.
preferably, the mass ratio of the nanoparticles to the binder is 20: 1-30: 1.
preferably, the mass ratio of the nanoparticles to the foaming agent is 15: 1-30: 1
Preferably, the rotating speed of the paste mixing machine is 500-1500 r/min.
Preferably, the paste mixing times are 3-6.
Preferably, the solid content of the copper nanoparticles in the ink is 50% -90%.
The selection of the adding reagent, the proportion and the preparation parameters of the copper nano conductive ink prepared by the method is based on the particularity of the copper nano particle preparation principle, the formula and the process of the copper nano conductive ink have the particularity, and particularly the addition of various organic solvents improves the oxidation resistance, the low-temperature sintering and the conductive and heat-conducting properties of the copper nano particles.
Furthermore, the green and environment-friendly conductive nano-copper ink is prepared by the preparation method.
The solid content of copper nanoparticles in the conductive nano-copper ink is 50-90%.
The invention provides the copper nanoparticle conductive ink prepared by the method, wherein the particle size of the nanoparticles is about 150nm, and the dispersibility of the nanoparticles is excellent. Compared with the prior art, the invention has the advantages that:
(1) the invention utilizes the unique chemical reaction characteristic of copper hydroxide and ascorbic acid, and dehydrogenated ascorbic acid molecules generated by the reaction are adsorbed on the surface of nano-particles to further prevent the nucleation and growth process of atoms, thereby realizing the copper nano-particles with uniform dispersion and uniform particle size. The byproduct generated by the reaction is water, and the reaction process is mild and pollution-free, so that the necessary conditions for realizing large-scale production by the reaction are provided for being safer, more reliable and more environment-friendly.
(2) The invention introduces the ultrasonic action, and accelerates the reaction by utilizing the special effect of high-energy ultrasonic in the liquid phase, thereby realizing better reaction effect and dispersion, which determine the adaptability and printability of the copper-based conductive ink in the process of printing electrons.
(3) The copper nanoparticles prepared by the method have the average particle size of about 150nm, have excellent dispersibility and uniform distribution of morphology and particle size, and can be used as a conductive filler required by a digital and high-automation ink-jet printing technology.
(4) The method has the advantages of no need of protective gas, low cost, simple process, environmental protection, ultrahigh efficiency, extremely high yield and suitability for mass production. In addition, the conductive ink prepared by the invention has good oxidation resistance and conductivity, and has wide application prospect in the field of printed electronics.
Description of the drawings:
FIG. 1 is a schematic diagram of the principle of sonochemical reaction during the process of example 1 of the present invention;
FIG. 2 is an XRD pattern of nano-copper particles obtained in example 1 of the present invention;
FIGS. 3a to 3b are SEM image and particle size distribution histogram of the nano-copper particles obtained in example 1 of the present invention;
FIGS. 4a to 4c are the UV and SEM images obtained in examples 1 to 3 of the present invention during the synthesis of copper nanoparticles under different ultrasonic parameters;
FIG. 5 is a pictorial representation of a printed electronic circuit obtained in example 1 of the present invention;
FIG. 6 is a graph comparing the resistivity of printed electronic pattern lines of examples 1-3 of the present invention.
The specific implementation mode is as follows:
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 3g of copper hydroxide, adding the copper hydroxide into 150ml of ethanol solvent, uniformly mixing, continuously stirring, heating to 50 ℃, and completely dissolving to obtain a solution a; weighing 15g of ascorbic acid as a reducing agent, weighing 2g of polyvinylpyrrolidone (K-20) as a protective agent, uniformly mixing the ascorbic acid and the protective agent, adding the mixture into 150ml of ethanol for dissolving, continuously stirring, heating to 50 ℃, and obtaining a solution b after complete dissolution.
(2) Solution b was placed in a pulsed ultrasonic device applying a direct downward action with preset ultrasonic parameters: power 1000W, frequency 20KHz, pulse ratio 3: 1, heating to 50 ℃, quickly pouring the solution a into the solution b for reaction for 10min, and obtaining a copper nanoparticle solution after the solution is changed from light blue to deep red.
(3) And (3) cooling the copper nanoparticle solution obtained in the step (2) to room temperature, and centrifugally washing the copper nanoparticle solution for 4 times at 4000r/min of deionized water to obtain pure copper nanoparticles.
(4) The preparation method comprises the following steps of (1) mixing freshly prepared copper nanoparticles, ethylene glycol, glycerol, terpineol, ethyl cellulose and the like in a mass ratio of 7: 1: 1: 0.5: 0.5, mixing uniformly, then placing the mixture into a special paste mixing machine with the rotating speed of 700r/min for mixing for 5 times, and finally obtaining the copper nano particle conductive ink.
Wherein, FIG. 1 is a schematic diagram of the principle of sonochemical reaction in the process of example 1 of the present invention; FIG. 2 is an XRD pattern of nano-copper particles obtained in example 1 of the present invention; FIGS. 3a to 3b are SEM image and particle size distribution histogram of the nano-copper particles obtained in example 1 of the present invention; FIG. 5 is a pictorial representation of a printed electronic circuit obtained in example 1 of the present invention.
Example 2
(1) Weighing 5g of copper acetate, adding the copper acetate into 100ml of ethanol solvent, uniformly mixing, continuously stirring, heating to 100 ℃, and completely dissolving to obtain a solution a; weighing 10g of sodium borohydride as a reducing agent, weighing 2g of polyvinylpyrrolidone (K-20) as a protective agent, uniformly mixing the sodium borohydride and the protective agent, adding the mixture into 100ml of ethanol for dissolving, continuously stirring, heating to 100 ℃, and obtaining a solution b after complete dissolution.
(2) Solution b was placed in a pulsed ultrasonic device applying a direct downward action with preset ultrasonic parameters: power 1200W, frequency 35KHz, pulse ratio 4: 1, heating to 100 ℃, quickly pouring the solution a into the solution b for reaction for 10min, and obtaining a copper nanoparticle solution after the solution is changed from light blue to deep red.
(3) And (3) cooling the copper nanoparticle solution obtained in the step (2) to room temperature, and centrifugally washing the copper nanoparticle solution for 4 times at 4000r/min of deionized water to obtain pure copper nanoparticles.
(4) The preparation method comprises the following steps of (1) mixing freshly prepared copper nanoparticles, ethylene glycol, glycerol, terpineol, ethyl cellulose and the like in a mass ratio of 7: 1: 1: 0.5: 0.5, mixing uniformly, then placing the mixture into a special paste mixing machine with the rotating speed of 700r/min for mixing for 5 times, and finally obtaining the copper nano particle conductive ink.
Example 3
(1) Weighing 10g of copper sulfate, adding the copper sulfate into 100ml of ethanol solvent, uniformly mixing, continuously stirring, heating to 80 ℃, and completely dissolving to obtain a solution a; weighing 20g of ascorbic acid as a reducing agent, weighing 5g of polyvinylpyrrolidone (K-30) as a protective agent, uniformly mixing the ascorbic acid and the protective agent, adding the mixture into 100ml of ethanol for dissolving, continuously stirring, heating to 80 ℃, and obtaining a solution b after complete dissolution.
(2) Solution b was placed in a pulsed ultrasonic device applying a direct downward action with preset ultrasonic parameters: power 1500W, frequency 40KHz, pulse ratio 5: 1, heating to 80 ℃, quickly pouring the solution a into the solution b for reaction for 10min, and obtaining a copper nanoparticle solution after the solution is changed from light blue to deep red.
(3) And (3) cooling the copper nanoparticle solution obtained in the step (2) to room temperature, and centrifugally washing the copper nanoparticle solution for 4 times at 4000r/min of deionized water to obtain pure copper nanoparticles.
(4) The preparation method comprises the following steps of (1) mixing freshly prepared copper nanoparticles, ethylene glycol, glycerol, terpineol, ethyl cellulose and the like in a mass ratio of 7: 1: 1: 0.5: 0.5, mixing uniformly, then placing the mixture into a special paste mixing machine with the rotating speed of 700r/min for mixing for 5 times, and finally obtaining the copper nano particle conductive ink.
FIGS. 4a to 4c are the UV and SEM images obtained in examples 1 to 3 of the present invention during the synthesis of the copper nanoparticles under different ultrasonic parameters, respectively; FIG. 6 is a graph comparing the resistivity of printed electronic pattern lines of examples 1-3 of the present invention.
Example 4
(1) Weighing 2g of graphite powder, adding the graphite powder into 35ml of 98% sulfuric acid solution, and uniformly stirring for 2 hours to obtain a solution a; then weighing 6g of KMnO4The powder was slowly added to solution a, reacted for 30min after constant stirring and heating to 40 ℃, and then the resulting solution was diluted with 90ml of water under vigorous stirring to give a dark brown suspension c.
(2) 150ml of distilled water and 30% of H are added to the suspension c2O2The reaction was terminated with a solution (10 ml). After stirring for 2 hours continuously, the solution was repeatedly subjected to centrifugal filtration using a 5% aqueous HCl solution to remove the remaining metal ions. Then, the mixture is distilled water to obtain the final productThe centrifugation process was repeated until the pH of the solution became neutral.
(3) 0.2g of the synthesized graphite oxide was redispersed in 200ml of distilled water and subjected to ultrasonication for 30min to exfoliate the graphite oxide into a monolayer of Graphene Oxide (GO) and further used for the synthesis of graphene.
(4) Dropwise adding NaOH solution into graphene oxide solution (0.2g/200m L) to adjust the pH value to 10, then adding 2m L hydrazine, carrying out ultrasonic irradiation on the whole reaction for 2 hours, wherein the reaction finishing temperature is about 60 +/-5 ℃, and obtaining graphene nanosheet solution after the reaction is finished.
(5) The obtained graphene nanoplatelets were thoroughly washed with distilled water and centrifuged at 12000rpm for 10 minutes to remove residues. This process is repeated several times until the synthesized product is free of trace impurities, thereby obtaining pure graphene nanoplatelets.
Example 5
(1) Weighing 0.01 mol% of ferrocene, dissolving and adding the solution into 50ml of p-xylene solution with the mass fraction of 99%, and uniformly stirring to obtain solution a; and then 2g of silicon powder (the diameter is 2-5mm) is weighed and slowly added into the solution a, and the reaction is carried out for 30min after the continuous and uniform stirring.
(2) An ultrasonic amplitude transformer with the diameter of 6mm is deeply inserted into the solution a, high-energy ultrasonic waves are continuously output to the solution for 20min under normal temperature and normal pressure through preset parameters of 200W of ultrasonic power and 65% of amplitude, and after the reaction is completed, the solution turns grey and black precipitates are generated.
(3) The resulting precipitate was thoroughly washed with distilled water and centrifuged at 12000rpm for 10 minutes to remove the residue. This process is repeated several times until the synthesized product is free from trace impurities, thereby obtaining pure carbon nanotubes.
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 (10)
1. A preparation method of copper nanoparticles for green and environment-friendly conductive ink is characterized by comprising the steps of adding a copper source into a solvent A according to the proportion of 0.2-2 mol/L, heating to 50-90 ℃ after uniform stirring to obtain a solution a, adding a reducing agent into the solvent A according to the proportion of 2-10 mol/L, adding a certain amount of a dispersing agent, uniformly stirring to obtain a solution b, placing the solution b into an ultrasonic device at the temperature of 50-90 ℃, applying ultrasonic waves to rapidly dissolve the solution b, rapidly pouring the solution a into the solution b after the solution b is uniformly mixed, continuing the ultrasonic waves for 0.1-1h, cooling to room temperature, and repeatedly centrifuging for multiple times to obtain precipitated copper nanoparticles.
2. The method of claim 1, wherein: the copper source is selected from at least one of copper nitrate, copper sulfate, copper hydroxide or copper chloride; the solvent A is one or a mixture of at least two of diethylene glycol, ethanol, glycol and glycerol; the reducing agent is selected from one or a mixture of at least two of sodium hypophosphite, ascorbic acid, hydrazine hydrate, potassium borohydride and methylamine.
3. The method of claim 1, wherein: the ultrasonic parameters are set as follows: the ultrasonic power is 1000-3000W, the ultrasonic frequency is 20-200kHz, and the ultrasonic intermittent pulse ratio is 1: 1-10: 1.
4. the method of claim 1, wherein: the temperature of the solution a is the same as that of the solution b; the centrifugation condition is 8000r/min at 5000-.
5. A preparation method of green environment-friendly conductive nano-copper ink is characterized by comprising the following steps: the preparation method comprises the following steps: mixing the copper nanoparticles prepared by the preparation method of any one of claims 1 to 3, the third solvent, the binder, the foaming agent and the like according to a certain mass ratio, and then putting the mixture into a special paste mixing machine for stirring uniformly to finally obtain the required nano-copper conductive ink.
6. The method according to claim 5, wherein the third solvent is selected from the group consisting of: the third solvent is one or a mixture of at least two of deionized water, ethanol, glycol and glycerol; the binder is selected from one or a mixture of at least two of glycerol, terpineol, ethyl cellulose, polyethylene, alcohol polyurethane and polyacrylate; the foaming agent is one or a mixture of at least two of N-nitroso compound, azodicarbonamide, ethylene glycol and amine nitrite.
7. The production method according to claim 5, characterized in that the solid content of copper nanoparticles in the ink is 50% to 90%.
8. The method according to claim 5 or 6, wherein the mass ratio of the copper nanoparticles to the third solvent is 2: 1-6: 1; the mass ratio of the nano particles to the binder is 20: 1-30: 1; the mass ratio of the nano particles to the foaming agent is 15: 1-30: 1.
9. An environment-friendly conductive nano copper ink, which is prepared by the preparation method of any one of claims 1 to 8.
10. The green and environment-friendly conductive nano-copper ink as claimed in claim 9, wherein the solid content of copper nano-particles in the ink is 50% -90%.
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