CN112608642A - Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof - Google Patents
Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof Download PDFInfo
- Publication number
- CN112608642A CN112608642A CN202011589079.8A CN202011589079A CN112608642A CN 112608642 A CN112608642 A CN 112608642A CN 202011589079 A CN202011589079 A CN 202011589079A CN 112608642 A CN112608642 A CN 112608642A
- Authority
- CN
- China
- Prior art keywords
- graphene
- silver
- conductive ink
- solution
- doped nano
- 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 64
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 23
- 239000001856 Ethyl cellulose Substances 0.000 claims description 12
- 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 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 229920001249 ethyl cellulose Polymers 0.000 claims description 12
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 12
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 11
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 99
- 239000000976 ink Substances 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 24
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 19
- 239000008103 glucose Substances 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 18
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 12
- 229910001961 silver nitrate Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 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 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001052 transient effect 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C09D11/30—Inkjet printing inks
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses an inkjet printing type graphene doped nano silver conductive ink and a preparation method thereof, and the preparation method comprises the following steps: s1, preparing a graphene dispersion liquid, preparing a silver solution system containing graphene, adjusting the pH value of the silver solution containing graphene and a dispersing agent, controlling the reaction temperature under the condition of ultrasonic stirring, dropping a reducing agent to reduce nano silver particles, and washing; and S2, adjusting viscosity, surface tension and solid content to prepare the conductive ink suitable for ink jet printing. The graphene-nano silver material obtained through the reduction reaction can be further prepared to directly prepare the conductive ink, and the method is simple and rapid and is suitable for industrial large-scale application.
Description
Technical Field
The invention belongs to the field of 3D ink-jet printing materials, and relates to ink-jet printing type graphene-doped nano-silver conductive ink and a preparation method thereof.
Background
With the development of electronic component products towards miniaturization, low cost and flexibility, the current traditional conductive paste screen printing process and the photoetching process cannot meet the electronic circuit requirements of various integrated intelligent systems such as thin film transistors, sensors, organic photovoltaics, flexible displays, radio frequency identification tags, wearable electronic products and other products. The ink jet printing provides a new idea and a problem solution for solving the problems of low cost and flexible preparation of interconnection wires with line widths between dozens of micrometers and several micrometers for printed circuits, and along with the multifunctionalization of electronic products, conductive ink is rapidly developed as one of key factors of a 3D ink jet printing technology, and conductive ink such as nano metal particle ink, conductive polymer ink, ceramic ink, carbon nanotube ink and graphene appears in recent years. However, the existing conductive ink still has many problems, such as the traditional metal nanoparticle ink is unstable in common solvents, easy to aggregate and stable to disperse only by stabilizers or chemical modification, and the metal nanoparticles are easy to oxidize after printing, so that the cost is high; the conductivity of the conductive polymer ink is low, and the chemical properties are unstable.
Silver in the metal material is widely applied to the conductive material due to the ultrahigh conductivity, ductility and good oxidation resistance, and the shape, size and content of the silver powder in the ink directly influence the conductivity and other properties of the silver paste. For example, the chinese patent application No. 201911377619.3 discloses a graphene-nano silver material and a method for preparing the same, the prepared nano silver is orderly arranged on the surface of graphene, and the material has a low resistivity after low temperature sintering. Graphene has excellent electron transport properties, electron mobility in the plane at room temperature is 15000cm2V-1s-1, and the resistivity corresponding to this value is 10-6 Ω · cm, slightly less than that of silver, 1.59 × 10-6 Ω · cm, so that graphene has excellent conductivity, and in addition, graphene has flexibility.
In the prior art, a large amount of high polymers are used in the preparation process of the nano-silver conductive ink to maintain the dispersibility of the nano-silver, and the high polymers are wrapped on the surface of the nano-silver to influence the conductivity of a printed conductive layer and increase the resistivity. On the other hand, in order to not block the nozzle, the size of graphene must be smaller than 1/100 of the nozzle, so that the conductivity of graphene conductive ink is far from practical application. The velocity and surface tension of the conductive ink fluid during printing affects the size, shape, and volume of the ejected ink drops, and the viscosity of the fluid affects the operating ejection frequency, and thus the printing speed. For high viscosity inks, the gutter fill rate decreases and the firing frequency decreases. At the same time, the transient pressure wave is not suppressed in time when the next pulse is reached. High frequency jetting can cause ink drops to be ejected that are unstable if the ink is not viscous enough. The type of ink determines its curing process by its surface tension. The ink curing process is usually accompanied by a volume reduction, and usually a "coffee ring" effect occurs when the solvent evaporation rate at the edge of the ink drop is faster.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the ink-jet printing type graphene-doped nano-silver conductive ink and the preparation method thereof, the nano-silver is reduced in the graphene dispersion liquid, the prepared nano-silver has the particle size range of 10-200nm, the nano-silver is uniformly distributed on the surface layer of the graphene, and the introduction of the graphene reduces the resistivity of the conductive ink. The graphene-doped nano-silver conductive ink prepared by selecting a proper ink system is suitable for ink-jet printing, and excellent printing adaptability, substrate compatibility and conductivity can be obtained by controlling the optimal addition amount of various addition aids such as adhesion promoters, solvents and the like.
The invention discloses a preparation method of inkjet printing type graphene doped nano silver conductive ink, which comprises the following steps:
s1, preparing a graphene dispersion liquid, preparing a silver solution system containing graphene, adjusting the pH value of the silver solution containing graphene and a dispersing agent, controlling the reaction temperature under the condition of ultrasonic stirring, dropping a reducing agent to reduce nano silver particles, and washing;
and S2, adjusting viscosity, surface tension and solid content to prepare the conductive ink suitable for ink jet printing.
Specifically, the graphene is obtained by adding crystalline flake graphite into an ethyl cellulose-containing ethanol solution for multiple times and carrying out high-frequency ultrasonic mechanical stripping. The graphene is graphene with 1-10 layers. Further 1-5 layers.
The solvent selected by the graphene-containing silver solution system is one or a combination of water, ethanol and N-methyl pyrrolidone.
The dispersing agent selected by the graphene-containing silver solution system is one or more of polyvinylpyrrolidone, polyurethane, acrylic resin, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose and cellulose nitrate. The dispersibility of the nano silver-graphene, the film forming property of the ink and the adhesive force with the base material are ensured. The addition amount is 1 to 2 times of the silver content, and further 1.3 to 1.5 times.
The PH of the silver solution system is adjusted by ammonia or sodium hydroxide, preferably sodium hydroxide,
in the silver solution system containing graphene, the mass ratio of graphene to silver ions is controlled to be 0.01: 100-0.5: 100. further, 0.1: 100-0.2: 100.
the process of reducing silver ions is carried out under the conditions of water bath and ultrasonic stirring.
The reducing agent can be one of formaldehyde, acetaldehyde, glucose, ascorbic acid, hydrogen peroxide, hydrazine hydrate and sodium borohydride, and the amount of the reducing agent to be added can be excessive relative to an aqueous solution system containing silver ions, and further is 1.1-1.3 times. Keeping ultrasonic and stirring, and slowly dropping a reducing agent to reduce the nano-silver particles by controlling the reaction temperature. The reaction temperature is controlled to be 20-70 ℃, and further, 40-50 ℃.
Further, in step S1, the concentration of silver ions in the graphene-containing silver solution system is 0.5-5 mol/L. Further, 1 to 2 mol/L.
Further, in step S1, the nano silver prepared by reduction has a particle size range of 10-200nm, and the nano silver is uniformly distributed on the graphene surface layer.
Further, in step S1, the graphene-doped nano silver solution is washed by a ceramic membrane separation method.
Further, in step S2, a solvent is added to replace the original solvent by a rotary distillation process, and the graphene-doped nano silver conductive ink is concentrated. The boiling point of the added solvent is higher than that of the original solvent, the original solvent is replaced in the rotary distillation process, the amount of the added solvent is calculated according to the concentration of the prepared conductive ink, 10-40% of silver powder and 60-90% of the solvent.
More specifically, when the displacement solvent is subjected to rotary distillation and concentration, the solvent is selected from one or more of cyclohexanone, ethylene glycol, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and modified hydrogenated castor oil.
Further, the solvent selected is a variety of terpineol, cyclohexanone, ethylene glycol, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, modified hydrogenated castor oil.
The conductive ink prepared by the preparation method of the ink-jet printing type graphene-doped nano-silver conductive ink has the solid content of 10-50 wt%, the viscosity of 10-200 cps and the surface tension of 10-100 dyn/cm.
Further preferably, the solid content of the conductive ink is 30-50 wt%, the viscosity of the ink is 10-50 cps, and the surface tension of the ink is 20-40 dyn/cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the graphene-nano silver material obtained through the reduction reaction can be further prepared to directly prepare the conductive ink, and the method is simple and rapid and is suitable for industrial large-scale application.
2. The graphene-doped nano silver solution is washed by a ceramic membrane separation method, so that the graphene nano silver is ensured to have good dispersibility, agglomeration is prevented, and the conductive ink is ensured to have good conductivity.
3. After the new solvent is added, the original solvent is replaced by adopting a rotary distillation method and the graphene-doped nano silver conductive ink is concentrated, so that the solid content, viscosity and surface tension of the ink are in a proper range for ink jet printing, and the ink jet printing is uniform and stable.
4. The prepared conductive ink has better applicability, and compared with the photoetching technology with expensive equipment and complex process, the ink-jet printing technology has the advantages of low cost, environmental friendliness, few processing procedures and the like; compared with silk-screen printing with lower patterning precision, the ink-jet printing has the advantages of high precision, high resolution, high flexibility and the like; compared with the soft printing and the nano printing which can realize large-area high-precision pattern processing, the ink-jet printing has the advantages of uniform pattern, good processing continuity and the like; inkjet printing is not selective to the substrate, does not require a template, and can efficiently pattern on flexible substrates.
Drawings
Fig. 1 is a transmission electron microscope (TEM image) of the graphene-nano silver particles obtained in example 1, wherein fig. b is a single graphene image;
fig. 2 is a picture of the effect of printing with conductive inks using different solvent systems in comparative example 1 and examples 1-5.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In a specific embodiment of the present invention, the graphene ethanol solution: adding 50mg/mL of crystalline flake graphite into an ethanol solution containing 1 wt% of ethyl cellulose for multiple times, performing high-frequency ultrasonic treatment for 4 hours, and centrifuging at 7500 r/m for 30 minutes to obtain few-layer graphene dispersed in a solvent. Diluting the obtained few-layer graphene with alcohol, centrifuging at a high speed of 11000 r/min for 3 hours, wherein the bottom layer is the few-layer graphene, the upper layer is ethyl cellulose alcohol dispersion liquid, and removing redundant ethyl cellulose to obtain the graphene ethanol solution.
Comparative example 1
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 10ml of terpineol solution, and removing ethanol and water in the system by a rotary distillation method, wherein the rotary speed is set to be 70 r/min and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
Example 1
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 10ml of tripropylene glycol monomethyl ether solution, and removing ethanol and water in the system by a rotary distillation method, wherein the rotation speed is set to 70 revolutions per minute and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
Example 2
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 10ml of diethylene glycol monobutyl ether solution, and removing ethanol and water in the system by a rotary distillation method, wherein the rotating speed is set to be 70 r/min and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
Example 3
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 4ml of diethylene glycol monobutyl ether and 6ml of tripropylene glycol monomethyl ether solution, and removing ethanol and water in the system by a rotary distillation method, wherein the rotating speed is set to 70 r/min and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
Example 4
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 3ml of triethylene glycol monobutyl ether, 3ml of cyclohexanone, 3.6ml of terpineol solution and 0.4ml of modified castor oil, removing ethanol and water in the system by a rotary distillation method, wherein the rotating speed is set to 70 revolutions per minute and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
Example 5
Dissolving 6g of silver nitrate in 40ml of deionized water to prepare 0.875mol/L solution, then adding 6.2g of PVP (K30) and 1g of ethyl cellulose, adding 60ml of graphene ethanol solution with the content of 0.3mg/ml after dissolution, fully shaking up, preparing 16ml of 0.1g/ml NaOH solution, dropwise adding the NaOH solution into the silver nitrate solution under the ultrasonic condition, dropwise adding for 5min, placing the solution in a water bath at 50 ℃ for constant temperature after half an hour, and simultaneously carrying out ultrasonic treatment; adding 16g of glucose into 16ml of water solution, and stirring until the glucose is fully dissolved; and dropwise adding the glucose solution into the constant-temperature solution, finishing dropwise adding for 5min, and finishing the reaction after 1.5 hours of ultrasonic treatment.
And (3) cleaning the reaction solution by using a ceramic membrane tube with the aperture of 50nm, wherein the cleaning solution is deionized water, and potassium dichromate and hydrochloric acid solution are used as indicators, and the cleaning is stopped until no precipitate is generated in clear liquid. Collecting the cleaned nano-silver graphene solution, adding 5ml of terpineol, 4.6ml of diethylene glycol monobutyl ether and 0.4ml of modified hydrogenated castor oil solution, removing ethanol and water in the system by a rotary distillation method, wherein the rotating speed is set to 70 revolutions per minute and the temperature is 60 ℃. The ink is printed on a polyimide substrate by an ink-jet printing mode and cured for 30min at 200 ℃.
TABLE 1
As can be seen by combining the attached drawings and the table 1, the raw solvent is replaced by the terpineol in the comparative example 1, the coffee ring effect appears after the ink jet printing, the sheet resistance measured after the low-temperature sintering and curing is larger, the ink jet printing in the examples 1 to 5 is uniform and stable, the sheet resistance measured is smaller, and after the ink jet printing is printed on the polyimide film, the bending resistance radius is smaller and the flexibility is better.
Claims (10)
1. A preparation method of inkjet printing type graphene doped nano silver conductive ink is characterized by comprising the following steps:
s1, preparing a graphene dispersion liquid, preparing a silver solution system containing graphene, adjusting the pH value of the silver solution containing graphene and a dispersing agent, controlling the reaction temperature under the condition of ultrasonic stirring, dropping a reducing agent to reduce nano silver particles, and washing;
and S2, adjusting viscosity, surface tension and solid content to prepare the conductive ink suitable for ink jet printing.
2. The method for preparing inkjet printing graphene-doped nano-silver conductive ink according to claim 1, wherein in step S1, the graphene is obtained by adding crystalline flake graphite into an ethyl cellulose-containing ethanol solution for multiple times and then mechanically stripping with high-frequency ultrasound.
3. The method for preparing the inkjet printing graphene-doped nano silver conductive ink according to claim 2, wherein in step S1, the concentration of silver ions in the graphene-containing silver solution system is 0.5-5 mol/L.
4. The preparation method of the ink-jet printing type graphene-doped nano-silver conductive ink according to claim 3, wherein the concentration of silver ions in the graphene-containing silver solution system is 1-2 mol/L.
5. The method for preparing inkjet printing graphene-doped nano silver conductive ink according to claim 3, wherein in step S1, the nano silver prepared by reduction has a particle size range of 10-200nm, and is uniformly distributed on the surface layer of the graphene.
6. The method for preparing the inkjet printing graphene-doped nano silver conductive ink according to claim 5, wherein in step S1, the graphene-doped nano silver solution is washed by a ceramic membrane separation method.
7. The method for preparing the inkjet printing type graphene-doped nano-silver conductive ink according to claim 6, wherein in step S2, the solvent is added, and the original solvent is replaced by a rotary distillation process, so as to concentrate the graphene-doped nano-silver conductive ink.
8. The method for preparing the inkjet printing graphene-doped nano-silver conductive ink according to claim 7, wherein when the solvent is replaced by rotary distillation and concentrated, the selected solvent is one or more of cyclohexanone, ethylene glycol, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and modified hydrogenated castor oil.
9. The method for preparing the inkjet printing type graphene doped nano-silver conductive ink according to claim 7, wherein the selected solvent is a plurality of terpineol, cyclohexanone, ethylene glycol, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and modified hydrogenated castor oil.
10. The conductive ink prepared by the preparation method of the inkjet printing type graphene doped nano silver conductive ink according to claims 1 to 9, wherein the solid content of the conductive ink is 10 to 50 wt%, the viscosity of the ink is 10 to 200cps, and the surface tension of the ink is 10 to 100 dyn/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589079.8A CN112608642A (en) | 2020-12-28 | 2020-12-28 | Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589079.8A CN112608642A (en) | 2020-12-28 | 2020-12-28 | Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112608642A true CN112608642A (en) | 2021-04-06 |
Family
ID=75248996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011589079.8A Pending CN112608642A (en) | 2020-12-28 | 2020-12-28 | Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608642A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115732117A (en) * | 2022-03-08 | 2023-03-03 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277592A (en) * | 2014-09-16 | 2015-01-14 | 中国科学院化学研究所 | Graphene-based water-based ink and application thereof in ink-jet printing of patterning transparent conducting electrode |
| CN106903324A (en) * | 2015-12-22 | 2017-06-30 | 湖南利德电子浆料股份有限公司 | A kind of preparation method of Graphene-nano silver dispersion |
| CN111292871A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Graphene-nano silver material and preparation method thereof |
| CN111560188A (en) * | 2020-06-01 | 2020-08-21 | 南京林业大学 | Nano-silver/graphene composite electromagnetic shielding ink and preparation method thereof |
-
2020
- 2020-12-28 CN CN202011589079.8A patent/CN112608642A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277592A (en) * | 2014-09-16 | 2015-01-14 | 中国科学院化学研究所 | Graphene-based water-based ink and application thereof in ink-jet printing of patterning transparent conducting electrode |
| CN106903324A (en) * | 2015-12-22 | 2017-06-30 | 湖南利德电子浆料股份有限公司 | A kind of preparation method of Graphene-nano silver dispersion |
| CN111292871A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Graphene-nano silver material and preparation method thereof |
| CN111560188A (en) * | 2020-06-01 | 2020-08-21 | 南京林业大学 | Nano-silver/graphene composite electromagnetic shielding ink and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115732117A (en) * | 2022-03-08 | 2023-03-03 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
| CN115732117B (en) * | 2022-03-08 | 2024-01-19 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867315B (en) | Preparation method and application of conductive ink based on metal nanowires and graphene oxide | |
| CN106928773B (en) | Graphene composite conductive ink for ink-jet printing and preparation method thereof | |
| US9449734B2 (en) | Conductive metal ink composition, and method for preparing a conductive pattern | |
| JP5982033B2 (en) | Metal fine particle dispersion, copper fine particle dispersion, method for producing copper fine particle dispersion, and method for producing conductive substrate | |
| TWI518146B (en) | Printable compositions containing silver nanoparticles, processes for producing electrically conductive coatings using the same, and coatings prepared thereby | |
| JP6005852B2 (en) | Metallic nanoparticle dispersion system | |
| CN102093774B (en) | Conductive ink and preparation method thereof | |
| US8481860B2 (en) | Conductive paste containing silver-decorated carbon nanotubes | |
| CN101805538A (en) | Lower-temperature sintered conductive ink | |
| CN102321402A (en) | Agranular transparent conductive ink and its preparation method | |
| US10113079B2 (en) | Conductive composition | |
| CN110248477B (en) | Manufacturing method of embedded flexible conductive circuit | |
| WO2010144790A1 (en) | Ink jettable silver/silver chloride compositions | |
| Zhang et al. | Fabrication of flexible copper patterns by electroless plating with copper nanoparticles as seeds | |
| CN112608642A (en) | Ink-jet printing type graphene-doped nano-silver conductive ink and preparation method thereof | |
| CN108084794B (en) | Preparation method and application of hyperbranched polymer-stabilized nano-silver jet printing conductive ink | |
| KR102458237B1 (en) | Catalyst Ink For Plating And Electroless Plating Pattern Forming Methods Using The Same | |
| JP5072228B2 (en) | Method for producing metal coating | |
| KR101679144B1 (en) | Composition for forming conductive copper pattern by light sintering including carbon nanostructures, method for preparing conductive copper pattern by light sintering, and electronic device including the conductive copper pattern prepared therefrom | |
| KR101416579B1 (en) | Conductive paste printed circuit board having plating layer and method for manufacturing the same | |
| CA2665219A1 (en) | Conductive patterns and methods of using them | |
| CN113789085A (en) | Preparation method of nano-silver of ink-jet conductive ink for polyimide substrate | |
| WO2013141174A1 (en) | Conductive ink, base material including conductor, and production method for base material including conductor | |
| CN113035448B (en) | Flexible conductive metal pattern, preparation method and application thereof, and conductive material | |
| KR20100031843A (en) | Ink composition for forming conductive metallic electrode and the method for producing thereof |
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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ma Jin Inventor after: Chen De Inventor before: Ma Jin |
|
| CB03 | Change of inventor or designer information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210406 |
|
| RJ01 | Rejection of invention patent application after publication |