CN104263082A - Graphene organic silver conductive printing ink and preparation method thereof - Google Patents
Graphene organic silver conductive printing ink and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention discloses a graphene organic silver conductive printing ink and a preparation method thereof. The conductive printing ink comprises a conductive function unit precursor, an organic silver complexing agent, an adhesive, a solvent and auxiliaries. The preparation method comprises the following steps: (A) stirring and ultrasonically dispersing the organic silver, the solvent and the organic silver complexing agent under a lucifugal condition to obtain an organic silver complexing solution; and (B) putting the graphene, the resin adhesive, the auxiliaries and the organic silver complexing solution in the lucifugal condition and stirring and ultrasonically dispersing in an environment lower than 10 DEG C, wherein the obtained uniform mixture is the graphene organic silver conductive printing ink. The graphene organic silver conductive printing ink prepared by the method disclosed by the invention is low in solid content, good in stability, good in printing performance and wide in application.
Description
Technical field
The present invention relates to electrically conductive ink field, particularly a kind of Graphene organic silver electrically conductive ink and preparation method thereof.
Background technology
Along with the high speed development of science and technology, the extensive use of unicircuit, microelectronic device is miniaturization more and more, the electronic circuit of printed wiring, intelligent label, flexible display device, sensor also to small, become more meticulous, diversity development, the mode of printing of its correspondence and base material kind get more and more.Printing process comprises method for printing screen, gravure process, engraving method, rotating coating, electro-plating method, chemical gaseous phase depositing process, inkjet printing methods, direct write method etc.; As the base material printed, rigid base material can be divided into, as glass, metal, semi-conductor, silicon chip, pottery, epoxy resin etc.; And flexible parent metal, as PET film, polyimide film etc.
Electrically conductive ink is made up of conducting function unit, solvent, binding agent, dispersion agent, property-modifying additive etc. usually, can be divided into metal or burning system, carbon system, compound system three major types; The conducting function unit of metal or burning system electrically conductive ink mainly contains bronze, silver powder, copper powder etc., and its performance is good, but bronze is expensive, and copper powder is easily because oxidation reduces electroconductibility; Therefore mainly use silver powder system electrically conductive ink at present, but silver powder easily moves, sintering process is easy to crack, bending resistance is poor, so be mainly used in low resistance rigid base material conducting channel.The conducting function unit of carbon series conductive ink mainly contains graphite, carbon black, acetylene black etc., its stable performance, not oxidizable, corrosion-resistant after solidification, but resistivity is lower, is mainly used in thin film switch.The ink material of above-mentioned material all also exists the relative merits of self, for improving printing part performance, expands the use range of electrically conductive ink, and the improvement of conducting function unit and the new conductive unit of exploration application are the trend of domestic and international electrically conductive ink research and development.
Graphene is the nano-carbon material of new generation of Geim group report in 2004, there is the features such as high electronic mobility, excellent thermal conductivity, the unusual quantum hall effect of room temperature, Dual-polarized electricity field-effect and high Young's modulus, in fields such as matrix material, energy storage device, transparency electrodes, there is great application prospect.Graphene conductive is high, and density is much smaller than copper, silver, and bending resistance is good, and itself is stable; Along with the maturation of Graphene preparation technology, price is more and more cheap, and therefore Graphene replacement copper, silver not only meet integrated, the light-weighted developing direction of microelectronic industry as the wire of printed wiring, can also reduce the consume of precious metal.
But there is lamellar interface resistance when utilizing Graphene to prepare electro-conductive material, prepared electrically conductive ink is easily reunited, bad dispersibility, actual electroconductibility and the theoretical electroconductibility of Graphene have a long way to go.The mode that nanometer silver is added in current employing in Graphene ensures that it leads performance, and the addition of the method nanometer silver is generally greater than 50 wt%; The preparation also very complicated of nanometer silver, this adds production cost undoubtedly; In addition, in the electrically conductive ink of this state, Graphene and argent are solid-state, difficulty is brought to the dispersion of particle in ink configuration and some mode of printing (as ink-jet, directly writing) application, therefore, the electrically conductive ink providing a kind of silver-colored presoma method being modulated into liquid state to prepare Graphene and silver-colored compound type is of great immediate significance.
Organic silver is the organic compound of silver, and be modulated into liquid state by complexing, but organic silver is unstable, additional component very easily causes its fast decoupled to reduce, and therefore in organic silver, other conductive unit of compound structure novel conductive ink does not have report.Our research confirm Graphene do not have reductibility or reductibility more weak, by reasonably configuring technique, Graphene and organic silver can be stablized and coexist.
Summary of the invention
The invention provides a kind of stable Graphene organic silver electrically conductive ink and preparation method thereof, compared with the electrically conductive ink being all Graphene or nanometer silver with conductive unit, this electrically conductive ink solid content is low, the good stability of ink, and printing performance is good, be widely used, the present invention is achieved in that a kind of Graphene organic silver electrically conductive ink, it is characterized in that, raw material and component as follows, by percentage to the quality, comprising:
Conducting function unit presoma 23-40%,
Organic silver complexing agent 25-57%,
Binding agent 3-10%
Solvent 0.5-20%,
Auxiliary agent 2.5-6%;
Described conducting function unit presoma is made up of Graphene and organic silver, and in Graphene and organic silver, the mass ratio of elemental silver is 4-92:96-8.
Preferably, in the present invention, in described conducting function unit presoma, in Graphene and organic silver, the mass ratio of elemental silver is 4-20:96-80 or 80-92:20-8.
Preferably, in the present invention, in described conducting function unit presoma, in Graphene and organic silver, the mass ratio of elemental silver is 4:96-82:18.
Preferably, in the present invention, described Graphene is the lamellar structure of single or multiple lift.
Preferably, in the present invention, described organic silver is pungent capric acid silver, beta-keto acid silver-colored, 2-[2-(2-methoxyethoxy) oxyethyl group] Silver monoacetate, butyric acid silver, silver citrate, succinic acid are silver-colored, oxysuccinic acid is silver-colored, one in silver tartrate, Silver monoacetate, silver oxalate.
Preferably, in the present invention, described binding agent is ethyl cellulose, Natvosol, polyvinyl alcohol, resol, vibrin, polyimide resin, epoxy resin, silicone resin, fluorocarbon resin, vibrin, Vinylite, acrylic resin, acrylate quasi-oligomer and reactive monomer, Synolac, synthetic cellulose, polyamide resin, vinyl chloride-vinyl acetate resin, urethane resin, polyvinylidene fluoride resin, thermoplastic resin, synthetic rubber, silicon-modified epoxy, polyurethane modified epoxy, epoxy modified acrylic resin, organosilicon-modified acrylic epoxy resin, acrylic resin modified, modified phenolic, one in modified alkyd resin.
Preferably, in the present invention, described organic silver complexing agent is aminated compounds or amido compounds; Wherein, described aminated compounds refers to ammoniacal liquor, Tri N-Propyl Amine, n-Butyl Amine 99, isobutylamine, normal hexyl Amine, n-octyl amine, 1,2-propylene diamine, 1,3-propylene diamine, Diisopropylamine, Di-n-Butyl Amine, diethanolamine, triethylamine, tripropyl amine or sec-butylamine; Described amido compounds refers to 2-(methylamino)-Ethanol, 3-aminopropyl Ethoxysilane or diethylaminoethanol.
Preferably, in the present invention, described solvent is one or more in water, aromatic hydrocarbon solvent, fat hydrocarbon solvent, ether solvent, alcoholic solvent, alcohol ether solvent, amide solvent, ketones solvent, esters solvent.
Preferably, in the present invention, described auxiliary agent is one or more in dispersion agent, stablizer, protective material, membrane-forming agent, coupling agent, softening agent, defoamer, thickening material, wetting agent, flow agent, thixotropic agent, linking agent, uv-absorbing agent.
A preparation method for Graphene organic silver electrically conductive ink of the present invention, its concrete steps are as follows:
A) in proportion organic silver, solvent and organic silver complexing agent are stirred 0.5-12 h under lucifuge condition, ultrasonic disperse 1-12 h, obtain organic silver complex solution;
B) mixed by organic silver complex solution stirring reaction 0.5-12 h or ultrasonic disperse 0.5-12 h or ball milling 0.5-1 h in lucifuge, temperature are lower than the environment of 10 ° of C that Graphene, binding agent, auxiliary agent and steps A obtain in proportion, products therefrom is Graphene organic silver electrically conductive ink.
Preferably, in the present invention, described organic silver obtains like this: slowly instill in corresponding organic solution by silver salt or silver suboxide solution, 0.5-2 h is stirred under lucifuge condition, by the washing of precipitate of acquisition, filtration, room temperature lucifuge is dried in the shade, and products therefrom is organic silver.
Beneficial effect of the present invention is:
1, the product conduction needs that the physical properties such as electrically conductive ink conductive unit ratio of components provided by the present invention, solid content, surface tension and viscosity can be printed according to actual needs regulates, this electrically conductive ink sintering temperature is minimum can to 150 ° of C, therefore the range of choice of its printed substrate is wider, as rigid base materials such as glass, pottery, metal, semi-conductor, silicon chip, pottery, epoxy resin; Because containing Graphene in electrically conductive ink, significantly improving fine silver ink bending resistance, meeting the print request of flexible device, it is also suitable for the flexible parent metals such as polyimide film.
2, the viscosity of Graphene organic silver electrically conductive ink that prepared by the inventive method can adjust in wider scope, change according to preparation method and concrete use procedure, be preferably 1-1500 cP, conductive ink as lower in viscosity is applicable to the multiple mode of printings such as ink jet printing, directly pen are write, rotating coating; The conductive ink that viscosity is higher then can be applied to the multiple mode of printing such as intaglio printing, silk screen printing.
3, conductivity is controlled, the present invention can be different to the requirement of conductivity according to printing device, by changing ratio of components and the solid content of Graphene and organic silver in conductive unit presoma in electrically conductive ink, while meeting service requirements, change and use Graphene and organic silver content, reduce ink cost.
4, printed matter good stability, compared with Graphene silver electrically conductive ink, in electrically conductive ink provided by the present invention, organic silver directly exists in ink in the form of a solution with organic additive complexing, does not need to consider that Argent grain is reunited the impact being difficult to effectively disperse end article conductivity.
5, the present invention is compared with silver-colored electrically conductive ink, Graphene silver electrically conductive ink, and the addition of conductive unit needed for identical electroconductibility reduces, and the thermal treatment temp of ink is extremely low, makes performance and cost obtain optimization.
6, not oxidizable, the performance temperature of electrically conductive ink printed matter of the present invention, corrosion-resistant, in electrically conductive ink of the present invention, silver content is lower, and electroconductibility significantly improves relative to Graphene ink, and electroconductibility is suitable with simple silver-colored ink, greatly reduce ink cost, be easy to apply; In addition, carbon slurry, the silver paste printing ink highly filled relative to tradition, the solid content of electrically conductive ink provided by the present invention is low, and stably dispersing will be got well, and easily stores and uses.
Embodiment
The present invention will be further described by the following examples, and embodiment is not limitation of the present invention.
Embodiment 1 prepares Graphene oxysuccinic acid silver electrically conductive ink
(1) preparation of oxysuccinic acid silver, under room temperature, 1.3g DL-sodium malate is dissolved in 50mL deionized water, then 2.5g Silver Nitrate is dissolved in 40mL deionized water, with dropper silver nitrate aqueous solution is slowly added dropwise in the sodium malate aqueous solution that (mol ratio of Silver Nitrate and sodium malate is 2:1, to ensure that Silver Nitrate is little over amount), occur white precipitate at once, lucifuge stirs 2 h, afterwards by washing of precipitate, filtration, room temperature lucifuge is dried in the shade, and obtains oxysuccinic acid silver solid.
(2) by mass percentage; take following raw material: the Graphene (thickness is about 7nm, number of plies <10) that the oxysuccinic acid that 20% step 1 obtains is silver-colored, prepared by 3% oxide-reduction method, 3% binding agent (urethane resin), 52% organic silver complexing agent (Diisopropylamine), 16% solvent (Terpineol 350), 5.5% dispersion protective material (span-80), 0.5% defoamer.
(3) oxysuccinic acid silver mixing Terpineol 350, Diisopropylamine and step 1 obtained in proportion, stirs 2 h with the rotating speed of 500 rpm, again with 80 KHz ultrasonic disperse 2 h, obtains homogeneous oxysuccinic acid silver complex solution under lucifuge is less than 10 ° of C conditions.
(4) oxysuccinic acid silver complex solution Graphene, urethane resin, Terpineol 350, span-80, defoamer and step 3 obtained stirs 2 h with the rotating speed of 800rpm under lucifuge, temperature are lower than the condition of 10 ° of C, again with rotating speed ball milling 2 min of 300rpm, the uniform sizing material mixture obtained is the silver-colored electrically conductive ink (Graphene and elemental silver mass ratio are about 80:20) of Graphene oxysuccinic acid.
The Graphene oxysuccinic acid silver electrically conductive ink using the method that is coated with embodiment 1 to be obtained is printed on Kapton, and 200 ° of C process 1 h, it is 0.9 Ω/ that four point probe resistance meter records square resistance.
Embodiment 2 prepares Graphene silver citrate electrically conductive ink
(1) silver citrate is prepared, under room temperature, 1.35g Trisodium Citrate is dissolved in 50mL deionized water, again 2.5g Silver Nitrate is dissolved in 40mL deionized water, with dropper, silver nitrate aqueous solution is slowly added dropwise in sodium citrate aqueous solution, occurs white precipitate at once, lucifuge stirs 2 h, afterwards by washing of precipitate, filtration, room temperature lucifuge is dried in the shade, obtained silver citrate solid.
(2) by mass percentage; take following raw material: silver citrate, 1% Physical that 34% step 1 obtains prepare single-layer graphene, 5% binding agent (Natvosol), 57% organic silver complexing agent (1,2-propylene diamine), 0.5% solvent (Virahol), 1.5% dispersion protective material (Si Ban-85), 0.5% defoamer, 0.5% stablizer.
(3) Virahol, 1,2-propylene diamine and silver citrate are mixed in proportion, under lucifuge is less than 10 ° of C conditions, stirring (500 r/min) 12 h, ultrasonic (80 KHz) disperse 2 h, obtain homogeneous silver citrate complex solution.
(4) silver citrate complex solution Graphene, binding agent, solvent, dispersion protective material, defoamer, stablizer and step 3 obtained stirs (800 r/min) 2 h under lucifuge, temperature are lower than the condition of 10 ° of C, ultrasonic (80 KHz) disperses 0.5 h, again with rotating speed ball milling 5 min of 300rpm; Graphene silver citrate is mixed, namely obtains Graphene silver citrate electrically conductive ink (Graphene and elemental silver mass ratio are about 4:96).
Graphene silver citrate electrically conductive ink embodiment 2 obtained is through silk screen printing on Kapton, and 200 ° of C process 1 h, it is 0.03 Ω/ that four point probe resistance meter records square resistance.
Embodiment 3 prepares Graphene silver citrate electrically conductive ink
(1) silver citrate is prepared, under room temperature, 1.35g Trisodium Citrate is dissolved in 50mL deionized water, again 2.5g Silver Nitrate is dissolved in 40mL deionized water, with dropper, silver nitrate aqueous solution is slowly added dropwise in sodium citrate aqueous solution, occurs white precipitate at once, lucifuge stirs 2 h, afterwards by washing of precipitate, filtration, room temperature lucifuge is dried in the shade, obtained silver citrate solid.
(2) by mass percentage; take following raw material: 36% step 1 obtain silver citrate, 3% chemical process prepare Graphene, 3% binding agent (acrylic resin modified), 54% organic silver complexing agent (1,2-propylene diamine), 1.5% solvent (Virahol), 1.5% dispersion protective material (Si Ban-85), 0.5% defoamer, 0.5% stablizer.
(3) Virahol, 1,2-propylene diamine and silver citrate are mixed in proportion, under lucifuge is less than 10 ° of C conditions, stirring (500 r/min) 12 h, ultrasonic (80 KHz) disperse 2 h, obtain homogeneous silver citrate complex solution.
(4) silver citrate complex solution Graphene, binding agent, solvent, dispersion protective material, defoamer, stablizer and step 3 obtained stirs (800 r/min) 2 h under lucifuge, temperature are lower than the condition of 10 ° of C, ultrasonic (80 KHz) disperses 0.5 h, again with rotating speed ball milling 3 min of 300rpm; Graphene silver citrate is mixed, namely obtains Graphene silver citrate electrically conductive ink (Graphene and elemental silver mass ratio are about 8:92).
Graphene silver citrate electrically conductive ink embodiment 3 obtained is through silk screen printing on Kapton, and 150 ° of C process 1 h, it is 17 Ω/ that four point probe resistance meter records square resistance.
Embodiment 4 prepares Graphene Silver monoacetate electrically conductive ink
(1) Silver monoacetate is prepared, under room temperature, be dissolved in by 0.6g sodium-acetate in 50mL deionized water, 2.5g Silver Nitrate is dissolved in 40mL deionized water, with dropper just silver nitrate aqueous solution be slowly added dropwise in sodium acetate aqueous solution,, there is white precipitate at once in (mol ratio of Silver Nitrate and sodium-acetate is 3:1, to ensure that Silver Nitrate is little over amount), lucifuge stirs 2 h, afterwards by washing of precipitate, filtration, room temperature lucifuge is dried in the shade, obtained Silver monoacetate solid.
(2) by mass percentage, following raw material is taken: single-layer graphene, 10% resin glue (acrylic resin), 25% organic silver complexing agent (2-(methylamino)-Ethanol), 20 % solvents (pimelinketone), 4.7% span-80 (dispersion protective material), 0.3% defoamer prepared by the Silver monoacetate that 4.5% step 1 obtains, 35.5% Physical.
(3) pimelinketone, 2-(methylamino)-Ethanol and Silver monoacetate are mixed in proportion, under lucifuge is less than 10 ° of C conditions, stirring (500 r/min) 12 h, ultrasonic (80 KHz) disperse 2 h, obtain homogeneous Silver monoacetate complex solution.
(4) Silver monoacetate complex solution Graphene, binding agent, solvent, dispersion protective material, defoamer and step 3 obtained stirs (800 r/min) 2 h under lucifuge, temperature are lower than the condition of 10 ° of C, ultrasonic (80 KHz) disperses 0.5h; again with rotating speed ball milling 3 min of 300rpm; Graphene Silver monoacetate is mixed, namely obtains Graphene Silver monoacetate electrically conductive ink (Graphene and elemental silver mass ratio are about 92:8).
Graphene Silver monoacetate electrically conductive ink embodiment 4 obtained is through silk screen printing on glass, and 250 ° of C process 1 h, it is 8 Ω/ that four point probe resistance meter records square resistance.
Embodiment 5 prepares the grapheme modified silver citrate electrically conductive ink of argent
(1) silver citrate is prepared, under room temperature, 1.35g Trisodium Citrate is dissolved in 50mL deionized water, then 2.5g Silver Nitrate is dissolved in 40mL deionized water, with dropper just silver nitrate aqueous solution be slowly added dropwise in sodium citrate aqueous solution,, there is white precipitate at once in (mol ratio of Silver Nitrate and Trisodium Citrate is 3:1, to ensure that Silver Nitrate is little over amount), lucifuge stirs 2 h, afterwards by washing of precipitate, filtration, room temperature lucifuge is dried in the shade, obtained silver citrate solid.
(2) prepare argent grapheme modified, under room temperature, be dispersed in 400mL deionized water by the graphene oxide of 56mg and the Silver Nitrate of 144mg, ultrasonic (80 KHz) disperses 1 h.Mixing solutions is placed in there-necked flask, stirred at ambient temperature 20 h, then 80% hydrazine hydrate adding 5mL, reductase 12 4 h under 95 ° of C.By deionized water and absolute ethanol washing product extremely neutrality, by product vacuum-drying under 30 ° of C, obtained argent is grapheme modified.
(3) by mass percentage; take following raw material: the argent that the silver citrate that 34.5% step 1 obtains, 5.5% step 2 obtain is grapheme modified, 5% resin glue (alkyd resin), 45% organic silver complexing agent (1,2-propylene diamine), 5% solvent (Virahol), 4.2% span-80 (dispersion protective material), 0.3% defoamer, 0.5% stablizer.
(4) in proportion by Virahol and the mixing of 1,2-propylene diamine, under lucifuge is less than 10 ° of C conditions, stirring (500 r/min) 12 h, ultrasonic (80 KHz) disperse 2 h, obtain homogeneous silver citrate complex solution.
(5) silver citrate complex solution Graphene, binding agent, solvent, dispersion protective material auxiliary agent, defoamer, stablizer and step 4 obtained stirs (800 r/min) 2 h under lucifuge, temperature are lower than the condition of 10 ° of C, ultrasonic (80 KHz) disperses 1 h; again with rotating speed ball milling 5 min of 400rpm; Graphene Silver monoacetate is mixed, namely obtains the grapheme modified silver citrate electrically conductive ink of argent (Graphene and the elemental silver mass ratio of modification are about 20:80).
The grapheme modified silver citrate electrically conductive ink of argent using the method that is coated with embodiment 5 to be obtained is printed on glass, and 250 ° of C process 1 h, it is 0.4 Ω/ that four point probe resistance meter records square resistance.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a Graphene organic silver electrically conductive ink, is characterized in that, raw material and component as follows, by percentage to the quality, comprising:
Conducting function unit presoma 23-40%,
Organic silver complexing agent 25-57%,
Binding agent 3-10%
Solvent 0.5-20%,
Auxiliary agent 2.5-6%;
Described conducting function unit presoma is made up of Graphene and organic silver, and in Graphene and organic silver, the mass ratio of elemental silver is 4-92:96-8.
2. Graphene organic silver electrically conductive ink according to claim 1, is characterized in that, in described conducting function unit presoma, in Graphene and organic silver, the mass ratio of elemental silver is 4-20:96-80 or 80-92:20-8.
3. Graphene organic silver electrically conductive ink according to claim 2, is characterized in that, described Graphene is the lamellar structure of single or multiple lift.
4. according to one of claim 1-3 described Graphene organic silver electrically conductive ink, it is characterized in that, described organic silver is pungent capric acid silver, beta-keto acid silver-colored, 2-[2-(2-methoxyethoxy) oxyethyl group] Silver monoacetate, butyric acid silver, silver citrate, succinic acid are silver-colored, oxysuccinic acid is silver-colored, one in silver tartrate, Silver monoacetate, silver oxalate.
5. according to one of claim 1-3 described Graphene organic silver electrically conductive ink, it is characterized in that, described binding agent is ethyl cellulose, Natvosol, polyvinyl alcohol, resol, vibrin, polyimide resin, epoxy resin, silicone resin, fluorocarbon resin, vibrin, Vinylite, acrylic resin, acrylate quasi-oligomer and reactive monomer, Synolac, synthetic cellulose, polyamide resin, vinyl chloride-vinyl acetate resin, urethane resin, polyvinylidene fluoride resin, thermoplastic resin, synthetic rubber, silicon-modified epoxy, polyurethane modified epoxy, epoxy modified acrylic resin, organosilicon-modified acrylic epoxy resin, acrylic resin modified, modified phenolic, one in modified alkyd resin.
6. according to one of claim 1-3 described Graphene organic silver electrically conductive ink, it is characterized in that, described organic silver complexing agent is aminated compounds or amido compounds;
Wherein, described aminated compounds refers to ammoniacal liquor, Tri N-Propyl Amine, n-Butyl Amine 99, isobutylamine, normal hexyl Amine, n-octyl amine, 1,2-propylene diamine, 1,3-propylene diamine, Diisopropylamine, Di-n-Butyl Amine, diethanolamine, triethylamine, tripropyl amine or sec-butylamine;
Described amido compounds refers to 2-(methylamino)-Ethanol, 3-aminopropyl Ethoxysilane or diethylaminoethanol.
7. according to one of claim 1-3 described Graphene organic silver electrically conductive ink, it is characterized in that, described solvent is one or more in water, aromatic hydrocarbon solvent, fat hydrocarbon solvent, ether solvent, alcoholic solvent, alcohol ether solvent, amide solvent, ketones solvent, esters solvent.
8. according to one of claim 1-3 described Graphene organic silver electrically conductive ink; it is characterized in that, described auxiliary agent is one or more in dispersion agent, stablizer, protective material, membrane-forming agent, coupling agent, softening agent, defoamer, thickening material, wetting agent, flow agent, thixotropic agent, linking agent, uv-absorbing agent.
9. the preparation method of Graphene organic silver electrically conductive ink as claimed in claim 1, its concrete steps are as follows:
A) in proportion organic silver, solvent and organic silver complexing agent are stirred 0.5-12 h under lucifuge condition, ultrasonic disperse 1-12 h, obtain organic silver complex solution;
B) mixed by organic silver complex solution stirring reaction 0.5-12 h or ultrasonic disperse 0.5-12 h or ball milling 0.5-1 h in lucifuge, temperature are lower than the environment of 10 ° of C that Graphene, binding agent, auxiliary agent and steps A obtain in proportion, products therefrom is Graphene organic silver electrically conductive ink.
10. the preparation method of Graphene organic silver electrically conductive ink according to claim 9, it is characterized in that, described organic silver obtains like this: slowly instill in corresponding organic solution by silver salt or silver suboxide solution, 0.5-2 h is stirred under lucifuge condition, by the washing of precipitate of acquisition, filtration, room temperature lucifuge is dried in the shade, and products therefrom is organic silver.
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