CN106816202A - A kind of Graphene denatured conductive silver paste and preparation method thereof - Google Patents
A kind of Graphene denatured conductive silver paste and preparation method thereof Download PDFInfo
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- CN106816202A CN106816202A CN201710081426.8A CN201710081426A CN106816202A CN 106816202 A CN106816202 A CN 106816202A CN 201710081426 A CN201710081426 A CN 201710081426A CN 106816202 A CN106816202 A CN 106816202A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The present invention provides a kind of Graphene denatured conductive silver paste and preparation method thereof, the Graphene denatured conductive silver paste its be mainly made up of nano silver wire, grapheme material, binding agent and solvent；The grapheme material include Graphene, graphene nanometer sheet, biomass Graphene or graphene oxide any one or at least two combination.In the present invention collectively as conductive agent both the nano silver wire and grapheme material, nano silver wire is filled between grapheme material lamella, so that being together in series with silver wire between graphene sheet layer and lamella, the two synergy, play its electric conductivity, and Graphene is covered in nano silver wire surface, the oxidation of nano silver wire can be avoided, more ensure that the stabilization performance of the stabilization and electric conductivity of system, and the adhesive force for causing system by other compositions such as binding agents is significantly improved, and increased the printability of conductive silver paste.
Description
Technical field
The invention belongs to electrocondution slurry field, it is related to a kind of graphene-based conductive silver paste and preparation method thereof.
Background technology
Conductive silver paste is the mixed slurry that a kind of metallic silver particles by high-purity, adhesive, solvent, auxiliary agent are constituted.
Today of electronics and information industry high speed development, the demand of electrocondution slurry increasingly increases, as electricity such as solar cell, printed circuits
The essential material of sub- industrial aspect, but cause the price of conductive silver paste of a relatively high because argent is expensive.
At present, in order to meet the requirement of electronic product high conductivity, the solid content of silver is high in 60-90% in conductive silver paste
The silver-colored particulate of content not only substantially increases preparation cost, while reducing the content of binding agent, causes curing performance and bonding
Intensity declines.And Graphene is a kind of good two-dimentional conductive carbon material, and price is relatively silver-colored relatively cheap, therefore, in conduction
Replace silver as conductive filler with Graphene in silver paste, it is possible to achieve increase the electric conductivity of silver paste while reduces cost.
CN104200875A discloses a kind of low silver content composite conducting silver paste, and the conductive silver paste is wrapped in terms of parts by weight
5-15 parts of graphene microchip is included, 30-50 weight portion silvered glass powder, 5-15 parts of macromolecule resin, 20-40 weight portions are organic molten
Agent, 1-4 parts of levelling agent and 0.1-0.5 parts of defoamer.It is equal with silvered glass powder from conductive particle graphene microchip in silver paste
It is laminated structure, reduces the gap between conductive particle, improve bulk density, increase intergranular contact area, improves conductive energy
Power.
CN103436099A discloses a kind of composite conducting ink, and meter includes by weight：Film-forming resin 5.0~30.0
Part, 20~40 parts of the mixture or flake silver powder of flake silver powder and nano-silver powder, the mixture of Graphene and nano graphite flakes or
0.1~5.0 part of Graphene, 1.5~11.0 parts of additive, balance of organic solvent.Although the composite conducting ink tool of the invention
There is relatively low silver content, but Graphene does not play a part of reduces cost really, and electric conductivity needs further raising.
CN104650653A discloses a kind of conductive nano silver paste and preparation method thereof, the conductive nano silver paste by comprising
The component of following weight portion is made：Nano Silver 0.5-5 parts, resin 10-30 parts, dispersant 0.01-2 parts, surface modifier 0.01-2
Part, anti-settling agent 0.01-2 parts, levelling agent 0.01-2 parts, nano assistant 0.1-2 parts, thickener 0.5-2 parts, organic solvent 50-95
Part, pigment 0.01-10 parts, curing agent 0.01-5 parts.Wherein nano assistant can select graphene nanometer sheet, but Nano Silver
Consumption is still a lot, and electric conductivity needs further raising.
Modified Nano Silver water-soluble conducting ink of a kind of Graphene and preparation method thereof, institute are disclosed in CN105936769A
Stating the modified Nano Silver water-soluble conducting ink of Graphene includes following material：Nano Silver 0.02-3 parts, Graphene modified additive
0.001-3 parts, nitrocellulose 0.02-10 parts, hexadecyltrimethylammonium chloride 0.001-3 parts, organically-modified poly dimethyl
Siloxanes 0.001-3 parts, dispersant 0.001-3 parts, wetting agent 0.1-2 parts, organic solvent 70-100 parts, in its preparation method
Using by Graphene modified additive and nitrocellulose, hexadecyltrimethylammonium chloride and organically-modified polydimethylsiloxanes
Alkane etc. is directly mixed, and causes the electric conductivity of preparation-obtained electrically conductive ink to have because Graphene may occur reunion
Treat further raising.
In actual applications, graphene sheet layer is susceptible to aggregation, and Graphene is very low in the addition of slurry, have impact on stone
The performance of black alkene performance, it is clear that be unfavorable for popularization and application.Therefore, expect that obtaining one kind can either reduce silver-colored consumption in the art
Graphene consumption can be increased again and improve the dispersed conductive silver paste of Graphene.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of Graphene denatured conductive silver paste and its preparation
Method.
It is that, up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of Graphene denatured conductive silver paste, its mainly by nano silver wire, grapheme material,
Binding agent and solvent are constituted；The grapheme material includes Graphene, graphene nanometer sheet, biomass Graphene, graphite oxide
Alkene any one or at least two combination.
In the present invention, in the present invention both the nano silver wire and grapheme material collectively as conductive agent, Yin Na
Rice noodles are filled between grapheme material lamella, are conducive to the dispersion of Graphene, and cause between graphene sheet layer and lamella
It is together in series with silver wire, the two synergy plays its electric conductivity, and Graphene is covered in nano silver wire surface, can be with
The oxidation of nano silver wire is avoided, the stabilization performance of the stabilization and electric conductivity of system is more ensure that.And by binding agent
The adhesive force for causing system etc. other compositions is significantly improved, and increased the printability of conductive silver paste.
Preferably, the grapheme material is biomass Graphene.
Wherein, biomass Graphene is to contain single-layer graphene, few layer graphene, graphite with biomass as prepared by raw material
Alkene nano-lamellar structure, and carried metal/nonmetallic compound, the number of plies are not more than 10 layers of two-dimensional nano Carbon Materials, or even can
Be more than on the basis of the carbon composite comprising graphitized charcoal, metal/non-metal compound；The biomass Graphene is also
Including the Graphene by being prepared to biomass resource hydrothermal carbonization method.
Preferably, the biomass Graphene uses the biomass Graphene of Jinan holy well company, i.e., with agriculture and forestry organic waste material
It is primary raw material, the carbon nanomaterial compound containing Graphene obtained by steps such as hydrolysis, catalytic treatment, heat treatments,
It is mainly characterized by containing Graphene, agraphitic carbon and non-carbon nonoxygen element, and the non-carbon nonoxygen element includes Fe, Si and Al unit
Element, the non-carbon nonoxygen element content is the 0.5wt%~6wt% of compound.If number of patent application is 201510819312.X
The product of preparation.The leading indicator of the biomass Graphene it is exemplary can be：Electrical conductivity ＞ 3000S/m, preferably ＞
5000S/m；Specific surface area ＞ 150m2/ g, preferably ＞ 300m2/g；Raman spectrum IG/ID ＞ 2, preferably ＞ 3；C/O ＞ 35.0.
Preferably, the binding agent includes bonded adhesive, and the bonded adhesive is epoxy resin, acrylic acid tree
One kind in fat, polyester resin, vinyl chloride resin, alkyd resin, organic siliconresin or cellulosic resin or at least two
Combination.
Preferably, the content of nano silver wire is 80~120 weight portions in the conductive silver paste, and the content of grapheme material is
80~120 weight portions；For example in the conductive silver paste content of nano silver wire be 80 weight portions, 83 weight portions, 85 weight portions,
88 weight portions, 90 weight portions, 93 weight portions, 95 weight portions, 98 weight portions, 100 weight portions, 105 weight portions, 108 weight portions,
110 weight portions, 113 weight portions, 115 weight portions, 118 weight portions or 120 weight portions, the content of grapheme material is 80 weight
Part, 83 weight portions, 85 weight portions, 88 weight portions, 90 weight portions, 93 weight portions, 95 weight portions, 98 weight portions, 100 weight portions,
105 weight portions, 108 weight portions, 110 weight portions, 113 weight portions, 115 weight portions, 118 parts or 120 parts；Preferably, the silver
The content of nano wire is 80~100 weight portions, and the content of grapheme material is 100~120 weight portions.
In the present invention, if not using the consumption of nano silver wire or nano silver wire very few, graphene dispersion is deteriorated,
And due to can not be carried out between graphene sheet layer and lamella it is conductive connect or understand some graphene sheet layer and lamella it
Between can not carry out conductive series connection, can cause that the electric conductivity of product is not good.
In the present invention, Nano silver piece or nano-silver powder are done if nano silver wire changed, due to Nano silver piece or may be received
Effect of the rice silver powder between graphene sheet layer can not be as nano silver wire, and it can be caused between graphene sheet layer and lamella
It is difficult to continuous series to get up or cause packing phenomenon, if the large usage quantity of silver powder and Nano silver piece, interface resistance is larger,
Therefore can cause that electric conductivity is not ideal enough.
In the present invention, in order to minimize cost, and electric conductivity is ensured, then take increases Graphene consumption as far as possible
Method, has certain interaction, when Graphene is excessive, due to receiving however as described above between nano silver wire and Graphene
The relative usage of meter Yin tails off, then can cause that cooperation is not reached preferable effect by the two, and causes electric conductivity loss of energy.
Preferably, the content of binding agent is 180~220 weight portions in the conductive silver paste, for example, can be 180 weight
Part, 183 weight portions, 185 weight portions, 188 weight portions, 190 weight portions, 193 weight portions, 195 weight portions, 198 weight portions, 200
Part or 220 parts of preferably 180~200 weight portions.
Preferably, the solvent includes deionized water, butyl acetate, triethyl phosphate, ethanol, n-butanol, butanone, different Buddhist
One kind or at least two combination in your ketone, toluene or dimethylbenzene.
Preferably, the content of solvent is 220~250 weight portions, such as 220 weight portions, 223 weight in the conductive silver paste
Part, 225 weight portions, 228 weight portions, 230 weight portions, 232 weight portions, 235 weight portions, 238 weight portions, 240 weight portions, 243
Weight portion, 245 weight portions, 248 weight portions or 250 weight portions.
Preferably, the conductive silver paste also includes cellulose.
In the present invention, producing ratio preferable effect is understood during several preferred celluloses below selection, can be with more obvious
The electric conductivity of the graphene-based conductive silver paste of ground lifting, also more can guarantee that the stability of conductive silver paste system, i.e., preferably, described
Cellulose is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium, acetylbutyrylcellulose, ethyl cellulose
Or the one kind in ethylhydroxyethylcellulose or at least two combination, further preferred acetylbutyrylcellulose and/or ethyl
Cellulose.
Preferably, the content of cellulose is 8~12 weight portions in the conductive silver paste, for example, can be 8 weight portions, 8.3
Weight portion, 8.5 weight portions, 8.8 weight portions, 9 weight portions, 9.3 weight portions, 9.5 weight portions, 9.8 weight portions, 10 weight portions,
10.3 weight portions, 10.5 weight portions, 10.8 weight portions, 11 weight portions, 11.3 weight portions, 11.5 weight portions, 11.8 weight portions or
12 weight portions, preferably 8~10 weight portions.
Graphene sheet layer can be kept apart using the long chain of cellulose in the present invention so that Graphene is difficult hair
It is raw to reunite, the addition of Graphene in system is increased, the overall electric conductivity of graphene-based conductive silver paste is improve, reduce expensive
The consumption of argent, reduces cost, and nano silver wire, Graphene and cellulose is fully dispersed, one-dimensional nano silver wire generation
It is filled between graphene sheet layer for traditional silver powder so that be together in series with silver wire between lamella and lamella, the graphite of few layer
The Sheet Graphite alkene that alkene has excellent charge-conduction ability, nanoscale can be very good covering silver nano line so that Yin Na
Rice noodles are difficult oxidation by air, and cause that the adhesive force of system is significantly improved by other compositions such as resins, increased conduction
The printability of silver paste.
In the present invention, cellulose can well utilize its long chain by graphene sheet layer as a kind of dispersant
Keep apart, it is to avoid the reunion of Graphene and influence the performance of electric conductivity, if the consumption of cellulose is crossed can cause it not at least
Can be adequately isolated graphene sheet layer, i.e., Graphene can not be fully dispersed, can cause reunite, reduce electric conductivity, and if with
Amount can excessively cause the relative reduction of conductive agent content in system, reduce electric conductivity.
Preferably, the conductive silver paste also includes thermoplastic resin.
Preferably, the thermoplastic resin is polyvinyl butyral resin.
Preferably, the content of thermoplastic resin is 8~12 weight portions, such as 8 weight portions, 8.3 weights in the conductive silver paste
Amount part, 8.5 weight portions, 8.8 weight portions, 9 weight portions, 9.3 weight portions, 9.5 weight portions, 9.8 weight portions, 10 weight portions, 10.3
Weight portion, 10.5 weight portions, 10.8 weight portions, 11 weight portions, 11.3 weight portions, 11.5 weight portions, 11.8 weight portions or 12 weights
Amount part, preferably 10~12 weight portions.
There is good compatibility between the binding agent and thermoplastic resin in the present invention, graphite can be jointly caused
Alkenyl conductive silver paste has good tack, increases printability, and cause that printed circuit is flexible good.
Preferably, the conductive silver paste also includes any one in auxiliary agent, curing agent or accelerator or at least two
Combination.
Preferably, the auxiliary agent include defoamer, levelling agent, antioxidant, anti-settling agent or dispersant any one or
At least two combination.
Preferably, the content of auxiliary agent is 3~7 weight portions, such as 3 weight portions, 3.4 weight portions, 3.8 in the conductive silver paste
Weight portion, 4 weight portions, 4.3 weight portions, 4.5 weight portions, 4.8 weight portions, 5 weight portions, 5.4 weight portions, 5.8 weight portions, 6 weights
Amount part, 6.4 weight portions, 6.8 parts or 7 parts.
Preferably, the curing agent is acid anhydride type curing agent, and the acid anhydride type curing agent includes hexamethyl phthalic anhydride, dioctyl phthalate
In acid anhydride, carbic anhydride, maleic anhydride and its addition product any one or at least two combination.
Preferably, in the conductive silver paste curing agent content be 8~12 weight portions, such as 8 weight portions, 8.3 weight portions,
8.5 weight portions, 8.8 weight portions, 9 weight portions, 9.3 weight portions, 9.5 weight portions, 9.8 weight portions, 10 weight portions, 10.3 weight
Part, 10.5 weight portions, 10.8 weight portions, 11 weight portions, 11.3 weight portions, 11.5 weight portions, 11.8 weight portions or 12 weight portions.
Preferably, the accelerator includes imidazoles accelerator, preferably 2-methylimidazole, 1- benzyl -2- ethyl imidazol(e)s, 1-
In cyanoethyl -2-ethyl-4-methylimidazole or 1- cyanoethyl substituted imidazoles any one or at least two combination.
Preferably, in the conductive silver paste accelerator content be 1~6 weight portion, such as 1 weight portion, 1.3 weight portions,
1.5 weight portions, 1.8 weight portions, 2 weight portions, 2.3 weight portions, 2.5 weight portions, 2.8 weight portions, 3 weight portions, 3.4 weight portions,
3.8 weight portions, 4 weight portions, 4.5 weight portions, 5 weight portions, 5.5 weight portions or 6 weight portions.
Preferably, the square resistance of graphene-based conductive silver paste of the invention is 20~50m Ω cm, such as 20m Ω
cm、23mΩ·cm、25mΩ·cm、28mΩ·cm、30mΩ·cm、33mΩ·cm、35mΩ·cm、38mΩ·cm、40m
Ω cm, 43m Ω cm, 45m Ω cm, 48m Ω cm or 50m Ω cm.
On the other hand, the invention provides the preparation method of graphene-based conductive silver paste as described above, methods described bag
Include following steps：
(1) nano silver wire, grapheme material are mixed with a part of solvent, is ground, obtain mixture a；
(2) binding agent and residual solvent are well mixed, obtain mixture b；
(3) it is mixture a obtained in step (1) and mixture b obtained in step (2) is well mixed, then grind, obtain
The graphene-based conductive silver paste；
Preferably, it is additionally added cellulose in step (1)；
Preferably, also need to add in step (2) thermoplastic resin, auxiliary agent, curing agent and accelerator any one or
At least two combination；
Preferably, when the grapheme material is graphene oxide, then reduction behaviour is being carried out to graphene oxide using preceding
Make, or restoring operation is carried out to the mixture after the mixture a, mixture b or step (3) grinding.
Preferably, the restoring operation is to be reduced using reducing agent.
Preferably, the reducing agent is vitamin C and/or hydrazine hydrate.
In the preparation process of graphene-based conductive silver paste, nano silver wire and grapheme material are mixed first, then with it is viscous
The other compositions mixing such as knot agent, can so cause that nano silver wire is fully filled between graphene sheet layer so that Graphene
It is together in series with silver wire between lamella and lamella, also can causes that Graphene is preferably disperseed simultaneously.
Preferably, cellulose is added in step (1), so in the preparation process of graphene-based conductive silver paste, first
Nano silver wire and Graphene are mixed with cellulose, then is mixed with the other compositions such as binding agent, can cause that cellulose is long
Strand keeps apart graphene sheet layer so that Graphene is not susceptible to reunite, can in increase system Graphene addition,
Electric conductivity is improved, the consumption of noble silver is reduced, cellulose has certain protective effect for Graphene in addition, can avoid
Grind the destruction to graphene-structured.
Preferably, the consumption of solvent described in step (1) is 90~110 parts, such as 90 weight portions, 93 weight portions, 95 weights
Amount part, 98 weight portions, 100 weight portions, 103 weight portions, 105 weight portions, 108 weight portions or 110 weight portions.
By binding agent and optionally, thermoplastic resin, auxiliary agent, curing agent, accelerator and residue are molten in step (2)
Agent is well mixed, and the mixture b that the mixture a for then obtaining step (1) is obtained with step (2) mixes, so that
In the case where be uniformly dispersed for Graphene and nano silver wire by step (1), then when being sufficiently mixed with mixture b, Ke Yibao
The fine dispersion of Graphene is demonstrate,proved without reuniting.
In the present invention, step (1) and step (2) described solvent can be the same or different.
Although can select to be added one by one in the mixture a that step (1) is obtained in theory binding agent, thermoplastic resin,
The method of auxiliary agent, curing agent, accelerator and residual solvent, but the method for using this mixing, in order to fully dispersed, it is ensured that
Graphene do not occur aggregation and system there is good stability etc., it is necessary to often add a kind of material again after be ground, and
Grinding number of times is excessive, though be also not fee under the protection of cellulose the structure of Graphene can be damaged, therefore, this hair
Bright selection step (2) mode for mixing each composition after well mixed with mixture a again.
Preferably, it is ground to be ground to grain graininess below 10 microns described in step (1) and step (3), such as 9 is micro-
Rice, 8.8 microns, 8.5 microns, 8.3 microns, 8 microns, 7.8 microns, 7.5 microns, 7.3 microns, 7 microns, 6.8 microns, it is 6.5 micro-
Rice, 5 microns, 5.5 microns, 4 microns, 3 microns, 2 microns or 1 micron etc..
Relative to prior art, the invention has the advantages that：
(1) both nano silver wire and Graphene are filled into Graphene collectively as conductive agent, nano silver wire in the present invention
Between lamella, be conducive to the dispersion of Graphene, and cause to be together in series with silver wire between graphene sheet layer and lamella, the two association
Same-action, plays its electric conductivity, and Graphene is covered in nano silver wire surface, can avoid the oxidation of nano silver wire, more
Plus ensure that the stabilization performance of the stabilization and electric conductivity of system.Graphene has excellent charge-conduction ability and relatively
Low cost, the consumption reduction of noble silver, reduces cost.
(2) long chain of present invention application cellulose keeps apart graphene sheet layer, further increases dividing for Graphene
Dissipate effect so that Graphene is not susceptible to reunite, and increases the addition of Graphene in system, improves graphene-based conductive silver
Overall electric conductivity is starched, one-dimensional nano silver wire has excellent electric conductivity and flexible resistance, the graphene-based conductive silver paste of preparation
Stock have it is flexible well.
(3) present invention can be fully dispersed by nano silver wire, Graphene and cellulose, and one-dimensional nano silver wire replaces tradition
Silver powder be filled between graphene sheet layer so that be together in series with silver wire between lamella and lamella, the Graphene of few layer has
Excellent charge-conduction ability, the Sheet Graphite alkene of nanoscale can be very good covering silver nano line so that nano silver wire is not
Easy oxidation by air, and cause that the adhesive force of system is significantly improved by other compositions such as binding agents, increased conductive silver paste
Printability.
(4) the preferred biomass Graphene of heretofore described Graphene, has widened the application field of biomass Graphene.
Brief description of the drawings
Fig. 1 is the microscope figure of the graphene-based conductive silver paste that the present invention is prepared.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to concrete restriction of the invention.
The biomass Graphene applied in following examples can be using the preparation method of biomass Graphene in the prior art
Prepare, such as number of patent application is the technology of 201510819312.X, it would however also be possible to employ the biomass stone of Jinan holy well group production
Black alkene.Nano silver wire and binding agent can buy acquisition, it would however also be possible to employ Jinan holy well group production nano silver wire with
And binding agent, other compositions also can buy acquisition.
Embodiment 1
(1) nano silver wire of 100 weight portions, the biomass Graphene of 100 weight portions and 110 part by weight of n-butanol are mixed
Uniformly, granularity is ground to less than 10 microns, obtains mixture a；
(2) 200 parts by weight epoxy resin and 110 part by weight of n-butanol are well mixed, obtain mixture b；
(3) mixture a and mixture b are well mixed, then three-roll grinder is ground to granularity less than 10 microns, obtains
The Graphene denatured conductive silver paste 1#.
The graphene-based conductive silver paste for preparing is characterized using microscope, as a result as shown in figure 1, can by figure
Know, between the crisscross Graphene being filled in of nano silver wire, connect mutually isolated graphene sheet layer as wire
Get up, build conductive network.
Embodiment 2
(1) nano silver wire of 80 weight portions, the biomass Graphene of 120 weight portions and 120 weight portion isophorones are mixed
Close uniform, be ground to granularity less than 10 microns, obtain mixture a；
(2) 180 parts by weight propylene acid resins and 120 weight portion isophorones are well mixed, obtain mixture b；
(3) mixture a and mixture b are well mixed, then three-roll grinder is ground to granularity less than 10 microns, obtains
The Graphene denatured conductive silver paste 2#.
Embodiment 3
(1) nano silver wire of 90 weight portions, the biomass Graphene of 100 weight portions and 110 weight portion butyl acetates are mixed
Close uniform, be ground to granularity less than 10 microns, obtain mixture a；
(2) 200 weight portion alkyd resins and 110 weight portion butyl acetates are well mixed, obtain mixture b；
(3) mixture a and mixture b are well mixed, then three-roll grinder is ground to granularity less than 10 microns, obtains
The Graphene denatured conductive silver paste 3#.
Embodiment 4
(1) nano silver wire of 120 weight portions, the biomass Graphene of 80 weight portions and 90 parts by weight of deionized water are mixed
Uniformly, granularity is ground to less than 10 microns, obtains mixture a；
(2) 220 weight portion organic siliconresins and 150 parts by weight of ethanol are well mixed, obtain mixture b；
(3) mixture a and mixture b are well mixed, then three-roll grinder is ground to granularity less than 10 microns, obtains
The Graphene denatured conductive silver paste 4#.
Embodiment 5
Different from embodiment 1 being only that in step (1) adds ethyl cellulose, the i.e. steps (1) to be：By 100 weight portions
Nano silver wire, the biomass Graphene of 100 weight portions, 8 weight portion ethyl celluloses and the mixing of 110 part by weight of n-butanol it is equal
It is even, granularity is ground to less than 10 microns, mixture a is obtained, so as to prepare Graphene denatured conductive silver paste 5#.
Embodiment 6-9
8 weight portion ethyl celluloses are replaced with 8 parts by weight acetic acid butyric acid fibers by be only that different from embodiment 5 respectively
Element, 8 weight portion carboxymethylcellulose calciums, 10 weight portion ethyl celluloses, 12 weight portion ethylhydroxyethylcelluloses, so as to be prepared into
To Graphene denatured conductive silver paste 6# (embodiment 6), 7# (embodiment 7), 8# (embodiment 8), 9# (embodiment 9).
Embodiment 10
The consumption that is only that ethyl cellulose different from embodiment 1 is 4 weight portions, with method same as Example 1
Prepare Graphene denatured conductive silver paste 10#.
Embodiment 11
The consumption that is only that ethyl cellulose different from embodiment 1 is 16 weight portions, with method same as Example 1
Prepare Graphene denatured conductive silver paste 11#.
Embodiment 12
Different from embodiment 1 is only that addition polyvinyl butyral resin, auxiliary agent, curing agent and accelerator in step (2),
I.e. step (2) is：By 200 parts by weight epoxy resin, 12 weight account polyethylene butyrals, 5 weight portion auxiliary agents, (defoamer is finished
Gram company, BYK-024), 10 weight portion curing agent (hexamethyl phthalic anhydride), 3 weight portion accelerator (1- cyanoethyl -2- ethyl -4- first
Base imidazoles) and 110 part by weight of n-butanol it is well mixed, obtain mixture b；So as to prepare Graphene denatured conductive silver paste
12#。
Embodiment 13
It is that step (2) is with the difference of embodiment 12：By 200 parts by weight epoxy resin, 10 weight account polyethylene alcohol
Butyral, 3 weight portion auxiliary agents (defoamer, Bi Ke companies, BYK-024), 8 weight portion curing agent (Di Nake acid anhydrides), 1 weight portion
Accelerator (2-methylimidazole) and 110 part by weight of n-butanol are well mixed, obtain mixture b；Change so as to prepare Graphene
Property conductive silver paste 13#.
Embodiment 14
It is that step (2) is with the difference of embodiment 12：By 200 parts by weight epoxy resin, 8 weight account polyethylene alcohol
Butyral, 7 weight portion auxiliary agents (defoamer, Bi Ke companies, BYK-024), 12 weight portion curing agent (maleic anhydride), 6 weights
Amount part accelerator (1- benzyl -2- ethyl imidazol(e)s) and 110 part by weight of n-butanol are well mixed, obtain mixture b；So as to be prepared into
To Graphene denatured conductive silver paste 14#.
Embodiment 15
Different from embodiment 5 is only that addition polyvinyl butyral resin, auxiliary agent, curing agent and accelerator in step (2),
I.e. step (2) is：By 200 parts by weight epoxy resin, 12 weight account polyethylene butyrals, 5 weight portion auxiliary agents, (defoamer is finished
Gram company, BYK-024), 10 weight portion curing agent (hexamethyl phthalic anhydride), 3 weight portion accelerator (1- cyanoethyl -2- ethyl -4- first
Base imidazoles) and 110 part by weight of n-butanol it is well mixed, obtain mixture b；So as to prepare Graphene denatured conductive silver paste
15#。
Embodiment 16
Difference from Example 1 is that the biomass Graphene that will be utilized in embodiment 1 replaces with the hexa-atomic element in Changzhou
" the model of material Science and Technology Co., Ltd. production：The Graphene of SE1231 ", so as to prepare Graphene denatured conductive silver
Slurry 16#.
Embodiment 17
Difference from Example 1 is that the biomass Graphene that will be utilized in embodiment 1 replaces with graphene oxide,
Graphene oxide carries out reduction treatment using 100 parts of hydrazine hydrates of preceding addition, so as to prepare Graphene denatured conductive silver paste
17#。
Embodiment 18
Difference from Example 1 is that the biomass Graphene that will be utilized in embodiment 1 replaces with the hexa-atomic element in Changzhou
" the model of material Science and Technology Co., Ltd. production：The Graphene of SE1430 ", so as to prepare Graphene denatured conductive silver
Slurry 18#.
Embodiment 19-21
Difference from Example 5 to be only that replace with Changzhou respectively by the biomass Graphene in embodiment 5 hexa-atomic
" the model of cellulosic material Science and Technology Co., Ltd. production：SE1231 ", graphene oxide (and using it is preceding by 100 parts hydration
Hydrazine reduction treatment), Changzhou No.6 Element Material Technology Co., Ltd. production " model：The Graphene of SE1430 ", so that
Graphene denatured conductive silver paste 19# (embodiment 19), 20# (embodiment 20) and 21# (embodiment 21) are prepared respectively.
Embodiment 22-24
Be the difference is that only with embodiment 12 and the biomass Graphene in embodiment 12 is replaced with into Changzhou the 6th respectively
" the model of element material Science and Technology Co., Ltd. production：SE1231 ", graphene oxide are (and using preceding by 100 parts of water
Close hydrazine reduction treatment), " model of Changzhou No.6 Element Material Technology Co., Ltd.'s production：The Graphene of SE1430 ", from
And Graphene denatured conductive silver paste 22# (embodiment 22), 23# (embodiment 23) and 24# (embodiment 24) are prepared respectively.
Comparative example 1
The comparative example difference from Example 1 is only that and do not use nano silver wire, remaining component and consumption and system
Preparation Method is same as Example 1.
Comparative example 2
The comparative example difference from Example 2 is only that the consumption of nano silver wire is 60 parts, remaining component and consumption
And preparation method is same as Example 2.
Comparative example 3
The comparative example difference from Example 5 is only that and do not use nano silver wire, remaining component and consumption and preparation
Method is same as Example 5.
Comparative example 4
The comparative example difference from Example 5 is only that the consumption of nano silver wire is 60 parts, remaining component and consumption
And preparation method is same as Example 5.
Comparative example 5
The comparative example difference from Example 1 is only that and does not use nano silver wire, and the consumption of Graphene is 200 parts, its
Remaining component and consumption and preparation method are same as Example 1.
Comparative example 6
Nano silver wire is replaced with nano-silver powder by the comparative example difference from Example 1, remaining component and consumption with
And preparation method is same as Example 1.
Comparative example 7
Nano silver wire is replaced with Nano silver piece by the comparative example difference from Example 1, remaining component and consumption with
And preparation method is same as Example 1.
Comparative example 8
The comparative example difference from Example 1 is 140 parts only in the consumption of Graphene, remaining component and consumption and
Preparation method is same as Example 1.
The square resistance of the Graphene denatured conductive silver paste prepared to embodiment 1-24 and comparative example 1-8 and system
Stability, its result is as shown in table 1-3.Whether signified system stability refers to occurs precipitation in 24h, does not occur being precipitated as good
It is good, appearance be precipitated as on a small quantity it is poor, occur it is a large amount of be precipitated as it is poor.
Table 1
Table 2
Table 3
It is conductive by Tables 1 and 2 as can be seen that Graphene denatured conductive silver paste of the invention has relatively low square resistance
Property it is good, conductive silver paste system has good stability.
The use of (comparative example 1) or nano silver wire when nano silver wire is not used is can be seen that by the contrast of table 3 and table 1-2
Measure very few (comparative example 2), then can cause that graphene dispersion is bad, reunites, and cause that system stability is poor, and Graphene
Can not be carried out between lamella and lamella it is conductive connect or understand conduction can not be carried out between some graphene sheet layer and lamella
Series connection so that the electric conductivity of product is not good, and square resistance is larger.In the case of using cellulose in system, if do not made
It is very few (comparative example 4) with the consumption of nano silver wire (comparative example 3) or nano silver wire, although Graphene can be under cellulose effect
Preferably disperseed, system stability is preferable, but electric conductivity still cannot improve, and square resistance is larger.Do not make
In the case of with nano silver wire, in order to increase electric conductivity, increase the consumption (comparative example 5) of Graphene, but electric conductivity is simultaneously
Undesirable, it causes that system stability is poor due to the aggtegation of excessive Graphene on the contrary.Received when nano silver wire is replaced with
When rice silver powder or Nano silver piece (comparative example 6-7), the square resistance of conductive silver paste is raised, electric conductivity reduction；Work as other compositions
Consumption it is constant and continue increase Graphene consumption when (comparative example 8), due to excessive Graphene produce aggregation cause system it is inadequate
Stablize, and electric conductivity is affected.
Applicant states that the present invention illustrates Graphene denatured conductive silver paste of the invention and its system by above-described embodiment
Preparation Method, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment ability real
Apply.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to the equivalent of each raw material of product of the present invention
Replacement and addition, the selection of concrete mode of auxiliary element etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of Graphene denatured conductive silver paste, it is characterised in that its mainly by nano silver wire, grapheme material, binding agent and
Solvent is constituted；The grapheme material includes any of Graphene, graphene nanometer sheet, biomass Graphene or graphene oxide
It is a kind of or at least two combination.
2. conductive silver paste according to claim 1, it is characterised in that the grapheme material is biomass Graphene；
Preferably, the binding agent include bonded adhesive, the bonded adhesive be epoxy resin, acrylic resin,
One kind or at least two group in polyester resin, vinyl chloride resin, alkyd resin, organic siliconresin or cellulosic resin
Close.
3. conductive silver paste according to claim 1 and 2, it is characterised in that the content of the nano silver wire is 80~120 weights
Amount part, the content of grapheme material is 80~120 weight portions；
Preferably, the content of the nano silver wire is 80~100 weight portions, and the content of grapheme material is 100~120 weight
Part.
4. the conductive silver paste according to any one of claim 1-3, it is characterised in that the content of the binding agent is 180
~220 weight portions, preferably 180~200 weight portions.
5. the conductive silver paste according to any one of claim 1-4, it is characterised in that the solvent include deionized water,
One kind in butyl acetate, triethyl phosphate, ethanol, n-butanol, butanone, isophorone, toluene or dimethylbenzene or at least two
Combination；
Preferably, the content of solvent is 220~250 weight portions in the conductive silver paste.
6. the conductive silver paste according to any one of claim 1-5, it is characterised in that the conductive silver paste also includes fiber
Element；
Preferably, the cellulose is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium, acetate butyrate fibre
One kind or at least two combination in dimension element, ethyl cellulose or ethylhydroxyethylcellulose, further preferred acetate butyrate
Cellulose and/or ethyl cellulose；
Preferably, the content of cellulose is 8~12 weight portions, preferably 8~10 weight portions in the conductive silver paste；
Preferably, the conductive silver paste also includes thermoplastic resin；
Preferably, the thermoplastic resin is polyvinyl butyral resin；
Preferably, the content of thermoplastic resin is 8~12 weight portions, preferably 10~12 weight portions in the conductive silver paste；
Preferably, combination of the conductive silver paste also including any one in auxiliary agent, curing agent or accelerator or at least two；
Preferably, the auxiliary agent include defoamer, levelling agent, antioxidant, anti-settling agent or dispersant any one or at least
Two kinds of combination；
Preferably, the content of auxiliary agent is 3~7 weight portions in the conductive silver paste；
Preferably, the curing agent be acid anhydride type curing agent, the acid anhydride type curing agent include hexamethyl phthalic anhydride, dicarboxylic acid anhydride,
In carbic anhydride, maleic anhydride and its addition product any one or at least two combination；
Preferably, the content of curing agent is 8~12 weight portions in the conductive silver paste；
Preferably, the accelerator includes imidazoles accelerator, preferably 2-methylimidazole, 1- benzyl -2- ethyl imidazol(e)s, 1- cyanogen second
In base -2-ethyl-4-methylimidazole or 1- cyanoethyl substituted imidazoles any one or at least two combination；
Preferably, the content of accelerator is 1~6 weight portion in the conductive silver paste.
7. the conductive silver paste according to any one of claim 1-6, it is characterised in that the square resistance of the conductive silver paste
It is 20~50m Ω cm.
8. the preparation method of the conductive silver paste according to any one of claim 1-7, it is characterised in that methods described includes
Following steps：
(1) nano silver wire, grapheme material are mixed with a part of solvent, is ground, obtain mixture a；
(2) binding agent and residual solvent are well mixed, obtain mixture b；
(3) it is mixture a obtained in step (1) and mixture b obtained in step (2) is well mixed, then grind, obtain described
Graphene denatured conductive silver paste；
Preferably, it is additionally added cellulose in step (1)；
Preferably, also need to add in step (2) thermoplastic resin, auxiliary agent, curing agent and accelerator any one or at least
Two kinds of combination.
9. preparation method according to claim 8, it is characterised in that when the grapheme material is graphene oxide, then
Carrying out restoring operation to graphene oxide using preceding, or to the mixture a, mixture b or step (3) grinding after
Mixture carries out restoring operation；
Preferably, the restoring operation is to be reduced using reducing agent；
Preferably, the reducing agent is vitamin C and/or hydrazine hydrate.
10. preparation method according to claim 8 or claim 9, it is characterised in that the consumption of solvent described in step (1) is 90
~110 parts；
Preferably, step (1) and step (3) are described is ground to be ground to grain graininess below 10 microns.
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