CN103614098A - Functional graphene-doped epoxy resin conductive adhesive and preparation method thereof - Google Patents
Functional graphene-doped epoxy resin conductive adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a functional graphene-doped epoxy resin conductive adhesive and a preparation method thereof, belonging to the technical field of conductive adhesives. The preparation method comprises the following steps: preparing a stably-dispersed graphene oxide colloid (GO) by a Hummers process, and inducing the growth of silver nanowires in situ on the GO laminae to prepare the silver nanowire/graphene nano hybrid material. The in-situ assembly of the silver nanowires and graphene generates a synergistic effect, so that the prepared nano composite material has very high conductivity and processing stability, avoids the phenomenon of aggregation of graphene in the epoxy resin, and can be uniformly dispersed as a filler in the epoxy resin to prepare the conductive adhesive with excellent conductivity. On the basis of the high conductivity of the graphene and silver nanowires, the conductivity and bonding strength of the adhesive are enhanced under given technological conditions; and the adhesive is especially suitable for conductive packaging and bonding of high-end refined electronic and electric apparatus components, and has wide application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of high conductivity nano silver wire functionalization graphene doping epoxide resin conductive adhesive, belong to conductive resin technical field, be improvements over the prior art, be specifically related to original position preparation and the application in epoxy resin thereof of Graphene-nano silver wire.
Background technology
Electrical and thermal conductivity is on the low side, poor reliability and on the high side be the bottleneck problem of restriction conductive resin development.The Graphene getting most of the attention in the world has superelevation and abnormal stable electrical and thermal conductivity and physical strength, be one of conductive filling material of tool prospect, but the problem that the application of Graphene in conductive resin faces is: be difficult to prepare on a large scale zero defect single-layer graphene, distinct electrical conduction mechanism is easily assembled, lacked to Graphene.
In recent years, around improving the specific conductivity of conductive resin and the stability aspect of contact resistance, do a large amount of research work both at home and abroad, also obtained many progress.(1) by controlling pattern and the particle diameter of nanoparticle, reduce excess effusion value and improve electroconductibility.When loading level one timing, the shape of conductive filler material and size have determined contact area and the contact probability between filler.Research discovery, nano-silver powder can couple together micron silver effectively, contributes to reduce the interface contact resistance between conductive filler material, thereby improves the specific conductivity of conductive resin.Than spherical and particulate state conductive filler material, [larger contact area and contact probability can be provided, and the specific conductivity of corresponding conductive resin is higher, percolation threshold is lower for laminal filler and bat wool.Especially usining sheet or bat wool and Ball-type packing is to improve the simple of conductivity and approach efficiently as conductive filler material.Yet, about difform conducting particles, in colloid, how to form and the key problem in science fail effectively to be solved such as after galvanic circle and loop form, how to conduct electricity, these problems are restricting the development of conductive resin, become the Focal point and difficult point of studying in conductive resin field, at home and abroad equal rarely seen reports.(2) by improving the interfacial property between filler and matrix.The resistivity of conductive resin depends primarily on contact resistance and the interface resistance of conductive resin, and these resistance all and between filler and matrix the constitutional features at interface closely related, therefore study conductive resin microstructure and evolutionary process is particularly important, yet at present the microtexture of conductive filler material and polymer-based carbon body interface is but rarely had to research.(3) by the silver-plated novel conductive filler of preparing of other matrix surfaces.Utilization has the more Graphene of high conductivity and chemical resistance can significantly improve the stability that silver is conductivity and the contact resistance of conductive resin.(4) research is thought, between conductive resin and base metal, the galvanic corrosion at interface is to cause the unsettled major cause of contact resistance.A lot of scholars are making trial aspect raising conductive resin contact resistance stability; there is the hygroscopic effort that reduces matrix resin; also have by adding some auxiliary agents and realize; as add the chemical corrosion of oxygen scavenger deferred telegram; add corrosion inhibitor to form inertia rete etc.; or add the metal-powder of low potential, and first corrosion is occurred on the metal that current potential is lower, thus protective substrate metal.But these methods can only be to a certain degree or certain hour in stable contact resistance, most commercial conductive resins still can not reach the contact resistance stabilized reference that U.S. NCMS proposes.
Before Graphene is found, based on carbon nanotube, be that conductive resin also appears in the newspapers repeatly.Compare with expensive carbon nanotube, the Graphene that professors Geim in 2004 etc. find first not only raw material is easy to get, and has more excellent performance, as the theoretical specific surface area (2630m of superelevation
2g
-1), under outstanding thermal conductivity (5000W/mK), high-strength (130GPa) Gao Mo (1060GPa), room temperature than the electronic mobility (15000cm of high 100 times of silicon
2/ (Vs), specific conductivity can be up to 7200S/cm.In developing, excavate potential performance and the application aspect of Graphene, matrix material based on Graphene also has been a great concern, and these matrix materials have shown superior performance and potential application in fields such as energy storage, liquid crystal device, electron device, biomaterial, sensing material, support of the catalyst.
Up to now, the flawless two-dimentional graphene film layer material of scale operation is still the bottleneck problem that restriction Graphene is applied in matrix material.In recent years, people had been developed the multiple preparation methods such as mechanically peel method, crystal epitaxial method, chemical Vapor deposition process, graphite oxide reduction method and organic synthesis, for the fundamental research based on Graphene and application and development provide raw material guarantee.But the Graphene surface of ideal structure does not have any functional group, a little less than the interaction of other solvents; There is strong model ylid bloom action power in graphene film interlayer simultaneously, all has the problem of reuniting and assembling in graphene oxide reduction, filtration or drying process, is difficult to obtain single-layer graphene.And numerous research shows, the physical and chemical performance of Graphene aggregate is similar to graphite, and the performance boost of polymer/graphene composite material does not have the effect that people obtain highly significant in imagining.In order to improve the consistency of Graphene and other matrixes, at present, great majority research is by graphene functionalized, as carried out finishing by covalent linkage and non covalent bond, to improve the dispersion stabilization of Graphene in polymkeric substance.But due to the introducing of functional group, make the π bond rupture in graphene oxide aspect, thereby lost the ability of conduction electron.Therefore, the natural graphite how to be easy to get from low price raw material, prepares structural integrity, and the graphene composite material with excellent electrical and thermal conductivity performance becomes the focus of research.
As previously mentioned, Graphene has outstanding conductivity and thundering electronic conduction ability, and the Graphene of introducing small amount in polymkeric substance is just expected to obtain high electrical conductivity, cost is low and have the conducting polymer composite of permanent electroconductibility.Dispersion state and the orientation of Graphene in matrix is the key factor of the conductivity of the graphene-based polymer composites of impact.Research shows, is not that Graphene disperses in matrix more even, and excess effusion value is lower.Be likely because Graphene dispersion is more even, on its surface, more easily superscribe one layer of polymeric, hindered the contact between particle; In contrast, the Graphene of reunion more easily forms conductive network.But it is pointed out that the decline that can cause matrix material machinery performance after Graphene is reunited.When Graphene is when outer field action issues raw orientation, the contact between sheet layer graphene reduces, and is difficult to form effective conductive path, inevitably will improve excess effusion value.For Graphene, there is the composite system of orientation, can by control Graphene aggregation extent or other conductive carbon material that adulterates to reduce excess effusion value and to improve electric conductivity.Graphene natural characteristics is another factor of the conductivity of the graphene-based polymer composites of impact.Existing theoretical model and test-results show that the conductivity of graphene-based polymer nano material depends on the length-to-diameter ratio of graphene sheet layer consumingly, and Graphene fold, folding or other imperfect configuration all can improve excess effusion value.
After obtaining the conduction high polymer matrix material of high conduction performance, how conductive network structure forms the emphasis that always is that academia pays close attention to.When matrix material experience outfield (as temperature field, the field of force, highfield etc.), do the used time, will certainly cause destruction and the reconstruction of conductive network.There is investigator from thermodynamics or dynamic (dynamical) viewpoint, development and the differentiation of near the network microstructure of the conducing composite material of melting temperature have been discussed.But the conductive adhesive system for low excess effusion value, nano conducting powders is scattered in after epoxy resin, the surface of superelevation can make it in nonequilibrium state, under force of cohesion effect, particularly when the action time that it is applied to outfield (temperature field, the field of force, electric field etc.) is enough fully time, nanoparticle can be attracted each other, and causes spacing of particle to reduce, and even assembles.In addition, Curing Process of Epoxy generation volumetric shrinkage, also may make nanoparticle migration occur and reset.
Summary of the invention
The present invention is directed to existing epoxy resin conductive adhesive rely on merely fill flake silver powder obtain conductivity, silver powder in using solidification process easily oxidation cause degradation shortcoming under conductivity, the conductive filler material that provides a kind of simple method to prepare Graphene-nano silver wire, and be applied to epoxy resin conductive adhesive.
First growth in situ nano silver wire on graphene sheet layer in epoxy resin conductive adhesive in the present invention, obtains the nano silver wire after Graphene protection, jointly forms two-dimensional network structure with Graphene.The high conduction performance that recycling Graphene and nano silver wire synergy produce, improved the technical barrier that is easily oxidized the conductivity decline causing in solidification process that simple use silver powder causes, thereby obtained extremely stable high conduction performance and prepare a kind of high conductivity nano silver wire functionalization graphene doping epoxy resin conductive adhesive.
The technical scheme that the present invention addresses the above problem is as follows: a kind of functionalization graphene doping epoxide resin conductive adhesive and preparation method thereof, carries out according to following step:
(1) the graphene oxide colloid (GO) of stable dispersion is prepared by Hummers method.
(2) first at normal temperatures the complex compound of graphene oxide colloid and Trisodium Citrate-Yin is stirred at lucifuge condition lower magnetic force, the time is between 12h ~ 15h.GO and Ag due to electronegative molecular function
+the electrostatic adsorption of-citrate complex ions, makes Ag ionic group install to GO surface, then by high-temp in-situ reduce (130 ℃, 3h) bound Ag ion, then on graphene sheet layer, growth in situ becomes nano silver wire.In preparation process, magnetic agitation lucifuge is processed.
(3) then GO by Trisodium Citrate mild conditions (80 ℃, be reduced into conductive graphene sheet under 6h), last fully centrifuge washing is dissolved in solvent dimethylformamide, is mixed with certain density nano silver wire/Graphene hybrid solution.Concentration is about 2 ~ 5mg/ml.Epoxy resin and the uniform solidifying agent of ground and mixed, curing catalyst are inserted to solution blending in there-necked flask, again a certain amount of Graphene dopant solution is added and vacuumizes (0.05MP) until there is no Bubble formation, follow ultrasonic concussion and process one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue.Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample.Thickness can be according to the amount adjustment of the epoxy resin of die size and cast.
In the present invention, silver: Graphene mass ratio can regulate, and is defined as between 1:2 ~ 1:5 herein.The amount of Silver Nitrate is more, and nano silver wire distributes more intensive on graphene sheet layer.Nano silver wire/Graphene hybrid, by the nano silver wire of one kettle way growth in situ on graphene sheet layer, is 40 ~ 80nm, and length can arrive 1 ~ 2um, disperses intercalation in graphene sheet layer.Concrete nano silver wire details all can be by regulating the amount of substance ratio of Trisodium Citrate and Silver Nitrate to obtain.
In the present invention, a kind of high conductivity nano silver wire functionalization graphene doping epoxy resin conductive adhesive, is characterized in that preparation method comprises the raw material of following epoxy systems weight percent: epoxy resin 96% ~ 97%, the uniform solidifying agent 2.72% ~ 3.63% of ground and mixed, curing catalyst 0.28% ~ 0.37%.Then the Graphene dopant solution that adds the nano silver wire modification of epoxy systems gross weight 5% ~ 10%.
In described nano silver wire/Graphene hybrid, the presoma of Graphene is natural flake graphite.Graphite specification is granularity 500um ~ 1um, carbon content 99.9 ~ 99.99%.In the present invention, silver-colored line is prepared by Silver Nitrate.
Further, epoxy resin conductive adhesive is characterised in that, described epoxy resin comprises one or both in the capable epoxy resin of dihydroxyphenyl propane and bisphenol f type epoxy resin.
Further, epoxy resin conductive adhesive is characterised in that, described solidifying agent is Dyhard RU 100.
Further, epoxy resin conductive adhesive is characterised in that, described curing catalyst is 2,4,6-tri-(dimethylamine methyl) phenol.
In the preparation of nano silver wire/Graphene hybrid, the reductive agent of graphene oxide can be Trisodium Citrate, and Trisodium Citrate quality is 10 ~ 20 times of graphene oxide.
The present invention relatively other conductive polymer fillers has advantage: 1) silver ions is because the GO that electrostatic interaction is assembled into oxy radical functionalization is surperficial, bound silver ions is through in-situ reducing, effectively improved the dispersity of silver particles, and silver particles size is less, the activity of conductive filler material and the utilization ratio of metal have been improved.2) nano silver wire has improved the solvability of graphene composite material by electrostatic adhesion.On the other hand, due to the pinning effect of oxy radical, the nano silver wire that is anchored is difficult for coming off and moving, and has not only improved the stability of Graphene but also has changed the static charge on Graphene surface, has improved the charge capacity of Nano silver grain on Graphene.3) Graphene parcel nano silver wire prevents that it is oxidized, thereby has strengthened the long-range stability of matrix material.In functionalization nano silver wire/Graphene hybrid process of preparing nano silver wire modification, required silver content is low, and in preparation process, lucifuge is processed, and has guaranteed the cheap of its preparation cost.4) there is no the extra process of preparing nano silver wire, avoided the loaded down with trivial details of preparation process.The nano composite material solution of preparing has higher stable homogeneous.5) adopt cheap and eco-friendly Trisodium Citrate as reductive agent, under oil bath condition, realized the gentleness of graphite oxide, controlled reduction, kept to the full extent the crystal structure of graphite.Be intended to lay the foundation for developing the new technology that a kind of simple chemical reduction prepares Graphene.6) superior electrical conductivity that in the present invention, the synergy of epoxy resin conductive adhesive based on Graphene and nano silver wire produces, under set processing condition, the conductive filler material of preparation is dispersed in epoxy resin-base, avoid the agglomeration traits of Graphene in polymkeric substance, thereby increased substantially conductivity and the bonding strength of epoxy resin stick.
Present method is also applicable to the preparation of graphene-based other materials and other polymkeric substance composite conducting materials.
Accompanying drawing explanation
Fig. 1 is the TEM figure of functionalization nano silver wire/Graphene hybrid of the prepared nano silver wire modification of the embodiment of the present invention 1.
embodiment:
Below in conjunction with embodiment, principle of the present invention and feature are described, example only limits the present invention.Except as otherwise noted.All per-cent all in mass in an embodiment.
Adopt to adopt four point probe resistance meter (tungsten pin spacing 5 mm, RTS-9), in 25 ℃, under standard environment, the following example and comparative example are obtained single-component epoxy resin electro-conductive adhesive solidify the volume specific resistance that print carries out testing conductive glue.
The graphene oxide colloid (GO) of stable dispersion is prepared by Hummers method, detailed process is: 10g natural flake graphite and 5 g SODIUMNITRATE are scattered in the 230 mL vitriol oils, under condition of ice bath, lentamente 30 g potassium permanganate are joined in reaction soln, in adition process, the temperature of reaction soln is controlled at below 15 ℃. and reaction soln is at low-temp reaction after for some time, reaction soln temperature is elevated to 35 ℃ of left and right, keep after 30 min, the deionized water of 460mL is joined in reaction soln, in this process, control solution temperature below 100 ℃.After deionized water adds, reaction soln is heated to 98 ℃ and keep 30 min.Reaction finish after by the H of the deionized water of 1400mL and 50mL
2o
2join in solution.When solution is warm, filter and use deionized water repetitive scrubbing 4 ~ 5 times and (use BaNO until can't detect sulfate ion in filtrate
3check), by products therefrom vacuum-drying 24 h at 60 ℃.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Embodiment 1:
(1) prepare respectively 1ml, the silver nitrate aqueous solution that concentration is 0.1M and 1ml, the sodium citrate aqueous solution that concentration is 0.1M, then mixes and fully shakes up.Add 10ml deionized water, ultrasonic 30 minutes.Splash into again 20ml, in the graphite oxide aqueous solution that concentration is 1.08mg/ml, ultrasonic 30 minutes, pour in the single port flask of 250 milliliters, then with aluminium film shading normal temperature lower magnetic force, stir 12 hours.
(2) then in oil bath pan, being heated to 130 ℃ keeps 3 hours.After add 0.216g Trisodium Citrate keep again 90 ℃ 10 hours.Product is moved to and on platform, is cooled to normal temperature, water ionized water, the abundant centrifuge washing of ethanolic soln.Be mixed with the ethanolic soln of 2mg/ml.
(3) the uniform curing agent dicyandiamide 1.089g of bisphenol A-type E-51 epoxy resin 28.8021g and ground and mixed, curing catalyst 2, 4, 6-tri-(dimethylamine methyl) phenol 0.1089g inserts solution blending in there-necked flask, again the Graphene dopant solution of 750ml (epoxy systems quality 5%) is added, under 80 ℃ of water bath condition, 300rpm stirs and carries out solution blending 2 hours, and vacuumize (0.05MP) until there is no Bubble formation, following ultrasonic concussion processes one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue.Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample.
Embodiment 2
(1) prepare respectively 1ml, the silver nitrate aqueous solution that concentration is 0.1M and 1ml, the sodium citrate aqueous solution that concentration is 0.05M, then mixes and fully shakes up.Add 10ml deionized water, ultrasonic 30 minutes.Splash into again 50ml, in the graphite oxide aqueous solution that concentration is 1.08mg/ml, ultrasonic 30 minutes, pour in the single port flask of 250 milliliters, then with aluminium film shading normal temperature lower magnetic force, stir 15 hours.
(2) then in oil bath pan, being heated to 130 ℃ keeps 3 hours.After add 1.08g Trisodium Citrate keep again 90 ℃ 10 hours.Product is moved to and on platform, is cooled to normal temperature, water ionized water, the abundant centrifuge washing of ethanolic soln.Be mixed with the ethanolic soln of 5mg/ml.
(3) the uniform curing agent dicyandiamide 0.816g of bisphenol f type epoxy resin 29.1g and ground and mixed, curing catalyst 2,4,6-tri-(dimethylamine methyl) phenol 0.084g inserts solution blending in there-necked flask, quality, be that 480ml (epoxy systems quality 8%) Graphene dopant solution adds again, under 80 ℃ of water bath condition, 300rpm stirs and carries out solution blending 2 hours, and vacuumize (0.05MP) until there is no Bubble formation, follow ultrasonic concussion and process one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue.Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample.
Embodiment 3
(1) prepare respectively 1ml, the silver nitrate aqueous solution that concentration is 0.1M and 1ml, the sodium citrate aqueous solution that concentration is 0.1M, then mixes and fully shakes up.Add 10ml deionized water, ultrasonic 30 minutes.Splash into again 50ml, in the graphite oxide aqueous solution that concentration is 1.08mg/ml, ultrasonic 30 minutes, pour in the single port flask of 250 milliliters, then with aluminium film shading normal temperature lower magnetic force, stir 14 hours.
(2) then in oil bath pan, being heated to 130 ℃ keeps 3 hours.After add 1.08g Trisodium Citrate keep 90 ℃ 10 hours.Product is moved to and on platform, is cooled to normal temperature, water ionized water, the abundant centrifuge washing of ethanolic soln.Be mixed with the ethanolic soln of 5mg/ml.
(3) the uniform curing agent dicyandiamide 0.8525g of bisphenol A-type E-51 epoxy resin 30.3125g and ground and mixed, curing catalyst 2, 4, 6-tri-(dimethylamine methyl) phenol 0.085g inserts solution blending in there-necked flask, the Graphene dopant solution that is 562.5ml (epoxy systems quality 9%) quality again adds, under 80 ℃ of water bath condition, 300rpm stirs and carries out solution blending 2 hours, and vacuumize (0.05MP) until there is no Bubble formation, following ultrasonic concussion processes one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue.Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample.
Embodiment 4:
(1) prepare respectively 1ml, the silver nitrate aqueous solution that concentration is 0.1M and 1ml, the sodium citrate aqueous solution that concentration is 0.1M, then mixes and fully shakes up.Add 10ml deionized water, ultrasonic 30 minutes.Splash into again 50ml, in the graphite oxide aqueous solution that concentration is 1.08mg/ml, ultrasonic 30 minutes, pour in the single port flask of 250 milliliters, then with aluminium film shading normal temperature lower magnetic force, stir 13 hours.
(2) then in oil bath pan, being heated to 130 ℃ keeps 3 hours.After add 1.08g Trisodium Citrate keep again 90 ℃ 10 hours.Product is moved to and on platform, is cooled to normal temperature, water ionized water, the abundant centrifuge washing of ethanolic soln.Be mixed with the ethanolic soln of 5mg/ml.
(3) the uniform curing agent dicyandiamide 1.0164g of bisphenol A-type E-51 epoxy resin 26.88g and ground and mixed, curing catalyst 2, 4, 6-tri-(dimethylamine methyl) phenol 0.1036g inserts solution blending in there-necked flask, the Graphene dopant solution that is 560ml (epoxy systems quality 10%) quality again adds, under 80 ℃ of water bath condition, 300rpm stirs and carries out solution blending 2 hours, and vacuumize (0.05MP) until there is no Bubble formation, following ultrasonic concussion processes one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue.Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample.
Comparative example
Conventional epoxies formula-do not add the formula of graphene-based epoxy resin: accurately take following various raw material, the uniform curing agent dicyandiamide 1.0164g of bisphenol A-type E-51 epoxy resin 26.88g and ground and mixed, curing catalyst 2,4,6-tri-(dimethylamine methyl) phenol 0.1036g inserts in there-necked flask, under 80 ℃ of water bath condition, 300rpm stirs and carries out solution blending 2 hours, then vacuumize (0.1MP) until there is no Bubble formation, then by ultrasonic concussion, process one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare conductive resin.Flow process is as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, goes straight up to respectively 90 ℃, 110 ℃ and 130 ℃ of maintenances and is cured reaction in two hours, more coolingly in air from mould, sample.
Table 1 is embodiment of the present invention specific conductivity test acquired results.Testing standard foundation: GB/T 1410-2006.
From table 1, data can be found out, first than, epoxy resin conductive adhesive of the present invention, conductivity is better, is especially suitable for conductive adhesive and the encapsulation of the electric components and parts of high-end refinement with conventional epoxies.
Table 1
| Embodiment | Volume specific resistance m Ω cm |
| Embodiment 1 | 30.12 |
| Embodiment 2 | 33.67 |
| Embodiment 3 | 35.29 |
| Embodiment 4 | 38.41 |
| Comparative example | 7.39 |
Claims (5)
1. functionalization graphene doping epoxide resin conductive adhesive and preparation method thereof, is characterized in that carrying out according to following step:
The graphene oxide colloid (GO) of stable dispersion is prepared by Hummers method;
At normal temperatures the complex compound of graphene oxide colloid and Trisodium Citrate-Yin is stirred at lucifuge condition lower magnetic force, the time is between 12h ~ 15h; In preparation process, magnetic agitation lucifuge is processed;
Then GO, by Trisodium Citrate at 80 ℃, is reduced into conductive graphene sheet under 6h, and last fully centrifuge washing is dissolved in solvent dimethylformamide, is mixed with certain density nano silver wire/Graphene hybrid solution;
Concentration is about 2 ~ 5mg/ml; Epoxy resin and the uniform solidifying agent curing catalyst of ground and mixed are inserted to solution blending in there-necked flask, again a certain amount of Graphene dopant solution is added and vacuumizes (0.05MP) until there is no Bubble formation, follow ultrasonic concussion and process one hour, finally by the method for solution casting, in tetrafluoroethylene mould, prepare compound-type conducting glue; Solidify flow process as follows: 80 ℃ vacuumize (0.1MP) and keep one hour bubble removing, rise to respectively 90 ℃, 110 ℃ and 130 ℃ and keep two hours, more coolingly in air from mould, sample; Thickness is according to the amount adjustment of the epoxy resin of die size and cast.
2. a kind of functionalization graphene doping epoxide resin conductive adhesive according to claim 1 and preparation method thereof, silver-colored in its characterization step (2): Graphene mass ratio is 1:2 ~ 1:5.
3. a kind of functionalization graphene doping epoxide resin conductive adhesive according to claim 1 and preparation method thereof, the uniform solidifying agent 2.72% ~ 3.63% of its characterization step (3) epoxy resin 96% ~ 97% and ground and mixed, curing catalyst 0.28% ~ 0.37%;
Then the Graphene dopant solution that adds the nano silver wire modification of epoxy systems gross weight 5% ~ 10%.
4. a kind of functionalization graphene doping epoxide resin conductive adhesive according to claim 1 and preparation method thereof, in the nano silver wire/Graphene hybrid described in its characterization step (3), the presoma of Graphene is natural flake graphite; Graphite specification is granularity 500um ~ 1um, carbon content 99.9 ~ 99.99%.
5. a kind of functionalization graphene doping epoxide resin conductive adhesive according to claim 1 and preparation method thereof, its feature, described epoxy resin comprises one or both in the capable epoxy resin of dihydroxyphenyl propane and bisphenol f type epoxy resin; Described solidifying agent is Dyhard RU 100, and described curing catalyst is 2,4,6-tri-(dimethylamine methyl) phenol, and the reductive agent of graphene oxide is Trisodium Citrate, and Trisodium Citrate quality is 10 ~ 20 times of graphene oxide.
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