CN102153976A - Preparation method of graphene/nano silver epoxy conductive adhesive - Google Patents
Preparation method of graphene/nano silver epoxy conductive adhesive Download PDFInfo
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- CN102153976A CN102153976A CN2011100484561A CN201110048456A CN102153976A CN 102153976 A CN102153976 A CN 102153976A CN 2011100484561 A CN2011100484561 A CN 2011100484561A CN 201110048456 A CN201110048456 A CN 201110048456A CN 102153976 A CN102153976 A CN 102153976A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004593 Epoxy Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000853 adhesive Substances 0.000 title abstract 6
- 230000001070 adhesive effect Effects 0.000 title abstract 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 53
- 239000004332 silver Substances 0.000 claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229940071536 silver acetate Drugs 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- HQNOODJDSFSURF-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propan-1-amine Chemical class NCCCC1=NC=CN1 HQNOODJDSFSURF-UHFFFAOYSA-N 0.000 claims description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000009766 low-temperature sintering Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229940100890 silver compound Drugs 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene/nano silver epoxy conductive adhesive, which comprises the following steps: (1) mixing graphite, promoter and organic solvent, then carrying out ultrasonic treatment at 20-50 DEG C for 3-6 hours, standing for 12 hours, centrifuging, and distilling; (2) dissolving epoxy resin and precursor in organic solvent, stirring at 20-50 DEG C for 5-30 minutes, adding a graphene solution to continue reacting for 10-40 minutes, distilling, and carrying out ultrasonic treatment for 5-20 minutes; and (3) adding silver sheets into the graphene-nano silver epoxy resin compound, and carrying out ultrasonic treatment to react at 20-60 DEG C for 30-120 minutes so as to obtain the graphene/nano silver epoxy conductive adhesive. The graphene/nano silver epoxy conductive adhesive disclosed by the invention ensures that the graphene-nano silver compound can be uniformly dispersed in the epoxy matrix, and avoids the problem that the prepared graphene conglobates when the epoxy resin is added, thereby being beneficial to realizing the low-temperature sintering of the nano silver and improving the conductivity and adhesive strength of the conductive adhesive.
Description
Technical field
The present invention relates to the in-situ preparing of Graphene-nano-ag composite and the application in epoxy conducting, be specifically related to the preparation method of a kind of Graphene/nanometer silver epoxy conducting.
Background technology
Novel two-dimentional carbon material Graphene has started the research boom of scientific circles immediately after the Novoselov by Univ Manchester UK in 2004 equals to utilize in 2004 the method for the high directed cracking graphite of tape stripping to obtain.The theoretical specific surface area of grapheme material is up to 2600m
2/ g has outstanding heat conductivility (3000 W/ (mK)) and mechanical property (1060GPa), and high speed electronic mobility (15000cm2/ (Vs)) under the room temperature.The structure that Graphene is special, a series of character such as specific conductivity that make it have perfect quantum tunneling effect, half integral quantum hall effect, never disappear.Professor Geim who finds Graphene once mentioned, and the most direct Application Areas of Graphene is a field of compound material.Graphene has special characteristic electron, and compares with carbon nanotube with the soccerballene of costliness, and Graphene is cheap, and raw material is easy to get, and is expected to become the high quality filler of polymer nanocomposites.
The instead traditional used for electronic packaging Sn/Pb alloy soldering paste of conductive resin is the unleaded environmentally friendly connection material of a kind of ideal.Conductive resin mainly is made up of polymer-bonded matrix and metallic conduction filler.Silver is because have good electroconductibility and chemical stability, and in air and oxidation hardly in the glue-line, and the oxide compound silver suboxide also has electroconductibility, and therefore silver such as gold and copper are a kind of very outstanding conductive filler materials.But also there is following shortcoming in conductive resin at present: electric conductivity is still lower than tin lead welding cream; Contact resistance instability under the hot and humid condition; And compare cohesive strength than wiping solder and be still waiting to improve, thereby its development and application have been limited.Utilize the low-temperature sintering of nanometer silver filler can be when guaranteeing the conductive resin high conductivity, nanometer silver instead of part micron silver reduces amount of filler, improves the conductive resin cohesive strength.
As the metal nanoparticle carrier, Graphene is owing to have same peculiar characteristic electron, and therefore bigger specific surface area, and preparation cost will be well below carbon nanotube is the support materials of the nano particle better than carbon nanotube.Metal refining nano particle on the Graphene lamella, demonstrate the good characteristic electron that Graphene possesses on the one hand, given play to the nano active of nanometer silver on the other hand, can in new hybrid material, show special performances, made its nanometer that becomes good preparation matrix material connect material.
Summary of the invention
The present invention is directed to present widespread oxidation reduction process and prepare the shortcoming that Graphene exists, a kind of method of simple liquid phase production Graphene is provided, original position generates nanometer silver in the preparation conductive resin simultaneously, prepare Graphene/nanometer silver epoxy conducting, improve the electric conductivity and the cohesive strength of conductive resin.
The inventive method at first is blended in graphite and Resins, epoxy promotor in a large amount of organic solvents simultaneously, carries out the ultrasonic graphene suspension that a few hours obtain peeling off of peeling off under certain power in ultrasonic apparatus, leaves standstill the centrifugal Graphene solution that obtains certain solubility.It is applied in the epoxy matrix, with Resins, epoxy promotor is the nanometer silver reductive agent, reductive agent is dispersed in the graphene film interlayer, by nanometer silver reductive agent and silver-colored source presoma (Silver Nitrate, or silver acetate) carries out coordination and form organometallic compound, complex compound decomposes generation nanometer silver uniform deposition on the Graphene lamella of peeling off during curing, and reductive agent is released the participation epoxy resin cure simultaneously, prepares high performance Graphene/nanometer silver epoxy conducting.
The object of the invention is achieved through the following technical solutions:
The preparation method of a kind of Graphene/nanometer silver epoxy conducting is characterized in that, comprises following concrete steps:
(1) graphite, promotor and organic solvent are mixed after, at 20 ~ 50 ℃ of ultrasonic 3 ~ 6h down, leave standstill 12h, get upper strata suspension and carry out centrifugal, distillation and obtain Graphene solution;
(2) Resins, epoxy and presoma are dissolved in the organic solvent, 20 ~ 50 ℃ are stirred 5 ~ 30min, add Graphene solution, after continuing to react 10 ~ 40min, and distillation, ultrasonic 5 ~ 20min obtains Graphene-nanometer silver epoxy resin composite;
(3) in above-mentioned Graphene-nanometer silver epoxy resin composite, add silver strip, apply ultrasonic, 20 ~ 60 ℃ the reaction 30 ~ 120min obtain Graphene/nanometer silver epoxy conducting;
Above-mentioned raw materials parts by weight consumption is as follows:
100 parts of Resins, epoxy
20～60 parts of promotor
1～5 part in graphite
10～50 parts of presomas
500～1000 parts of silver strips.
Described organic solvent is one or more the mixture in acetonitrile, acetone, methylene dichloride, methyl alcohol, ethanol, tetrahydrofuran (THF) or the dimethyl sulfoxide (DMSO);
Described presoma is one or both in silver acetate or the Silver Nitrate;
Described graphite is one or more the mixture in natural flake graphite, expanded graphite or the expansible black lead.
Described Resins, epoxy is one or more the mixture in Racemic glycidol ethers bisphenol A-type, bisphenol f type epoxy resin, ethylene oxidic ester epoxy resin, aliphatic epoxy resin or the cycloaliphatic epoxy resin.
Described promotor is one or more the mixture in 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 3-aminopropyl imidazoles or the Methylimidazole.
The particle diameter of described silver strip is: 2～10 μ m.
Described centrifugal speed is 4000r/min.
Described raw materials in part by weight is preferably:
100 parts of Resins, epoxy
40～60 parts of promotor
1～5 part in graphite
20～40 parts of presomas
800～1000 parts of silver strips;
Described solvent is an acetonitrile.
The present invention compared with prior art has following advantage:
(1) the present invention overcomes and generally adopts oxidation reduction process to prepare Graphene at present exist to destroy original crystal structure of graphite, reduce even lose the shortcoming of partial properties, peel off in the liquid phase organic solvent for ultrasonic and to obtain Graphene, unlikely destruction crystal structure of graphite keeps original excellent electrical simultaneously.
(2) the present invention is the carrier of nano silver particles with the sheet layer graphene.The nanometer silver reductive agent is dispersed in the sheet interlayer, and reduction generates nanometer silver and makes nano silver particles homodisperse on the Graphene matrix during curing.
(3) the present invention's original position in Graphene-epoxy matrix generates Graphene-nanometer silver-epoxy cpd, guaranteed that Graphene-nano-ag composite is dispersed in the epoxy matrix, avoided adding behind the preparation Graphene agglomeration traits of Resins, epoxy, help realizing the nanometer silver low-temperature sintering, improve the electroconductibility and the cohesive strength of conductive resin.
Embodiment
Comparative Examples 1:
Do not add Graphene-nano-ag composite, directly add silver strip and prepare conductive resin:
Raw materials in part by weight is as follows:
862 100 parts of epoxy resins
2E4MZ-CN:40 part
Silver strip: 800 parts
With epoxy resin 862,2E4MZ-CN and silver strip, stir 60min, obtain epoxy conducting.Adopt its resistance behind 150 ℃ of curing 3h of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 4x10
-4Ohmcm.
Embodiment 1
(1) preparation Graphene:
Accurately take by weighing crystalline graphite powder 0.2g, join in the there-necked flask that fills organic solvent acetonitrile and 2E4MZ-CN, after the mixing, insert in the ultrasonic apparatus and descend ultrasonic 6h, leave standstill 12h at 30 ℃, take out the upper strata aaerosol solution, add acetonitrile and dilute once more, diluting soln is obtained the graphene suspension of homodisperse black transparent behind centrifugal 20min under the 4000r/min speed, graphene suspension is carried out underpressure distillation, remove most of acetonitrile solvent, obtain Graphene solution.
(2) preparation conductive resin:
Dispose conductive resin by described parts by weight:
862 100 parts of epoxy resins
60 parts of 2E4MZ-CN
30 parts of silver acetates
800 parts of silver strips (10 μ m)
2 parts in graphite
Be dissolved in epoxy resin 862 and silver acetate in the acetonitrile solvent together, 30 ℃ are stirred 10min down, add Graphene solution and continue reaction 10min, the part organic solvent is removed in underpressure distillation, and ultrasonic 10min obtains homodisperse Graphene-nanometer silver epoxy resin composite.Add silver strip ultrasonic reaction 30min down at 60 ℃, obtain Graphene/nanometer silver epoxy conducting.
Adopt its resistance behind 150 ℃ of curing 3h of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 7.0x10
-5Ohmcm.
Embodiment 2
(1) preparation Graphene:
Accurately take by weighing crystalline graphite powder 0.5g, join in the there-necked flask that fills organic solvent acetonitrile and 2E4MZ-CN, after the mixing, insert in the ultrasonic apparatus and descend ultrasonic 3h, leave standstill 12h at 50 ℃, take out the upper strata aaerosol solution, add acetonitrile and dilute once more, diluting soln is obtained the graphene suspension of homodisperse black transparent behind centrifugal 20min under the 4000r/min speed, graphene suspension is carried out underpressure distillation, remove most of acetonitrile solvent, obtain Graphene solution.
(2) preparation conductive resin:
Dispose conductive resin by described parts by weight:
862 100 parts of epoxy resins
60 parts of 2E4MZ-CN
40 parts of silver acetates
800 parts of silver strips (2 μ m)
5 parts in graphite
Be dissolved in epoxy resin 862 and silver acetate in the acetonitrile solvent together, 20 ℃ are stirred 30min down, add Graphene solution and continue reaction 20min, excessive organic solvent is removed in underpressure distillation, and ultrasonic 20min obtains homodisperse Graphene-nanometer silver epoxy resin composite.Add silver strip ultrasonic reaction 120min down at 20 ℃, obtain Graphene/nanometer silver epoxy conducting.
Adopt its resistance behind 150 ℃ of curing 3h of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 8.1x10
-5Ohmcm.
Embodiment 3
(1) preparation Graphene:
Accurately take by weighing expanded graphite powder 0.2g, join in the there-necked flask that fills organic solvent-acetone and 2E4MZ, after the mixing, insert in the ultrasonic apparatus and descend ultrasonic 4h, leave standstill 12h, take out the upper strata aaerosol solution at 40 ℃, adding acetonitrile dilutes once more, diluting soln is obtained the graphene suspension of homodisperse black transparent behind centrifugal 20min under the 4000r/min speed, graphene suspension is carried out underpressure distillation, remove most of acetonitrile solvent.Obtain Graphene solution, obtain Graphene solution.
(2) preparation conductive resin:
Dispose conductive resin by described parts by weight:
862 100 parts of epoxy resins
41.5 parts of 2E4MZ
30 parts of silver acetates
800 parts of silver strips (2 μ m)
2 parts in graphite
Be dissolved in epoxy resin 862 and silver acetate in the acetone solvent together, 50 ℃ are stirred 5min down, add Graphene solution and continue reaction 40min, excessive organic solvent is removed in underpressure distillation, and ultrasonic 5min obtains homodisperse Graphene-nanometer silver epoxy resin composite.Add silver strip reaction 60min down at 40 ℃, obtain Graphene/nanometer silver epoxy conducting.
Adopt its resistance behind 150 ℃ of curing 3h of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 7.5x10
-5Ohmcm.
Embodiment 4
(1) preparation Graphene:
Accurately take by weighing expanded graphite powder 0.5g, join in the there-necked flask that fills organic solvent acetonitrile and 2E4MZ-CN, after the mixing, insert in the ultrasonic apparatus and descend ultrasonic 3h, leave standstill 12h at 60 ℃, take out the upper strata aaerosol solution, add acetonitrile and dilute once more, diluting soln is obtained the graphene suspension of homodisperse black transparent behind centrifugal 20min under the 4000r/min speed, graphene suspension is carried out underpressure distillation, remove most of acetonitrile solvent, obtain Graphene solution.
(2) preparation conductive resin:
Dispose conductive resin by described parts by weight:
862 100 parts of epoxy resins
60 parts of 2E4MZ-CN
40 parts of silver acetates
800 parts of silver strips (10 μ m)
2 parts in graphite
Be dissolved in epoxy resin 862 and silver acetate in the acetonitrile solvent together, 40 ℃ are stirred 10min down, add Graphene solution and continue reaction 30min, excessive organic solvent is removed in underpressure distillation, and ultrasonic 15min obtains homodisperse Graphene-nanometer silver epoxy resin composite.Add silver strip ultrasonic reaction 90min down at 30 ℃, obtain Graphene/nanometer silver epoxy conducting.
Adopt its resistance behind 150 ℃ of curing 3h of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 8.2x10
-5Ohmcm.
Claims (9)
1. the preparation method of Graphene/nanometer silver epoxy conducting is characterized in that, comprises following concrete steps:
(1) graphite, promotor and organic solvent are mixed after, at 20 ~ 50 ℃ of ultrasonic 3 ~ 6h down, leave standstill 12h, get upper strata suspension and carry out centrifugal, distillation and obtain Graphene solution;
(2) Resins, epoxy and presoma are dissolved in the organic solvent, 20 ~ 50 ℃ are stirred 5 ~ 30min, add Graphene solution, after continuing to react 10 ~ 40min, and distillation, ultrasonic 5 ~ 20min obtains Graphene-nanometer silver epoxy resin composite;
(3) in above-mentioned Graphene-nanometer silver epoxy resin composite, add silver strip, apply ultrasonic, 20 ~ 60 ℃ the reaction 30 ~ 120min obtain Graphene/nanometer silver epoxy conducting;
Above-mentioned raw materials parts by weight consumption is as follows:
100 parts of Resins, epoxy
20～60 parts of promotor
1～5 part in graphite
10～50 parts of presomas
500～1000 parts of silver strips.
2. preparation method according to claim 1 is characterized in that, described organic solvent is one or more the mixture in acetonitrile, acetone, methylene dichloride, methyl alcohol, ethanol, tetrahydrofuran (THF) or the dimethyl sulfoxide (DMSO).
3. preparation method according to claim 1 and 2 is characterized in that, described presoma is one or both in silver acetate or the Silver Nitrate.
4. preparation method according to claim 3 is characterized in that, described graphite is one or more the mixture in natural flake graphite, expanded graphite or the expansible black lead.
5. preparation method according to claim 4, it is characterized in that described Resins, epoxy is one or more the mixture in Racemic glycidol ethers bisphenol A-type, bisphenol f type epoxy resin, ethylene oxidic ester epoxy resin, aliphatic epoxy resin or the cycloaliphatic epoxy resin.
6. preparation method according to claim 5 is characterized in that, described promotor is one or more the mixture in 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 3-aminopropyl imidazoles or the Methylimidazole.
7. preparation method according to claim 6 is characterized in that, the particle diameter of described silver strip is: 2～10 μ m.
8. preparation method according to claim 7 is characterized in that, described centrifugal speed is 4000r/min.
9. preparation method according to claim 8 is characterized in that, described raw materials in part by weight is:
100 parts of Resins, epoxy
40～60 parts of promotor
1～5 part in graphite
20～40 parts of presomas
800～1000 parts of silver strips;
Described solvent is an acetonitrile.
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|---|---|---|---|
| CN 201110048456 CN102153976B (en) | 2011-03-01 | 2011-03-01 | Preparation method of graphene/nano silver epoxy conductive adhesive |
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|---|---|---|---|
| CN 201110048456 CN102153976B (en) | 2011-03-01 | 2011-03-01 | Preparation method of graphene/nano silver epoxy conductive adhesive |
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| CN102153976B CN102153976B (en) | 2013-05-08 |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746808A (en) * | 2012-07-27 | 2012-10-24 | 清华大学深圳研究生院 | High-conductivity graphene conducting resin and preparation method thereof |
| CN102863824A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing unsaturated carboxylic zinc salt functionalized graphene |
| CN102862976A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing functionalized graphene and composite material of functionalized graphene |
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| CN107686705A (en) * | 2016-08-04 | 2018-02-13 | 深圳光启高等理工研究院 | A kind of heat radiating type conductive silver glue and preparation method thereof |
| CN108531118A (en) * | 2018-03-29 | 2018-09-14 | 深圳瑞隆新能源科技有限公司 | A kind of conduction glue caking agent and preparation method thereof, soft-package battery plate lug connecting method |
| CN109688641A (en) * | 2019-01-17 | 2019-04-26 | 佛山市昂达电器有限公司 | Heater and preparation method thereof and exothermic material and electric heating towel rack |
| CN111171772A (en) * | 2020-02-24 | 2020-05-19 | 桂林电子科技大学 | Preparation method of epoxy conductive adhesive |
| CN111292871A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Graphene-nano silver material and preparation method thereof |
| CN111360452A (en) * | 2020-03-17 | 2020-07-03 | 深圳第三代半导体研究院 | Preparation method of graphite-nano silver composite soldering paste sintering material |
| CN115260957A (en) * | 2022-08-10 | 2022-11-01 | 深圳市计量质量检测研究院 | Low-temperature curing bi-component silver conductive adhesive containing conductive auxiliary agent and preparation method thereof |
| CN115975595A (en) * | 2023-01-04 | 2023-04-18 | 佛山市元通胶粘实业有限公司 | Antistatic conductive adhesive for circuit board |
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| CN102863824A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing unsaturated carboxylic zinc salt functionalized graphene |
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| CN104774573A (en) * | 2015-03-30 | 2015-07-15 | 中国电子科技集团公司第三十八研究所 | High-performance conductive silver adhesive containing graphene and preparation method thereof |
| CN104774573B (en) * | 2015-03-30 | 2019-04-23 | 中国电子科技集团公司第三十八研究所 | A kind of high-performance conductive silver paste of containing graphene and preparation method thereof |
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| CN107686705A (en) * | 2016-08-04 | 2018-02-13 | 深圳光启高等理工研究院 | A kind of heat radiating type conductive silver glue and preparation method thereof |
| CN107011631B (en) * | 2017-05-25 | 2019-04-05 | 杭州本松新材料技术股份有限公司 | One kind heat filling containing crystalline flake graphite and the preparation method and application thereof |
| CN107011631A (en) * | 2017-05-25 | 2017-08-04 | 杭州本松新材料技术股份有限公司 | A kind of heat filling containing crystalline flake graphite and preparation method and application |
| CN107437440A (en) * | 2017-08-04 | 2017-12-05 | 郴州国盛新材科技有限公司 | A kind of graphene nano silver electronic paste |
| CN107400492A (en) * | 2017-09-26 | 2017-11-28 | 安徽大松树脂有限公司 | A kind of heat-proof combustion-resistant epoxy resin adhesive |
| CN108531118A (en) * | 2018-03-29 | 2018-09-14 | 深圳瑞隆新能源科技有限公司 | A kind of conduction glue caking agent and preparation method thereof, soft-package battery plate lug connecting method |
| CN109688641A (en) * | 2019-01-17 | 2019-04-26 | 佛山市昂达电器有限公司 | Heater and preparation method thereof and exothermic material and electric heating towel rack |
| CN111292871A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Graphene-nano silver material and preparation method thereof |
| CN111171772A (en) * | 2020-02-24 | 2020-05-19 | 桂林电子科技大学 | Preparation method of epoxy conductive adhesive |
| CN111360452A (en) * | 2020-03-17 | 2020-07-03 | 深圳第三代半导体研究院 | Preparation method of graphite-nano silver composite soldering paste sintering material |
| CN115260957A (en) * | 2022-08-10 | 2022-11-01 | 深圳市计量质量检测研究院 | Low-temperature curing bi-component silver conductive adhesive containing conductive auxiliary agent and preparation method thereof |
| CN115260957B (en) * | 2022-08-10 | 2024-01-09 | 深圳市计量质量检测研究院 | Low-temperature-curing bi-component silver conductive adhesive containing conductive auxiliary agent and preparation method thereof |
| CN115975595A (en) * | 2023-01-04 | 2023-04-18 | 佛山市元通胶粘实业有限公司 | Antistatic conductive adhesive for circuit board |
| CN115975595B (en) * | 2023-01-04 | 2023-08-29 | 佛山市元通胶粘实业有限公司 | Antistatic conductive adhesive for circuit board |
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