CN108257710B - A kind of graphene conductive slurry and preparation method thereof - Google Patents
A kind of graphene conductive slurry and preparation method thereof Download PDFInfo
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- CN108257710B CN108257710B CN201711485090.8A CN201711485090A CN108257710B CN 108257710 B CN108257710 B CN 108257710B CN 201711485090 A CN201711485090 A CN 201711485090A CN 108257710 B CN108257710 B CN 108257710B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- 239000002002 slurry Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title description 11
- 238000007613 slurry method Methods 0.000 title description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 94
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 94
- -1 siloxanes Chemical class 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- 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 45
- 238000003756 stirring Methods 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 229910015900 BF3 Inorganic materials 0.000 claims description 19
- 229930185605 Bisphenol Natural products 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical group CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical class OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 claims description 3
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 claims description 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 3
- NOYXQFBTCCSKQG-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)cyclohexyl]oxymethyl]oxirane Chemical compound C1OC1COC1CCCCC1OCC1CO1 NOYXQFBTCCSKQG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 2
- BFHIGGJUBGXSIG-UHFFFAOYSA-N C(C1CO1)OC(C1C(C(=O)O)C=CCC1)=O Chemical compound C(C1CO1)OC(C1C(C(=O)O)C=CCC1)=O BFHIGGJUBGXSIG-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229940106691 bisphenol a Drugs 0.000 claims 2
- 235000009508 confectionery Nutrition 0.000 claims 2
- JPADPHKEIXYMNG-UHFFFAOYSA-N ethenyl(silyloxy)silane Chemical compound [SiH3]O[SiH2]C=C JPADPHKEIXYMNG-UHFFFAOYSA-N 0.000 claims 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims 2
- 229940116351 sebacate Drugs 0.000 claims 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006557 surface reaction Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 240000000146 Agaricus augustus Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229940117955 isoamyl acetate Drugs 0.000 description 2
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- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical group C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This application involves electrocondution slurry fields, and in particular to a kind of graphene conductive slurry.The graphene conductive slurry includes following components: graphene 1-10 parts by weight, epoxy resin 4-15 parts by weight, epoxy-modified siloxanes 2-6 parts by weight, epoxy active diluent 2-6 parts by weight and the latent curing agent 0.1-0.8 parts by weight of epoxy-functional.Further, which also includes through silane coupler modified conductive black 5-20 parts by weight.Present invention also provides the methods for preparing the graphene conductive slurry, and epoxy-modified and each component the mixing of epoxy-functional, siloxanes including graphene powder further comprises the modification of conductive black.The graphene conductive slurry of the application realizes the good dispersion of graphene and the good adhesion of electrocondution slurry, and conductive black can reduce the dosage of graphene, reduce cost.
Description
Technical field
This application involves electrocondution slurry technical fields, and in particular to a kind of graphene conductive slurry and preparation method thereof.
Background technique
In recent years, electrocondution slurry is as a kind of base electronic material with specific function, printed circuit board (PCB),
Printed circuit-board assembly (PCBA), solar battery, RFID radio-frequency antenna, touch screen route, flexible print circuit (FPC), electricity
The field of electronic circuitry such as hotting mask are used widely.Currently, electrocondution slurry is mainly using metal powder as conductive agent, it is especially silver-colored
Powder is currently the most important ones electrocondution slurry as the electrocondution slurry of conductive agent.For the high conductivity for guaranteeing slurry, must just increase
The loading of conductive agent, but as the increase of metal powder, the adhesive property of slurry decline therewith, brittleness, density gradually increase.
To solve this problem, researcher prepares conductive paste as conductive agent using graphene-supported metallic particles
Material.See, for example: CN103500812A, a kind of method of doped graphene preparation high-conductivity slurry；CN103839605A, it is a kind of
Electrocondution slurry and its preparation method and application；CN104021842A, a kind of graphene complex copper thick film conductor paste and its preparation
Method.Graphene is a kind of flat film being made of carbon atom, and the connection between internal carbon atom is very flexible.Graphene exists
Its electron mobility is more than 15000cm under room temperature2/ (Vs), thermal coefficient are up to 5300W/ (mK), and resistivity about 10-6Ω cm, it is lower than copper or silver, it is the current the smallest material of world resistivity.Since graphene has the above special advantage,
Only need a small amount of addition graphene that can largely improve the electric conductivity of slurry in electrocondution slurry.
However, graphene powder during preparing electrocondution slurry there are dispersion problem, lead to the phenomenon that reuniting.Ability
Field technique personnel are to solve dispersion problem, carry out oxidation to graphene and form graphene oxide, and is living using exhibiting high surface
Property agent and dispersing agent help the evenly dispersed of graphene powder.But for electrocondution slurry, surfactant and dispersion
Agent itself is not involved in conduction, this will affect electronic device electric property in use and stability.
Summary of the invention
The purpose of the application is to provide a kind of new graphene conductive slurry and preparation method thereof, to overcome the prior art
Dispersion problem obtains the graphene conductive slurry that electric property is excellent, stability is good, cost reduces.
Therefore, in a first aspect, the present invention provides a kind of graphene conductive slurry, which includes following
Component: graphene 1-10 parts by weight, epoxy resin 4-15 parts by weight, the epoxy-modified siloxanes 2-6 weight of epoxy-functional
Part, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1-0.8 parts by weight.
Preferably, which is the epoxy resin with pi bond structure.It is highly preferred that the epoxy resin is with benzene
The epoxy resin of ring structure.It is more preferred still that the epoxy resin be bisphenol A type epoxy resin or bisphenol f type epoxy resin, especially
It is electron level bisphenol A type epoxy resin or bisphenol f type epoxy resin.Most preferably, which is bisphenol F type epoxy
Resin, because bisphenol f type epoxy resin has good high-temperature stability, to multiple materials such as metal, plastics, rubber, ceramics
With good adhesive property.
The graphene of the epoxy-functional is made by the way that graphene powder is carried out surface functionalization with the epoxy resin,
Wherein the weight ratio of the epoxy resin and the graphene powder is 1:4-3:1.Preferably, with bisphenol f type epoxy resin by graphite
Alkene powder carries out surface functionalization.
The epoxy-modified siloxanes is, wherein asphalt mixtures modified by epoxy resin obtained by being modified siloxanes with the epoxy resin
The weight ratio of rouge and the siloxanes is 1:3-2:1, and wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyl dihydro two
At least one of siloxanes, tetramethyl divinyl disiloxane or t etram-ethyltetravinylcyclotetrasiloxane.Preferably, it uses
Silicone powder is carried out surface functionalization by bisphenol f type epoxy resin.
Preferably, which also includes 5-20 parts by weight through silane coupler modified conductive black.
The silane coupler modified conductive black is, wherein silane obtained by being modified conductive black with silane coupling agent
Coupling agent accounts for the 0.8%-2.5% of the weight of the conductive black.Preferably, which is γ-(2,3- the third oxygen of epoxy)
Propyl trimethoxy silicane (KH560).
Preferably, the graphene conductive slurry also include 0.2-1 parts by weight the agent of tension silk and 0.05-0.2 parts of antioxygen
Agent.The tension silk agent can prevent the graphene conductive slurry from occurring wire drawing phenomenon in use, and the antioxidant
Help to prevent the oxidation of graphene conductive slurry.
Graphene used in the graphene conductive slurry is graphene powder well known in the art, preferably high conductivity
Graphene powder is less than in graphene powder preparation process using element dopings graphene, the numbers of plies of graphene powder such as N, B
5 layers.The available commercial quotient of this graphene is, for example, Xi Wang new material Science and Technology Co., Ltd., Shenzhen, the hexa-atomic element in Changzhou
Limited liability company, Changzhou two dimension carbon Science and Technology Co., Ltd. etc..
Conductive black used in the graphene conductive slurry is conductive black well known in the art, such as Japanese lion princes and dukes
Take charge of the serial superconducting carbon black (Ketjenblack EC-300J and EC-600JD) of Ketjenblack (Ketjen black), the U.S. of (LION)
The VXC series of conductive carbon black of Cabot Co., Ltd (CABOT) wins the production of wound Degussa (Evonik Degussa) company
PRINTEX XE2-B, PRINTEX L6, HIBLAXK 40B2 etc..
The epoxy active diluent is ethylene glycol diglycidylether, butanediol diglycidyl ether, 1,6- cyclohexandiol
Diglycidyl ether, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester, 1,2- hexamethylene two
At least one of alcohol diglycidyl ether or resorcinolformaldehyde resin.
The latent curing agent is group of the lanthanides boron trifluoride acetic acid complex compound La (BF3·C4H7O4)n、Sm(BF3·C4H7O4)n、
Dy(BF3·C4H7O4)n、Er(BF3·C4H7O4) n or Yb (BF3·C4H7O4At least one of) n, wherein (BF3·C4H7O4)n
Indicate that boron trifluoride acetic acid anion, n indicate complexing coefficient.
The tension silk agent is at least one of nano-titanium dioxide, nano zine oxide, Nano carbon white.It is highly preferred that
The tension silk agent is A380 white carbon black.
The antioxidant is bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyl) sebacates, bis- (2,2,6,6-
Tetramethyl -4- piperidyl) sebacate, 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-) amino] -2,6- di-t-butyl
At least one of phenol, dimethylsuccinic acid esters -4- hydroxyl -2,2,6,6- tetramethyl -4- piperidine alcohols.
In second aspect, the present invention provides a kind of method for preparing graphene conductive slurry, method includes the following steps:
The epoxy-functional of graphene powder: graphene powder is subjected to epoxy-functional with epoxy resin, wherein the ring
The weight ratio of oxygen resin and the graphene powder is 1:4-3:1；
Siloxanes it is epoxy-modified: siloxanes is modified with epoxy resin, wherein the epoxy resin and the siloxanes
Weight ratio be 1:3-2:1；
Mixing: by surface functionalized graphene powder 1-10 parts by weight, through epoxy-modified siloxanes 2-6 weight
Measure part, epoxy resin 4-15 parts by weight, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1-0.8 parts by weight
Low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation are carried out, the graphene conductive slurry is made.
Preferably, which is the epoxy resin with pi bond structure.It is highly preferred that the epoxy resin is with benzene
The epoxy resin of ring structure.It is more preferred still that the epoxy resin be bisphenol A type epoxy resin or bisphenol f type epoxy resin, especially
It is electron level bisphenol A type epoxy resin or bisphenol f type epoxy resin.Most preferably, which is bisphenol F type epoxy
Resin, because bisphenol f type epoxy resin has good high-temperature stability, to multiple materials such as metal, plastics, rubber, ceramics
With good adhesive property.
Preferably, the epoxy-functional step of the graphene powder includes by the graphene powder and epoxy resin anhydrous
In solvent, in 20-120 DEG C of temperature, power 500W-4800W, frequency is ultrasonic wave, the 300rpm- of 30KHz-120KHz
Concussion processing 1-8 hours under the rotation of 3500rpm, then vacuum filter is dry under conditions of being lower than 50 DEG C, removes solvent, system
The graphene of epoxy-functional is obtained, wherein the solvent is dehydrated alcohol, isopropanol, butanol, ethyl acetate, butyl acetate, acetic acid
One of pentyl ester, isoamyl acetate, isoamyl acetate, n-methyl-2-pyrrolidone (NMP) or several mixtures.
Preferably, the epoxy-modified step of the siloxanes includes by toluene, epoxy resin, catalyst platinum tetrachloride in logical nitrogen
15min is stirred under conditions of gas, wherein the weight ratio of toluene and the epoxy resin is 1.2:1-3.0:1, catalyst four
Platinum chloride accounts for the 0.008%-0.05% of weight epoxy, and gained mixture is then warming up to 70 DEG C in a nitrogen atmosphere,
The 1:1-5:1 mixed liquor 1h of toluene and siloxanes, the reaction was continued 6h is added dropwise, vacuum distillation removes toluene solvant, obtains epoxy and changes
The siloxanes of property, wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyldihydrogendisiloxane, tetramethyl divinyl
At least one of base disiloxane or t etram-ethyltetravinylcyclotetrasiloxane.
It preferably, further include being changed conductive black in acidic aqueous solution with silane coupling agent before the mixing step
Property, wherein the silane coupling agent accounts for the 0.8%-2.5% of the weight of the conductive black；The mixing step includes being additionally added 5-20 weight
The modified conductive black for measuring part carries out mixing.Preferably, which is γ-(2,3- the third oxygen of epoxy) propyl three
Methoxy silane (KH560).
Preferably, which includes being additionally added the agent of tension silk and 0.05-0.2 parts anti-oxidant of 0.2-1 parts by weight
Agent carries out mixing.
Preferably, which carries out in contactless planet stirring vacuum defoamation all-in-one machine, the contactless row
The vacuum degree of planetary stirring vacuum deaeration all-in-one machine is -0.095MPa；When low speed dispersion stirring, revolution revolving speed is 100-
500rpm, the ratio between revolution and rotational velocity are 1:5-2:1, time 10min-120min；When high speed dispersion stirs, revolution revolving speed is
800-5000rpm, the ratio between revolution and rotational velocity are 1:2-3:1, time 15min-80min.
The graphene, the conductive black, the epoxy active diluent, the latent curing agent, the tension silk agent and this is anti-
Oxidant is as described in the first aspect of the invention.
Moreover, it is noted that carrying out ring to the graphene for the first aspect of the present invention and second aspect
The functionalized epoxy resin of oxygen carries out epoxy-modified epoxy resin to the siloxanes and as the master of the graphene conductive slurry
The epoxy resin of one of body component can be identical or can not be identical.Such as the graphene carries out the asphalt mixtures modified by epoxy resin of epoxy-functional
Rouge, the epoxy that one of epoxy-modified epoxy resin and the host component as the graphene conductive slurry are carried out to the siloxanes
Resin can be each independently bisphenol A type epoxy resin or bisphenol f type epoxy resin.
Beneficial effects of the present invention
Key of the invention is to carry out surface to graphene powder using epoxy resin especially bisphenol f type epoxy resin
Functionalization, wherein the bisphenol f type epoxy resin containing conjugate ring and graphene pass through the pi-conjugated formation non-covalent modification of π-.
It is surface-functionalized to handle the compatibility for solving the ingredients such as graphene powder and epoxy resin, conductive black, curing agent, graphene
Powder has good dispersibility in slurry system, can avoid the defects of powder is reunited, after graphene conductive slurry curing
The graphene conductive electrode arrived stable electrical properties in use.
By the present invention in that siloxanes is carried out with epoxy resin especially bisphenol f type epoxy resin it is epoxy-modified so that
Graphene conductive slurry of the invention is when on being applied to substrate (such as in silk-screen printing on organic high molecular layer (PET)), tool
There is good adhesive strength, while realizing good flexibility and fast light thermal degradation effect, greatly improves resulting graphene and lead
Mechanical property, electric heating property and the stability of electrode.
Graphene conductive slurry of the invention uses conductive black, it is possible to reduce the use of the graphene of price costly
Amount, reduces the cost of the graphene conductive slurry, while being kept substantially the electric property of the graphene conductive slurry.By making
Conductive black is modified with silane coupling agent, silane coupling agent (such as KH560) is hydrolyzed with water in acid condition
Reaction generates silanol Si (OH)3, thus in conjunction with conductive black, at the same the epoxy group in KH560 can promote conductive black with
The compatibility of epoxy resin, graphene powder.
Group of the lanthanides boron trifluoride acetic acid complex compound latent curing agent is at room temperature to the epoxy not no energy of curing reaction substantially
Power, and when temperature reaches 150 DEG C, catalytic activity will be very high, only just graphene of the invention can be made to lead with a few minutes
The epoxy resin of plasma-based material is fully cured.This makes electrocondution slurry convenient storage, and use is easy to operate, shortens cure cycle, mentions
High efficiency.
The present invention uses contactless planetary stirring vacuum deaeration one blank preparation technics, stirs according to low speed dispersion
It mixes, 3 high speed dispersion stirring, vacuum defoamation steps, by designing the ratio between suitable revolving speed, revolution and rotational velocity, the time, true
The parameters such as reciprocal of duty cycle, it is ensured that each component proportion such as graphene, conductive black, resin is accurate, is uniformly dispersed, raising production efficiency,
It reduces material loss, volatilize without dust, production process safety and environmental protection.
Therefore, the electrocondution slurry that graphene conductive slurry of the invention overcomes the prior art uses metal powder as leading
The technologies such as high filler loading capacity caused by electric agent, brittleness, density are big, bonding force is bad, the difficult dispersion of graphene is easy to reunite, at high cost are asked
Topic.Graphene conductive slurry of the invention gives full play to the excellent electric conductivity of graphene, and does not occur in process
Reunite and segregation phenomena, raising conductive compared with the electrocondution slurry of the prior art, service life increase, weight reduction, toughness increase
The advantages that adding, while the advantages that preparation method is simple, at low cost.
Specific embodiment
Below by embodiment, invention is further described in detail.These embodiments are exemplary, and can not be managed
Solution is to limit the invention.
Embodiment 1
In the present embodiment, the epoxy resin of epoxy-functional is carried out to graphene, carries out epoxy-modified ring to siloxanes
The epoxy resin of one of oxygen resin and host component as graphene conductive slurry is all made of bisphenol A type epoxy resin.This pair
Phenol A type epoxy resin is purchased from Shenzhen Jia Dida Chemical Co., Ltd., model NPEL-128E.
By the 2g graphene powder (graphene of the high conductivity of Xi Wang new material Science and Technology Co., Ltd., Shenzhen preparation
Powder), 3.5g bisphenol A type epoxy resin and 200g dehydrated alcohol be added in high speed rotation cavity testing machine.The high speed is revolved
Turn cavity testing machine and is configured with supersonic generator and heating constant-temperature equipment.By mixture at 20-120 DEG C, 1600rpm high speed is revolved
Turn and 2000W, frequency 80KHz ultrasonic wave under shake 1-8h hour, then vacuum filter is done under conditions of lower than 50 DEG C
It is dry, solvent is removed, the graphene powder of surface functionalization is made.
200g toluene, 80g bisphenol A type epoxy resin, 0.02g catalyst platinum tetrachloride are added in glass container,
Under the mixing speed of 200rpm, 15min is stirred under conditions of logical nitrogen.Then mixture is heated up in a nitrogen atmosphere
To 70 DEG C.The mixed liquor 1h of 80g toluene and 20g tetramethyl tetrahydro cyclotetrasiloxane is added dropwise using dropping funel.After being added dropwise,
The reaction was continued 6h, vacuum distillation remove toluene solvant, obtain epoxy-modified siloxanes.
Siloxanes epoxy-modified obtained by graphene powder surface-functionalized obtained by 10g, 4g, 10g is bis-
Phenol A type epoxy resin, 4g ethylene glycol diglycidylether, 0.5g La (BF3·C4H7O4) n, 0.5gA380 white carbon black and 0.1g
Bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) sebacates are added in glass container, in the mixing speed of 120rpm
Under be stirred until homogeneous.Then the contactless planet stirring vacuum defoamation one that vacuum degree is -0.095MPa is fed the mixture into
In machine, low speed dispersion stirring is first carried out, revolution revolving speed is 100-500rpm, and the ratio between revolution and rotational velocity are 1:5-2:1, stirring
Time is 40min, and when then carrying out high speed dispersion stirring, revolution revolving speed is 800~5000rpm, the ratio between revolution and rotational velocity
For 1:2-3:1, mixing time 30min, then vacuum removal bubble, is made the graphene conductive slurry of the present embodiment.
Embodiment 2
In the present embodiment, the epoxy resin of epoxy-functional is carried out to graphene, carries out epoxy-modified ring to siloxanes
The epoxy resin of one of oxygen resin and host component as graphene conductive slurry be all made of bisphenol f type epoxy resin replace it is real
The bisphenol A type epoxy resin in example 1 is applied, remaining is same as Example 1.The bisphenol f type epoxy resin is purchased from the good enlightening in Shenzhen
Up to Chemical Co., Ltd., model NPEF-170.
Embodiment 3
In the present embodiment, the epoxy resin of epoxy-functional is carried out to graphene and carries out epoxy-modified ring to siloxanes
Oxygen resin is all made of the bisphenol A type epoxy resin in embodiment 1, the epoxy of one of host component as graphene conductive slurry
For resin using the bisphenol f type epoxy resin in embodiment 2, remaining is same as Example 1.
Embodiment 4
In the present embodiment, the epoxy resin of epoxy-functional is carried out to graphene and carries out epoxy-modified ring to siloxanes
Oxygen resin is all made of the bisphenol f type epoxy resin in embodiment 2, the epoxy of one of host component as graphene conductive slurry
For resin using the bisphenol A type epoxy resin in embodiment 1, remaining is same as Example 1.
Embodiment 5-8
Embodiment 5-8 is corresponding with embodiment 1-4 respectively, but carries out the modified step in surface to conductive black increasing
Suddenly, graphene conductive slurry and by the modified conductive black in obtained surface is prepared together with remaining component.
Specifically, it using the conductive carbon black Ketjenblack EC-300J of Japanese lion princes and dukes department (LION), and uses
It is modified that KH560 silane coupling agent carries out surface to the conductive black.By 100g conductive carbon black Ketjenblack EC-300J and
1.2g KH560 silane coupling agent concentration be 0.5% dilute sulfuric acid aqueous solution in, 40~80 DEG C at a temperature of reaction 0.6~
2 hours, obtain the modified conductive black in surface.
For embodiment 5, the modified conductive black in the resulting surface 20g is mixed with each component described in embodiment 1
Stirring is closed, wherein the graphene of epoxy-functional is changed to 1g by 10g, and presses described in embodiment 1 in contactless planet stirring
Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in vacuum defoamation all-in-one machine, obtain graphene conductive slurry.
For embodiment 6, the modified conductive black in the resulting surface 15g is mixed with each component as described in example 2
Stirring is closed, wherein the graphene of epoxy-functional is changed to 2.5g by 10g, and stirs by described in embodiment 1 in contactless planet
It mixes and carries out low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation in vacuum defoamation all-in-one machine, obtain graphene conductive slurry.
For embodiment 7, the modified conductive black in the resulting surface 10g is mixed with each component described in embodiment 3
Stirring is closed, wherein the graphene of epoxy-functional is changed to 5g by 10g, and presses described in embodiment 1 in contactless planet stirring
Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in vacuum defoamation all-in-one machine, obtain graphene conductive slurry.
For embodiment 8, the modified conductive black in the resulting surface 5g is mixed with each component as described in example 4
Stirring, wherein the graphene of epoxy-functional is changed to 7.5g by 10g, and presses described in embodiment 1 in contactless planet stirring
Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in vacuum defoamation all-in-one machine, obtain graphene conductive slurry.
Comparative example 1-8
Comparison of design example 1-8, corresponding with embodiment 1-8 respectively, the wherein nano-silver powder of comparative example 1-4 identical weight
(S817957 nano-silver powder, 99.5%, 60-120nm；Shanghai Mike's woods biochemical technology Co., Ltd) replace phase in embodiment 1-4
The graphene for the surface functionalization answered, the nano silver of comparative example 5-6 identical weight replace corresponding surface official in embodiment 5-8
The total amount for the conductive black that the graphene of energyization and surface are modified, prepares the conductive silver slurry of comparison respectively.
Electrocondution slurry performance measurement
1. measuring method
For conductive silver slurry prepared by graphene conductive slurry prepared by above embodiments 1-8 and comparative example 1-8,
According to following standard test fineness, resistivity, adhesive force, curing time.The standard is herein incorporated by reference.
The measurement of GB/T17473.2-2008 fineness
The measurement of GB/T17473.3-2008 sheet resistance
The measurement of GB/T17473.4-2008 adhesive force
The measurement of GB 12007.7-1989 epoxy cure time
2. measurement result
The performance measurement result of embodiment 1-8 and comparative example 1-8 are as shown in the table.Used surface is also provided a comparison of in table
Functionalized graphene, surface modified electrically conductive graphite and/or conductive silver powder.
Table 1: the performance measurement result of embodiment 1-8 and comparative example 1-8
As seen from the above table, when graphene conductive slurry of the invention has fineness similar with conductive silver slurry and solidification
Between, but sheet resistance and adhesive force are substantially better than conductive silver slurry.
Use above specific example is expounded the present invention, is merely used to help understand the present invention, not to
The limitation present invention.The design of those skilled in the art according to the present invention can also be made and several simply push away
It drills, deform or replaces.These are deduced, deformation or alternative are also fallen into scope of the presently claimed invention.
Claims (15)
1. a kind of graphene conductive slurry, which is characterized in that the graphene conductive slurry includes following components: epoxy-functional
Graphene 1-10 parts by weight, epoxy resin 4-15 parts by weight, epoxy-modified siloxanes 2-6 parts by weight, epoxy-reactive dilution
Agent 2-6 parts by weight and latent curing agent 0.1-0.8 parts by weight.
2. graphene conductive slurry according to claim 1, which is characterized in that the epoxy resin is with pi bond structure
Epoxy resin；The graphene of the epoxy-functional is by the way that graphene powder is carried out surface function with the epoxy resin
Change and be made, wherein the weight ratio of the epoxy resin and the graphene powder is 1:4-3:1；The epoxy-modified silicon oxygen
Alkane be it is obtained by being modified siloxanes with the epoxy resin, wherein the weight of the epoxy resin and the siloxanes
Than for 1:3-2:1, wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyldihydrogendisiloxane, tetramethyl two
At least one of vinyl disiloxane or t etram-ethyltetravinylcyclotetrasiloxane.
3. graphene conductive slurry according to claim 2, which is characterized in that the epoxy resin is with benzene ring structure
Epoxy resin.
4. graphene conductive slurry according to claim 3, which is characterized in that the epoxy resin with benzene ring structure
For bisphenol A type epoxy resin or bisphenol f type epoxy resin.
5. graphene conductive slurry according to claim 2, which is characterized in that the graphene conductive slurry also includes 5-
20 parts by weight through silane coupler modified conductive black, the silane coupler modified conductive black is by with silane
Coupling agent conductive black is modified it is obtained, wherein the silane coupling agent accounts for the 0.8%- of the weight of the conductive black
2.5%。
6. graphene conductive slurry according to any one of claims 1-5, which is characterized in that the graphene conductive slurry
Material also the tension silk agent comprising 0.2-1 parts by weight and 0.05-0.2 parts of antioxidant.
7. graphene conductive slurry according to claim 6, which is characterized in that the epoxy active diluent is ethylene glycol
Diglycidyl ether, butanediol diglycidyl ether, 1,6- cyclohexandiol diglycidyl ether, tetrahydrophthalic acid two are shunk
Glyceride, hexahydrophthalic acid 2-glycidyl ester, 1,2- cylohexanediol diglycidyl ether or resorcinol two shrink sweet
At least one of oily ether；The latent curing agent is group of the lanthanides boron trifluoride acetic acid complex compound La (BF3·C4H7O4)n、Sm
(BF3·C4H7O4)n、Dy(BF3·C4H7O4)n、Er(BF3·C4H7O4) n or Yb (BF3·C4H7O4At least one of) n,
In (BF3·C4H7O4) n expression boron trifluoride acetic acid anion, n expression complexing coefficient；The tension silk agent is nano-silica
Change at least one of titanium, nano zine oxide, Nano carbon white；The antioxidant is bis- (1- octyloxy -2,2,6,6- tetramethyls
Base -4- piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 4- [(the pungent sulfenyl -1 of 4,6- bis-,
3,5- triazine -2- base) amino] -2,6 di t butyl phenol, dimethylsuccinic acid esters -4- hydroxyl -2,2,6,6- tetramethyl -4-
At least one of piperidine alcohols.
8. a kind of method for preparing graphene conductive slurry, which is characterized in that the described method comprises the following steps:
The epoxy-functional of graphene powder: graphene powder is subjected to epoxy-functional with epoxy resin, wherein the epoxy
The weight ratio of resin and the graphene powder is 1:4-3:1；
Siloxanes it is epoxy-modified: siloxanes is modified with epoxy resin, wherein the epoxy resin and the siloxanes
Weight ratio be 1:3-2:1；
Mixing: by the surface functionalized graphene powder 1-10 parts by weight, through epoxy-modified siloxanes 2-6 weight
Measure part, the epoxy resin 4-15 parts by weight, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1-0.8 weight
Part carries out low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation, and the graphene conductive slurry is made.
9. according to the method described in claim 8, it is characterized in that, the epoxy resin is the epoxy resin with pi bond structure；
The epoxy-functional step of the graphene powder include by the graphene powder and the epoxy resin in anhydrous solvent,
In 20-120 DEG C of temperature, power 500W-4800W, frequency is the ultrasonic wave of 30KHz-120KHz, 300rpm-3500rpm
Rotation lower concussion processing 1-8 hours, then vacuum filter is dry under conditions of being lower than 50 DEG C, removes solvent, and epoxy official is made
The graphene of energyization；The epoxy-modified step of the siloxanes includes that toluene, the epoxy resin, catalyst platinum tetrachloride exist
It is stirred 15min under conditions of logical nitrogen, wherein the weight ratio of toluene and the epoxy resin is 1.2:1-3.0:1, catalysis
Agent platinum tetrachloride accounts for the 0.008%-0.05% of weight epoxy, and gained mixture is then warming up to 70 in a nitrogen atmosphere
DEG C, the 1:1-5:1 mixed liquor 1h of toluene and siloxanes, the reaction was continued 6h is added dropwise, vacuum distillation removes toluene solvant, obtains epoxy
Modified siloxanes, wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyldihydrogendisiloxane, tetramethyl two
At least one of vinyl disiloxane or t etram-ethyltetravinylcyclotetrasiloxane；It further include using before the mixing step
Conductive black is modified by silane coupling agent in acidic aqueous solution, wherein the silane coupling agent accounts for the conductive black
The 0.8%-2.5% of weight；The mixing step includes being additionally added the modified conductive blacks of 5-20 parts by weight to be mixed
Material.
10. according to the method described in claim 9, it is characterized in that, the epoxy resin is the asphalt mixtures modified by epoxy resin with benzene ring structure
Rouge.
11. according to the method described in claim 10, it is characterized in that, the epoxy resin with benzene ring structure is bisphenol-A
Type epoxy resin or bisphenol f type epoxy resin.
12. according to the method described in claim 9, it is characterized in that, the mixing step includes being additionally added 0.2-1 parts by weight
The agent of tension silk and 0.05-0.2 parts of antioxidant carry out mixing.
13. according to the method for claim 12, which is characterized in that the tension silk agent is nano-titanium dioxide, nano oxygen
Change at least one of zinc, Nano carbon white；The antioxidant is bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidines
Base) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, the 4- [(pungent sulfenyl -1,3,5- triazine-of 4,6- bis-
2- yl) amino] -2,6 di t butyl phenol, in dimethylsuccinic acid esters -4- hydroxyl -2,2,6,6- tetramethyl -4- piperidine alcohols
It is at least one.
14. the method according to any one of claim 8-13, which is characterized in that the mixing step is in contactless row
It being carried out in star stirring vacuum deaeration all-in-one machine, the vacuum degree of the contactless planetary stirring vacuum deaeration all-in-one machine is-
0.095MPa；When low speed dispersion stirring, revolution revolving speed is 100-500rpm, and the ratio between revolution and rotational velocity are 1:5-2:1, time
10min-120min；When high speed dispersion stirs, revolution revolving speed is 800-5000rpm, and the ratio between revolution and rotational velocity are 1:2-3:
1, time 15min-80min.
15. according to the method for claim 14, which is characterized in that the epoxy active diluent shrinks sweet for ethylene glycol two
Oily ether, butanediol diglycidyl ether, 1,6- cyclohexandiol diglycidyl ether, tetrahydrophthalic acid 2-glycidyl ester,
In hexahydrophthalic acid 2-glycidyl ester, 1,2- cylohexanediol diglycidyl ether or resorcinolformaldehyde resin
It is at least one；The latent curing agent is group of the lanthanides boron trifluoride acetic acid complex compound La (BF3·C4H7O4)n、Sm(BF3·
C4H7O4)n、Dy(BF3·C4H7O4)n、Er(BF3·C4H7O4) n or Yb (BF3·C4H7O4At least one of) n, wherein
(BF3·C4H7O4) n expression boron trifluoride acetic acid anion, n expression complexing coefficient.
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| CN111671163A (en) * | 2020-07-13 | 2020-09-18 | 诸暨初升新材料科技有限公司 | Preparation method of graphene heat-conducting ceramic heating body of electronic cigarette atomizer |
| CN112349448B (en) * | 2020-11-02 | 2021-08-06 | 山东华冠智能卡有限公司 | Graphene conductive slurry, preparation method and RFID electronic tag |
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| CN112757724B (en) * | 2020-12-29 | 2022-05-20 | 杭州宜联研仿科技有限公司 | Preparation method of flexible metal-based graphene electrothermal material |
| CN113903937B (en) * | 2021-09-02 | 2023-10-13 | 北京华胜信安电子科技发展有限公司 | Rapid mould pressing composite graphite bipolar plate, preparation method thereof and fuel cell |
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