CN116631672A - Low-temperature sintering liquid metal conductive paste and preparation method thereof - Google Patents
Low-temperature sintering liquid metal conductive paste and preparation method thereof Download PDFInfo
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- CN116631672A CN116631672A CN202310405524.8A CN202310405524A CN116631672A CN 116631672 A CN116631672 A CN 116631672A CN 202310405524 A CN202310405524 A CN 202310405524A CN 116631672 A CN116631672 A CN 116631672A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000009766 low-temperature sintering Methods 0.000 title abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011231 conductive filler Substances 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- -1 EP-184 Chemical compound 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000012495 reaction gas Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000003723 Smelting Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
Abstract
The invention discloses a low-temperature sintering liquid metal conductive paste and a preparation method thereof, comprising the following steps: adding metal powder into Ga-based liquid metal alloy and uniformly mixing to obtain liquid metal heat conduction paste; introducing reaction gas into the liquid metal heat conduction paste to react to obtain conductive filler; and repeatedly mixing and coating the conductive filler, the adhesive and the coupling agent by using mixing equipment to obtain the conductive slurry. The invention solves the problems of high sintering temperature, poor conductivity and high cost of the conductive paste.
Description
Technical Field
The invention relates to the technical field of new polymer materials, in particular to a low-temperature sintering liquid metal conductive paste and a preparation method thereof.
Background
At present, the conductive silver paste widely applied to photovoltaic module connection and integrated circuit encapsulation at home and abroad is basically high-temperature sintering paste with silver powder as filler and glass powder as binder. The cost of silver powder is high, so that the cost of the conductive silver paste in the photovoltaic module is up to 8-10%, and the cost is difficult to reduce. Meanwhile, currently, the main stream in the industry is still high-temperature sintering conductive paste at about 500 ℃, and low-temperature sintering conductive paste below 250 ℃ is needed to reduce energy consumption and thermal stress in the preparation process, but the technology of low-temperature sintering conductive paste is still mastered in an external enterprise, and the industry is in urgent need of low-cost low-temperature sintering conductive paste.
The conductive paste is an adhesive with certain conductive performance after solidification or drying, and generally takes an adhesive, a coupling agent and conductive fillers, namely conductive particles, as main components, and the conductive particles are combined together to form a conductive path through the bonding action of the adhesive and the coupling agent so as to realize conductive connection of the adhered materials. The most widely used conductive pastes have traditionally used silver powder and copper powder as the conductive filler. Silver powder has good conductivity, and because the oxide of the silver powder also has certain conductivity, silver powder or silver-plated materials are widely used as conductive fillers, silver powder conductive paste is generally used in some fields requiring the conductive paste to have good conductive performance, but the silver powder conductive paste is easy to generate electromigration phenomenon in a humid environment, so that the reliability of the conductive paste is reduced. The silver powder conductive paste has higher cost and poorer sedimentation stability; copper powder has better conductivity and the cost is greatly lower than silver powder, but copper conductive paste is easy to oxidize, the conductivity is greatly reduced after oxidation, even a conductive path cannot be formed, the copper conductive paste has been developed for decades, and the instability is still a long-term problem.
Disclosure of Invention
In order to solve the problems of high cost, high sintering temperature and unstable conductivity of the conductive paste, the invention provides a preparation method of low-temperature sintering liquid metal conductive paste, which comprises the following steps:
adding metal powder into Ga-based liquid metal alloy and uniformly mixing to obtain liquid metal heat conduction paste;
CO is processed by 2 Introducing gas into the liquid metal heat conduction paste to react to obtain an electric conduction filler;
the conductive filler, the adhesive and the coupling agent are repeatedly mixed and coated by mixing equipment to obtain conductive paste, and the Ga-based liquid metal alloy comprises: 50 to 95% by weight of Ga, 0 to 50% by weight of In and 0 to 30% by weight of Sn.
Preferably, the metal powder is one or more of copper powder, tungsten powder, nickel powder, silver powder or magnesium powder.
Preferably, the mass ratio of the metal powder to the Ga-based liquid metal alloy is 1-20: 100.
preferably, the mass ratio of the conductive filler to the adhesive to the coupling agent is as follows: 50% -90): 10 to 50 percent.
Preferably, the CO 2 The purity of the gas is 5% -98%.
Preferably, the adhesive and the coupling agent comprise an adhesive, a curing agent, an accelerator, a coupling agent, a diluent, a defoaming agent and an antioxidant.
Preferably, the components of the adhesive and the coupling agent are as follows: 100 parts of adhesive, 10-20 parts of curing agent, 0-1.5 parts of accelerator, 0-3 parts of coupling agent, 0-18 parts of diluent, 0-1 part of defoamer and 0-0.8 part of antioxidant.
Preferably, the adhesive is one or more of gallium metal powder, indium metal powder, tin metal powder, zinc metal powder and lead-free glass powder; the curing agent is one or more of polythiol, isocyanate, triethanolamine, 2-ethyl-4-methylimidazole, methyl hexahydrophthalic anhydride, methyl T-31 modified amine, YH-82 modified amine, aliphatic polyamine, alicyclic polyamine, polyamide, 2-undecylimidazole, aromatic polyamine, anhydride, phenolic adhesive, amino adhesive, dicyandiamide and hydrazide; the promoter is one or more of triethylamine, imidazole, DMP-30, EP-184, BDMA, CT-152X, DBU, EP-184, 399, K-61B, CT-152X and 2E4 MZ; the coupling agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-allylmethoxyethoxy) silane, titanate, aluminate, gamma-trimercapto propyl triethoxysilane and 3-aminopropyl triethoxysilane; the diluent is one or more of alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, C12-14 fatty glycidyl ether, benzyl glycidyl ether and 1, 6-hexanediol diglycidyl ether; the defoaming agent is one or more of emulsified silicone oil, high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane and phosphate defoaming agent.
The invention also provides a low-temperature sintered liquid metal conductive paste, which is prepared by adopting the method.
The invention utilizes low-melting-point metal alloy with low melting point and high electrical conductivity to carry out in-situ compounding with graphene to obtain the liquid metal heat conduction paste, and the liquid metal heat conduction paste is used as filler to be compounded with low-melting-point metal powder and a coupling agent to obtain the novel conductive paste, and has the following advantages: the melting point of the common liquid metal is 8-10 ℃, the common liquid metal has the advantage of natural low-temperature liquid state, and the common liquid metal is convenient for low-temperature sintering by only converting the binder into liquid state; the liquid metal material has high conductivity and the cost is about 50% of that of silver powder, so that the cost of the conductive paste can be greatly reduced; on the premise of ensuring good conductivity, the production cost is greatly reduced; the filler is partially oxidized on the premise of ensuring good conductivity, so that the material is effectively prevented from being oxidized in the use process to reduce the electric conductivity and the heat conductivity of the material, and the stability of the material is greatly improved; the novel conductive paste has higher heat conductivity coefficient because the conductive filler contains the graphene material with high heat conductivity coefficient; the low-melting-point metal powder can be melted at a lower temperature, so that low-temperature sintering is realized; the metal powder has good mechanical properties after being melted and solidified on the base material, and improves the tensile shear strength and the adaptability of the conductive paste after solidification. Indium metal can be simultaneously soaked with copper or a silicon substrate, and is a suitable liquid metal low-temperature bonding material.
Drawings
Fig. 1 is a flow chart of the preparation of a low temperature sintered liquid metal conductive paste.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of low-temperature sintering liquid metal conductive paste, which comprises the following specific steps as shown in fig. 1:
s100, adding metal powder into Ga-based liquid metal alloy, and uniformly mixing to obtain liquid metal heat conduction paste; heating 69.5 parts of Ga, 20.5 parts of In and 10 parts of Sn to 80 ℃ for smelting to obtain the liquid metal alloy; the smelting time is 1-2 h, and the mixture is cooled to room temperature for standby after smelting; adding 5% copper powder particles to the liquid metal alloy, and uniformly mixing and stirring to prepare liquid metal heat conduction paste;
s200, CO 2 Introducing gas into the liquid metal heat conduction paste to react to obtain conductive filler, and introducing CO 2 The function is that partial gallium can be oxidized to generate simple substance carbon or graphene at the same time, and the gallium in gallium-based liquid metal enables CO to be generated 2 Activated at room temperature to decompose into solid carbon, and different high-performance carbon materials can be obtained by changing different reaction temperatures. Transferring the liquid metal thermal paste to a reaction vessel (where the reaction vessel includes but is not limited to a beaker, a conical flask, a bubble column reactor, etc.), and introducing CO 2 Setting CO 2 The flow rate is 75mL/min, the reaction temperature is 120 ℃, and the ventilation time is 2.5h; after the reaction is completed, transferring the liquid metal heat conduction paste into a stirring tank for stirring and mixing to obtain an in-situ composite material of the liquid metal in-situ composite graphene, namely the conductive filler;
and S300, repeatedly mixing and coating the conductive filler, the adhesive and the coupling agent by using rolling equipment to obtain the conductive paste. Weighing a metal indium powder adhesive, titanate and ethylene glycol with the D50 particle size of 2um according to the proportion of 100:20:3:10, and stirring for 30min by using a magnetic stirrer to obtain the adhesive and the coupling agent; mixing the conductive filler with the adhesive and the coupling agent according to the mass ratio of 100:15, stirring for 40min by a solder paste stirrer to obtain conductive slurry, or mixing the conductive filler with the adhesive and the coupling agent by adopting rolling equipment, centrifugal stirring equipment, planetary ball mill, high-speed dispersing machine, solder paste stirrer and other equipment to obtain the conductive slurry.
The conductive paste was tested and melted and cured on a substrate at 156 c with a volume resistivity of 5.30 x 10 -5 Omega cm, shear strength of 10.5MPa and thermal conductivity of 24W/m.K.
Example 2
The embodiment provides a preparation method of low-temperature sintering liquid metal conductive paste, which comprises the following specific steps as shown in fig. 1:
s100, adding metal powder into Ga-based liquid metal alloy, and uniformly mixing to obtain liquid metal heat conduction paste; heating 69.5 parts of Ga, 20.5 parts of In and 10 parts of Sn to 80 ℃ for smelting to obtain the liquid metal alloy; the smelting time is 1-2 h, and the mixture is cooled to room temperature for standby after smelting; and adding nickel powder particles with the mass fraction of 10% into the liquid metal alloy, and uniformly mixing and stirring to prepare the liquid metal heat conduction paste.
S200, CO 2 Introducing gas into the liquid metal heat conduction paste to react to obtain an electric conduction filler; transferring the liquid metal thermal paste to a reaction vessel (where the reaction vessel includes but is not limited to a beaker, a conical flask, a bubble column reactor, etc.), and introducing CO 2 Setting CO 2 The flow rate is 80mL/min, the reaction temperature is 180 ℃, and the ventilation time is 5h; after the reaction is completed, transferring the liquid metal heat conduction paste into a stirring tank for stirring and mixing to obtain an in-situ composite material of the liquid metal in-situ composite graphene, namely the conductive filler;
and S300, repeatedly mixing and coating the conductive filler, the adhesive and the coupling agent by using rolling equipment to obtain the conductive paste. According to the proportion of 100:18:3:10:2, weighing a metal indium tin alloy (containing 52.0 percent of indium and 48.0 percent of tin) powder adhesive, an amino adhesive, titanate, ethanol and emulsified silicone oil with the D50 particle size of 2um, stirring for 30min by using a magnetic stirrer to obtain the adhesive and the coupling agent, and stirring for 30min by using the magnetic stirrer to obtain the adhesive and the coupling agent; mixing the conductive filler, the adhesive and the coupling agent according to the mass ratio of 100:7, and stirring for 40min by a solder paste stirrer to obtain the conductive paste.
The conductive paste was tested, and the conductive paste was melted and cured on the substrate at 232 c with a volume resistivity of 2.3 x 10 -5 Omega cm, shear strength of 19.7MPa and thermal conductivity of 28W/m.K.
Example 3
The embodiment provides a preparation method of low-temperature sintering liquid metal conductive paste, which comprises the following specific steps as shown in fig. 1:
s100, adding metal powder into Ga-based liquid metal alloy, and uniformly mixing to obtain liquid metal heat conduction paste; heating 69.5 parts of Ga, 20.5 parts of In and 10 parts of Sn to 80 ℃ for smelting to obtain the liquid metal alloy; the smelting time is 1-2 h, and the mixture is cooled to room temperature for standby after smelting; and adding nickel powder particles with the mass fraction of 10% into the liquid metal alloy, and uniformly mixing and stirring to prepare the liquid metal heat conduction paste.
S200, CO 2 Introducing gas into the liquid metal heat conduction paste to react to obtain an electric conduction filler; transferring the liquid metal thermal paste to a reaction vessel (where the reaction vessel includes but is not limited to a beaker, a conical flask, a bubble column reactor, etc.), and introducing CO 2 Setting CO 2 The flow rate is 80mL/min, the reaction temperature is 180 ℃, and the ventilation time is 5h; after the reaction is completed, transferring the liquid metal heat conduction paste into a stirring tank for stirring and mixing to obtain an in-situ composite material of the liquid metal in-situ composite graphene, namely the conductive filler;
and S300, repeatedly mixing and coating the conductive filler, the adhesive and the coupling agent by using rolling equipment to obtain the conductive paste. According to the proportion of 100:18:3:10:2, weighing a lead-free glass powder adhesive, an amino adhesive, titanate, ethanol and emulsified silicone oil with the D50 particle size of 5um, stirring for 30min by using a magnetic stirrer to obtain the adhesive and the coupling agent, and stirring for 30min by using the magnetic stirrer to obtain the adhesive and the coupling agent; mixing the conductive filler, the adhesive and the coupling agent according to the mass ratio of 100:6, and stirring for 40min by a solder paste stirrer to obtain the conductive paste.
The conductive paste was tested and melted and cured on a substrate at 476 c with a volume resistivity of 9.6×10 -5 Omega cm, shear strength of 24.2MPa and thermal conductivity of 2W/m.K.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the low-temperature sintered liquid metal conductive paste is characterized by comprising the following steps of:
adding metal powder into Ga-based liquid metal alloy and uniformly mixing to obtain liquid metal heat conduction paste;
CO is processed by 2 Introducing gas into the liquid metal heat conduction paste to react to obtain an electric conduction filler;
and repeatedly mixing and coating the conductive filler, the adhesive and the coupling agent by using mixing equipment to obtain the conductive slurry.
2. The method of preparing a low temperature sintered liquid metal conductive paste according to claim 1, wherein the Ga-based liquid metal alloy comprises 50 to 95 wt% Ga, 0 to 50 wt% In, and 0 to 30 wt% Sn.
3. The method of preparing a low temperature sintered liquid metal conductive paste according to claim 1, wherein the metal powder is one or more of copper powder, tungsten powder, nickel powder, silver powder, or magnesium powder.
4. The method for preparing a low-temperature sintered liquid metal conductive paste according to claim 3, wherein the mass ratio of the metal powder to the Ga-based liquid metal alloy is 0 to 20:100.
5. the method for preparing the low-temperature sintered liquid metal conductive paste according to claim 1, wherein the mass ratio of the conductive filler to the adhesive to the coupling agent is as follows: 60-90: 4-10: 1 to 3.
6. The method for preparing a low temperature sintered liquid metal conductive paste according to claim 1, wherein said CO 2 The purity of the gas is 5% -98%.
7. The method of preparing a low temperature sintered liquid metal conductive paste according to claim 1, wherein the binder comprises one or more of gallium metal powder, indium metal powder, tin metal powder, zinc metal powder, and lead-free glass powder.
8. The method of preparing a low temperature sintered liquid metal conductive paste according to claim 7, wherein the binder or coupling agent comprises one or more of a binder, a curing agent, an accelerator, a coupling agent, a diluent, an antifoaming agent, or an antioxidant; the promoter is one or more of triethylamine, imidazole, DMP-30, EP-184, BDMA, CT-152X, DBU, EP-184, 399, K-61B, CT-152X and 2E4 MZ; the coupling agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-allylmethoxyethoxy) silane, titanate, aluminate, gamma-trimercapto propyl triethoxysilane and 3-aminopropyl triethoxysilane; the diluent is one or more of alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, C12-14 fatty glycidyl ether, benzyl glycidyl ether and 1, 6-hexanediol diglycidyl ether; the defoaming agent is one or more of emulsified silicone oil, high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane and phosphate defoaming agent.
9. A low temperature sintered liquid metal conductive paste prepared by the method of any one of claims 1 to 8.
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