CN111180102B - Preparation method of conductive silver paste based on silver-coated graphite conductive agent - Google Patents
Preparation method of conductive silver paste based on silver-coated graphite conductive agent Download PDFInfo
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- CN111180102B CN111180102B CN202010007292.7A CN202010007292A CN111180102B CN 111180102 B CN111180102 B CN 111180102B CN 202010007292 A CN202010007292 A CN 202010007292A CN 111180102 B CN111180102 B CN 111180102B
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- silver
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- pyrrole
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 60
- 239000004332 silver Substances 0.000 title claims abstract description 60
- 239000006258 conductive agent Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 8
- 239000010439 graphite Substances 0.000 title claims abstract description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 59
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 229910052946 acanthite Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940056910 silver sulfide Drugs 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 sodium polysulfide modified carbon Chemical class 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000006230 acetylene black Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 8
- 239000004020 conductor Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 13
- 229910021389 graphene Inorganic materials 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000009738 saturating Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 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 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- RRKGBEPNZRCDAP-UHFFFAOYSA-N [C].[Ag] Chemical compound [C].[Ag] RRKGBEPNZRCDAP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020275 Na2Sx Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000003466 welding 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- 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 relates to a conductive material synthesis technology, and aims to provide a preparation method of conductive silver paste based on a silver-coated graphite conductive agent. The method comprises the following steps: adding a carbon conductive agent into a sodium polysulfide solution, soaking after ultrasonic vibration, filtering and drying to obtain a sodium polysulfide modified carbon material; dispersing the silver sulfide into a silver ammonia solution, and stirring for reaction to obtain a silver sulfide supported carbon material; adding NaCl to reduce the silver sulfide into metallic silver, filtering, washing and drying to obtain a silver-supported carbon material; adding pyrrole into the cyclodextrin solution, and carrying out ultrasonic treatment to obtain a pyrrole cyclodextrin inclusion compound solution; dropwise adding hydrogen peroxide, adding a silver supported carbon material, uniformly stirring, and heating to remove water to obtain the conductive silver paste. The silver-supported carbon material obtained by the invention has the characteristics of low density, low silver consumption and equal conductivity. The silver conductive coating can effectively reduce the usage amount of silver, reduce the cost and be beneficial to using the minimum silver to realize the maximum exertion of the silver conductivity and the silver thermal conductivity.
Description
Technical Field
The invention relates to a conductive material synthesis technology, in particular to a novel conductive agent adopting silver to coat nano graphite to reduce contact resistance between graphite conductors and reduce cost of conductive silver paste and a preparation method thereof.
Background
Printed wiring boards, solar cell panels, radiation protective coatings all require highly conductive materials as the major component of the conductive paste. The silver powder has good corrosion resistance and high conductivity and is widely applied to film switches and flexible circuit boards with PET as a base material, low-temperature silver paste for single-plate ceramic capacitors, silver paste for piezoresistors and thermistors, silver paste for piezoelectric ceramics, silver electrode paste for carbon film potentiometers and the like. The silver powder is classified according to the particle size, and the average particle size is less than 0.1 mu m (100nm) and is nano silver powder; 0.1 micron < average grain size <10.0 micron is silver micro powder; the average particle size >10.0 μm is a coarse silver powder. Silver powders for the electronic industry are classified into seven types: firstly, sintering silver conductive paste at high temperature by using high sintering activity silver powder; secondly, sintering the silver conductive paste at high temperature with high-dispersion silver powder; high-conductivity reduced silver powder and silver powder for electronic industry; bright silver powder; flake silver powder; sixthly, nano silver powder; seventhly, the coarse silver powder is collectively called silver micro powder (or reduction powder);
the coarse silver powder is mainly used in the electrical aspects of silver alloy and the like. The low-temperature normal-temperature curing conductive silver adhesive has the characteristics of low curing temperature, extremely high bonding strength, stable electrical property, suitability for screen printing and the like. The adhesive is suitable for electric conduction and heat conduction adhesion in normal temperature curing welding occasions, such as quartz crystals, infrared pyroelectric detectors, piezoelectric ceramics, potentiometers, flash lamps, shielding, circuit repair and the like, and can also be used for electric conduction adhesion in the radio instrument industry; conductive bonding can also be achieved instead of solder paste.
Silver powder is prepared by various methods, such as a physical method (plasma and atomization method) and a chemical method (silver nitrate thermal decomposition method and liquid phase reduction). Since silver is a noble metal and is easily reduced to return to a simple substance state, the liquid phase reduction method is the most important method for preparing silver powder. The silver powder is prepared by dissolving silver salt (silver nitrate and the like) in water, adding a chemical reducing agent (such as hydrazine hydrate and the like) to deposit silver powder, washing and drying to obtain silver reducing powder, wherein the average particle size is 0.1-10.0 mu m, the reducing agent is selected, the reaction conditions are controlled, and a surfactant is used, so that silver micro powder (particle morphology, dispersion degree, average particle size, particle size distribution, specific surface area, apparent density, tap density, grain size, crystallinity and the like) with different physicochemical characteristics can be prepared, and the reducing powder is mechanically processed (ball milling and the like) to obtain bright silver powder (polarized silver powder) and flake silver powder (silver flake silver).
The three types of silver powder or combination of silver powder of different types are required to be used as conductive filler for forming the conductive silver paste, even different silver powder is required to be used as conductive functional material for different formulas in each type, so that the maximum utilization of silver conductivity and thermal conductivity is realized by using the minimum silver powder under a determined formula or film forming process, and the optimization of film performance and cost are related. The silver powder content of the traditional conductive silver paste is as high as 80 wt%, and the silver powder further comprises about 10 wt% of a curing agent and 10 wt% of an additive, as shown in the following table:
| composition (I) | Mass percent | Description of the ingredients |
| Silver powder | 78-82％ | Conductive filler |
| Bisphenol A epoxy resin | 8-12％ | Resin composition |
| Acid anhydride curing agent | 1-3％ | Curing agent |
| Methyl imidazole | 0-1％ | Accelerator |
| Acetic acid butyl ester | 4-6％ | Non-reactive diluents |
| Active diluent 692 | 1-2％ | Reactive diluent |
| Tetraethyl titanate | 0-1％ | Adhesion promoter |
| Polyamide wax | 0-1％ | Anti-settling agent |
However, silver is a precious metal, which is high in cost and limited in resources, and a conductive agent with light weight, good conductivity, good corrosion resistance and low cost needs to be developed to replace the traditional silver powder.
The traditional carbon conductive agent such as acetylene black, super P, Keqin black, XC-72 and other conductive carbon materials have the advantages of light weight, low cost and wide resources. Carbon nanotubes and graphene have better electron conductivity as a novel graphite material, but the conductivity of the carbon nanotubes and graphene is not as good as that of silver powder. Since the conductive mechanism of the above conductive carbon material is conjugated electron conduction rather than metal-like free electron conduction, the contact resistance between carbon particles is a main cause of poor conductivity of the carbon material. Therefore, silver plating on carbon particles is an effective method for reducing contact resistance between carbon particles. However, carbon materials are generally hydrophobic, silver has poor affinity for carbon, uniform coverage of silver on the surface of carbon particles is difficult to achieve by simple electroless plating, and the thickness of the silver plating layer is difficult to control, and uniformity of conductivity is difficult to ensure.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of conductive silver paste based on a silver coated graphite conductive agent.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the conductive silver paste based on the silver coated graphite conductive agent comprises the following steps:
(1) dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain a sodium sulfide solution; then adding 0.3-0.7 mol of sulfur, stirring for reaction for 24 hours, and filtering to obtain a sodium polysulfide solution;
(2) taking 100mL of sodium polysulfide solution, adding 10-30 g of carbon conductive agent (a commercial product), carrying out ultrasonic vibration treatment for 10-30 min, and continuously soaking for 2-12 h to enable the carbon material to be saturated and absorb agglomerated sodium sulfide; filtering and drying to obtain a sodium polysulfide modified carbon material;
(3) taking 50mL of silver nitrate solution with the mass concentration of 2 wt%, and dropwise adding 2 wt% diluted ammonia water under ultrasonic until the precipitate is just completely dissolved to obtain silver ammonia solution; dispersing 6.3-10 g of a sodium polysulfide modified carbon material in a silver ammonia solution, and stirring for reacting for 2 hours; transferring the silver sulfide loaded carbon material obtained by the reaction into an aluminum beaker, adding 5g of NaCl, and stirring for 24 hours to reduce the silver sulfide into metallic silver; filtering, washing with deionized water, and drying to obtain a silver-supported carbon material;
(4) taking 6g of beta-cyclodextrin, adding the beta-cyclodextrin into 100mL of deionized water at 90 ℃ under nitrogen atmosphere, and dissolving to obtain a cyclodextrin solution; continuously adding 0.9g of pyrrole, and carrying out ultrasonic vibration treatment for 30 minutes to enable pyrrole molecules to enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of the pyrrole so as to obtain a pyrrole cyclodextrin inclusion compound solution; 0.2mL of hydrogen peroxide with the mass concentration of 10 wt% is taken and added into the pyrrole cyclodextrin inclusion compound solution, and ultrasonic vibration treatment is carried out for 30 minutes; adding 30-60 g of silver-supported carbon material, stirring uniformly, heating to boil, and removing 50-80 mL of water to obtain the conductive silver paste.
In the invention, the carbon conductive agent is acetylene black, super P, Ketjen black, XC-72, a carbon nano-tube or graphene carbon material.
In the present invention, the frequency of the ultrasonic vibration treatment is 40 kHz.
In the present invention, in the step (3), when NaCl is added and then stirred, the stirring speed is 10 rpm.
Description of the inventive principles:
sulfur and sodium sulfide react to form a series of sodium polysulfides with varying polarities:
(x-1)S+Na2S＝Na2Sx
the polarity of the sodium polysulphide decreases with increasing sulphur atoms. Hydrophobic carbon material to highly polysodium sulfide such as Na with small polarity2S6And Na2S8Has high adsorption capacity.
Na of low polarity when the carbon conductive agent is immersed in the sodium polysulfide solution2S6And Na2S6Preferentially adsorbing the sodium polysulfide modified carbon material on a hydrophobic carbon surface, filtering and drying to obtain the sodium polysulfide modified carbon material. When the sodium polysulfide modified carbon material is added into silver ammonia solution, the silver ammonia solution reacts with the sodium polysulfide to generate silver sulfide which is loaded on the surface of carbon, when the product is moved to an aluminum beaker, NaCl is added and stirred at low speedDuring the process, the silver sulfide on the carbon surface is continuously contacted with the wall of the aluminum beaker to form a transient microbattery, from which the reduction of the silver sulfide to metallic silver occurs
3Ag2S+2Al+6H2O＝6Ag+2Al(OH)3↓+3H2S↑
Filtering, washing with deionized water, and drying to obtain the silver-supported carbon material.
Pyrrole is added into the cyclodextrin solution, pyrrole molecules enter the cyclodextrin cavity to form a cyclodextrin inclusion compound of the pyrrole due to the hydrophobicity of the cyclodextrin cavity, and the pyrrole molecules are wrapped by the cyclodextrin molecules. Hydrogen peroxide as a pyrrole initiator is hydrophilic and is difficult to enter an obtained pyrrole cyclodextrin cavity, so that the free radical polymerization of pyrrole in the cyclodextrin cavity cannot be promoted, the free radical polymerization of pyrrole at the opening of the cyclodextrin cavity can only be promoted, once the pyrrole is polymerized, the obtained polypyrrole and polypyrrole can penetrate into the cyclodextrin cavity and extend out from the other opening of the cyclodextrin cavity, and the pyrrole at the openings of two adjacent cyclodextrin cavities can be polymerized, so that the linear polypyrrole penetrating through the cyclodextrin cavity is formed. The 2 pi electrons in the conjugated double bonds of the long-chain molecules of polypyrrole in the cyclodextrin cavity are not fixed to a carbon atom, and they can be translocated from one carbon atom to another, i.e. have a tendency to extend throughout the molecular chain. Namely, the superposition of pi electron clouds in the molecules generates a common energy band of the whole molecules, pi electrons are similar to free electrons in a metal conductor, and electrons forming pi bonds can move along a molecular chain, so that the transfer of the electrons in a cyclodextrin molecule cavity is realized, and the conductive adhesive is obtained. And a plurality of hydroxyl groups outside the cyclodextrin molecules form strong hydrophilicity and bonding capability, the conductive bonding agent bonds the silver-loaded carbon material, and the electron transmission among the silver-loaded carbon materials is completed by the linear polypyrrole penetrating through the cyclodextrin cavity, so that the contact resistance among the conductive agent particles is effectively reduced.
Compared with the prior art, the invention has the beneficial effects that:
1. different from the conventional silver powder conductive agent, the silver-loaded carbon material obtained by the invention has the characteristics of low density, low silver consumption and equal conductivity, and the silver plating layer on the carbon surface is effectively contacted with the conductive adhesive, so that the electronic conduction capability between the silver-loaded carbon materials is effectively improved. The conductive silver paste disclosed by the invention uses the silver-loaded carbon material, so that the use amount of silver can be effectively reduced, the cost is reduced, and furthermore, the conductive adhesive is used for replacing an insulating traditional adhesive, so that the maximum exertion of the conductivity and the thermal conductivity of the silver can be realized by using the minimum silver.
2. The conductivity of the carbon silver-loaded material containing 10 wt% of Ag is equivalent to that of pure silver powder, and the bulk density of the carbon silver-loaded material is only one sixth of that of the pure silver powder, so that the use amount and the cost are effectively reduced. The pyrrole cyclodextrin inclusion polymer has electronic conductivity, and replaces the traditional bisphenol A binder with the pyrrole cyclodextrin inclusion polymer as the binder, so that the electronic conductivity among conductive particles is effectively improved, and compared with the traditional conductive silver paste which uses pure silver powder as the conductive agent and insulating polymer such as bisphenol A as the binder, the conductive silver paste prepared by using the carbon-supported silver as the conductive agent and the pyrrole cyclodextrin inclusion polymer as the binder uses less silver and can achieve better conductivity.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1: preparation of sodium polysulfide solution
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.3 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S4And (3) solution.
Example 2: acetylene black adsorbing agglomerated sodium sulfide
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.5 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S6And (3) solution.
Taking the above Na2S6Adding 10g of commercial acetylene black into 100mL of the solution, carrying out ultrasonic treatment for 10min at the ultrasonic frequency of 40kHz, and soaking for 2 h; saturating acetylene black, adsorbing sodium sulfide, filtering and drying to obtain Na2S6And modifying acetylene black.
Example 3: conductive carbon material super P adsorbing sodium sulfide
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.7 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S8And (3) solution.
Taking the above Na2S8Adding 20g of conductive carbon material super P from vendor into 100mL of the solution, performing ultrasonic treatment for 20min at an ultrasonic frequency of 40kHz, and soaking for 6 h; saturating conductive carbon material super P to absorb sodium sulfide, filtering and drying to obtain Na2S8The super P is modified.
Example 4: keqin black absorbing agglomerated sodium sulfide
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.7 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S8And (3) solution.
Taking the above Na2S8Adding 30g of ketjen black into 100mL of the solution, carrying out ultrasonic treatment for 30min at the ultrasonic frequency of 40kHz, and soaking for 12 h; saturating Ketjen black, adsorbing sodium sulfide, filtering, and drying to obtain Na2S8Modifying Keqin black.
Example 5: preparation of silver sulfide supported XC-72
Na was taken as obtained in example 32S8Adding 30g of vendor XC-72 carbon material into 100mL of the solution, performing ultrasonic treatment for 30min at the ultrasonic frequency of 40kHz, and soaking for 12 h; saturating XC-72 to adsorb sodium sulfide, filtering and drying to obtain Na2S8XC-72 was modified.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. Taking the above Na2S810g of modified XC-72 carbon material is dispersed in the silver ammonia solution, and stirred and reacted for 2 hours to obtain silver sulfide supported XC-72.
Example 6: preparation of silver-supported carbon nanotubes
Na was taken as obtained in example 32S8Adding 20g carbon nanotube into 100mL solution, ultrasonic treating for 30min at ultrasonic frequency of 40kHz, and soaking12 h; saturating the carbon nano tube to absorb the sodium sulfide, filtering and drying to obtain Na2S8And modifying the carbon nano tube.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. Taking the above Na2S8And dispersing 10g of modified nanotubes in the silver-ammonia solution, stirring for reacting for 2h to obtain silver sulfide-loaded carbon nanotubes, transferring to an aluminum beaker, adding 5g of NaCl, stirring at a low speed (10rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-loaded carbon nanotubes.
Example 7: conductive silver paste prepared based on graphene
Na was taken as obtained in example 32S8Adding 30g of vendor graphene into 100mL of the solution, carrying out ultrasonic treatment for 30min at the ultrasonic frequency of 40kHz, and soaking for 12 h; saturating graphene, adsorbing sodium sulfide, filtering and drying to obtain Na2S8Modifying graphene.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. Taking the above Na2S8Dispersing 10g of graphene in the silver ammonia solution, stirring and reacting for 2h to obtain silver sulfide loaded graphene, transferring to an aluminum beaker, adding 5g of NaCl, stirring at a low speed (10rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver loaded graphene.
Under the conditions of nitrogen atmosphere and 90 ℃, 6g of beta-cyclodextrin is dissolved by adding 100mL of deionized water to obtain a cyclodextrin solution, 0.9g of pyrrole is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a pyrrole cyclodextrin inclusion compound to obtain a pyrrole cyclodextrin inclusion compound solution, 0.2mL of hydrogen peroxide (10 wt%) is added, the hydrogen peroxide is slowly dripped into the pyrrole cyclodextrin inclusion compound solution, 30g of silver-supported graphene is added after ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, the mixture is uniformly stirred, the mixture is heated to boil, and 80mL of water is removed to obtain the conductive silver paste.
Example 8: conductive silver paste prepared based on carbon nanotubes
Under the conditions of nitrogen atmosphere and 90 ℃, 6g of beta-cyclodextrin is dissolved by adding 100mL of deionized water to obtain a cyclodextrin solution, 0.9g of pyrrole is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a pyrrole cyclodextrin inclusion compound to obtain a pyrrole cyclodextrin inclusion compound solution, 0.2mL of hydrogen peroxide (10 wt%) is added, the hydrogen peroxide is slowly dripped into the pyrrole cyclodextrin inclusion compound solution, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, 45g of silver-supported carbon nanotubes obtained in example 6 are added, the mixture is uniformly stirred and heated to boil, and 65mL of water is removed to obtain the conductive silver paste.
Example 9: conductive silver paste prepared based on acetylene black
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.7 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S8And (3) solution. Adding 30g of merchantable acetylene black into 100mL of the solution, carrying out ultrasonic treatment for 30min at the ultrasonic frequency of 40kHz, and soaking for 12 h; saturating acetylene black, adsorbing sodium sulfide, filtering and drying to obtain Na2S8And modifying acetylene black.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. Taking the above Na2S88g of modified acetylene black is dispersed in the silver-ammonia solution, stirring and reacting are carried out for 2h to obtain silver sulfide-loaded acetylene black, the silver sulfide-loaded acetylene black is moved to an aluminum beaker, 5g of NaCl is added, stirring is carried out at a low speed (10rpm) for 24h, then the silver sulfide is reduced to metallic silver, and the silver-loaded acetylene black is obtained after filtering, washing with deionized water and drying.
Under the conditions of nitrogen atmosphere and 90 ℃, 6g of beta-cyclodextrin is dissolved by adding 100mL of deionized water to obtain a cyclodextrin solution, 0.9g of pyrrole is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a pyrrole cyclodextrin inclusion compound to obtain a pyrrole cyclodextrin inclusion compound solution, 0.2mL of hydrogen peroxide (10 wt%) is added, the hydrogen peroxide is slowly dripped into the pyrrole cyclodextrin inclusion compound solution, after ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, 60g of silver-supported acetylene black is added, after uniform stirring, heating is carried out until boiling is carried out, and 50mL of water is removed to obtain the conductive silver paste.
Example 10: conductive silver paste prepared based on super P
Dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain sodium sulfide solution, adding 0.7 mol of sulfur, stirring for reacting for 24 hours, and filtering to obtain Na2S8And (3) solution. Adding 30g vendor super P into 100mL of the solution, performing ultrasonic treatment for 30min at the ultrasonic frequency of 40kHz, and soaking for 12 h; saturating super P to adsorb sodium sulfide, filtering and drying to obtain Na2S8The super P is modified.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. Taking the above Na2S8Dispersing modified super P (6.3g) in the silver ammonia solution, stirring for reacting for 2h to obtain silver sulfide supported super P, transferring to an aluminum beaker, adding 5g of NaCl, stirring at a low speed (10rpm) for 24h to reduce the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver supported super P, wherein the silver content is 10 wt%.
Under the conditions of nitrogen atmosphere and 90 ℃, 6g of beta-cyclodextrin is dissolved by adding 100mL of deionized water to obtain a cyclodextrin solution, 0.9g of pyrrole is added, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, pyrrole molecules enter a cyclodextrin cavity to form a pyrrole cyclodextrin inclusion compound to obtain a pyrrole cyclodextrin inclusion compound solution, 0.2mL of hydrogen peroxide (10 wt%) is added, the hydrogen peroxide is slowly dripped into the pyrrole cyclodextrin inclusion compound solution, ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for dispersion for 30 minutes, the silver-supported super P (60g) is added, the mixture is uniformly stirred and heated to boil, and 50mL of water is removed to obtain the conductive silver paste.
The conductive silver paste was applied to a glass plate having a size of 3cm x 3cm and dried in the air for surface resistance test, and the results showed that the surface resistance of the coating obtained by using the conductive silver paste of the present invention was equivalent to that of the coating obtained by using the conductive silver paste of the vendor in an amount of 80 wt%, but the amount of silver used in the conductive silver paste of the present invention was only one sixth of that of the conductive silver paste of the vendor.
Finally, the foregoing disclosure is directed to only certain embodiments of the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. A preparation method of conductive silver paste based on a silver coated graphite conductive agent is characterized by comprising the following steps:
(1) dissolving 0.1 mol of anhydrous sodium sulfide in 200 ml of tetrahydrofuran to obtain a sodium sulfide solution; then adding 0.3-0.7 mol of sulfur, stirring for reaction for 24 hours, and filtering to obtain a sodium polysulfide solution;
(2) taking 100mL of poly sodium sulfide solution, adding 10-30 g of carbon conductive agent, carrying out ultrasonic vibration treatment for 10-30 min, and continuing to dip for 2-12 h to enable the carbon material to be saturated and absorb the poly sodium sulfide; filtering and drying to obtain a sodium polysulfide modified carbon material;
(3) taking 50mL of silver nitrate solution with the mass concentration of 2 wt%, and dropwise adding 2 wt% diluted ammonia water under ultrasonic until the precipitate is just completely dissolved to obtain silver ammonia solution; dispersing 6.3-10 g of a sodium polysulfide modified carbon material in a silver ammonia solution, and stirring for reacting for 2 hours; transferring the silver sulfide loaded carbon material obtained by the reaction into an aluminum beaker, adding 5g of NaCl, and stirring for 24 hours to reduce the silver sulfide into metallic silver; filtering, washing with deionized water, and drying to obtain a silver-supported carbon material;
(4) taking 6g of beta-cyclodextrin, adding the beta-cyclodextrin into 100mL of deionized water at 90 ℃ under nitrogen atmosphere, and dissolving to obtain a cyclodextrin solution; continuously adding 0.9g of pyrrole, and carrying out ultrasonic vibration treatment for 30 minutes to enable pyrrole molecules to enter a cyclodextrin cavity to form a cyclodextrin inclusion compound of the pyrrole so as to obtain a pyrrole cyclodextrin inclusion compound solution; 0.2mL of hydrogen peroxide with the mass concentration of 10 wt% is taken and added into the pyrrole cyclodextrin inclusion compound solution, and ultrasonic vibration treatment is carried out for 30 minutes; adding 30-60 g of silver-supported carbon material, stirring uniformly, heating to boil, and removing 50-80 mL of water to obtain the conductive silver paste.
2. The method according to claim 1, wherein the carbon conductive agent is acetylene black, super P, ketjen black, XC-72, carbon nanotubes, or a graphenic carbon material.
3. The method of claim 1, wherein the ultrasonic vibration treatment has a frequency of 40 kHz.
4. The method according to claim 1, wherein in the step (3), the stirring speed is 10rpm when the stirring is performed after the NaCl is added.
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| CN112331792B (en) * | 2020-10-19 | 2021-12-10 | 浙江大学 | Light-emitting device based on polypyrrole conductive layer for flexible display screen |
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| KR101078079B1 (en) * | 2008-12-10 | 2011-10-28 | 엘에스전선 주식회사 | Conductive Paste Containing Silver-Decorated Carbon Nanotubes |
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| CN1919933A (en) * | 2006-09-01 | 2007-02-28 | 清华大学 | Method of preparing electric conductive adhesive by chemical plating silver on graphite powder surface |
| CN101256903A (en) * | 2008-03-20 | 2008-09-03 | 上海交通大学 | Silver-graphitic electrical contact composite plating layer and method of preparing the same |
| TW201416314A (en) * | 2012-10-17 | 2014-05-01 | Nat Univ Tsing Hua | Method for decoration of silver onto carbon materials |
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