CN110355381B - Nano silver powder and preparation method and application thereof - Google Patents
Nano silver powder and preparation method and application thereof Download PDFInfo
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- CN110355381B CN110355381B CN201910771107.9A CN201910771107A CN110355381B CN 110355381 B CN110355381 B CN 110355381B CN 201910771107 A CN201910771107 A CN 201910771107A CN 110355381 B CN110355381 B CN 110355381B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000000843 powder Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000002270 dispersing agent Substances 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 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 claims abstract description 9
- 239000007921 spray Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000108 ultra-filtration Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012263 liquid product Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 23
- 238000009826 distribution Methods 0.000 abstract description 7
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- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 238000000889 atomisation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Computer Hardware Design (AREA)
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- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a preparation method and application of nano silver powder, which comprises the following steps: mixing silver salt and a dispersing agent solution according to a certain proportion, performing water bath treatment, and uniformly stirring to obtain a mixed solution; injecting the mixed solution into a reaction kettle, stirring at a low speed, firstly dropwise adding an alcohol reducing agent into the mixed solution at a constant speed, and then slowly dropwise adding a pH regulator at a constant speed to obtain a nano silver powder mixed solution; removing soluble impurities from the nano silver powder mixed solution by membrane separation equipment to obtain a nano silver powder dispersion liquid; spray drying the nano silver powder dispersion liquid by adopting a high-speed centrifugal spray dryer to obtain nano silver powder; the preparation method provided by the invention is simple and convenient to operate, low in production cost and high in efficiency, and the obtained nano silver powder is uniform in particle size, narrow in particle size distribution range, good in dispersibility and excellent in conductivity.
Description
Technical Field
The invention relates to the technical field of nano silver preparation processes, in particular to nano silver powder and a preparation method and application thereof.
Background
The chemical reduction method is a common method for preparing the nano silver powder, and metal ions are reduced into a nano metal simple substance by a reducing agent under the wrapping of a surfactant in a solvent system or an aqueous solution, so that the method has the advantages of simple operation, low equipment cost, relatively concentrated particle size distribution and the like, but in large-scale production, the reaction conditions need to be accurately controlled to prepare the nano silver powder with uniform particle size and regular shape, and the main factors influencing the particle size of the silver powder are not only the properties of reactants, the reaction temperature, the addition mode, the stirring form and degree, the use of the surfactant and the like, but also relatively serious aggregation is easy to occur among silver powder particles; because the nano materials, especially nano powder, have high activity energy due to the large specific surface area, usually several or more crystal grains are agglomerated together, the surface treatment of the nano silver powder usually uses an organic protective agent, but the organic protective agent needs to be removed by multiple washing and heating treatments at the later stage.
Patent No. CN105855562B proposes that anhydrous ethanol and maleic anhydride are used as dispersants to modify the surface of silver nanoparticles, so that the silver nanoparticles can be kept in a primary particle state and do not agglomerate or agglomerate, but maleic anhydride is used as a dispersant to only treat the existing silver nanoparticles and cannot participate in the preparation of silver nanoparticles, and after the reaction, the nano-metal and the solvent, the unreacted raw materials, the surfactant, and the reaction by-products are mixed together, so how to separate the nano-metal from the impurities is still a problem.
Meanwhile, compared with micron-sized silver particles in industrial silver paste, the surface sintering temperature of the nano silver powder is lower, and the conductive silver paste prepared from the nano silver powder has higher conductivity and lower specific contact resistivity, but because the nano silver powder has smaller particle size, higher surface activation energy and is difficult to disperse, the agglomeration phenomenon is easy to occur, and the conductivity of the conductive silver paste is seriously influenced, for example, in the patent with the patent number of CN102262914B, the conductive silver paste is prepared and applied to a solar cell by adopting a mixture of the nano silver powder and micro silver powder, the conductivity of the obtained solar cell is not excellent, and the problem that the nano silver powder still has agglomeration and poor dispersibility is mainly considered, so that the conductivity is poor, and how to improve the dispersion stability of the nano silver powder in the silver paste is always a hotspot of research.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the preparation method of the nano silver powder, the process method is simple and convenient to operate, the production cost is low, the efficiency is high, and the obtained nano silver powder is uniform in particle size, narrow in particle size distribution range, good in dispersity and excellent in conductivity.
The technical scheme of the invention is as follows:
the invention provides a preparation method of nano silver powder, which comprises the following steps:
s1, mixing the silver salt and the dispersing agent solution according to a certain proportion, treating the mixture for 0.5 to 1 hour in water bath at the temperature of 30 to 50 ℃, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 150-200 r/min, simultaneously dropwise adding an alcohol reducing agent with the concentration of 0.1-5 mol/L into the mixed solution at a constant speed of 10-30 mL/min, then slowly dropwise adding a pH regulator at a constant speed of 1-10 mL/min until the pH value is 8-10, heating to 100-120 ℃, and reacting for 2-4 hours to obtain a nano silver powder mixed solution;
s3, removing soluble impurities from the mixed solution of the silver nanoparticles in the step S2 through membrane separation equipment to obtain a silver nanoparticle dispersion liquid;
and S4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3000-4000 r/min and the air inlet temperature of 120-140 ℃ to obtain the nano silver powder.
According to the invention, the dispersing agent and the silver salt are mixed, the alcohol reducing agent and the pH regulator are added at a uniform speed in a sub-step manner, the alcohol reducing agent is added to help delay the hydrolysis speed of the silane coupling agent, a small amount of nano silver powder crystal seeds are reduced at the same time, then the pH regulator is added to not only promote the generation of the nano silver powder, but also accelerate the hydrolysis of the silane coupling agent, the silanol group generated by hydrolysis can generate a dehydration reaction with the surface of the nano silver powder to form a hydrogen bond, and the silane coupling agent is coated on the surface of the nano silver powder to avoid the agglomeration of the nano silver powder.
In a further aspect of the present invention, the mass percentage of the dispersant to the silver salt in the dispersant solution in step S1 is 0.5% to 2.5%.
As a further limitation of the present invention, the method for preparing the dispersant solution in step S1 includes the following steps:
s1, adding the long-chain-containing acrylate and the double-bond-containing silane coupling agent into an organic solvent to prepare a solution with the mass concentration of 25-40%, introducing nitrogen, heating to 80-120 ℃, and uniformly stirring to obtain a reaction system;
s2, adding an initiator dropwise into the reaction system obtained in the step S1, continuing to react for 1-3 hours after the addition is finished to obtain a crude product, and carrying out reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing long-chain silane;
s3, dissolving 0.01-1 part of the coupling agent containing long-chain silane obtained in the step S2 in 1200-2000 parts of alcohol-water solution at the temperature of 20-50 ℃ under the stirring condition, and stirring for 5-30 min to obtain a dispersing agent solution.
As a further limitation of the present invention, the long-chain acrylate is one or more of polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, 2-ethylhexyl acrylate, trimethylolpropane triacrylate; the long-chain end group containing the long-chain acrylate is selected to have a reducing functional group and can participate in reducing the nano silver powder.
As a further limitation of the invention, the double-bond-containing silane coupling agent is one or more of gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl trimethoxy silane and vinyl triethoxy silane; the mass ratio of the long-chain-containing acrylate to the double-bond-containing silane coupling agent is 0.8-1.2: 1; the organic solvent is one or more of toluene, xylene, n-butanol, n-butyl acetate and tri-1, 2-propylene glycol monomethyl ether.
As a further limitation of the invention, the initiator is one or more of azobisisobutyronitrile, tert-butyl peroxy-2-ethylhexanoate and benzoyl peroxide; the mass ratio of the initiator to the total amount of the monomers is 0.01-0.04: 1; the alcohol-water solution is one or a mixture of more of 60-80% by mass of ethanol solution, 60-80% by mass of methanol solution and 60-80% by mass of isopropanol solution.
As a further limitation of the present invention, the silver salt in step S1 is at least one of silver nitrate, silver sulfate, silver carbonate and silver complex.
As a further limitation of the present invention, the pH adjusting agent in step S2 is at least one of ammonia, acetic acid, sodium acetate, sodium hydroxide, and hydrochloric acid; the alcohol reducing agent is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol and 1, 3-butanediol.
As a further limitation of the present invention, the membrane separation device in step S3 includes an ultrafiltration membrane or a nanofiltration membrane, a material tank, and a circulation pump, where the ultrafiltration membrane or the nanofiltration membrane is made of at least one of cellulose and its derivatives, polypropylene, polyethylene, polystyrene, polycarbonate, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyacrylonitrile, polyamide, polysulfonamide, sulfonated polysulfone, cross-linked polyvinyl alcohol, and modified acrylic acid polymer; the pore diameter range of the ultrafiltration membrane or the nanofiltration membrane is 10-60 nm.
The invention also provides a conductive silver paste which can be applied to the field of printing fine circuits, in particular to a circuit with smaller line width; for example, it is used for producing an FPC board or a substrate for a photoelectric conversion module.
The invention also provides a solar cell, which comprises a silicon substrate and a conductive grid line positioned on the silicon substrate, wherein the conductive grid line is obtained by screen printing conductive silver paste on the silicon substrate, drying and sintering.
The beneficial technical effects of the invention are as follows:
1. the preparation method has the characteristics of simple and convenient operation, low production cost and high efficiency, and is suitable for industrial production.
2. The dispersing agent provided by the invention selects the silane coupling agent with the reducing end group, the silane coupling agent can participate in reduction to prepare the nano silver powder, and the silane coupling agent is hydrolyzed by an alcohol-water solvent and an alkaline environment to generate silicon hydroxyl which is subjected to hydrolysis polycondensation with hydroxyl on the surface of the nano silver powder, so that the nano silver powder is dispersed, and the dispersing agent plays double roles of a reducing agent and a dispersing agent in the reaction, so that the production process can be simplified, the utilization rate of the reagent is improved, the production cost can be reduced, and the purity of the nano silver powder product is ensured.
3. According to the invention, the mixed solution is stirred at a low speed, and meanwhile, the polyol reducing agent is firstly dripped at a low speed and a uniform speed, so that the polyol reducing agent and the dispersing agent are fully contacted with silver salt to form a small amount of nano silver powder crystal seeds, and the crystal seeds are uniformly distributed and have controllable quality; then, the pH regulator is dropwise added at a constant speed, nano silver particles can be grown on the basis of the seed crystal, the large-scale preparation of the nano silver powder can be guaranteed, meanwhile, the silane coupling agent is rapidly hydrolyzed and coated on the surface of the nano silver powder, and the agglomeration of the nano silver powder is avoided, so that the uniform particle size, the narrow particle size distribution range and the high purity of the nano silver powder are guaranteed.
4. The dispersing agent disclosed by the invention contains a long-chain silane coupling agent, and the steric hindrance can be increased by the long-chain group, so that the nano silver particles are kept in a primary particle state and are not hard to agglomerate or agglomerate, and the dispersion of the nano silver powder is facilitated.
5. The spray drying equipment has high drying speed, the surface area of the nano silver dispersion liquid is greatly increased after atomization, the nano silver dispersion liquid can be dried instantly without crushing and screening after drying, and the added dispersing agent can avoid the agglomeration of nano particles and is beneficial to the dispersion of the nano silver powder in the process of preparing silver paste.
Drawings
FIG. 1 is a schematic view of a process for preparing nano silver powder according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying fig. 1 and the embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percent of 0.5% of the dispersant and the silver nitrate, treating the mixture in water bath at 30 ℃ for 1h, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 150r/min, simultaneously dropwise adding 0.1mol/L glycol into the mixed solution at a constant speed, wherein the dropwise adding speed is 10mL/min, then slowly dropwise adding ammonia water at a constant speed, the dropwise adding speed is 1mL/min until the pH value is 8, heating to 100 ℃, and reacting for 4 hours to obtain a nano silver powder mixed solution;
s3, treating the nano silver powder mixed solution in the step S2 through a polypropylene ultrafiltration membrane with the aperture of 10nm, and removing impurities to obtain a nano silver powder dispersion liquid;
and S4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3000r/min and the air inlet temperature of 140 ℃ to obtain the nano silver powder with the average particle size of 203 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing polyethylene glycol acrylate and vinyl trimethoxy silane according to the mass ratio of 0.8: adding the mixture of 1 into toluene in a ratio to prepare a solution with the mass concentration of 25%, introducing nitrogen, heating to 80 ℃, and uniformly stirring to obtain a reaction system;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.01: 1, continuously reacting for 1h after the dropwise addition is finished to obtain a crude product, and performing reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing long-chain silane;
s3, dissolving 0.01 part of the coupling agent containing the long-chain silane obtained in the step S2 in 1200 parts of 60% by mass ethanol solution at the temperature of 20 ℃ under the stirring condition, and stirring for 5min to obtain a dispersing agent solution.
Example 2
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percentage of 2.5% of the dispersant and the silver sulfate, treating the mixture in a water bath at 50 ℃ for 0.5h, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 200r/min, simultaneously dropwise adding 1, 3-propylene glycol with the concentration of 5mol/L at a constant speed into the mixed solution, wherein the dropwise adding speed is 30mL/min, then slowly dropwise adding sodium hydroxide at a constant speed, wherein the dropwise adding speed is 10mL/min until the pH value is 10, heating to 120 ℃, and reacting for 2 hours to obtain a nano silver powder mixed solution;
s3, processing the nano silver powder mixed solution in the step S2 through a polycarbonate ultrafiltration membrane with the aperture of 60nm, and removing impurities to obtain a nano silver powder dispersion liquid;
and S4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 4000r/min and the air inlet temperature of 120 ℃ to obtain the nano silver powder with the average particle size of 211 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing polyethylene glycol methacrylate and gamma- (methacryloyloxy) propyl trimethoxy silane according to the mass ratio of 1.2: 1 is added into dimethylbenzene to prepare a solution with the mass concentration of 40 percent, nitrogen is introduced, the temperature is raised to 120 ℃, and a reaction system is obtained after uniform stirring;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.04: 1, continuously reacting for 3 hours after dropwise adding the tert-butyl peroxy-2-ethylhexanoate to obtain a crude product, and distilling the crude product under reduced pressure to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely a coupling agent containing long-chain silane;
s3, dissolving 1 part of the coupling agent containing the long-chain silane obtained in the step S2 in 2000 parts of 80 mass percent methanol solution at the temperature of 50 ℃ under the stirring condition, and stirring for 30min to obtain a dispersing agent solution.
Example 3
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percent of 1.5% of the dispersant and the silver nitrate, treating the mixture in water bath at 40 ℃ for 0.8h, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 180r/min, simultaneously dropwise adding 1, 2-propylene glycol with the concentration of 3mol/L at a constant speed into the mixed solution, wherein the dropwise adding speed is 15mL/min, then slowly dropwise adding sodium hydroxide at a constant speed, wherein the dropwise adding speed is 5mL/min until the pH value is 9, heating to 110 ℃, and reacting for 3 hours to obtain a nano silver powder mixed solution;
s3, processing the nano silver powder mixed solution in the step S2 through a polyethylene ultrafiltration membrane with the aperture of 30nm, and removing impurities to obtain a nano silver powder dispersion liquid;
and S4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3500r/min and the air inlet temperature of 130 ℃ to obtain the nano silver powder with the average particle size of 205 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing polyethylene glycol acrylate and vinyl tri (beta-methoxyethoxy) silane according to the mass ratio of 1: 1 is added into dimethylbenzene to prepare a solution with the mass concentration of 30 percent, nitrogen is introduced, the temperature is raised to 100 ℃, and a reaction system is obtained after uniform stirring;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.02: 1, continuously reacting for 2 hours after the dropwise addition of the azodiisobutyronitrile to obtain a crude product, and performing reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing the long-chain silane;
s3, dissolving 0.05 part of the coupling agent containing the long-chain silane obtained in the step S2 in 1500 parts of methanol solution with the mass percent of 72% at the temperature of 30 ℃ under the stirring condition, and stirring for 15min to obtain the dispersing agent solution.
Example 4
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percentage of 0.5% of the dispersant and the silver carbonate, carrying out water bath treatment at 30 ℃ for 1h, and uniformly stirring to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 150r/min, simultaneously dropwise adding 1 and 2-butanediol with the concentration of 0.1mol/L into the mixed solution at a constant speed, wherein the dropwise adding speed is 10mL/min, then slowly dropwise adding sodium acetate at a constant speed, wherein the dropwise adding speed is 1mL/min until the pH value is 8, heating to 100 ℃, and reacting for 4 hours to obtain a nano silver powder mixed solution;
s3, treating the nano silver powder mixed solution in the step S2 through a polystyrene ultrafiltration membrane with the aperture of 10nm, and removing impurities to obtain a nano silver powder dispersion liquid;
and S4, spray-drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3000r/min and the air inlet temperature of 140 ℃ to obtain the nano silver powder with the average particle size of 202 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing 2-ethylhexyl acrylate and vinyl triethoxysilane by a mass ratio of 0.8: adding the mixture of 1 into n-butanol to prepare a solution with the mass concentration of 25%, introducing nitrogen, heating to 80 ℃, and uniformly stirring to obtain a reaction system;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.01: 1, continuously reacting for 1h after the dropwise addition is finished to obtain a crude product, and carrying out reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing the long-chain silane;
s3, dissolving 0.01 part of the coupling agent containing the long-chain silane obtained in the step S2 in 1200 parts of 60% by mass of isopropanol solution at the temperature of 20 ℃ under the stirring condition, and stirring for 5min to obtain a dispersing agent solution.
Example 5
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percentage of 0.5% of the dispersant and the silver complex, treating the mixture in a water bath at 50 ℃ for 0.5h, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 150r/min, simultaneously dropwise adding 5mol/L glycol into the mixed solution at a constant speed, wherein the dropwise adding speed is 30mL/min, then slowly dropwise adding ammonia water at a constant speed, the dropwise adding speed is 10mL/min until the pH value is 10, heating to 120 ℃, and reacting for 2 hours to obtain a nano silver powder mixed solution;
s3, processing the nano silver powder mixed solution in the step S2 through a polyvinyl chloride ultrafiltration membrane with the aperture of 60nm, and removing impurities to obtain a nano silver powder dispersion liquid;
and S4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 4000r/min and the air inlet temperature of 120 ℃ to obtain the nano silver powder with the average particle size of 214 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing trimethylolpropane triacrylate and vinyl tri (beta-methoxyethoxy) silane according to the mass ratio of 1.2: adding the mixture of 1 into n-butyl acetate in a ratio to prepare a solution with the mass concentration of 40%, introducing nitrogen, heating to 120 ℃, and uniformly stirring to obtain a reaction system;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.04: 1, continuously reacting for 3 hours after the dropwise addition is finished to obtain a crude product, and carrying out reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing the long-chain silane;
s3, dissolving 1 part of the coupling agent containing the long-chain silane obtained in the step S2 in 2000 parts of isopropanol solution with the mass percent of 80% at the temperature of 50 ℃ under the stirring condition, and stirring for 30min to obtain the dispersing agent solution.
Example 6
The embodiment provides a method for preparing nano silver powder, which comprises the following steps:
s1, mixing the dispersant solution according to the mass percent of 1.5% of the dispersant and the silver nitrate, treating the mixture in water bath at 40 ℃ for 0.8h, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 180r/min, simultaneously dropwise adding 3mol/L1 and 3-butanediol into the mixed solution at a constant speed, wherein the dropwise adding speed is 15mL/min, then slowly dropwise adding ammonia water at a constant speed, wherein the dropwise adding speed is 5mL/min until the pH value is 9, heating to 110 ℃, and reacting for 3 hours to obtain a nano silver powder mixed solution;
s3, treating the mixed solution of the silver nanopowder obtained in the step S2 through a polyvinylidene fluoride ultrafiltration membrane with the aperture of 30nm, and removing impurities to obtain a silver nanopowder dispersion liquid;
and S4, spray-drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3500r/min and the air inlet temperature of 130 ℃ to obtain the nano silver powder with the average particle size of 210 nm.
The preparation method of the dispersant solution described in this embodiment includes the following steps:
s1, mixing polypropylene glycol methacrylate and vinyl triethoxysilane in a mass ratio of 1: adding the 1 into 1, 2-propylene glycol monomethyl ether in proportion to prepare a solution with the mass concentration of 30%, introducing nitrogen, heating to 100 ℃, and uniformly stirring to obtain a reaction system;
s2, dropwise adding the mixture into the reaction system of the step S1, wherein the mass ratio of the mixture to the total amount of the monomers is 0.02: 1, continuously reacting for 2 hours after dropwise adding the tert-butyl peroxy-2-ethylhexanoate to obtain a crude product, and distilling the crude product under reduced pressure to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely a coupling agent containing long-chain silane;
s3, dissolving 0.05 part of the coupling agent containing the long-chain silane obtained in the step S2 in 1500 parts of 72% by mass ethanol solution at the temperature of 30 ℃ under the stirring condition, and stirring for 15min to obtain a dispersing agent solution.
Comparative example 1
The silver nanoparticles powder of the present comparative example was prepared according to the method of CN 105855562B.
Comparative example 2
The nano silver powder of this comparative example was prepared in the same manner as in example 3, except that the dispersant was vinyltriethoxysilane.
Comparative example 3
The nano silver powder of this comparative example was prepared by the same method as in example 6, except that the dispersant was vinyltrimethoxysilane.
Test example 1
The nano silver powders prepared according to examples 1 to 6 of the present invention were compared with the particle size distribution of the comparative example, and the comparison results are shown in the following table.
Test example 2
The nano silver powder prepared in examples 1 to 6 and comparative examples 1 to 3 is uniformly mixed with an adhesive, a solvent and an auxiliary agent to obtain conductive silver paste, the conductive silver paste is printed on a silicon substrate in a screen printing mode, the silicon substrate is dried and sintered, the conductive silver paste is cured to form a conductive grid line, each solar cell is prepared, and the photoelectric conversion efficiency of each solar cell is tested respectively to obtain the results shown in table 1.
TABLE 1
| Photoelectric conversion efficiency% | |
| Example 1 | 19 |
| Example 2 | 21 |
| Example 3 | 21.5 |
| Example 4 | 21 |
| Example 5 | 20 |
| Example 6 | 22 |
| Comparative example 1 | 12 |
| Comparative example 2 | 8 |
| Comparative example 3 | 11 |
According to the experimental results, the particle size distribution of the nano silver powder in the examples 1 to 6 is between 50 nm and 500nm, and the particle size distribution is narrow; in addition, the photoelectric conversion rate of the solar cell sheet prepared from the nano silver powder of the embodiments 1 to 6 is about 20%, which not only shows that the conductive property of the conductive silver paste is excellent, but also shows that the dispersibility of the nano silver powder is good.
While the embodiments of the present invention have been disclosed above, it is not limited to the applications listed in the description and embodiments, but is fully applicable to various fields suitable for the present invention, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principle and spirit of the present invention, and therefore the present invention is not limited to the specific details without departing from the general concept defined in the claims and the scope of equivalents thereof.
Claims (8)
1. The preparation method of the nano silver powder is characterized by comprising the following steps of:
s1, mixing the silver salt and the dispersing agent solution according to a certain proportion, treating the mixture for 0.5 to 1 hour in water bath at the temperature of 30 to 50 ℃, and uniformly stirring the mixture to obtain a mixed solution;
s2, injecting the mixed solution obtained in the step S1 into a reaction kettle, stirring at a low speed of 150-200 r/min, simultaneously dropwise adding an alcohol reducing agent with the concentration of 0.1-5 mol/L into the mixed solution at a constant speed of 10-30 mL/min, then slowly dropwise adding a pH regulator at a constant speed of 1-10 mL/min until the pH value is 8-10, heating to 100-120 ℃, and reacting for 2-4 hours to obtain a nano silver powder mixed solution;
s3, removing soluble impurities from the mixed solution of the silver nanoparticles in the step S2 through membrane separation equipment to obtain a silver nanoparticle dispersion liquid;
s4, spray drying the nano silver powder dispersion liquid obtained in the step S3 by a high-speed centrifugal spray dryer at the rotating speed of 3000-4000 r/min and the air inlet temperature of 120-140 ℃ to obtain nano silver powder;
the preparation method of the dispersant solution in the step S1 includes the following steps:
s1, adding the long-chain-containing acrylate and the double-bond-containing silane coupling agent into an organic solvent to prepare a solution with the mass concentration of 25-40%, introducing nitrogen, heating to 80-120 ℃, and uniformly stirring to obtain a reaction system;
s2, adding an initiator dropwise into the reaction system obtained in the step S1, continuing to react for 1-3 hours after the addition is finished to obtain a crude product, and carrying out reduced pressure distillation on the crude product to remove low-boiling-point fractions to obtain a colorless transparent liquid product, namely the coupling agent containing long-chain silane;
s3, dissolving 0.01-1 part of the coupling agent containing long-chain silane obtained in the step S2 into 1200-2000 parts of alcohol-water solution at the temperature of 20-50 ℃ under the stirring condition, and stirring for 5-30 min to obtain a dispersing agent solution;
the long-chain acrylate is one or more of polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, 2-ethylhexyl acrylate and trimethylolpropane triacrylate;
the double-bond-containing silane coupling agent is one or more of gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl trimethoxy silane and vinyl triethoxy silane;
the mass ratio of the long-chain-containing acrylate to the double-bond-containing silane coupling agent is 0.8-1.2: 1;
the organic solvent is one or more of toluene, xylene, n-butanol, n-butyl acetate and tri-1, 2-propylene glycol monomethyl ether.
2. The method according to claim 1, wherein the mass percentage of the dispersant to the silver salt in the dispersant solution in step S1 is 0.5% to 2.5%.
3. The preparation method of claim 1, wherein the initiator is one or more of azobisisobutyronitrile, tert-butyl peroxy-2-ethylhexanoate and benzoyl peroxide;
the mass ratio of the initiator to the total amount of the monomers is 0.01-0.04: 1;
the alcohol-water solution is one or a mixture of more of 60-80% by mass of ethanol solution, 60-80% by mass of methanol solution and 60-80% by mass of isopropanol solution.
4. The method according to claim 1, wherein the silver salt in step S1 is at least one of silver nitrate, silver sulfate, silver carbonate, and a silver complex.
5. The method according to claim 1, wherein the pH adjusting agent in step S2 is at least one of ammonia water, acetic acid, sodium acetate, sodium hydroxide, and hydrochloric acid;
the alcohol reducing agent is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol and 1, 3-butanediol.
6. The method according to claim 1, wherein the membrane separation device in step S3 includes an ultrafiltration membrane or a nanofiltration membrane, a material tank, and a circulation pump, and the ultrafiltration membrane or the nanofiltration membrane is made of at least one of cellulose and its derivatives, polypropylene, polyethylene, polystyrene, polycarbonate, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyacrylonitrile, polyamide, polysulfonamide, sulfonated polysulfone, cross-linked polyvinyl alcohol, and modified acrylic acid polymer;
the pore diameter range of the ultrafiltration membrane or the nanofiltration membrane is 10-60 nm.
7. A silver nanopowder prepared by the process according to any one of claims 1 to 6.
8. Conductive silver paste comprising the silver nanoparticle of claim 7.
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| CN116072350B (en) * | 2023-04-07 | 2023-08-15 | 江西理工大学南昌校区 | Method for preparing conductive silver paste for solar cell electrode in situ |
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