CN111673091B - Silver powder preparation method with low dispersant content and high conductivity and silver powder - Google Patents
Silver powder preparation method with low dispersant content and high conductivity and silver powder Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000243 solution Substances 0.000 claims abstract description 83
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000032683 aging Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 8
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 8
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 22
- 230000001070 adhesive effect Effects 0.000 abstract description 22
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 oleic ester Chemical class 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isopentyl alcohol Natural products CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- B22F1/0003—
Abstract
The invention discloses a method for preparing silver powder with low dispersant content and high conductivity, which comprises the following steps: step one, preparing a silver nitrate aqueous solution, sequentially adding a dispersing agent and a defoaming agent diluent, and keeping the temperature to 30-35 ℃ to obtain a first solution; step two, preparing an alkali metal carbonate solution with the mass concentration of 14-15%, adding carboxylic acid to adjust the pH value to 9.0-10.0, and keeping the temperature to 30-35 ℃ to form a second solution; adding 50-55% of the second solution into the first solution to obtain a third solution; adding a reducing agent solution containing aldehyde groups into the third solution to obtain a fourth solution; adding the aging assistant into the remaining 45-50% of the second solution, and then adding the solution into the fourth solution; and step six, washing the powder slurry, carrying out suction filtration, and carrying out alcohol and vacuum drying treatment. The invention also discloses silver powder which is used as a conductive phase of the conductive adhesive of the organosilicon resin system and has low resistivity.
Description
Technical Field
The invention belongs to the technical field of conductive adhesives, and particularly relates to a silver powder preparation method with low dispersant content and high conductivity and silver powder.
Background
A laminated tile solar cell module is a photovoltaic module with high power and high photoelectric conversion efficiency, and is characterized in that a cell slice redesigned from a front electrode grid line is cut into small slices with reasonable patterns, then each small slice is overlapped and arranged, a laminated tile conductive adhesive material is used for welding the small slices into strings, and then the strings and the parallel tiles are arranged in series and parallel, and then the laminated tile solar cell module is laminated into a module. The conductive adhesive is one of the key materials of the laminated tile assembly, the conductive adhesive is composed of silver powder particles and a polymer matrix, the silver powder particles determine conductivity, and the polymer matrix is a carrier of a conductive phase of the silver powder particles and determines the curing speed, the adhesive force, the ageing resistance and other properties of the conductive adhesive.
The organic carrier of the tile-stacked conductive adhesive comprises an epoxy system, an acrylate system and an organic silicon-based system. The organic silicon resin system has good high temperature and low temperature resistance, can bear cold and hot changes between minus 60 ℃ and 200 ℃, does not crack, keeps elasticity and has good heat conduction capability, and is particularly suitable for the conductive bonding of solar components needing weather resistance. In the curing process of the organic silicon resin, a catalyst is required to be added to enable the resin to be crosslinked and cured, and the catalyst is easily polluted by foreign organic matters containing phosphorus, sulfur and nitrogen atoms to cause poisoning, so that the organic silicon resin is not cured to cause failure of the conductive adhesive. The conductive phase silver powder in the conductive adhesive is usually coated with an organic dispersant on the surface during manufacturing, and the added dispersant can cause the poisoning of a silicone resin catalyst and reduce the conductivity of the silver powder.
The preparation method of the silver powder comprises a physical method and a chemical method, wherein the physical method is to crush blocky metal silver to a micron level by using the physical method, such as spray cooling, vapor physical deposition, ball milling and the like after the metal silver is heated to form a metal melt; the silver powder prepared by the chemical method is prepared by the chemical reduction reaction of soluble salt of silver and a reducing agent in aqueous solution. The chemical reduction method is the most widespread and economical method for producing silver powder.
Because the silver is easy to reduce, the reduction of the silver powder to obtain the compact crystalline silver powder needs a slower reduction reaction speed, the silver atoms are ensured to obtain the crystalline silver powder according to a diffusion growth mode in the reduction process, and then the monodisperse crystalline silver powder forms the silver powder in an agglomerated state under the control of a later-stage reduction aging condition.
In the patent "conductive adhesive for a tiled photovoltaic module and preparation thereof" (CN 201811631721.7), epoxy modified organic silicon resin is used as a carrier, flake silver powder with a flake diameter of 3-8 μm is filled with part of nano silver particles to improve conductivity, the flake silver powder can be obtained by mechanical ball milling of reduced silver powder, and nano silver is additionally added to enhance conductivity (reduce volume resistivity). Patent "preparation method of silver powder for low-temperature conductive silver pasteCN 109332723A) describes an oleic acid, stearic acid, oleic ester dispersion with a specific surface of 1.56m 2 According to the preparation method of the agglomerated silver powder, the obtained silver powder is thin in particle size, the specific surface is large, the viscosity of the obtained silver conductive adhesive is high, and the silver conductive adhesive is easy to cause catalyst poisoning and lose efficacy when the dispersing agent is added and applied to an organic silicon resin system.
Disclosure of Invention
One of the objects of the present invention is to provide a method for preparing silver powder with low dispersant content and high conductivity, wherein the silver powder prepared by the method can be used as a conductive phase of a conductive adhesive of a silicone resin system to obtain low volume resistivity after curing.
It is another object of the present invention to provide a silver powder having a low dispersant content and high conductivity.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
a method for preparing silver powder with low dispersant content and high conductivity, the method for preparing the silver powder comprises the following steps:
step one, weighing silver nitrate, preparing a silver nitrate water solution with the mass volume concentration of 100-220 g/L, sequentially adding a dispersing agent and a defoaming agent diluent, dissolving the mixture clearly, heating, and keeping the temperature to 30-35 ℃ to obtain a first solution;
the addition amount of the dispersing agent is 1.5-2.1% of the mass of the silver nitrate; each liter of the first solution contains 1-3 ml of defoamer diluent;
secondly, weighing alkali metal carbonate according to 0.58-0.75 mass percent of silver nitrate, preparing into an alkali metal carbonate solution with the mass concentration of 14-15%, adding carboxylic acid to adjust the pH value to 9.0-10.0, heating, and keeping the temperature to 30-35 ℃ to form a second solution;
step three, adding 50-55% of the second solution into the first solution, and then, spontaneously increasing the temperature to obtain a third solution with the pH value of 6.0-6.5 and the temperature kept at 37 +/-2 ℃;
adding a reducing agent solution containing aldehyde groups into the third solution to obtain a fourth solution;
the molar ratio of the reducing agent to the silver nitrate is 0.5-1: 1;
step five, adding the aging assistant into the remaining 45-50% of the second solution, heating and preserving the temperature to 30-35 ℃ to obtain a fifth solution; adding the fifth solution into the fourth solution at a speed of 100-300 ml/min, continuously stirring, raising the temperature to 65-70 ℃ after the dropwise addition, and continuously heating and stirring for 1-3 hours;
the mass of the aging assistant is 0.05-2 per mill of the mass of the silver nitrate;
and step six, washing the powder slurry until the conductivity is less than 10 mu S/m, then carrying out suction filtration, alcohol dispersion and vacuum drying treatment.
According to the invention, the second solution (namely the buffer solution) is formed by matching the alkali metal carbonate and the carboxylic acid, so that the reduction reaction speed can be reduced, and the crystalline silver powder is obtained; the silver powder is reduced in the first step to form monodisperse and uniform large-particle-size crystalline silver powder, the silver powder is aged in the second step to form agglomerated silver powder, a trace ageing agent is added, and the agglomerated silver powder with a micro-agglomerated structure is formed at a higher aging temperature, and has lower volume resistivity.
Further, in the second step, the number of carbon atoms of the carboxylic acid is less than 10.
Further, the carboxylic acid comprises one or a mixture of several of formic acid, acetic acid, propionic acid, butyric acid and the like.
Further, in the first step, the dispersant comprises one of PVP and PVA;
the molecular weight of the dispersant is 2.5-3.5 ten thousand;
the defoaming agent is an organic silicon surface additive BYK333.
Further, in the second step, the alkali metal carbonate is sodium carbonate or potassium carbonate.
Further, in the fourth step, the reducing agent solution includes one or a mixed solution of two or more of formaldehyde, acetaldehyde and glyoxal.
Further, in the fifth step, the aging aid is an anionic surfactant.
Further, the anionic surfactant is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
Further, in the sixth step, the temperature of the drying treatment is 40-70 ℃, and the drying time is 22-24 hours.
In order to achieve the second purpose, the invention adopts the following technical scheme:
silver powder with low dispersant content and high conductivity, which is prepared according to the silver powder preparation method.
The invention has the beneficial effects that:
1. the invention can prepare the agglomerated high-conductivity crystalline silver powder with low organic residue and low specific surface area, the silver powder can be directly used as a conductive phase of a conductive adhesive of an organic silicon resin system without ball milling or adding nano silver to obtain the cured low bulk resistivity, and the silver powder can be applied to other related conductive silver pastes and silver conductive adhesives.
2. The invention adopts simple water-soluble polyvinylpyrrolidone PVP and polyvinyl alcohol PVA macromolecules as dispersing agents, and common silver powder reducing dispersing agents, namely animal gum (bone gum, gelatin and casein) and vegetable gum (guar gum and Arabic gum) which are difficult to wash away are not adopted, and the colloids as hydrolysate molecules of protein contain S, N and P atoms which can poison catalysts.
3. The silver powder process adopts a conventional filter cloth filtering and washing method, and the later washing of the silver powder can wash away the water-soluble dispersing agent PVP, PVA and the anionic surface dispersing agent on the surface of the silver powder to the maximum extent, so that the residual quantity of the dispersing agent of the silver powder is ensured to be less than 0.1 percent, and the specific surface area is ensured<0.2m 2 (g) tap density range of 2.0-5.5 g/cm 3 。
4. The silver powder preparation method has economical efficiency and controllability, and the used raw materials are common and easily-obtained chemical raw materials.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention.
Example 1:
1. 8250g of silver nitrate is added into 37.5L of pure water, stirred and dissolved, then 173.25g of PVP with the mark of K25 and 37.5ml of defoaming agent BYK333 (diluted by pure water with the mass ratio of 1;
2. weighing 4.785kg of 34.18kg of sodium carbonate solution with the mass concentration of 14%, adjusting the pH value of the solution to 10.0 by using acetic acid, heating and keeping the temperature to 35 ℃ to form a second solution;
3. adding 50% of the second solution into the first solution, wherein the temperature of the solution is 35 ℃, and the pH value of the solution is 6.5 to form a third solution;
4. adding 2700ml of an acetaldehyde solution (concentration: 40%) to the third solution to obtain a fourth solution;
5. weighing 0.42g of an aging aid sodium dodecyl sulfate, adding the aging aid sodium dodecyl sulfate into a 50% second solution, stirring, dissolving, heating to 35 ℃, and preserving heat to form a fifth solution; dropwise adding the fifth solution into the fourth solution according to 300ml/min, and maintaining the stirring speed at 130rpm; and after the dropwise addition is finished and the solution is clarified, raising the temperature of the reduction system to 65 ℃, and continuing stirring and aging for 2 hours.
6. After filtering, washing and centrifugal separation, vacuum drying is carried out for 24 hours at 40 ℃ and then the silver powder is obtained by sieving through a 420-mesh sieve.
The silver powder has d10:2.037 μm, d50:4.994 μm, d100:8.415 μm, and specific surface area of 0.19m 2 The organic content is 0.05% (measuring condition: burning loss weight loss method, 610 ℃/60 min).
The silver powder is used for preparing a conductive adhesive with the silver content of 52 percent and taking organic silicon resin as a carrier, and the formula is as follows: 50g of vinyl-terminated silicone oil, 15g of hydrogen-containing silicone oil, 0.04g of platinum catalyst, 2g of silicon coupling agent, 60g of silver powder and 1g of 2-vinyl isoamyl alcohol, wherein the obtained silver conductive adhesive is completely cured after being dried for 1h at 150 ℃ according to the national standard, and has the volume resistivity: 1.56X 10 -5 Ω·cm。
Example 2:
1. adding 50000g of silver nitrate into 500L of pure water, adding 750g of 17K PVP and 3331500ml of defoaming agent BYK (diluted by pure water with the mass ratio of 1;
2. weighing 37.5kg of 250kg of potassium carbonate solution with the mass concentration of 15%, adjusting the pH value to 9.0 by using propionic acid, heating to 30 ℃, and preserving heat to form a second solution;
3. adding 55% of the second solution into the first solution, wherein the temperature of the solution is 39 ℃, and the pH value of the solution is 6.0 to form a third solution;
4. adding 13500ml of formaldehyde solution (with the concentration of 37%) into the third solution with stirring to form a fourth solution;
5. weighing 100g of sodium dodecyl benzene sulfonate serving as an aging agent, adding the sodium dodecyl benzene sulfonate into 45% of the second solution, stirring, dissolving, heating to 30 ℃, and preserving heat to form a fifth solution; dripping the fifth solution into the fourth solution according to the concentration of 100ml/min, and maintaining the stirring speed at 130rpm; and after the dropwise addition is finished and the clarification is finished, raising the temperature of the reduction system to 70 ℃, and continuing stirring and aging for 1 hour.
6. After being filtered, washed and centrifugally separated, the silver powder is dried in vacuum at 55 ℃ for 22 hours and then is sieved by a 400-mesh sieve to obtain the silver powder.
The silver powder has d10:7.744 μm, d50:12.86 μm, d100:19.16 μm and specific surface area of 0.17m 2 The organic content is 0.08% (measuring condition: burning loss weight loss method, 610 ℃/60 min).
The silver powder is used for preparing conductive adhesive with the silver content of 52 percent and organic silicon resin as a carrier, and the formula is as follows: 50g of vinyl-terminated silicone oil, 15g of hydrogen-containing silicone oil, 0.04g of platinum catalyst, 2g of silicon coupling agent, 60g of silver powder and 1g of 2-vinyl isoamyl alcohol, wherein the obtained silver conductive adhesive is completely cured after being dried for 1h at 150 ℃ according to the national standard, and has the volume resistivity: 1.16X 10 -5 Ω·cm。
Example 3:
1. adding 11113g of silver nitrate into 52.5L of pure water, stirring for dissolving, then adding 200g of PVA with the mark number of K30, adding a defoaming agent BYK333105ml (diluted by 100 mass ratio of pure water to 1);
2. weighing 7.38kg of 50.54kg of sodium carbonate solution with the mass concentration of 14.6%, adjusting the pH value to 9.5 by using mixed acid of acetic acid and butyric acid in a mass ratio of 1;
3. adding the 52% second solution into the first solution, and forming a third solution at the temperature of 37 ℃ and the pH value of 6.3;
4. 4500ml of formaldehyde solution (with the concentration of 40%) is weighed and added into the third solution to obtain a fourth solution;
5. weighing 11.72g of ageing agent sodium dodecyl sulfate, adding the ageing agent sodium dodecyl sulfate into the 48% second solution, stirring, dissolving, heating to 33 ℃, and preserving heat to form a fifth solution; dripping the fifth solution into the fourth solution according to 200ml/min, and maintaining the stirring speed at 130rpm; after the dropwise addition is finished and the temperature is 51 ℃ after clarification, the temperature of the reduction system is raised to 65 ℃, and the reaction is finished after heat preservation, continuous stirring and aging for 3 hours.
6. After filtering, washing and centrifugal separation, vacuum drying at 70 ℃ for 23 hours, and sieving with a 400-mesh sieve to obtain the silver powder.
The silver powder has d10:6.260 μm, d50:12.24 μm, d100:18.78 μm, and specific surface area of 0.16m 2 The organic content is 0.07% (measuring condition: burning loss weight loss method, 610 ℃/60 min).
The silver powder is used for preparing conductive adhesive with the silver content of 52 percent and organic silicon resin as a carrier, and the formula is as follows: 50g of vinyl-terminated silicone oil, 15g of hydrogen-containing silicone oil, 0.04g of platinum catalyst, 2g of silicon coupling agent, 60g of silver powder and 1g of 2-vinyl isoamylol, wherein the obtained silver conductive adhesive is completely cured after being dried for 1 hour at 150 ℃ according to national standards, and has the volume resistivity: 1.36X 10 -5 Ω·cm。
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the embodiments of the present invention.
Claims (8)
1. A method for preparing silver powder with low dispersant content and high conductivity is characterized by comprising the following steps:
step one, weighing silver nitrate, preparing a silver nitrate water solution with the mass volume concentration of 100-220 g/L, sequentially adding a dispersing agent and a defoaming agent diluent, dissolving the mixture clearly, heating, and keeping the temperature to 30-35 ℃ to obtain a first solution;
the addition amount of the dispersing agent is 1.5-2.1% of the mass of the silver nitrate; each liter of the first solution contains 1-3 ml of defoamer diluent;
secondly, weighing alkali metal carbonate according to 0.58-0.75 mass percent of silver nitrate, preparing into an alkali metal carbonate solution with the mass concentration of 14-15%, adding carboxylic acid to adjust the pH value to 9.0-10.0, heating, and keeping the temperature to 30-35 ℃ to form a second solution;
step three, adding 50-55% of the second solution into the first solution, and then, spontaneously increasing the temperature to obtain a third solution with the pH value of 6.0-6.5 and the temperature kept at 37 +/-2 ℃;
adding a reducing agent solution containing aldehyde groups into the third solution to obtain a fourth solution;
the molar ratio of the reducing agent to the silver nitrate is 0.5-1: 1;
step five, adding the aging assistant into the remaining 45-50% of the second solution, heating and keeping the temperature to 30-35 ℃ to obtain a fifth solution; adding the fifth solution into the fourth solution at a speed of 100-300 ml/min, continuously stirring, heating to 65-70 ℃ after the dropwise addition is finished, and continuously heating and stirring for 1-3 h;
the mass of the aging assistant is 0.05-2 per mill of the mass of the silver nitrate;
in the fifth step, the aging auxiliary agent is an anionic surfactant;
the anionic surfactant is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;
and step six, washing the powder slurry until the conductivity is less than 10 mu S/m, then carrying out suction filtration, alcohol dispersion and vacuum drying treatment.
2. The method for producing silver powder according to claim 1, wherein in the second step, the number of carbon atoms of the carboxylic acid is less than 10.
3. The method for producing silver powder according to claim 2, wherein the carboxylic acid comprises one or a mixture of formic acid, acetic acid, propionic acid and butyric acid.
4. The method for preparing silver powder according to any one of claims 1 to 3, wherein in the first step, the dispersant comprises one of PVP and PVA;
the defoaming agent is an organic silicon surface additive BYK333.
5. The method for producing silver powder according to any one of claims 1 to 3, wherein in the second step, the alkali metal carbonate is sodium carbonate or potassium carbonate.
6. The method for producing silver powder according to any one of claims 1 to 3, wherein in step four, the reducing agent solution comprises a mixed solution of one or two or more of formaldehyde, acetaldehyde and glyoxal.
7. The method for producing silver powder according to any one of claims 1 to 3, wherein in the sixth step, the temperature of the drying treatment is 40 to 70 ℃ and the drying time is 22 to 24 hours.
8. A silver powder having a low dispersant content and high conductivity, characterized in that said silver powder is produced according to the silver powder producing method of any one of claims 1 to 7.
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