CN111889695A - Preparation method of micro-nano silver powder with controllable particle size - Google Patents
Preparation method of micro-nano silver powder with controllable particle size Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 claims abstract description 43
- 239000004332 silver Substances 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000011085 pressure filtration Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 4
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 4
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 4
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 3
- 229940100684 pentylamine Drugs 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 claims description 2
- QCMJHCAWPQZNMQ-UHFFFAOYSA-N octadecanoic acid;propan-2-one Chemical compound CC(C)=O.CCCCCCCCCCCCCCCCCC(O)=O QCMJHCAWPQZNMQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- FSEPMQBEESWQEX-UHFFFAOYSA-N silver;ethane-1,2-diamine;nitrate Chemical compound [Ag+].NCCN.[O-][N+]([O-])=O FSEPMQBEESWQEX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Images
Classifications
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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
- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a preparation method of micro-nano silver powder with controllable particle size, which comprises the steps of mixing organic acid containing C1-C20 or organic amine containing C1-C20, silver nitrate, ammonia water, a sodium hydroxide solution and a reducing agent for reaction to precipitate silver particles, adding a certain amount of stearic acid-ethanol mixed solution to generate silver paste, carrying out reduced pressure filtration, and washing with water and ethanol successively to obtain silver cakes. And (3) decompressing, dehydrating and drying the silver cake, and crushing the silver cake at room temperature to obtain spherical micro-nano silver particles which can be easily dispersed in water and an organic solvent. Compared with the prior art, the silver powder prepared by the invention has the advantages of high tap density, narrow particle size distribution, good dispersibility, difficult agglomeration, stable particle size of 100nm-3 mu m, low production cost and easy large-scale production.
Description
Technical Field
The invention relates to a preparation method of silver powder, in particular to a preparation method of micro-nano silver powder with controllable particle size.
Background
The micro-nano silver powder is a functional raw material widely applied to the electronic industry, has excellent catalytic performance, magnetic performance, electrical performance and the like, is a noble metal powder which is most widely applied and used in the electronic industry, is used for manufacturing electronic slurry, conductive coating, electromagnetic shielding material, conductive ink, conductive plastic, conductive ceramic and the like, and is a key material for producing various electronic component products.
At present, the preparation method of micro-nano silver powder is divided into a physical method and a chemical method, the process of the silver powder prepared by the physical method is complex, and the prepared silver powder has poor performance. At present, the micro-nano silver powder is mainly prepared by a chemical method, wherein a chemical reduction method, an electrolytic method and a sol-gel method are commonly used. The chemical reduction method is the most common method for preparing the micro-nano silver powder at present, and has the advantages of simple equipment, low production cost, controllable product performance and good repeatability.
The technical point of preparing silver powder by the liquid phase reduction method is to control the dispersibility, size and uniformity of reduced silver particles, because ultrafine powder is easy to agglomerate in aqueous solution, the dispersibility is poor, the requirements of printing and sintering of common electronic paste, especially high-end silver paste, for example, the patent with the application number of CN200510128715.6 needs subsequent heat treatment, and the concentration of reactants is low, the output per unit volume is low, thus being not beneficial to large-scale industrial production. Patent No. CN200710049490.4 has a high silver nitrate concentration, but does not relate to the selection of additives such as surfactants, and the dispersibility of the powder obtained by reduction is difficult to control. Chinese patent document CN105345023B discloses a method for preparing superfine silver powder with good dispersibility, which comprises the steps of mixing a silver nitrate solution with a hydrazine hydrate aqueous solution, reacting the mixed solution at 60-90 ℃ for 30-60 min, washing the reduced superfine silver powder, and carrying out secondary treatment by using absolute ethyl alcohol and water as dispersion media through ultrasonic crushing. In addition, the process is not suitable for scale-up production.
Chinese patent document CN102335751B discloses a method for preparing highly dispersed ultrafine spherical silver powder, which comprises mixing silver nitrate-ethylenediamine mixed solution and mixed reducing solution containing hydrazine hydrate, nano gold colloid, potassium sulfate and surfactant uniformly for reaction, and cleaning and drying the obtained precipitate to obtain highly dispersed ultrafine spherical silver powder. The reduction reaction carried out by adopting the method needs to add a plurality of auxiliary chemicals, on one hand, the process flow is complex and is not suitable for large-scale production, and on the other hand, a plurality of sub-group chemicals are added in the preparation process, and the prepared silver powder inevitably carries impurities.
Therefore, the key of the silver powder production technology is how to control the production cost, the product purity, the morphology and the characteristics of particles, the particle size, the dispersibility, the tap density and the like of the silver powder during mass production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of micro-nano silver powder with controllable particle size, and the prepared silver powder has the advantages of high tap density, narrow particle size dispersion range, high particle sphericity, good dispersibility, difficult agglomeration and stable micro-nano silver particles with the particle size of 100nm-3 mu m, and is low in production cost and easy for large-scale production.
The purpose of the invention can be realized by the following technical scheme: a preparation method of micro-nano silver powder with controllable particle size comprises the following steps:
step (1): uniformly mixing silver nitrate, ammonia water and sodium hydroxide solution with certain concentration to obtain silver ammonia solution;
step (2): adding organic acid containing C1-C20 or organic amine containing C1-C20 into the silver-ammonia solution to obtain silver-ammonia complex ion aqueous solution;
and (3): adding a reducing agent solution with a certain concentration into the silver-ammonia complex ion aqueous solution prepared in the step (2), uniformly mixing to obtain a mixed reaction solution, and carrying out reduction reaction on the mixed reaction solution to separate out silver particles;
and (4): and (3) after the mixed reaction liquid is subjected to reduction reaction to precipitate silver particles, adding a stearic acid-ethanol mixed solution (the volume ratio of stearic acid to ethanol is 1: 50-100) with the mass of 0.5-5% of silver or a stearic acid-acetone mixed solution (stearic acid: acetone is 1: 10-20) with the mass of 0.5-5% of silver to generate silver paste, carrying out reduced pressure filtration, and washing with water and ethanol for 3-6 times to obtain a silver cake. The silver cake is put into a vacuum pressure reducer for decompression, dehydrated at room temperature for 2-6 hours and crushed at room temperature to obtain spherical silver particles with the particle size distribution of 100nm-3 mu m, which can be easily dispersed in water and organic solvents.
According to the preparation method of the micro-nano silver powder with the controllable particle size, silver powder with the particle size distribution of 100-300 nm can be prepared by regulating the concentration of an ammonia solution and the concentration of a sodium hydroxide solution in a silver-ammonia complex aqueous solution.
The silver powder with the particle size distribution of 800 nm-3 mu m can be prepared by changing and controlling the ammonia solution concentration and the sodium hydroxide solution concentration in the silver-ammonia complex aqueous solution.
According to the preparation method of the micro-nano silver powder with the controllable particle size, the concentration of silver nitrate is below 5%, and the total amount of ammonia added in the silver powder synthesis process is below 4 times of the mass of silver nitrate required for forming silver-ammonia composite ions; the concentration of the added sodium hydroxide solution is 0.1-0.5%.
The C1-C20 organic acid is a saturated or unsaturated organic acid having 1 to 20 carbon atoms and containing at least 1 or more carboxyl groups.
The organic amine of C1-C20 is selected from ethylenediamine, triethylamine, glycol amine, Propylamine (Propylamine), Butylamine (Butylamine), Pentylamine (pentaylamine), Hexylamine (Hexylamine), Heptylamine (heptaylamine), Octylamine (octalamine), Nonylamine (Nonylamine), Decylamine (Decylamine), Tridecylamine (Tridecylamine), Tetradecylamine (Tetradecylamine), Pentadecylamine (Pentadecylamine), Hexadecylamine (Hexadecylamine), Hexadecylamine (Heptadecylamine), Octadecylamine (Octadecylamine).
The reducing agent in the step (3) is preferably hydrazine hydrate aqueous solution, and the amount of the reducing agent substance is 0.18-0.9 times of that of the silver nitrate substance.
The mixing reaction of the invention refers to: pouring and mixing, controlling the reaction temperature at 0-30 ℃ and the reaction time at 0.5-1.0 h.
The organic acid containing C1-C20 or the organic amine containing C1-C20 used in step (2) of the present invention is used to control the particle size of the silver powder, and may be added to the silver ammonia solution before the addition of the reducing agent or may be added to the silver ammonia solution together after being mixed with the reducing agent.
The micro-nano silver powder obtained by the invention is easily dispersed in water and an organic solvent, and the silver powder dispersed in the water and the organic solvent can be secondarily dispersed by ultrasonic waves when the micro-nano silver powder is used.
Compared with the prior art, the micro-nano spherical silver powder prepared by the method has the particle size of 0.1-3.0 um, and has the following characteristics: the prepared silver powder has high tap density, narrow particle size distribution, good dispersibility, difficult agglomeration, low production cost and easy large-scale production. The production process is simple, heating is not needed in the production process, ultrasonic crushing is carried out, auxiliary additives are few, the obtained silver paste is directly subjected to reduced pressure filtration, and water and ethanol are used for washing successively to obtain the silver cake. And (3) decompressing, dehydrating and drying the silver cake, and crushing the silver cake at room temperature to obtain spherical micro-nano silver particles which can be easily dispersed in water and an organic solvent. The particle size can be regulated and controlled, the distribution is narrow, and the silver powder with the particle size distribution of 100-300 nm or 800 nm-3 mu m can be prepared by adding the organic acid containing C1-C20 or the organic amine containing C1-C20 and changing the concentration of the ammonia solution and the concentration of the sodium hydroxide solution in the reactant.
Drawings
FIG. 1 is an SEM photograph of silver powder obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph of silver powder obtained in example 2 of the present invention.
FIG. 3 shows the results of laser particle size analysis of silver powder obtained in example 1 of the present invention.
FIG. 4 shows the results of laser particle size analysis of silver powder obtained in example 2 of the present invention.
Detailed Description
Specific examples of the present invention will be described in further detail below. It should be understood that the description herein of embodiments of the invention is not intended to limit the scope of the invention.
Example 1
To 200mL of an aqueous silver nitrate solution containing 17g/L of silver nitrate was added 5.6mL of 25% by mass aqueous ammonia, 5.3mL of a 30g/L aqueous sodium hydroxide solution, and 0.3g of an acrylic acid-containing silver ammonia complex solution. The liquid temperature of the silver-ammonia complex aqueous solution was kept at 25 ℃, and 32mL of a 2% by mass hydrazine hydrate solution was added to precipitate silver particles. And adding a stearic acid-ethanol mixed solution with the mass of 2% of that of silver to generate silver paste, filtering under reduced pressure, washing with water, and removing residual stearic acid by using ethanol to obtain a silver cake. The silver cake was put into a vacuum pressure reducer and dehydrated at room temperature (25 ℃ C.) for 3 hours to obtain dehydrated silver powder. The test shows that the cumulative 50% by mass particle diameter (average particle diameter D50) is 1.467 μm, the loose packed density is 2.45, the tap density: 3.35. the SEM photograph is shown in figure 1, and the particle size distribution is shown in figure 3.
Example 2
To 200mL of a silver nitrate aqueous solution containing 10g/L of silver nitrate were added 11.2mL of 25% by mass aqueous ammonia, 3.5mL of a 30g/L aqueous sodium hydroxide solution, and 0.3g of a silver-ammonia complex solution prepared from octylamine. The liquid temperature of the silver-ammonia complex aqueous solution was kept at 25 ℃, and 32mL of a 2% by mass hydrazine hydrate solution was added to precipitate silver particles. And adding a stearic acid-ethanol mixed solution with the mass of 2% of that of silver to generate silver paste, filtering under reduced pressure, washing with water, and removing residual stearic acid by using ethanol to obtain a silver cake. The silver cake was put into a vacuum pressure reducer and dehydrated at room temperature (25 ℃ C.) for 3 hours to obtain dehydrated silver powder. The particle diameter at 50% of the cumulative mass (average particle diameter D50) measured was 172nm, the loose packed density was 2.45, the tap density: 3.35. the SEM photograph is shown in FIG. 2, and the particle size distribution is shown in FIG. 4.
Example 3
To 200mL of a silver nitrate aqueous solution containing 10g/L of silver nitrate were added 11.2mL of 25% by mass aqueous ammonia, 3.5mL of a 30g/L aqueous sodium hydroxide solution, and 0.3g of a silver-ammonia complex solution prepared from octadecylamine. The liquid temperature of the silver-ammonia complex aqueous solution was kept at 25 ℃, and 32mL of a 2% by mass hydrazine hydrate solution was added to precipitate silver particles. And adding a stearic acid-ethanol mixed solution with the mass of 2% of that of silver to generate silver paste, filtering under reduced pressure, washing with water, and removing residual stearic acid by using ethanol to obtain a silver cake. The silver cake was put into a vacuum pressure reducer and dehydrated at room temperature (25 ℃ C.) for 3 hours to obtain dehydrated silver powder. The particle diameter at 50% of the test cumulative mass (average particle diameter D50) is 160nm, the loose packed density is 2.55, the tap density: 3.55.
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, and any modifications, equivalents or improvements that are within the spirit of the present invention are intended to be covered by the following claims.
Claims (9)
1. A preparation method of micro-nano silver powder with controllable particle size is characterized by comprising the following steps:
step (1): uniformly mixing silver nitrate, ammonia water and sodium hydroxide solution with certain concentration to obtain silver ammonia solution;
step (2): adding organic acid containing C1-C20 or organic amine containing C1-C20 into the silver-ammonia solution to obtain silver-ammonia complex ion aqueous solution;
and (3): adding a reducing agent solution with a certain concentration into the silver-ammonia complex ion aqueous solution prepared in the step (2), uniformly mixing to obtain a mixed reaction solution, and carrying out reduction reaction on the mixed reaction solution to separate out silver particles;
and (4): and (3) after the mixed reaction liquid is subjected to reduction reaction to precipitate silver particles, adding a stearic acid-ethanol mixed solution (the volume ratio of stearic acid to ethanol is 1: 50-100) with the mass of 0.5-5% of silver or a stearic acid-acetone mixed solution (stearic acid: acetone is 1: 10-20) with the mass of 0.5-5% of silver to generate silver paste, carrying out reduced pressure filtration, and washing with water and ethanol for 3-6 times to obtain a silver cake. And (3) putting the silver cake into a vacuum pressure reducer for pressure reduction, dehydrating for 2-6 hours at room temperature, and crushing at room temperature to obtain spherical silver particles with the particle size distribution of 100nm-3 mu m, wherein the spherical silver particles can be easily dispersed in water and an organic solvent.
2. The method for preparing micro-nano silver powder with controllable particle size according to claim 1, wherein silver powder with particle size distribution of 100-300 nm can be prepared by adjusting and controlling the concentration of ammonia solution and sodium hydroxide solution in silver-ammonia complex aqueous solution.
3. The method for preparing micro-nano silver powder with controllable particle size according to claim 1, wherein silver powder with particle size distribution of 800 nm-3 μm can be prepared by adjusting and controlling the concentration of ammonia solution and sodium hydroxide solution in silver-ammonia complex aqueous solution.
4. The method for preparing micro-nano silver powder with controllable particle size according to any one of claims 1 to 3, wherein the concentration of silver nitrate is below 5%, and the total amount of ammonia added in the silver powder synthesis process is below 4 times of the amount of silver nitrate needed for forming silver-ammonia complex ions; the concentration of the added sodium hydroxide solution is 0.1-0.5%.
5. The method for preparing particle size-controllable micro-nano silver powder according to any one of claims 1 to 3, wherein the C1-C20 organic acid is a saturated or unsaturated organic acid having 1 to 20 carbon atoms and containing at least 1 or more carboxyl groups.
6. The method for preparing micro-nano silver powder with controllable particle size according to any one of claims 1 to 3, wherein the organic amine of C1-C20 is selected from ethylenediamine, triethylamine, ethylenediamine, Propylamine (Propylamine), Butylamine (Butylamine), Pentylamine (Pentylamine), Hexylamine (Hexylamine), Heptylamine (Heptylamine), Octylamine (Octylamine), Nonylamine (Nonylamine), Decylamine (Decylamine), Tridecylamine (Tridecylamine), Tetradecylamine (Tetradecylamine), Pentadecylamine (Pentadecylamine), Hexadecylamine (Hexadecylamine), Hexadecylamine (Heptadecylamine), Octadecylamine (Octadecylamine).
7. The method for preparing the micro-nano silver powder with the controllable particle size according to any one of claims 1 to 3, wherein the reducing agent in the step (3) is a hydrazine hydrate aqueous solution, and the amount of the reducing agent is 0.18 to 0.9 times of the amount of the silver nitrate.
8. The method for preparing the micro-nano silver powder with the controllable particle size according to any one of claims 1 to 3, wherein the mixing reaction temperature is 0 to 30 ℃ and the reaction time is 0.5 to 1.0 hour.
9. The method for preparing micro-nano silver powder with controllable particle size according to any one of claims 1 to 3, wherein the organic acid containing C1-C20 or the organic amine containing C1-C20 in step (2) is used for controlling the particle size of the silver powder, and can be added to the silver ammonia solution before or after being mixed with the reducing agent.
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