CN113953523B - Preparation method of polyhedral submicron silver powder - Google Patents
Preparation method of polyhedral submicron silver powder Download PDFInfo
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- CN113953523B CN113953523B CN202111184893.6A CN202111184893A CN113953523B CN 113953523 B CN113953523 B CN 113953523B CN 202111184893 A CN202111184893 A CN 202111184893A CN 113953523 B CN113953523 B CN 113953523B
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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
Abstract
A method for preparing polyhedral submicron silver powder, which comprises the following steps: preparing a solution A, wherein the solution A is prepared from silver nitrate, ion exchange water, ammonia water and polyvinylpyrrolidone; dissolving polyvinylpyrrolidone in the ion-exchanged water, and adding the polyvinylpyrrolidone into the silver ammonia complexing aqueous solution to prepare the solution A; preparing a solution B, wherein the solution B is prepared from potassium sulfite and ion exchange water; heating the solution A and the solution B to 30-50 ℃, and then injecting the solution B into the solution A and stirring; maintaining the temperature of the mixture of the solution A and the solution B at 30-100 ℃ and carrying out reduction reaction for 3-5 hours to form silver suspension; filtering the silver suspension, and cleaning a silver powder cake obtained by filtering; providing an ultrasonic cleaner, using the ultrasonic cleaner to carry out ultrasonic cleaning on the sodium hexametaphosphate and the silver powder cake, and filtering and separating polyhedral silver powder and silver flakes. The preparation method can easily separate the silver flakes from the silver powder, thereby forming the micro-nano silver powder with controllable particle size.
Description
Technical Field
The invention relates to a preparation method of silver powder, in particular to a preparation method of polyhedral submicron silver powder with the particle size of 100-400 nm.
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 noble metal powder which is the most widely applied and used in the electronic industry, such as being used for manufacturing electronic paste, conductive paint, electromagnetic shielding material, conductive ink, conductive plastic, conductive ceramic and the like, and is a key material for producing various electronic component products.
The existing preparation methods of micro-nano silver powder are divided into a physical method and a chemical method, and the silver powder prepared by the physical method has complex process and poor performance. So at present, the micro-nano silver powder is mainly prepared by a chemical method, wherein the chemical reduction method, the electrolytic method and the sol-gel method are commonly used. The chemical reduction method is the most commonly used 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.
When synthesizing submicron silver powder with the grain diameter of 100-400 nm by the prior method, amine or carboxylic acid surfactant is added into the silver ammine complex as grain shape control agent. In this synthetic route, a strong reducing agent such as hydrazine hydrate or L-ascorbic acid is used. However, silver nanoparticles as primary particles are formed immediately after the addition of the reducing agent, and these nanoparticles are aggregated into spherical or indefinite-shaped secondary particles of submicron size, thereby making it difficult to form micro-nano silver powder having a particle size of 100 to 400nm and a controllable particle size.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of polyhedral submicron silver powder.
A method for preparing polyhedral submicron silver powder, which comprises the following steps:
preparing a solution A, wherein the solution A is prepared from silver nitrate, ion exchange water, ammonia water and polyvinylpyrrolidone;
dissolving silver nitrate in ion-exchanged water, and adding the ammonia water to prepare an aqueous silver-ammonia complex solution;
dissolving polyvinylpyrrolidone in the ion-exchanged water, and adding the polyvinylpyrrolidone into the silver ammonia complexing aqueous solution to prepare the solution A;
preparing a B solution which is prepared from potassium sulfite and ion exchange water, wherein the B solution is prepared from potassium sulfite dissolved in the ion exchange water;
heating the solution A and the solution B to 30-50 ℃, and then injecting the solution B into the solution A and stirring;
maintaining the temperature of the mixture of the solution A and the solution B at 30-100 ℃ and carrying out reduction reaction for 3-5 hours to form silver suspension;
filtering the silver suspension, and cleaning a silver powder cake obtained by filtering;
washing the silver cake with ethanol to prevent agglomeration;
drying the silver powder cake;
providing sodium hexametaphosphate, and adding the dried silver powder cake into the sodium hexametaphosphate;
providing an ultrasonic cleaner, using the ultrasonic cleaner to carry out ultrasonic cleaning on the sodium hexametaphosphate and silver powder cake, and filtering and separating polyhedral silver powder and silver flakes, wherein the polyhedral silver powder has unimodal distribution.
Further, in the reaction process of the solution A and the solution B, a particle shape controlling agent is added to control the shape of the silver powder formed.
Further, the particle shape controlling agent is one of gum arabic, thiol compound, protein, and polymer amino acid peptide compound.
Further, the solution B is a reducing solution, the reducing solution contains an inorganic reducing agent, and the inorganic reducing agent is sulfite or hydrazine.
Further, the solution B is a reducing solution, the reducing solution contains an organic reducing agent, and the organic reducing agent is an organic reducing agent with aldehyde groups or ketone groups.
Further, the organic reducing agent having an aldehyde group or a ketone group is L-ascorbic acid.
Compared with the prior art, the preparation method of the polyhedral submicron silver powder provided by the invention has the advantages that the organic matters and the reducing agent of the particle morphology control agent are added into the aqueous solution of the silver-ammonia complex, the silver-containing suspension is separated out, the silver cake after filtering and cleaning is added with alcohol at room temperature, and the alcohol is dried and crushed under reduced pressure, so that the high-crystallization polyhedral submicron silver powder with the drying decrement of 1-2% and without agglomeration in water and an organic solvent is obtained, and the nanometer silver powder with the particle size of 100-400 nm can be prepared. Meanwhile, before adding the reducing agent into the silver-ammonia complex, the particle control agent and the ammonia concentration in the silver-ammonia complex aqueous solution are changed, so that submicron-sized polyhedral silver powder and hexagonal flaky silver with a diagonal size of microns are synthesized at the same time, and the polyhedral silver powder and the flaky silver can be broken and separated by ultrasonic waves in the aqueous solution containing the surfactant. In the separation step, the submicron silver powder is dispersed in the solution, and the silver flakes are precipitated, so that the submicron silver powder and the silver flakes can be easily separated, and the micron-nanometer silver powder with controllable particle size is formed.
Drawings
FIG. 1 is one of SEM pictures of the silver powder obtained in example 1 of the present invention.
FIG. 2 is a second SEM image of the silver powder obtained in example 1 of the present invention.
FIG. 3 is a graph showing the particle distribution of the silver powder obtained in example 1 of the present invention.
Detailed Description
Specific embodiments of the present invention are described in further detail below. It should be understood that the description herein of the embodiments of the invention is not intended to limit the scope of the invention.
The invention provides a preparation method of polyhedral submicron silver powder, which comprises the following steps:
STEP101, preparing solution A, wherein the solution A is prepared from silver nitrate, ion exchange water, ammonia water and polyvinylpyrrolidone;
STEP102, dissolving silver nitrate in ion exchange water, and adding the ammonia water to prepare a silver ammonia complex aqueous solution;
STEP103, dissolving polyvinylpyrrolidone in the ion-exchanged water, and adding the polyvinylpyrrolidone into the silver ammonia complexing aqueous solution to prepare the solution A;
STEP104, preparing a solution B, wherein the solution B is prepared from potassium sulfite and ion exchange water, and the solution B is prepared from potassium sulfite dissolved in the ion exchange water;
STEP105, after heating the solution A and the solution B to 30-50 ℃, injecting the solution B into the solution A and stirring;
STEP106, maintaining the temperature of the mixture of the solution A and the solution B at 30-100 ℃ and carrying out reduction reaction for 3-5 hours to form silver suspension;
STEP107, filtering the silver suspension, and cleaning silver powder cake obtained by filtering;
STEP108, washing the silver powder cake with ethanol to prevent agglomeration;
STEP109, drying the silver powder cake;
STEP110, providing sodium hexametaphosphate, and adding the dried silver powder cake into the sodium hexametaphosphate;
STEP111, providing an ultrasonic cleaner, using the ultrasonic cleaner to carry out ultrasonic cleaning on the sodium hexametaphosphate and the silver powder cake, and transitionally separating polyhedral silver powder and flake silver, wherein the polyhedral silver powder has unimodal distribution.
In STEP101, the silver nitrate, ion-exchanged water, ammonia water, and polyvinylpyrrolidone are known in the art, and the characteristics and preparation method thereof are not described herein. In STEP102, i.e., during silver synthesis, the total amount of ammonia added is in the range of 2.1-5.0 times the amount of silver nitrate required to form the silver ammine complex.
In STEP104, the characteristics and preparation method of potassium sulfite and ion-exchanged water are prior art, and are not described herein.
In STEP105, the B solution and the a solution may be stirred using a magnetic stirrer to uniformly stir.
In STEP106, when the reduction reaction is performed, the solution B is a reducing solution, and an inorganic reducing agent or an organic reducing agent may be added to increase the reduction rate, and the inorganic reducing agent may be sulfite or hydrazine. The organic reducing agent may be an organic reducing agent having an aldehyde group or a ketone group.
In STEP106, a particle shape controlling agent is added during the reaction of the a solution and the B solution to control the shape of the silver powder formed. The particle shape controlling agent may be a rubbery polysaccharide such as one of gum arabic, thiol compound, protein, and polymer amino acid peptide compound. The shape of the reduced silver particles can be ensured by the addition of the particle shape controlling agent.
In STEP110, oxidation of the silver powder can be avoided by sodium hexametaphosphate.
Compared with the prior art, the preparation method of the polyhedral submicron silver powder provided by the invention has the advantages that the organic matters and the reducing agent of the particle morphology control agent are added into the aqueous solution of the silver-ammonia complex, the silver-containing suspension is separated out, the silver cake after filtering and cleaning is added with alcohol at room temperature, and the alcohol is dried and crushed under reduced pressure, so that the high-crystallization polyhedral submicron silver powder with the drying decrement of 1-2% and without agglomeration in water and an organic solvent is obtained, and the nanometer silver powder with the particle size of 100-400 nm can be prepared. Meanwhile, before adding the reducing agent into the silver-ammonia complex, the particle control agent and the ammonia concentration in the silver-ammonia complex aqueous solution are changed, so that submicron-sized polyhedral silver powder and hexagonal flaky silver with a diagonal size of microns are synthesized at the same time, and the polyhedral silver powder and the flaky silver can be broken and separated by ultrasonic waves in the aqueous solution containing the surfactant. In the separation step, the submicron silver powder is dispersed in the solution, and the silver flakes are precipitated, so that the submicron silver powder and the silver flakes can be easily separated, and the micron-nanometer silver powder with controllable particle size is formed.
Examples
Two solutions of solution A and solution B were prepared.
Liquid A silver ammine complex aqueous solution was prepared by dissolving 5.00g of silver nitrate in 30g of ion-exchanged water and adding 4.6g of 25% aqueous ammonia. 0.4g of polyvinylpyrrolidone was dissolved in 50g of ion-exchanged water and added to the aqueous silver ammine complex solution.
Solution B5.00 g of potassium sulfite was dissolved in 30g of ion-exchanged water.
When liquid a and liquid B were heated to 60 ℃, liquid B was injected into liquid a and stirred with a magnetic stirrer.
After reacting at 40 ℃ for 3-4 hours, the produced silver-containing suspension is decompressed and filtered, the silver powder cake obtained by washing with plasma water is washed with ethanol solvent. After the silver powder biscuits were dried, 3.25g of silver powder cakes whose weight was reduced by about 8% were put into a vacuum dryer having an internal volume of 8L, decompressed and dehydrated at room temperature (25 ℃) for 3 hours, to obtain 3.16g of anhydrous powder. The dehydrated powder thereof was crushed at room temperature with an agate mortar and teflon rod to obtain 3.14g of crushed powder.
A sample of 0.015g silver powder was added to 30mL of 0.2% sodium hexametaphosphate and the particle size was measured using a dynamic light scattering particle size distribution test using a 50W ultrasonic cleaner for more than 5 minutes.
The silver powder thus obtained was seen as a flake and a particle from the SEM images as shown in fig. 1 and 2. Further, as can be seen from FIG. 3, the particle size distribution of most silver powder is around 200 nm.
The above is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalent substitutions or improvements within the spirit of the present invention are intended to be covered by the claims of the present invention.
Claims (1)
1. A method for preparing polyhedral submicron silver powder, which comprises the following steps:
preparing a solution A, wherein the solution A is prepared from silver nitrate, ion exchange water, ammonia water and polyvinylpyrrolidone;
dissolving silver nitrate in ion-exchanged water, and adding the ammonia water to prepare an aqueous silver-ammonia complex solution;
dissolving polyvinylpyrrolidone in the ion-exchanged water, and adding the polyvinylpyrrolidone into the silver ammonia complexing aqueous solution to prepare the solution A;
preparing a solution B, wherein the solution B is prepared from potassium sulfite and ion exchange water, the solution B is prepared by dissolving potassium sulfite in ion exchange water, the solution B is a reducing solution, the reducing solution contains an inorganic reducing agent, and the inorganic reducing agent is sulfite or hydrazine;
heating the solution A and the solution B to 30-50 ℃, and then injecting the solution B into the solution A and stirring;
maintaining the temperature of the mixture of the solution A and the solution B at 30-100 ℃ and carrying out reduction reaction for 3-5 hours to form silver suspension, and adding a particle shape control agent in the reaction process of the solution A and the solution B to control the shape of the silver powder formed, wherein the particle shape control agent is one of gum arabic, a thiol compound, a protein and a polymer amino acid peptide compound;
filtering the silver suspension, and cleaning a silver powder cake obtained by filtering;
washing the silver cake with ethanol to prevent agglomeration;
drying the silver powder cake;
providing sodium hexametaphosphate, and adding the dried silver powder cake into the sodium hexametaphosphate;
providing an ultrasonic cleaner, using the ultrasonic cleaner to ultrasonically clean the sodium hexametaphosphate and silver powder cake, filtering and separating polyhedral silver powder and flake silver, wherein the particle sizes of the silver powder and the flake silver are 100-400 nm, and the particle sizes of the polyhedral silver powder are distributed in a unimodal manner.
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| US8470066B2 (en) * | 2004-10-29 | 2013-06-25 | Clarkson University | Aqueous-based method for producing ultra-fine metal powders |
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| JPH08134513A (en) * | 1994-11-07 | 1996-05-28 | Sumitomo Metal Mining Co Ltd | Production of fine silver powder |
| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| KR20050116544A (en) * | 2004-06-08 | 2005-12-13 | 주식회사 씨에라인더스트리 | Method of manufacturing silver powder by chemical reduction |
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| CN104148665A (en) * | 2014-07-22 | 2014-11-19 | 西北大学 | Preparation method of crystalized sliver powder |
| CN104070180A (en) * | 2014-07-30 | 2014-10-01 | 天津市职业大学 | Production method for high-density silver powder for solar cell conductive silver paste |
| CN111331150A (en) * | 2020-04-07 | 2020-06-26 | 郑州卓而泰新材料科技有限公司 | Preparation method of high-dispersion spheroidal superfine silver powder with controllable particle size |
| CN111618316A (en) * | 2020-06-29 | 2020-09-04 | 河南金渠银通金属材料有限公司 | Surface-modified silver powder and coating preparation method thereof |
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