CN113953523A - Preparation method of polyhedral submicron silver powder - Google Patents
Preparation method of polyhedral submicron silver powder Download PDFInfo
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- CN113953523A CN113953523A CN202111184893.6A CN202111184893A CN113953523A CN 113953523 A CN113953523 A CN 113953523A CN 202111184893 A CN202111184893 A CN 202111184893A CN 113953523 A CN113953523 A CN 113953523A
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- 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 preparation method of polyhedral submicron silver powder 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 exchange water, and adding the dissolved polyvinylpyrrolidone into the silver-ammonia complex aqueous solution to prepare a 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 and filtering to obtain a silver powder cake; and providing an ultrasonic cleaning machine, carrying out ultrasonic cleaning on the sodium hexametaphosphate and the silver powder cake by using the ultrasonic cleaning machine, and filtering and separating the polyhedral silver powder and the silver flakes. The preparation method can easily separate the silver flakes from the silver powder, so that the micro-nano silver powder with controllable particle size is formed.
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 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.
When the submicron silver powder with the particle size of 100-400 nm is synthesized by the existing method, an amine or carboxylic acid surfactant is added into a silver-ammonia complex as a particle size control agent. In this synthetic route, a strong reducing agent such as hydrazine hydrate or L-ascorbic acid is used. However, once the reducing agent is added, silver nanoparticles are formed as primary particles, and the silver nanoparticles are aggregated into submicron-sized spherical or irregularly-shaped secondary particles, so that it is difficult to form the micron-nano silver powder with a controllable particle size of 100-400 nm.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of polyhedral submicron silver powder.
A preparation method of polyhedral submicron silver powder 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 exchange water, and adding the ammonia water to prepare a silver-ammonia complex aqueous solution;
dissolving polyvinylpyrrolidone in the ion exchange water, and adding the dissolved polyvinylpyrrolidone into the silver-ammonia complex aqueous solution to prepare a solution A;
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;
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 and filtering to obtain a silver powder cake;
washing the silver powder 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 cleaning machine, carrying out ultrasonic cleaning on the sodium hexametaphosphate and the silver powder cake by using the ultrasonic cleaning machine, and filtering and separating polyhedral silver powder and silver flakes, wherein the polyhedral silver powder has unimodal distribution.
Further, during the reaction of the a solution and the B solution, a particle shape controlling agent is added to control the shape of the formed silver powder.
Further, the particle shape controlling agent is one of gum arabic, thiol compounds, proteins, and polymer amino acid peptide compounds.
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 is characterized in that an organic matter and a reducing agent of a particle morphology control agent are added into an aqueous solution of a silver-ammonia complex to precipitate a suspension containing silver, an alcohol is added into a silver cake obtained after filtering and cleaning the suspension at room temperature, and the suspension is dried and crushed under reduced pressure to obtain the high-crystalline polyhedral submicron silver powder with the drying decrement of 1-2% and no agglomeration in water and an organic solvent, so that the nano silver powder with the particle size of 100-400 nm can be prepared. Meanwhile, in the silver-ammonia complex, before adding the reducing agent, polyhedral silver powder of submicron size and hexagonal flaky silver of diagonal size are synthesized simultaneously by changing the concentration of the particle controlling agent and ammonia in the aqueous solution of the silver-ammonia complex, and the polyhedral silver powder and the flaky silver are crushed and separated by ultrasonic waves in the aqueous solution containing the surfactant. In the separation step, because the submicron silver powder is dispersed in the solution and the flake silver is precipitated, the submicron silver powder and the flake silver can be easily separated, and the micron-nanometer silver powder with controllable particle size is formed.
Drawings
FIG. 1 is an SEM photograph of silver powder obtained in example 1 of the present invention.
FIG. 2 is a second SEM image of silver powder obtained in example 1 of the present invention.
FIG. 3 is a particle distribution diagram of silver powder obtained in example 1 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.
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 exchange water, and adding the polyvinylpyrrolidone into the silver-ammonia complex aqueous solution to prepare the solution A;
STEP104, preparing a solution B, wherein the solution B is prepared by dissolving potassium sulfite and ion exchange water;
STEP105, 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 deg.C, and performing reduction reaction for 3-5 hr to form silver suspension;
STEP107, filtering the silver suspension, and cleaning and filtering to obtain a silver powder cake;
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 cleaning machine, and using the ultrasonic cleaning machine to ultrasonically clean the sodium hexametaphosphate and the silver powder cake to transitionally separate polyhedral silver powder and flake silver, wherein the polyhedral silver powder has unimodal distribution.
In STEP101, the silver nitrate, the ion-exchanged water, the ammonia water, and the polyvinylpyrrolidone are known per se, and their characteristics and preparation method 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 needed to form a silver-ammonia complex.
In STEP104, the characteristics and preparation method of the potassium sulfite and the ion exchange water are prior art and are not described in detail herein.
In STEP105, when stirring the solution B and the solution a, a magnetic stirrer may be used for stirring to stir uniformly.
In STEP106, the solution B is a reducing solution when a reduction reaction is performed, and an inorganic reducing agent, which may be sulfite or hydrazine, or an organic reducing agent may be added to increase the reduction rate. 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 to control the shape of the silver powder formed during the reaction of the a solution and the B solution. The particle shape controlling agent may be a rubbery polysaccharide such as one of gum arabic, thiol compounds, proteins, and polymer amino acid peptide compounds. The shape of the reduced silver particles can be ensured by the addition of the particle shape-controlling agent.
In STEP110, the silver powder is prevented from being oxidized by sodium hexametaphosphate.
Compared with the prior art, the preparation method of the polyhedral submicron silver powder provided by the invention is characterized in that an organic matter and a reducing agent of a particle morphology control agent are added into an aqueous solution of a silver-ammonia complex to precipitate a suspension containing silver, an alcohol is added into a silver cake obtained after filtering and cleaning the suspension at room temperature, and the suspension is dried and crushed under reduced pressure to obtain the high-crystalline polyhedral submicron silver powder with the drying decrement of 1-2% and no agglomeration in water and an organic solvent, so that the nano silver powder with the particle size of 100-400 nm can be prepared. Meanwhile, in the silver-ammonia complex, before adding the reducing agent, polyhedral silver powder of submicron size and hexagonal flaky silver of diagonal size are synthesized simultaneously by changing the concentration of the particle controlling agent and ammonia in the aqueous solution of the silver-ammonia complex, and the polyhedral silver powder and the flaky silver are crushed and separated by ultrasonic waves in the aqueous solution containing the surfactant. In the separation step, because the submicron silver powder is dispersed in the solution and the flake silver is precipitated, the submicron silver powder and the flake silver can be easily separated, and the micron-nanometer silver powder with controllable particle size is formed.
Examples
Two solutions, solution A and solution B, were prepared.
Liquid A5.00 g of silver nitrate was dissolved in 30g of ion exchange water, and 4.6g of 25% ammonia water was added to prepare a silver-ammonia complex aqueous solution. 0.4g of polyvinylpyrrolidone was dissolved in 50g of ion-exchanged water and added to the aqueous silver-ammonia 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 poured into liquid A and stirred with a magnetic stirrer.
After reacting at 40 ℃ for 3-4 hours, the resulting silver-containing suspension was filtered under reduced pressure, and the resulting silver powder cake was washed with plasma water and then with an ethanol solvent. After drying the silver powder cake, 3.25g of the silver powder cake reduced by about 8% was put into a vacuum drier having an internal volume of 8L, and dehydrated at room temperature (25 ℃ C.) under reduced pressure for 3 hours to obtain 3.16g of an anhydrous powder. The dehydrated powder was crushed at room temperature with an agate mortar and a teflon bar to obtain 3.14g of a crushed powder.
0.015g of silver powder sample is added into 30mL of 0.2 percent sodium hexametaphosphate, and the mixture is subjected to ultrasonic cleaning for 5 minutes by using an ultrasonic cleaner with the power of 50W, and the particle size is measured by using a dynamic light scattering particle size distribution test.
The silver powder obtained was as shown in FIGS. 1 and 2, and from the SEM images, it was found that the silver powder obtained was plate-like and granular. Further, as can be seen from FIG. 3, most of the silver powders had a particle size distribution of about 200 nm.
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 (6)
1. A preparation method of polyhedral submicron silver powder 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 exchange water, and adding the ammonia water to prepare a silver-ammonia complex aqueous solution;
dissolving polyvinylpyrrolidone in the ion exchange water, and adding the dissolved polyvinylpyrrolidone into the silver-ammonia complex aqueous solution to prepare a solution A;
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;
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 and filtering to obtain a silver powder cake;
washing the silver powder 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 cleaning machine, carrying out ultrasonic cleaning on the sodium hexametaphosphate and the silver powder cake by using the ultrasonic cleaning machine, and filtering and separating polyhedral silver powder and flake silver, wherein the particle size of the polyhedral silver powder has unimodal distribution.
2. The method for preparing polyhedral submicron silver powder according to claim 1, wherein: during the reaction of the A solution and the B solution, a particle shape controlling agent is added to control the shape of the formed silver powder.
3. The method for preparing polyhedral submicron silver powder according to claim 1, wherein: the particle shape controlling agent is one of gum arabic, thiol compounds, proteins, and polymer amino acid peptide compounds.
4. The method for preparing polyhedral submicron silver powder according to claim 1, wherein: the solution B is a reducing solution, the reducing solution contains an inorganic reducing agent, and the inorganic reducing agent is sulfite or hydrazine.
5. The method for preparing polyhedral submicron silver powder according to claim 1, wherein: 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 group or ketone group.
6. The method for preparing polyhedral submicron silver powder according to claim 1, wherein: the organic reducing agent having an aldehyde group or a ketone group is L-ascorbic acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116550988A (en) * | 2023-07-03 | 2023-08-08 | 长春黄金研究院有限公司 | Flake and sphere-like morphology mixed superfine silver powder and preparation method thereof |
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| CN116550988A (en) * | 2023-07-03 | 2023-08-08 | 长春黄金研究院有限公司 | Flake and sphere-like morphology mixed superfine silver powder and preparation method thereof |
| CN116550988B (en) * | 2023-07-03 | 2023-09-05 | 长春黄金研究院有限公司 | Flake and sphere-like morphology mixed superfine silver powder and preparation method thereof |
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