CN114309632A - Micron-sized silver powder and preparation method thereof - Google Patents
Micron-sized silver powder and preparation method thereof Download PDFInfo
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- CN114309632A CN114309632A CN202111376675.2A CN202111376675A CN114309632A CN 114309632 A CN114309632 A CN 114309632A CN 202111376675 A CN202111376675 A CN 202111376675A CN 114309632 A CN114309632 A CN 114309632A
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Abstract
The invention relates to micron-sized silver powder and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving a silver source in deionized water, adding a dispersing agent A, and stirring and dissolving to obtain a silver precursor solution A; dissolving a reducing agent A into deionized water to obtain a reducing agent solution A; adding the reducing agent solution A into the precursor solution A to obtain a silver core solution; dissolving another silver source into the solvent B to obtain a silver precursor solution B; adding the silver core solution into the precursor solution B to obtain a reaction solution; and carrying out hydrothermal reaction on the reaction liquid to obtain solid precipitate, carrying out solid-liquid separation on the reaction system after the reaction is finished, and washing and drying to obtain the silver powder. According to the invention, the silver powder is prepared by a crystal nucleus method through two steps, firstly, a trace amount of silver source is used for stirring and reducing to obtain a silver core, and then, the silver core is continuously grown through reduction by a hydrothermal method, so that the morphology of the silver powder can be better controlled, the surface of the generated silver powder is smooth, the edge is regular, no agglomeration exists, and the preparation of the high-crystallinity silver powder is realized.
Description
Technical Field
The invention relates to the technical field of metal powder and preparation thereof, in particular to micron-sized silver powder and a preparation method thereof.
Background
The silver powder is widely applied to a plurality of fields such as decorative materials, contact materials, glow materials, photosensitive materials, superconductor materials, conductive frame materials, energy industry, composite materials, catalysts, medicines, antibacterial materials and the like due to the stable chemical properties and excellent conductive and heat-conducting properties of the silver powder. The conductive paste is widely applied to the production of various electronic components, such as solar cell electrode plates, capacitors, multilayer ceramic capacitors, thick-film hybrid integrated circuits, printed and high-resolution conductors, conductive adhesives and the manufacture of other electronic components, and the like, as a functional material. Since silver is the main functional phase of the conductive paste, the demand of silver powder in the electronic paste industry is increasing in recent years.
Silver powder is the most important raw material in the production of the conductive paste, and the quality of the silver powder directly influences the performance of the conductive paste and the finally formed conductor because the silver powder has important influence on parameters such as film forming property, film thickness, electrical property, weldability, adhesiveness and the like in the preparation process. Therefore, the development of high-quality silver powder has become the key to the development of conductive paste, and is more and more emphasized by various countries.
When the high-crystallinity silver powder is used for preparing the conductive silver paste, the dispersibility and the filling property in the silver paste are good, the heat shrinkage resistance is excellent, meanwhile, the surface of the high-crystallinity silver powder is smooth, impurities are easy to clean, the contained impurities are few, and the performance of the obtained conductive silver paste is better, so that the high-performance electronic paste generally requires that the silver powder has high crystallinity.
At present, silver powder of various varieties and performances developed in China can basically meet the requirements of middle and low-end markets in China, but high-end slurry products such as solar cell front silver slurry have very high requirements on the particle size distribution, crystallinity, sphericity, surface dispersing agent and the like of the silver powder, and the silver powder capable of meeting the requirements is few.
Disclosure of Invention
In order to meet the requirements of high-performance slurry on the performance of the silver powder, the invention provides a preparation method of micron-sized silver powder, the silver powder with high crystallinity and good dispersibility is prepared by adopting a chemical reduction method, and the silver powder can be used as a function and correspondingly used for preparing high-performance conductive silver paste.
The invention adopts the following technical scheme:
the preparation method of the micron-sized silver powder is characterized by comprising the following preparation steps:
s1, dissolving a silver source in deionized water, adding a dispersing agent A, and stirring and dissolving to obtain a silver precursor solution A;
s2, dissolving the reducing agent A into deionized water to obtain a reducing agent solution A;
s3, adding the reducing agent solution A into the precursor solution A to obtain a silver core solution;
s4, dissolving another silver source into the solvent B to obtain a silver precursor solution B;
s5, adding the silver core solution into the precursor solution B to obtain a reaction solution;
and S6, carrying out hydrothermal reaction on the reaction liquid to obtain solid precipitate, carrying out solid-liquid separation on the reaction system after the reaction is finished, and washing and drying to obtain the silver powder.
Further, in the step S1, the silver source is silver nitrate, and the concentration after dissolution is 0.01-0.1mol/L, and more preferably 0.01-0.05 mol/L.
Further, in step S1, the dispersant a includes one or more of polyvinylpyrrolidone, sodium dodecyl sulfate and cetyltrimethylammonium bromide, preferably, sodium dodecyl sulfate is used as the dispersant, and the amount of the dispersant is 50% to 200% by mass of the silver source, and more preferably, 100% to 150% by mass.
Further, the reducing agent a in the step S2 includes one of sodium borohydride and hydrazine hydrate, the addition amount of the reducing agent a is 1 to 2 times, more preferably 1.1 to 1.5 times of the theoretical amount required for reducing the silver source in the step S1, and the concentration of the reducing agent after dissolution is 0.1 to 1.5 mol/L.
Further, in the step S4, the silver source is silver nitrate, and the concentration of the dissolved silver nitrate is 0.1-1mol/L, and more preferably 0.5-1 mol/L.
Further, the solvent B in the step S4 is one of isopropanol, ethylene glycol and butanediol, and the solvent used in this step serves as both a reducing agent and a dispersing agent, and no additional reducing agent and dispersing agent are required to be added subsequently.
Further, the reaction temperature in the step S5 is 100-200 ℃, and the reaction time is 1-10 h.
Preferably, the reaction temperature in the step S5 is 150-200 ℃, and the reaction time is 2-5 h.
Further, in the step S5, the volume ratio of the silver core solution to the precursor solution B is 1: (10-100).
The invention also provides micron-sized silver powder prepared by the preparation method of the micron-sized silver powder.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the silver powder is prepared by a crystal nucleus method through two steps, firstly, a trace amount of silver source is used for stirring and reducing to obtain a silver core, and then, the silver core is continuously grown through reduction by a hydrothermal method, so that the morphology of the silver powder can be better controlled, the surface of the generated silver powder is smooth, the edge is regular, no agglomeration exists, and the preparation of the high-crystallinity silver powder is realized.
The crystal nucleus method is combined with the hydrothermal method, so that the generated silver powder particles are more uniform and have good sphericity, and the batch stability of the product is higher. In the second step of hydrothermal reduction, the solvent is simultaneously used as a reducing agent and a dispersing agent in the growth process of the silver nuclei, and the reducing agent and the dispersing agent do not need to be added, so that the post-treatment difficulty can be reduced; the prepared silver powder has good crystallinity, is suitable for preparing high-performance electronic paste, has more excellent sintering performance, and meets the use requirement of high-end paste products.
Drawings
FIG. 1 is a SEM photograph of silver powder prepared in example 1;
FIG. 2 is a SEM photograph of the silver powder obtained in example 2;
FIG. 3 is an SEM photograph of the silver powder obtained in comparative example 1.
Detailed Description
The present invention is further illustrated by the following specific examples.
The method for preparing the micron-sized silver powder comprises the following specific steps:
s1, dissolving a silver source in deionized water, adding a dispersing agent A, and stirring and dissolving to obtain a silver precursor solution A; wherein the concentration of the silver source is 0.01-0.1mol/L, and the more preferable concentration is 0.01-0.05 mol/L; the dosage of the dispersant is 50-200% of the mass of the silver source, and more preferably 100-150%;
s2, dissolving the reducing agent A into deionized water to obtain a reducing agent solution A; the addition amount is 1 to 2 times of the theoretical amount needed by the silver source in the reduction step S1, the further optimization is 1.1 to 1.5 times, and the concentration of the reducing agent after dissolution is 0.1 to 1.5 mol/L;
s3, adding the reducing agent solution A into the precursor solution A to obtain a silver core solution;
s4, dissolving another silver source into the solvent B to obtain a silver precursor solution B; wherein the concentration of the silver source is 0.1-1mol/L, and the preferable concentration is 0.5-1 mol/L;
s5, adding the silver core solution into the precursor solution B to obtain a reaction solution, and transferring the reaction solution into a reaction kettle; wherein the mass ratio of the silver core solution to the precursor solution B is 1: (10-100);
and S6, placing the reaction kettle in an oven, carrying out hydrothermal reaction to obtain solid precipitate, carrying out solid-liquid separation on the reaction system after the reaction is finished, and washing and drying to obtain the silver powder. The silver powder surface impurities can be removed by washing with deionized water and ethanol, and the drying method includes but is not limited to vacuum drying, natural drying, heating drying and forced air drying.
Example 1
Dissolving 0.1g of silver nitrate into 50g of deionized water to obtain a silver nitrate solution; dissolving 0.2g of sodium dodecyl sulfate into the silver nitrate solution, and fully stirring and dissolving to obtain a precursor solution A of silver;
dissolving 0.03g of sodium borohydride in 10g of deionized water to obtain a sodium borohydride solution;
adding the sodium borohydride solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain a silver core solution;
adding 50g of silver nitrate into 300g of isopropanol, and fully stirring and dissolving to obtain a silver precursor solution B;
and adding 10g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 100 ℃, reacting for 10 hours, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying for 2 hours in a 70 ℃ oven to obtain the silver powder.
Example 2
Adding 0.1g of silver nitrate into 50g of deionized water to obtain a silver nitrate solution; dissolving another 0.5g of polyvinylpyrrolidone into the silver nitrate solution; fully stirring and dissolving to obtain a precursor solution A of silver;
dissolving 0.03g of hydrazine hydrate in 10g of deionized water to obtain a hydrazine hydrate solution;
adding the hydrazine hydrate solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain the silver core solution.
Adding 50g of silver nitrate into 600g of ethylene glycol, and fully stirring and dissolving to obtain a silver precursor solution B;
and adding 10g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 150 ℃, reacting for 5 hours, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying for 2 hours in a 70 ℃ oven to obtain the silver powder.
Example 3
Adding 0.15g of silver nitrate into 10g of deionized water to obtain a silver nitrate solution; dissolving 0.15g of sodium dodecyl sulfate into the silver nitrate solution, and fully stirring and dissolving to obtain a precursor solution A of silver;
dissolving 0.04g of sodium borohydride in 5g of deionized water to obtain a sodium borohydride solution;
adding the sodium borohydride solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain a silver core solution;
adding 50g of silver nitrate into 300g of isopropanol, and fully stirring and dissolving to obtain a silver precursor solution B;
adding 3g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 200 ℃, reacting for 2h, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying for 2h in a 70 ℃ oven to obtain the silver powder.
Example 4
Adding 0.1g of silver nitrate into 50g of deionized water to obtain a silver nitrate solution; dissolving another 0.5g of polyvinylpyrrolidone into the silver nitrate solution; fully stirring and dissolving to obtain a precursor solution A of silver;
dissolving 0.03g of hydrazine hydrate in 10g of deionized water to obtain a hydrazine hydrate solution;
adding the hydrazine hydrate solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain the silver core solution.
Adding 50g of silver nitrate into 600g of ethylene glycol, and fully stirring and dissolving to obtain a silver precursor solution B;
and adding 10g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 150 ℃, reacting for 5 hours, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying for 2 hours in a 70 ℃ oven to obtain the silver powder.
Example 5
Adding 0.1g of silver nitrate into 10g of deionized water to obtain a silver nitrate solution; dissolving 0.15g of sodium dodecyl sulfate into the silver nitrate solution, and fully stirring and dissolving to obtain a precursor solution A of silver;
dissolving 0.04g of sodium borohydride in 20g of deionized water to obtain a sodium borohydride solution;
adding the sodium borohydride solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain a silver core solution;
adding 60g of silver nitrate into 300g of isopropanol, and fully stirring and dissolving to obtain a silver precursor solution B;
and adding 30g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 130 ℃, reacting for 8 hours, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying in a 70 ℃ oven for 2 hours to obtain the silver powder.
Example 6
Adding 0.02g of silver nitrate into 10g of deionized water to obtain a silver nitrate solution; dissolving 0.03g of sodium dodecyl sulfate into the silver nitrate solution, and fully stirring and dissolving to obtain a silver precursor solution A;
dissolving 0.001g of sodium borohydride in 4g of deionized water to obtain a sodium borohydride solution;
adding the sodium borohydride solution into the silver precursor solution A at a constant speed, and stirring to completely react to obtain a silver core solution;
adding 60g of silver nitrate into 300g of isopropanol, and fully stirring and dissolving to obtain a silver precursor solution B;
and adding 30g of silver core solution into the silver precursor solution B, transferring the reaction solution into a reaction kettle, setting the reaction temperature at 130 ℃, reacting for 8 hours, separating the solid and liquid of the reaction solution after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying in a 70 ℃ oven for 2 hours to obtain the silver powder.
Comparative example 1
Adding 50g of silver nitrate into 300g of isopropanol (isopropanol is used as a dispersing agent and a reducing agent), transferring the reaction liquid into a reaction kettle, setting the reaction temperature at 100 ℃, reacting for 10 hours, separating solid and liquid of the reaction liquid after the reaction is finished, washing with deionized water and ethanol to remove surface impurities, and drying in a 70 ℃ oven for 2 hours to obtain the silver powder.
The silver powders prepared in example 1, example 2 and comparative example 1 were observed under an electron microscope to obtain electron microscope images as shown in FIGS. 1 to 3;
FIG. 1 shows that the silver powder prepared in example 1 has high surface smoothness, regular edges and high crystallinity of silver powder particles; FIG. 3 is a silver powder directly prepared in one step without using the crystal nucleus method in comparative example 1, and it can be seen that the silver powder prepared using the comparative example is more non-uniform in size, the surface of the silver powder particles is not smooth and flat, and does not have the excellent properties of the highly crystallized silver powder, in comparison with FIGS. 1 and 2.
Claims (10)
1. The preparation method of the micron-sized silver powder is characterized by comprising the following preparation steps:
s1, dissolving a silver source in water, adding a dispersing agent A, and stirring and dissolving to obtain a silver precursor solution A;
s2, dissolving the reducing agent A into water to obtain a reducing agent solution A;
s3, adding the reducing agent solution A into the precursor solution A to obtain a silver core solution;
s4, dissolving another silver source into the solvent B to obtain a silver precursor solution B;
s5, adding the silver core solution into the precursor solution B to obtain a reaction solution;
and S6, carrying out hydrothermal reaction on the reaction liquid to obtain solid precipitate, carrying out solid-liquid separation on the reaction system after the reaction is finished, and washing and drying to obtain the silver powder.
2. The method for preparing micron-sized silver powder according to claim 1, wherein the silver source is silver nitrate and the concentration after dissolution is 0.01 to 0.1mol/L in the step S1.
3. The method for preparing micron-sized silver powder according to claim 1, wherein in the step S1, the dispersant A comprises one or more of polyvinylpyrrolidone, sodium dodecyl sulfate and cetyl trimethyl ammonium bromide, and the mass of the dispersant A is 50-200% of that of the silver source.
4. The method for preparing micron-sized silver powder according to claim 1, wherein the reducing agent a in the step S2 comprises one of sodium borohydride and hydrazine hydrate, which is added in an amount of 1 to 2 times the amount theoretically required for reducing the silver source in the step S1, and the concentration of the reducing agent after dissolution is 0.1 to 1.5 mol/L.
5. The method for preparing micron-sized silver powder according to claim 1, wherein the silver source in the step S4 is silver nitrate, and the concentration of the dissolved silver nitrate is 0.1-1 mol/L.
6. The method for preparing micron-sized silver powder according to claim 1, wherein the solvent B in the step S4 is any one of isopropyl alcohol, ethylene glycol and butylene glycol.
7. The method for preparing micron-sized silver powder according to claim 1, wherein the reaction temperature in the step S5 is 100-200 ℃, and the reaction time is 1-10 h.
8. The method for preparing micron-sized silver powder according to claim 1, wherein the reaction temperature in the step S5 is 150 ℃ to 200 ℃, and the reaction time is 2-5 h.
9. The method for preparing micron-sized silver powder according to claim 1, wherein the mass ratio of the silver core solution to the precursor solution B in the step S5 is 1: (10-100).
10. A micron-sized silver powder, characterized in that it is produced by the method for producing a micron-sized silver powder according to any one of claims 1 to 9.
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| CN106583746A (en) * | 2016-11-30 | 2017-04-26 | 中国东方电气集团有限公司 | Preparation method of solar battery panel silver powder |
| CN110355380A (en) * | 2019-08-13 | 2019-10-22 | 山东建邦胶体材料有限公司 | A kind of preparation method of hexagonal flake micron crystalline substance silver powder |
| CN111590086A (en) * | 2020-06-02 | 2020-08-28 | 江西贝特利新材料有限公司 | Ultrathin flake silver powder with smooth surface and preparation method thereof |
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2021
- 2021-11-19 CN CN202111376675.2A patent/CN114309632A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4539041A (en) * | 1982-12-21 | 1985-09-03 | Universite Paris Vii | Process for the reduction of metallic compounds by polyols, and metallic powders obtained by this process |
| CN101920340A (en) * | 2010-08-20 | 2010-12-22 | 山东省科学院新材料研究所 | Method for preparing superfine spherical silver powder on large scale |
| JP2014098212A (en) * | 2012-03-07 | 2014-05-29 | Sumitomo Metal Mining Co Ltd | Silver powder and method for producing the same |
| CN105436517A (en) * | 2015-12-24 | 2016-03-30 | 苏州思美特表面材料科技有限公司 | Method for preparing metal powder by utilizing nano crystal seed induction |
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