CN115519129B - Preparation method of silver powder for conductive paste - Google Patents
Preparation method of silver powder for conductive paste Download PDFInfo
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- CN115519129B CN115519129B CN202210936670.9A CN202210936670A CN115519129B CN 115519129 B CN115519129 B CN 115519129B CN 202210936670 A CN202210936670 A CN 202210936670A CN 115519129 B CN115519129 B CN 115519129B
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Abstract
The invention discloses a preparation method of silver powder for conductive paste, which comprises the steps of preparing wet silver powder by using a silver-containing solution and a reducing agent solution, adding water into an organic solvent mixed by a hydrophobic surfactant and a solvent for emulsification to prepare a surface treating agent, and coating the surface treating agent and the wet silver powder to prepare the silver powder. The surface treating agent adopts a hydrophobic surfactant and is emulsified to form a water-in-oil type emulsion, the surface treating agent is added after the wet silver powder is prepared, the silver powder can be completely coated, the prepared silver powder particles have good dispersibility and no agglomeration and can be dispersed in a nonpolar solvent again, the silver powder particles have uniform particle size, narrow particle size distribution, small average particle size, high silver powder yield and short production period.
Description
Technical Field
The invention relates to a preparation method of silver powder, in particular to a preparation method of silver powder for conductive paste.
Background
A process for preparing nm silver and its synthesizing method (China, publication No. 109079154B, publication No. 2022-03-01) includes such steps as adding wet silver powder to hydrophilic surface treating agent, heating while stirring to obtain nm silver sol, and adding settling agent to make the surface of silver powder become hydrophobic structure.
A surface treating liquid and its adding mode (China, publication No. 112024906A, publication date: 2020-12-04) in the silver powder preparation process disclose that a lipophilic surfactant, a hydrophobic defoaming agent and an organic solvent are mixed to obtain the surface treating liquid, then the surface treating liquid is added into a silver powder synthesis system, stirred and mixed, and then washed and dried. The surface treatment liquid overcomes the problems of poor dispersibility and easy agglomeration of the silver powder in the prior art, simultaneously saves the trouble of heating the surface treatment agent for multiple times, improves the operation efficiency, reduces the operation error, and saves time and labor. In a silver synthesis system, the hydrophobic defoaming agent attracts a hydrophobic end of the surfactant, so that the hydrophobic defoaming agent becomes hydrophilic, the concentration and the tension of the surfactant in a bubble film in the silver synthesis system are reduced, and a defoaming effect is achieved; the organic solvent can dissolve the lipophilic surfactant and the hydrophobic defoaming agent, so that the melting points of the two lipophilic surfactants and the hydrophobic defoaming agent are reduced.
However, the silver powder surface treating agent in the method is easy to separate out, floats on the surface layer, is incompletely coated, and has wide particle size distribution and large average particle size of the finished silver powder.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of silver powder for conductive paste, and the finished silver powder with narrow particle size distribution and uniform particle size is obtained.
The technical scheme is as follows: a preparation method of silver powder for conductive paste comprises the following steps:
step S10, preparing wet silver powder: reacting silver-containing solution with reducing agent solution to generate silver precipitate and form wet silver powder;
step S20, preparing a surface treatment agent: mixing hydrophobic surfactant and solvent to form organic solvent, heating to form solution, adding hot water, and stirring to form surface treating agent of emulsion;
step S30, coating: and adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Further, in step S10, the silver-containing solution is silver ammonia solution or Ag 2 O suspensions or Ag 2 CO 3 One of the suspensions, the reducing agent solution is one of glucose, formaldehyde, hydrazine hydrate, ascorbic acid, sodium erythorbate and p-diphenol.
Further, in step S10, after the silver precipitate is generated, a dispersing agent is added and mixed uniformly to form the wet silver powder.
Furthermore, the dispersant is one or more of polyvinylpyrrolidone, citrate, oleylamine and organic compounds with methyl siloxy functional groups.
Furthermore, the dosage of the dispersant is 0.01 to 5 percent of the silver content of the wet silver powder by mol percent.
Further, in step S20: the dosage of the hydrophobic surfactant is 0.0001-20% of the silver content of the wet silver powder by mass percent; mixing hydrophobic surfactant and solvent in the mass ratio of 1: 80-10: 80 to form organic solvent; the hot water and the hydrophobic surfactant are used according to the mass ratio of 1: 1-10: 1.
Further, in step S20, the hydrophobic surfactant is C 6 ～C 22 Saturated fatty acid, C 6 ～C 22 Unsaturated fatty acid, C 6 ～C 22 Esters, C 6 ～C 22 Amines, C 6 ～C 22 Fatty amines, C 6 ～C 22 One or at least two of fatty acid amides are mixed, and the solvent is one or at least two of ethanol, acetone, glycol and toluene.
Further, in step S20, the heating conditions are 30 ℃ to 100 ℃ and the hot water temperature is 30 ℃ to 100 ℃.
Further, in step S20, the emulsion is formed by stirring the mixture with a homogenizer at a speed of 1000 to 30000r/min for 1 to 3 minutes, preferably at a stirring speed which allows the emulsion to be formed and which does not cause splashing of the liquid.
Further, in step S30, the surface treatment agent is cooled to the temperature of the wet silver powder and then added to the wet silver powder.
Has the advantages that: the invention has the advantages that: the surface treating agent used in the silver powder preparation adopts a hydrophobic surfactant and is emulsified to form a water-in-oil type emulsion, the surface treating agent is added after the wet silver powder is prepared, the silver powder can be completely coated, so that the prepared silver powder particles have good dispersibility and no agglomeration and can be dispersed in a nonpolar solvent again, the silver powder particles have uniform particle size, narrow particle size distribution, small average particle size, high silver powder yield and short production period.
Drawings
FIG. 1 is a microscopic view of the silver powder obtained in example 1;
FIG. 2 is a microscopic view of the silver powder obtained in comparative example 1.
Detailed Description
The invention is further elucidated with reference to the drawings and the embodiments.
A process for preparing the silver powder used as electrically conducting slurry includes such steps as preparing wet silver powder from the solution containing Ag and reducer, adding disperser, mixing hydrophobic surfactant with solvent, adding water, emulsifying to obtain surface treating agent, and coating said surface treating agent with said wet silver powder.
The silver-containing solution is silver ammonia solution or Ag 2 O suspensions or Ag 2 CO 3 One of the suspensions, the reducing agent solution is one of glucose, formaldehyde, hydrazine hydrate, ascorbic acid, sodium erythorbate, p-diphenol, etc. The dispersant is one or more of polyvinylpyrrolidone, citrate, oleylamine and organic compounds with methyl siloxy functional group, and the organic compounds with methyl siloxy functional group can be BYK-167, BYK-191, BYK-230 and the like. The hydrophobic surfactant is C 6 ～C 22 Saturated fatty acid, C 6 ～C 22 Unsaturated fatty acid, C 6 ～C 22 Esters, C 6 ～C 22 Amines, C 6 ～C 22 Fatty amines, C 6 ～C 22 One or at least two of fatty acid amides can be selected from oleylamine, oleamide, erucamide, dodecylamine, octadecylamine, triethanolamine, stearic acid, glyceryl monostearate, sorbitan laurate, polyoxyethylene sorbitan monostearate, etc., and the solvent is selected from one or at least two of ethanol, acetone, ethylene glycol, and toluene.
The dosage of the dispersant is 0.01 to 5 percent of the silver content of the wet silver powder by mol percent. The dosage of the hydrophobic surfactant is 0.0001-20% of the silver content of the wet silver powder by mass percent. The hydrophobic surface active agent and the solvent are mixed into the organic solvent according to the mass ratio of 1: 80-10: 80. The hot water and the hydrophobic surfactant are used according to the mass ratio of 1: 1-10: 1.
The following examples, based on the above raw material selections.
Example 1
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 And mixing the O suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate and form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into oleamide, mixing and stirring at 80 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding 80 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of oleamide is 0.01 percent of the silver content of the wet silver powder, the oleamide and ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the oleamide are used according to the mass ratio of 1: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 2
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: mixing a certain amount of silver ammonia solution and sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding polyvinylpyrrolidone, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into oleamide, mixing and stirring at 80 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding 80 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 1 minute to form the surface treating agent of the emulsion.
The usage amount of the polyvinylpyrrolidone is 0.01 percent of the silver content of the wet silver powder, the usage amount of the oleamide is 0.01 percent of the silver content of the wet silver powder, the oleamide and the ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the oleamide are used according to the mass ratio of 4: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 3
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 CO 3 And mixing the suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding sodium citrate, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into oleamide, mixing and stirring at 100 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding hot water at 100 ℃ into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the sodium citrate is 0.01 percent of the silver content of the wet silver powder, the using amount of the oleamide is 0.01 percent of the silver content of the wet silver powder, the oleamide and the ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the oleamide are used according to the mass ratio of 6: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 4
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 CO 3 And mixing the suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding sodium citrate, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treatment agent: adding acetone into dodecylamine, mixing and stirring at 90 ℃ until all the acetone is dissolved to obtain an organic solvent, adding hot water at 90 ℃ into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the sodium citrate is 0.01 percent of the silver content of the wet silver powder, the using amount of the laurylamine is 0.01 percent of the silver content of the wet silver powder, the laurylamine and the acetone are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the laurylamine are used according to the mass ratio of 8: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 5
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 And mixing the O suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding BYK-167, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treating agent: adding ethanol into stearic acid, mixing and stirring at 80 ℃ until all the ethanol is dissolved to obtain an organic solvent, adding 80 ℃ hot water into the organic solvent, and stirring and treating for 3 minutes at 30000r/min by adopting a homogenizer to form the surface treating agent of the emulsion.
The using amount of BYK-167 is 0.01 percent of the silver content of the wet silver powder, the using amount of stearic acid is 0.01 percent of the silver content of the wet silver powder, the stearic acid and ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the using amount of hot water and the stearic acid is 10: 1 according to the mass ratio.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 6
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 CO 3 The suspension is mixed with sufficient glucose solution to carry out redox reaction,silver precipitate is generated, and BYK-191 is added and mixed evenly to form wet silver powder.
Step S20, preparing a surface treating agent: adding acetone into triethanolamine, mixing and stirring at 90 ℃ until the acetone is completely dissolved to obtain an organic solvent, adding hot water at 90 ℃ into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the BYK-191 is 0.01 percent of the silver content of the wet silver powder, the using amount of the triethanolamine is 0.0001 percent of the silver content of the wet silver powder, the triethanolamine and the acetone are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the triethanolamine are used according to the mass ratio of 8: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Embodiment 7 a method for preparing silver powder for conductive paste, comprising the steps of:
step S10, preparing wet silver powder: mixing a certain amount of silver ammonia solution with sufficient glucose solution to generate oxidation-reduction reaction to generate silver precipitate, adding BYK-230, and mixing uniformly to form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into oleamide, mixing and stirring at 80 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding 80 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 1 minute to form the surface treating agent of the emulsion.
The using amount of BYK-230 is 5% of the silver content of the wet silver powder, the using amount of oleamide is 0.01% of the silver content of the wet silver powder, the oleamide and ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the using amount of hot water and the oleamide is 4: 1 according to the mass ratio.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 8
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: a certain amount of Ag 2 CO 3 And mixing the suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding sodium citrate, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into oleamide, mixing and stirring at 100 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding 100 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the sodium citrate is 0.01 percent of the silver content of the wet silver powder, the using amount of the oleamide is 20 percent of the silver content of the wet silver powder, the oleamide and the ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the oleamide are used according to the mass ratio of 6: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 9
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: a certain amount of Ag 2 And mixing the O suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding BYK-167, and uniformly mixing to form wet silver powder.
Step S20, preparing a surface treating agent: adding ethanol into stearic acid, mixing and stirring at 80 ℃ until all the ethanol is dissolved to obtain an organic solvent, adding 80 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 30000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of BYK-167 is 0.01 percent of the silver content of the wet silver powder, the using amount of stearic acid is 0.01 percent of the silver content of the wet silver powder, the stearic acid and ethanol are mixed into an organic solvent according to the mass ratio of 1: 80, and the hot water and the stearic acid are used according to the mass ratio of 10: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 10
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: a certain amount of Ag 2 CO 3 And mixing the suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate, adding sodium citrate, and uniformly mixing to form the wet silver powder.
Step S20, preparing a surface treating agent: adding acetone into octadecylamine, mixing and stirring at 90 ℃ until all the acetone is dissolved to obtain an organic solvent, adding hot water at 90 ℃ into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the sodium citrate is 0.01 percent of the silver content of the wet silver powder, the using amount of the octadecylamine is 20 percent of the silver content of the wet silver powder, the octadecylamine and the acetone are mixed into an organic solvent according to the mass ratio of 10: 80, and the using amount of the hot water and the octadecylamine is 8: 1 according to the mass ratio.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 11
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: adding a certain amount of Ag 2 And mixing the O suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate to form the wet silver powder.
Step S20, preparing a surface treating agent: adding ethanol into sorbitan laurate, mixing and stirring at 30 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding hot water at 30 ℃ into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The using amount of the sorbitan laurate is 0.01 percent of the silver content of the wet silver powder, the sorbitan laurate and ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and the hot water and the sorbitan laurate are used according to the mass ratio of 1: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Example 12
The preparation method of the silver powder for the conductive paste specifically comprises the following steps:
step S10, preparing wet silver powder: a certain amount of Ag 2 And mixing the O suspension with sufficient glucose solution to perform oxidation-reduction reaction to generate silver precipitate and form wet silver powder.
Step S20, preparing a surface treatment agent: adding ethanol into polyoxyethylene sorbitan monostearate, mixing and stirring at 70 ℃ until the ethanol is completely dissolved to obtain an organic solvent, adding 70 ℃ hot water into the organic solvent, and stirring by adopting a homogenizer at the speed of 10000r/min for 3 minutes to form the surface treating agent of the emulsion.
The usage amount of the polyoxyethylene sorbitan monostearate is 0.01 percent of the silver content of the wet silver powder, the polyoxyethylene sorbitan monostearate and ethanol are mixed into an organic solvent according to the mass ratio of 10: 80, and hot water and the polyoxyethylene sorbitan monostearate are used according to the mass ratio of 1: 1.
Step S30, coating: and when the surface treating agent is cooled to the temperature of the wet silver powder system, adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
Comparative example 1
The difference from example 1 is that: the homogenizer was stirred at a speed of 400r/min for 3 minutes.
Comparative example 2
The difference from example 1 is that: hydrophilic surfactant-polyvinyl alcohol is used to replace hydrophobic surfactant-oleic acid amide.
Comparative example 3
The difference from example 1 is that: the mass ratio of the hot water to the oleamide is 0.5: 1.
Comparative example 4
The difference from example 5 is that: the mass ratio of the hot water to the stearic acid is 11: 1.
Comparative example 5
The differences from example 5 are: the homogenizer was stirred at 40000r/min for 3 minutes.
Comparative example 6
The differences from example 5 are: the homogenizer was stirred at 30000r/min for 0.5 min.
Comparative example 7
The difference from example 4 is that: the homogenizer was stirred at 10000r/min for 5 minutes.
Comparative example 8
The difference from example 1 is that: and step S20, adding ethanol into oleamide, mixing and stirring at 80 ℃ until all the obtained organic solvent is dissolved to be used as a surface treating agent, and emulsifying without heating water in the step.
Comparative example 9
The difference from example 3 is that: the heating conditions were 25 ℃ and the hot water temperature was 25 ℃.
The silver powders prepared in the examples and the respective proportions are compared by detecting the quality as follows:
| serial number | Average particle diameter of μm | Specific surface area m 2 /g | Tap density g/cm 3 |
| Example 1 | 0.5 | 1.5 | 6.3 |
| Example 2 | 0.8 | 1.1 | 6.2 |
| Example 3 | 1.0 | 0.9 | 6.1 |
| Example 4 | 1.5 | 0.4 | 5.8 |
| Example 5 | 2 | 0.3 | 5.5 |
| Example 6 | 1.6 | 0.4 | 5.6 |
| Example 7 | 0.7 | 1.2 | 6.2 |
| Example 8 | 0.9 | 1.0 | 6.1 |
| Example 9 | 1.9 | 0.3 | 5.5 |
| Example 10 | 1.2 | 0.6 | 6.0 |
| Example 11 | 0.6 | 1.5 | 6.4 |
| Example 12 | 0.6 | 1.5 | 6.3 |
| Comparative example 1 | 2.2 | 0.3 | 5.2 |
| Comparative example 2 | 2.5 | 0.2 | 5.1 |
| Comparative example 3 | 2.1 | 0.3 | 5.5 |
| Comparative example 4 | 2.8 | 0.15 | 5.1 |
| Comparative example 5 | 2.3 | 0.3 | 5.2 |
| Comparative example 6 | 2.4 | 0.3 | 5.2 |
| Comparative example 7 | 1.5 | 0.4 | 5.8 |
| Comparative example 8 | 3.0 | 0.15 | 5.0 |
| Comparative example 9 | 2.8 | 0.15 | 5.5 |
The silver powder prepared by the method can be used for preparing low-temperature curing type conductive paste, the conductive paste is applied to HJT batteries, membrane switches, medical PVC pipes, touch screens and mobile phone antennas, and can also be used for preparing high-temperature sintering type conductive paste, and the conductive paste is applied to TOPcon batteries, PERC batteries, piezoelectric ceramics, chip resistors, chip capacitors, chip inductors, automobile glass and 5G antennas.
The silver powder preparation method has the following action principle: the preparation of the surface treating agent adopts a hydrophobic surface active agent, and a small amount of water is added in the preparation process to form water-in-oil emulsion, the prepared surface treating agent is added after the preparation of the wet silver powder, the silver powder can be completely coated, so that the prepared silver powder particles have good dispersibility and no agglomeration and can be dispersed in a nonpolar solvent again, the particle size distribution of the silver powder particles is narrow, and the average particle size is small.
The detection data analysis of the embodiment of the application is as follows:
1. as is clear from comparison of the examples, when the surface treatment agent was prepared, the ratio of the amount of hot water used for emulsification to the amount of the hydrophobic surfactant was increased by mass, the particle diameter of the silver powder obtained was increased, and the amount of the solvent mixed with the hydrophobic surfactant to form the organic solvent was increased, and the particle diameter of the silver powder obtained was decreased. The silver powder prepared by the preparation method has the advantages that the particle size range can be controlled to be 0.5-2 mu m, the particle size distribution of the silver powder particles is narrow, the average particle size is small, the smaller the particle size is, the larger the specific surface area is, the larger the tap density is, and the specific surface area range can reach 0.3-1.5 m 2 The tap density can reach 5.5 to 6.5g/cm 3 And the particle dispersibility is good.
2. As is clear from comparison between example 1 and comparative example 1 and comparison between example 5 and comparative example 5, when the surface-treating agent was prepared, the stirring and emulsifying rotational speed was less than 1000r/min or more than 30000r/min, and the quality of the silver powder obtained was remarkably lowered. FIGS. 1 and 2 are micrographs of the silver powders obtained in example 1 and comparative example 1, respectively, and the magnifications thereof were 10000 times, and it can be seen that the silver powder obtained in example 1 has uniform particle diameter, narrow particle diameter distribution, small average particle diameter, and good dispersibility.
3. As is clear from comparison between example 1 and comparative example 2, when the surface-treating agent was prepared, the hydrophilic surfactant was used as the active agent, and the quality of the silver powder obtained was remarkably lowered.
4. As is clear from comparison of example 1 with comparative example 3 and comparison of example 5 with comparative example 4, when the surface-treating agent was prepared, the mass ratio of the amount of emulsified hot water to the amount of hydrophobic surfactant was less than 1: 1 or more than 10: 1, and the quality of the silver powder obtained was significantly reduced.
5. As is clear from comparison between example 5 and comparative example 6, the emulsion stirring time was less than 1min when the surface treating agent was prepared, and the quality of the silver powder obtained was significantly reduced; as is clear from comparison between example 4 and comparative example 7, the emulsion stirring time was more than 3min when the surface treatment agent was prepared, and the quality of the silver powder obtained was comparable without any improvement, but the electricity cost and the time cost were increased.
6. As is clear from comparison between example 1 and comparative example 8, when the surface treating agent was prepared, the silver powder obtained was significantly deteriorated in quality by emulsification with unheated water.
7. As is clear from comparison between example 3 and comparative example 9, the dispersibility of the silver powder obtained is closely related to the heating conditions and the hot water temperature during the preparation of the surface-treating agent. Wherein, when the heating condition and the hot water temperature are in the range of 80-100 ℃, the surface treating agent has good emulsifying effect and high silver powder dispersibility; when the heating condition and the hot water temperature are in the range of 30-80 ℃, the temperature greatly contributes to the emulsifying effect of the surface treating agent, generally speaking, when the temperature is increased, the smaller the liquid beads wrapped in a material system of the surface treating agent is, the silver powder is fully wrapped, and the prepared silver powder has better dispersibility. That is, when the temperature is lower than 30 ℃, the particle size of the liquid beads formed during the emulsification process is large, and the emulsification may not be achieved.
8. The silver powder with good dispersibility and narrow particle size distribution can be prepared by heating the surface treating agent to 30-100 ℃ and hot water to 30-100 ℃, preferably heating to 80-100 ℃ and hot water to 80-100 ℃, and selecting the hydrophobic surfactant with the hydrophilic-lipophilic balance (HLB) of 0-10; the silver powder with good dispersibility and narrow particle size distribution can be prepared by heating to 30-80 deg.C and heating to 30-80 deg.C with water at 30-80 deg.C and selecting hydrophobic surfactant with hydrophilic-lipophilic balance (HLB) of 8-10 (such as example 11 and example 12).
Claims (8)
1. The preparation method of the silver powder for the conductive paste is characterized by comprising the following steps of:
step S10, preparing wet silver powder: reacting silver-containing solution with reducing agent solution to generate silver precipitate and form wet silver powder;
step S20, preparing a surface treatment agent: mixing hydrophobic surfactant and solvent to form organic solvent, heating to form solution, adding hot water, and stirring to form surface treating agent of emulsion;
mixing hydrophobic surfactant and solvent in the mass ratio of 1: 80-10: 80 to form organic solvent; the hot water and the hydrophobic surfactant are used according to the mass ratio of 1: 1-10: 1; the hydrophobic surfactant is C 6 ～C 22 Saturated fatty acid, C 6 ～C 22 Unsaturated fatty acid, C 6 ～C 22 Esters, C 6 ～C 22 Amines, C 6 ～C 22 Fatty amines, C 6 ～C 22 One or at least two of fatty amides are mixed, and the solvent is one or at least two of ethanol, acetone, glycol and toluene; the heating condition is 30-100 ℃, and the hot water temperature is 30-100 ℃;
step S30, coating: and adding the surface treating agent into the wet silver powder, coating, and drying to obtain the silver powder.
2. The method for producing silver powder for conductive paste according to claim 1, characterized in that: in step S10, the silver-containing solution is silver ammonia solution or Ag 2 O suspensions or Ag 2 CO 3 One of the suspensions, the reducing agent solution is one of glucose, formaldehyde, hydrazine hydrate, ascorbic acid, sodium erythorbate and p-diphenol.
3. The method for producing silver powder for conductive paste according to claim 1, characterized in that: in step S10, after the silver precipitate is generated, adding a dispersing agent, and uniformly mixing to form the wet silver powder.
4. The method for producing silver powder for conductive paste according to claim 3, characterized in that: the dispersant is one or more of polyvinylpyrrolidone, citrate, oleylamine and organic compound with methyl siloxy functional group.
5. The method for producing silver powder for conductive paste according to claim 3, characterized in that: the dosage of the dispersant is 0.01 to 5 percent of the silver content of the wet silver powder by mol percent.
6. The method for producing silver powder for conductive paste according to claim 1, characterized in that: in step S20: the dosage of the hydrophobic surfactant is 0.0001-20% of the silver content of the wet silver powder by mass percent.
7. The method for producing silver powder for conductive paste according to claim 1, characterized in that: in step S20, the mixture is stirred and treated for 1 to 3 minutes by a homogenizer at a speed of 1000 to 30000r/min to form an emulsion.
8. The method for producing silver powder for conductive paste according to claim 1, characterized in that: in step S30, the surface treating agent is cooled to the temperature of the wet silver powder and then added into the wet silver powder.
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