CN114042909A - Composite micro-nano silver powder and preparation method thereof - Google Patents
Composite micro-nano silver powder and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000000843 powder Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 102
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 239000013081 microcrystal Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 35
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920000084 Gum arabic Polymers 0.000 claims description 6
- 241000978776 Senegalia senegal Species 0.000 claims description 6
- 235000010489 acacia gum Nutrition 0.000 claims description 6
- 239000000205 acacia gum Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001000 micrograph Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- -1 shape Chemical compound 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- General Physics & Mathematics (AREA)
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Abstract
The invention belongs to the technical field of silver powder preparation methods, and particularly relates to composite micro-nano silver powder and a preparation method thereof; the silver powder comprises silver particles with two sizes, wherein the ratio of the diameters of the two silver particles is 2-15, and the specific surface area of the silver powder is not more than 5m2(g), tap density not less than 3g/cm3(ii) a Silver nitrate is used as a raw material, and a silver microcrystal suspension is prepared at a specified temperature by a liquid phase chemical reduction method; then preparing micron silver powder at a specified temperature by using a liquid-phase chemical reduction one-step method, adding the silver microcrystal suspension liquid in the growth process of the micron silver powder, and adjusting the size and the mixing mass ratio of the nano silver powder by controlling the addition amount distribution of the reducing agent before and after the silver microcrystal suspension liquid is added;the composite micro-nano silver powder has good sintering activity when being fired below 200 ℃.
Description
Technical Field
The invention belongs to the technical field of silver powder preparation methods, and particularly relates to composite micro-nano silver powder and a preparation method thereof.
Background
The silver powder is used in a large amount in the photovoltaic silver paste due to good conductivity, and the photovoltaic silver paste consists of a conductive phase, a binding phase and an organic carrier, wherein the conductive phase is a functional phase of the photovoltaic silver paste, namely the silver powder.
In the application field of the front silver paste of the crystalline silicon solar cell, the silver powder with the spherical shape is generally used, the mass percentage of the silver powder in the paste is higher than 90%, and the sintering activity and the screen printing performance of the front silver paste are directly influenced by the characteristics of the silver powder, such as shape, specific surface area, size distribution, crystallinity and the like. Particularly, in order to adapt to the sintering process of the crystalline silicon solar cell, higher requirements are put forward on the sintering activity of the silver powder, and along with the rapid development of novel efficient cell technology, the silver powder is required to have better sintering activity at lower temperature. Reducing the size of silver powder and preparing nano-sized silver powder is an effective way to solve the above problems. For example, in the existing patent-CN 111992734A, a liquid phase reduction method is used for preparing the nano-silver paste, but the preparation temperature is too high, the product is difficult to completely dry and separate, and the method is not beneficial to industrial application; the microcrystalline silver powder with the nano-silver surface structure prepared in the prior patent CN111922356A has the advantages that the generation of nano-silver is controlled and the microcrystalline silver surface coating is realized by adding a large amount of surfactant in the reaction process, the process is complex, and the pH of a reactant is adjusted by using concentrated nitric acid, so that high safety risk exists.
Disclosure of Invention
In order to overcome the problems, the invention provides composite micro-nano silver powder and a preparation method thereof, and the preparation method is a preparation method for uniformly mixing silver powder with nano size and micron size, which has simple process, high efficiency and easy realization of industrial amplification, wherein the sizes of the nano silver powder and the micron silver powder are controllable, and the composite silver powder with a series of sizes and uniform mixing is prepared by finely adjusting reaction conditions; the composite micro-nano silver powder has good sintering activity when being fired below 200 ℃.
The composite micro-nano silver powder comprises silver particles with two sizes, wherein the ratio of the diameters of the two silver particles is 2-15, and the specific surface area of the silver powder is not more than 5m2(g), tap density not less than 3g/cm3。
The invention also provides a preparation method of the composite micro-nano silver powder, which comprises the following steps:
step one, taking 500ml of reducing agent solution 2 and 500ml of dispersing agent solution, adding the reducing agent solution and the dispersing agent solution into the silver nitrate solution 2 together, and stirring for 5min in a stirrer with the constant temperature of 25 ℃ and the rotating speed of 300r/min to generate microcrystal suspension;
pouring the silver nitrate solution 1 with the volume of V into a reaction kettle filled with 5L of reducing agent solution 1, stirring at constant temperature for 30min, and reducing to generate silver powder suspension;
step three, pouring the microcrystalline suspension obtained in the step one into the reaction kettle in the step two, simultaneously pouring the silver nitrate solution 1 with the volume of 5-V into the reaction kettle, stirring at constant temperature for 30min, and completing a reduction reaction to obtain a composite micro-nano silver powder suspension;
and step four, carrying out solid-liquid separation, washing and drying on the reactant prepared in the step three, namely the composite micro-nano silver powder suspension to obtain the composite micro-nano silver powder with two particle size distributions.
And the volume V of the silver nitrate solution 1 used in the second step is L, the minimum value of V is 0.1, namely the sum of the volume V and the addition amount of the silver nitrate solution 1 in the third step is 5L.
And adjusting the ratio of the diameters of the two silver particles in the finally obtained composite micro-nano silver powder by adjusting the volume of the silver nitrate solution 1 participating in the reaction in the step two and the volume of the silver nitrate solution 1 participating in the reaction in the step three, wherein the larger the volume V of the silver nitrate solution 1 participating in the reaction in the step two is, the larger the ratio of the diameters of the two silver particles is finally obtained.
And step two, reacting at a constant temperature of 25 ℃ in a reaction kettle, and continuously stirring for 30min by using a stirrer with the rotating speed of 300 r/min.
The silver nitrate solution 1 is a silver nitrate solution with the concentration of 100g/L, and the preparation method comprises the following steps: prepared in a kettle with an effective volume of 10L, and stirred and dissolved at a constant temperature of 25 ℃ by using 500g of silver nitrate and 5L of pure water.
The reducing agent solution 1 is an ascorbic acid solution with the concentration of 172g/L, and the preparation method comprises the following steps: the mixture was placed in a 10-liter pot having an effective volume, 960g of ascorbic acid and 5 liters of pure water were used, and 146g of gum arabic was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
The preparation method of the silver nitrate solution 2 comprises the following steps: 1L of purified water was added to a 2L beaker, and 0.34g of silver nitrate was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
The preparation method of the reducing agent solution 2 comprises the following steps: 500ml of pure water was added to a 1L beaker, and 0.1g of sodium borohydride was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
The preparation method of the dispersant solution comprises the following steps: 500ml of purified water was added to a 1L beaker, and 0.15g of gum arabic was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
The invention has the beneficial effects that:
the sizes of the nano silver powder and the micron silver powder are controllable, and the composite silver powder with a series of sizes and uniform mixing is prepared by finely adjusting reaction conditions; the composite micro-nano silver powder has good sintering activity when being fired below 200 ℃.
Drawings
Fig. 1 is a scanning electron microscope image of the composite micro-nano silver powder prepared in embodiment 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the composite micro-nano silver powder prepared in the embodiment 1 of the present invention sintered at 200 ℃ for 20 min.
Fig. 3 is a scanning electron microscope image of the composite micro-nano silver powder prepared in embodiment 2 of the invention.
FIG. 4 is a scanning electron microscope image of the composite micro-nano silver powder prepared in embodiment 2 of the present invention sintered at 200 ℃ for 20 min.
Fig. 5 is a scanning electron microscope image of the composite micro-nano silver powder prepared in embodiment 3 of the invention.
FIG. 6 is a scanning electron microscope image of the composite micro-nano silver powder prepared in embodiment 3 of the present invention sintered at 200 ℃ for 20 min.
FIG. 7 is a scanning electron micrograph of a silver powder having a diameter of one micrometer prepared in comparative example 1 of the present invention.
FIG. 8 is a scanning electron microscope photograph of the silver powder prepared in comparative example 1 of the present invention sintered at 200 ℃ for 20 min.
Detailed Description
The invention provides composite micro-nano silver powderThe composite micro-nano silver powder consists of two silver particles with size distribution, the diameter D (50) ratio of the two silver particles is 2-15, the mass ratio of the two silver particles is 8-3000, and the specific surface area of the silver powder is not more than 5m2(g), tap density not less than 3g/cm3。
When the mass ratio of the two silver particles of the composite micro-nano silver powder is 2, the sintering temperature can be reduced to 200 ℃.
The invention also provides a preparation method of the composite micro-nano silver powder, which comprises the following steps:
step one, taking 500ml of reducing agent solution 2 and 500ml of dispersing agent solution, adding into the silver nitrate solution 2 together within 5 seconds, and stirring for 5min in a stirrer with the constant temperature of 25 ℃ and the rotating speed of 300r/min to generate a microcrystal suspension;
pouring the silver nitrate solution 1 with the volume V into a reaction kettle filled with 5L of reducing agent solution 1 within 5 seconds, stirring at constant temperature for 30min, and reducing to generate silver powder suspension;
step three, pouring the microcrystalline suspension obtained in the step one into the reaction kettle in the step two, simultaneously pouring the silver nitrate solution 1 with the volume of 5-V into the reaction kettle, stirring at constant temperature for 30min, and completing a reduction reaction to obtain a composite micro-nano silver powder suspension;
and step four, carrying out solid-liquid separation, washing and drying on the reactant prepared in the step three, namely the composite micro-nano silver powder suspension to obtain the composite micro-nano silver powder with two particle size distributions.
And the volume V of the silver nitrate solution 1 used in the second step is L, the minimum value of V is 0.1, namely the sum of the volume V and the addition amount of the silver nitrate solution 1 in the third step is 5L.
And adjusting the ratio of the diameters of the two silver particles in the finally obtained composite micro-nano silver powder by adjusting the volume of the silver nitrate solution 1 participating in the reaction in the step two and the volume of the silver nitrate solution 1 participating in the reaction in the step three, wherein the larger the volume V of the silver nitrate solution 1 participating in the reaction in the step two is, the larger the ratio of the diameters of the two silver particles is finally obtained.
And step two, reacting at a constant temperature of 25 ℃ in a reaction kettle, and continuously stirring for 30min by using a stirrer with the rotating speed of 300 r/min.
Silver nitrate is used as a raw material, and a silver microcrystal suspension is prepared at a specified temperature by a liquid phase chemical reduction method; and then preparing the micron silver powder at a specified temperature by using a liquid-phase chemical reduction one-step method, adding the silver microcrystal suspension in the growth process of the micron silver powder, and regulating the size and the mixing mass ratio of the nano silver powder by controlling the addition amount distribution of the reducing agent before and after the silver microcrystal suspension is added.
The present invention is described in detail with reference to specific examples, which are provided to facilitate the understanding of the technical solutions of the present invention by those skilled in the art, and the implementation or use of the present invention is not limited by the description of the present invention.
Solution preparation:
silver nitrate solution 1: preparing silver nitrate solution with the concentration of 100g/L in a kettle with the effective volume of 10L, using 500g of silver nitrate and 5L of ultrapure water, and stirring and dissolving at the constant temperature of 25 ℃.
Reducing agent solution 1: an ascorbic acid solution having a concentration of 172g/L was prepared in a 10-L pot having an effective volume, 960g of ascorbic acid and 5L of ultrapure water were used, 146g of gum arabic was added thereto, and the mixture was dissolved by stirring at a constant temperature of 25 ℃.
Silver nitrate solution 2: 1L of ultrapure water was added to a 2L beaker, and 0.34g of silver nitrate was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
Reducing agent solution 2: 500ml of ultrapure water was added to a 1L beaker, and 0.1g of sodium borohydride was added thereto, and dissolved with stirring at a constant temperature of 25 ℃.
Dispersant solution: 500ml of ultrapure water was added to a 1L beaker, and 0.15g of gum arabic was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
Example 1
Preparing composite micro-nano silver particles:
and adding 500ml of reducing agent solution 2 and 500ml of dispersing agent solution into the silver nitrate solution 2 within 3 seconds, and stirring at the constant temperature of 25 ℃ and the rotating speed of 300r/min for 5min to generate a microcrystal suspension.
5L of reducing agent solution 1 is poured into a reaction kettle, 0.1L of silver nitrate solution 1 is added into the reaction kettle within 5 seconds, the reaction process is carried out at the constant temperature of 25 ℃, the stirring is continuously carried out for 30min at the rotating speed of 300r/min, and the silver powder suspension is generated by reduction.
Pouring the microcrystalline suspension into a reaction kettle filled with the silver powder suspension, simultaneously pouring the rest 4.9L of silver nitrate solution 1 into the reaction kettle, stirring at constant temperature for 30min, and completing the reduction reaction to obtain the composite micro-nano silver powder suspension.
And (3) carrying out solid-liquid separation, washing and drying on the reactant to obtain the composite micro-nano silver powder with two particle size distributions, wherein the ratio of the particle size D (50) of silver particles with the two particle size distributions is 2.
The composite micro-nano silver powder prepared by the method is shown in figure 1
The composite micro-nano silver powder prepared in the embodiment is subjected to appearance analysis by a scanning electron microscope, and the result is shown in fig. 1. As can be seen from the figure, the prepared composite micro-nano silver powder is spherical in shape and good in dispersity, and the particle sizes of the two sizes are distributed and uniformly mixed together.
Taking 3g of the composite micro-nano silver powder prepared by the method, loosely paving the composite micro-nano silver powder on a glass surface dish, heating the oven to 200 ℃, putting the composite micro-nano silver powder into the oven, timing for 20min after the temperature is stable, and taking out the silver powder.
The composite micro-nano silver powder prepared by the method is shown in figure 2
The microstructure of the sintered composite micro-nano silver powder in the embodiment is observed by a scanning electron microscope, and the result is shown in fig. 2. As can be seen from the figure, the silver powder particles have all melted to form bridges connecting adjacent silver powder particles to form good conductive paths.
Example 2
Preparation of composite micro-nano silver particles
And adding 500ml of reducing agent solution 2 and 500ml of dispersing agent solution into the silver nitrate solution 2 within 5 seconds, and stirring at the constant temperature of 25 ℃ and the rotating speed of 300r/min for 5min to generate a microcrystal suspension.
5L of reducing agent solution 1 is poured into a reaction kettle, 1.5L of silver nitrate solution 1 is added into the reaction kettle filled with 5L of reducing agent solution 1 within 5 seconds, the reaction process is kept at the constant temperature of 25 ℃, the rotating speed is 300r/min, the stirring is continuously carried out for 30min, and the silver powder suspension is generated through reduction.
And pouring the microcrystalline suspension into the reaction kettle filled with the silver powder suspension in the second step, pouring the rest 3.5L of silver nitrate solution 1 into the reaction kettle, stirring at constant temperature for 30min, and completing the reduction reaction to obtain the composite micro-nano silver powder suspension.
And (3) carrying out solid-liquid separation, washing and drying on the reactant to obtain the composite micro-nano silver powder with two particle size distributions, wherein the ratio of the particle size D (50) of silver particles with the two particle size distributions is 5.
The composite micro-nano silver powder prepared by the method is shown in figure 3
Taking 3g of the composite micro-nano silver powder prepared by the method, loosely paving the composite micro-nano silver powder on a glass surface dish, heating the oven to 200 ℃, putting the composite micro-nano silver powder into the oven, timing for 20min after the temperature is stable, and taking out the silver powder.
The composite micro-nano silver powder prepared by the method is shown in figure 4
The microstructure of the sintered composite micro-nano silver powder in the embodiment is observed by a scanning electron microscope, and the result is shown in fig. 4. As can be seen from the figure, the powder contact part is partially melted to form a connected reticular conductive network structure, and at the moment, the silver paste used as the conductive filler can also obtain better conductive performance.
Example 3
Preparation of composite micro-nano silver particles
And adding 500ml of reducing agent solution 2 and 500ml of dispersing agent solution into the silver nitrate solution 2 within 3 seconds, and stirring at the constant temperature of 25 ℃ and the rotating speed of 300r/min for 5min to generate a microcrystal suspension.
Pouring 5L of reducing agent solution 1 into a reaction kettle, adding 4.9L of silver nitrate solution 1 into the reaction kettle filled with 5L of reducing agent solution 1 within 5 seconds, keeping the temperature of 25 ℃ in the reaction process, and continuously stirring at the rotating speed of 300r/min for 30min to reduce and generate silver powder suspension.
And (4) pouring the microcrystalline suspension into the reaction kettle filled with the silver powder suspension in the second step, pouring the rest 0.1L of silver nitrate solution 1 into the reaction kettle, stirring at constant temperature for 30min, and completing the reduction reaction to obtain the composite micro-nano silver powder suspension.
And (3) carrying out solid-liquid separation, washing and drying on the reactant to obtain the composite micro-nano silver powder with two particle size distributions, wherein the ratio of the particle size D (50) of silver particles with the two particle size distributions is 15.
The composite micro-nano silver powder prepared by the method is shown in figure 5
The composite micro-nano silver powder prepared in the embodiment is subjected to appearance analysis by a scanning electron microscope, and the result is shown in fig. 5.
Taking 3g of the composite micro-nano silver powder prepared by the method, loosely paving the composite micro-nano silver powder on a glass surface dish, heating the oven to 200 ℃, putting the composite micro-nano silver powder into the oven, timing for 20min after the temperature is stable, and taking out the silver powder.
The composite micro-nano silver powder prepared by the method is shown in figure 6.
Comparative example 1
And adding 5L of silver nitrate solution 1 into 5L of reducing agent solution 1 within 5 seconds, keeping the temperature of 25 ℃ in the reaction process, continuously stirring at the rotating speed of 300r/min, and reducing to generate the micron silver powder suspension.
And carrying out solid-liquid separation, washing and drying on the reactant to obtain the micron silver powder with single particle size.
The composite micro-nano silver powder prepared by the method is shown in figure 7
Taking 3g of the composite micro-nano silver powder prepared by the method, loosely paving the composite micro-nano silver powder on a glass surface dish, heating the oven to 200 ℃, putting the composite micro-nano silver powder into the oven, timing for 20min after the temperature is stable, and taking out the silver powder.
The composite micro-nano silver powder prepared by the method is shown in figure 8
And observing the microstructure of the sintered composite micro-nano silver powder in the embodiment by adopting a scanning electron microscope. As can be seen from fig. 8, the powder particles were dispersed and no sintering and melting occurred.
The above description is only an example and a comparative example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The composite micro-nano silver powder is characterized by comprising silver particles with two sizes, wherein the ratio of the diameters of the two silver particles is 2-15, and the specific surface area of the silver powder is not more than 5m2(g), tap density not less than 3g/cm3。
2. A preparation method of composite micro-nano silver powder is characterized by comprising the following steps:
step one, taking 500ml of reducing agent solution 2 and 500ml of dispersing agent solution, adding the reducing agent solution and the dispersing agent solution into the silver nitrate solution 2 together, and stirring for 5min in a stirrer with the constant temperature of 25 ℃ and the rotating speed of 300r/min to generate microcrystal suspension;
pouring the silver nitrate solution 1 with the volume of V into a reaction kettle filled with 5L of reducing agent solution 1, stirring at constant temperature for 30min, and reducing to generate silver powder suspension;
step three, pouring the microcrystalline suspension obtained in the step one into the reaction kettle in the step two, simultaneously pouring the silver nitrate solution 1 with the volume of 5-V into the reaction kettle, stirring at constant temperature for 30min, and completing a reduction reaction to obtain a composite micro-nano silver powder suspension;
and step four, carrying out solid-liquid separation, washing and drying on the reactant prepared in the step three, namely the composite micro-nano silver powder suspension to obtain the composite micro-nano silver powder with two particle size distributions.
3. The method for preparing composite micro-nano silver powder according to claim 2, wherein the volume of the silver nitrate solution 1 used in the second step is V, the unit of the volume V is L, and the minimum value of V is 0.1, i.e. the sum of the volume V and the addition amount of the silver nitrate solution 1 in the third step is 5L.
4. The method for preparing composite micro-nano silver powder according to claim 3, wherein the ratio of the diameters of the two silver particles in the finally obtained composite micro-nano silver powder is adjusted by adjusting the volume of the silver nitrate solution 1 participating in the reaction in the second step and the volume of the silver nitrate solution 1 participating in the reaction in the third step, wherein the larger the volume V of the silver nitrate solution 1 participating in the reaction in the second step is, the larger the ratio of the diameters of the two silver particles is finally obtained.
5. The method for preparing composite micro-nano silver powder according to claim 4, wherein the second step is carried out in a reaction kettle at a constant temperature of 25 ℃ while stirring for 30min by using a stirrer with a rotation speed of 300 r/min.
6. The method for preparing composite micro-nano silver powder according to claim 2, wherein the silver nitrate solution 1 is a silver nitrate solution with a concentration of 100g/L, and the preparation method comprises the following steps: prepared in a kettle with an effective volume of 10L, and stirred and dissolved at a constant temperature of 25 ℃ by using 500g of silver nitrate and 5L of pure water.
7. The method for preparing composite micro-nano silver powder according to claim 2, wherein the reducing agent solution 1 is an ascorbic acid solution with a concentration of 172g/L, and the preparation method comprises the following steps: the mixture was placed in a 10-liter pot having an effective volume, 960g of ascorbic acid and 5 liters of pure water were used, and 146g of gum arabic was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
8. The method for preparing composite micro-nano silver powder according to claim 2, wherein the preparation method of the silver nitrate solution 2 comprises the following steps: 1L of purified water was added to a 2L beaker, and 0.34g of silver nitrate was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
9. The method for preparing composite micro-nano silver powder according to claim 2, wherein the method for preparing the reducing agent solution 2 comprises the following steps: 500ml of pure water was added to a 1L beaker, and 0.1g of sodium borohydride was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
10. The method for preparing composite micro-nano silver powder according to claim 2, wherein the preparation method of the dispersant solution comprises the following steps: 500ml of purified water was added to a 1L beaker, and 0.15g of gum arabic was added thereto and dissolved with stirring at a constant temperature of 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111282194.5A CN114042909B (en) | 2021-11-01 | 2021-11-01 | Composite micro-nano silver powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111282194.5A CN114042909B (en) | 2021-11-01 | 2021-11-01 | Composite micro-nano silver powder and preparation method thereof |
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| CN116713475A (en) * | 2023-05-30 | 2023-09-08 | 上海银波生物科技有限公司 | Method for preparing silver powder with high specific surface area for TOPCO solar cell |
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