CN116809945B - Spherical silver powder and preparation method thereof - Google Patents
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- CN116809945B CN116809945B CN202310526429.3A CN202310526429A CN116809945B CN 116809945 B CN116809945 B CN 116809945B CN 202310526429 A CN202310526429 A CN 202310526429A CN 116809945 B CN116809945 B CN 116809945B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 42
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 38
- 239000002270 dispersing agent Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 45
- 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 42
- 238000006243 chemical reaction Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011668 ascorbic acid Substances 0.000 claims description 21
- 229960005070 ascorbic acid Drugs 0.000 claims description 21
- 235000010323 ascorbic acid Nutrition 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 45
- 239000004332 silver Substances 0.000 abstract description 45
- 230000006911 nucleation Effects 0.000 abstract description 19
- 238000010899 nucleation Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 239000002003 electrode paste Substances 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000001000 micrograph Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a spherical silver powder and a preparation method thereof, which specifically comprise the following steps: preparing silver nitrate solution; preparing a reducing agent solution; preparing a dispersant solution added with a neutralizing agent; and simultaneously dripping the silver nitrate solution and the reducing agent solution into the dispersing agent solution in a parallel flow mode, and separating, washing and drying to obtain the spheroidal silver powder. The grain diameter of the silver powder prepared by the method is 0.5-4.0 mu m, the tap density is more than 5.5g/cm 3, the grading regulation and control of the silver powder nucleation and growth process are realized, and the silver powder with larger grain diameter can be prepared; the seed crystal is not required to be additionally added, the equipment and the process are simple, the production cost and the period are saved, and the amplification and the industrialization application are easy; the prepared silver powder has good dispersibility, narrow size distribution, high activity and high tap density, and has wide application prospect in the fields of silver paste for solar cells and/or electrode paste for electronic components and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of new noble metal materials, and particularly relates to a spherical silver powder and a preparation method thereof.
Background
With the increasing exhaustion of non-renewable energy sources such as petroleum, coal and the like, the development of renewable energy sources is attracting more attention, and solar energy is becoming more abundant and main clean energy source, so how to improve the efficiency of photovoltaic power generation is becoming the focus of research. The photovoltaic silver paste is a main raw material for printing the solar cell panel due to the excellent rheological property and conductivity, and the silver powder is used as a main conductive phase in the silver paste of the solar cell, and the mass ratio of the silver powder in the silver paste is about 90%, so that the rheological property and the conductivity of the silver paste are decisive. With the increasing demands of the market for the photoelectric conversion efficiency of solar cells, the preparation of silver powder with excellent sintering activity and printing performance is the focus of attention.
At present, the preparation of silver powder mainly uses a liquid phase method, the method mainly uses silver salt or a complex thereof as an oxidant, and micron-sized silver powder is prepared by a redox method, wherein the process is a conversion process of silver ions to silver simple substances, and the nucleation and growth of silver particles are involved, so that reasonable control of the nucleation and growth rate of the silver particles is a main method for determining the performance of the silver powder. Generally, the size and morphology of silver powder are adjusted by controlling the reaction temperature/pH/reactant concentration/reactant species and the feeding rate to influence the reaction rate. However, the above method cannot accurately control the nucleation and growth processes of silver particles, and if the nucleation and growth processes of silver particles occur simultaneously in the oxidation-reduction process, the silver particles will have uneven size distribution, and the controllable maximum particle size is limited.
Patent CN115620958a discloses a method for preparing micron silver powder with controllable particle size, which controls the nucleation and growth process of silver particles by preparing different oxidation/reduction solutions and controlling the size of silver particles by the strength of the oxidation-reduction capability. The method for regulating and controlling the size of the silver particles is more severe, the size cannot be accurately controlled, and the stability is poor; when silver particles with different particle diameters are prepared, different organic solvents or dispersing agents are needed, and the method is not suitable for large-scale industrial production and has a great risk.
The patent CN102528069A discloses a silver powder preparation method, which comprises the steps of adding alkali, alkaline oxide, weak acid strong alkali salt, weak acid weak alkali salt and organic matters which can be ionized into weak acid weak alkali salt into a reducing agent to serve as a pH regulator, wherein the core is that H + is generated in the neutralization reaction process, and hard aggregation of silver particles is prevented when the silver particles reach the isoelectric point; because the reducing agent with various reducing strengths exists in the reducing solution, the reaction process is more severe, the stability of the reaction process is poor, and a large amount of H + generated in the severe reaction process can be neutralized by adding a large amount of neutralizing agent, so that the hard agglomeration of silver particles is weakened, the reaction process is further aggravated, the soft mass of the silver particles is caused, the burning loss of silver powder is increased due to the aggravation of the reaction process, and the market application of the silver powder is not facilitated.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention discloses a spherical silver powder and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the first aspect of the present invention provides a method for preparing spherical silver powder, comprising the steps of:
(1) Preparing silver nitrate solution, wherein the mass concentration of the silver nitrate is 10-25%;
(2) Preparing a reducing agent solution, wherein the mass concentration of the reducing agent is 5% -15%;
(3) Preparing a dispersing agent solution: uniformly mixing a neutralizing agent and a dispersing agent in deionized water, and dispersing the solution;
(4) Under the stirring condition, synchronously dripping the silver nitrate solution in the step (1) and the reducing agent solution in the step (2) into the dispersing agent solution in the step (3) in a parallel flow mode to obtain silver powder slurry;
(5) Separating silver powder in the step (4), washing and drying to obtain spherical-like silver powder;
Preferably, the pH of the silver nitrate solution is adjusted to 2-6;
preferably, the pH of the reducing agent solution is adjusted to 1-5;
preferably, the pH of the dispersant solution is adjusted to 2-5;
further, the reducing agent is one or more selected from glucose, sodium borohydride, formaldehyde, ascorbic acid, hydrazine hydrate, hydroquinone, alkanolamine or hydrogen peroxide;
further, the reducing agent is 20% -50% of the silver nitrate by mass;
further, the neutralizer in the step (3) is one or more selected from glucose, sodium borohydride, formaldehyde, ascorbic acid, hydrazine hydrate, alkanolamine, ammonia water, ammonium bicarbonate or sodium hydroxide;
Further, the dispersing agent in the step (3) is selected from one or more of polyethylene glycol, polyvinyl alcohol, gelatin, sodium dodecyl benzene sulfonate, tween 80, polyvinylpyrrolidone or gum arabic;
Further, the dispersing agent in the step (3) is 10% -30% of the silver nitrate by mass; the neutralizing agent is 1 to 35 percent of the mass of the silver nitrate;
further, the stirring speed in the step (4) is 100-400 r/min, and the reaction temperature is 10-30 ℃;
further, the dropping time of the nitrate solution in the step (4) is 1-20 min; the dropping time of the reducing agent solution in the step (4) is 1-20 min;
Further, the drying temperature in the step (5) is 50-90 ℃ and the drying time is 20-60 min;
Preferably, the drying temperature in the step (5) is 55-80 ℃ and the drying time is 30-50 min.
The second aspect of the present invention provides a spherical-like silver powder produced by the above production method, wherein the particle diameter of the silver powder is 0.5-4.0 μm, and the tap density is 5.5g/cm 3 or more.
The invention has the advantages that but is not limited to:
(1) According to the invention, a certain amount of neutralizer and design of reactivity of oxidant/reducer are added into the dispersing agent solution, so that the silver powder nucleation and the graded regulation and control of the growth process are realized, the nucleation reaction is mainly completed in the initial stage of the reaction, the newly generated silver simple substance can uniformly grow on silver crystal nucleus, silver powder with larger particle size can be prepared, and meanwhile, the silver powder has the characteristics of high sphericity and good dispersibility and uniformity;
(2) According to the invention, the activity and/or the type of the neutralizer are adjusted, the nucleation reaction intensity and the nucleation quantity of silver particles are controlled, the particle size of the silver particles can be effectively regulated and controlled, the precise regulation and control of the nucleation process are realized, the reaction process does not need to additionally add seed crystals, the equipment and the process are simple, the production cost is saved, the production period is short, and the amplification and the industrialized application are easy.
(3) The particle size of the spherical silver powder prepared by the method is 0.5-4.0 mu m, the burning loss is less than 0.6%, the tap density is more than 5.5g/cm 3, the prepared silver powder is good in dispersibility, narrow in size distribution, low in burning loss, high in activity and high in tap density, and the spherical silver powder has a wide application prospect in the fields of silver paste for solar cells and/or electrode paste for electronic components and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the spherical-like silver powder prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the spherical-like silver powder prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the spherical-like silver powder prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of the spherical-like silver powder prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of the spherical-like silver powder prepared in example 5 of the present invention;
FIG. 6 is a scanning electron microscope image of the spherical-like silver powder produced in example 6 of the present invention;
FIG. 7 is a scanning electron microscope image of the spherical-like silver powder produced in comparative example 1 of the present invention;
FIG. 8 is a scanning electron microscope image of the spherical-like silver powder produced in comparative example 2 of the present invention.
Detailed Description
The invention is illustrated but not limited by the following examples. Simple alternatives and modifications of the invention will be apparent to those skilled in the art and are within the scope of the invention as defined by the appended claims.
Example 1:
Preparation of spherical-like silver powder 1# with D50 of 3.6 μm under weak reaction intensity
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid was added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 3.6 mu m, the tap density is 6.50g/m 3, the scanning electron microscope image is shown in figure 1, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 1.
Example 2:
2# of spherical silver powder with D50 of 3.1 μm is prepared after the nucleation reaction intensity is increased
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid and 4g of sodium hydroxide were added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 3.1 mu m, the tap density is 6.50g/m 3, the scanning electron microscope image is shown in figure 2, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 2.
Example 3:
Preparation of spherical silver powder 3# with D50 of 2.9 μm after increasing nucleation intensity
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid and 20g of sodium hydroxide were added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 2.9 mu m, the tap density is 6.47g/m 3, the scanning electron microscope image is shown in figure 3, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 3.
Example 4:
preparation of spherical silver powder 4# with D50 of 2.3 μm after increasing nucleation intensity
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid and 32g of sodium hydroxide were added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 2.3 mu m, the tap density is 6.30g/m 3, the scanning electron microscope image is shown in figure 4, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 4.
Example 5:
Preparation of spherical silver powder 5# with D (50) of 1.4 μm after increasing the nucleation intensity
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid and 44g of sodium hydroxide were added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 1.4 mu m, the tap density is 6.18g/m 3, the scanning electron microscope image is shown in figure 5, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 5.
Example 6:
preparation of spherical silver powder 6# with D (50) of 0.9 μm after increasing the nucleation intensity
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 4.47%; 0.224Kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.06Kg of hydrazine hydrate was added thereto as a neutralizing agent.
The temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, the silver nitrate solution A and the reducing agent solution B are respectively added into the dispersing agent solution C in a parallel flow feeding mode, and the adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The actual particle diameter D50 of the silver powder is 0.9 mu m, the tap density is 6.1g/m 3, the scanning electron microscope image is shown in figure 6, and the silver powder has concentrated particle diameter distribution, uniform morphology and good dispersibility as shown in figure 6.
Comparative example 1:
Preparation of spheroid silver powder D1#)
Comparative example 1 silver powder was prepared in substantially the same manner as in example 1 except that a silver colloid was used in place of the neutralizing agent, specifically comprising the steps of:
weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.38kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66% and 0.48kg of ascorbic acid was added thereto as a neutralizing agent.
1.5G of silver colloid with the particle size of 40nm (the silver particle content is 6.0 per mill, and the silver particles have hydrophilic surfaces) is weighed, added into the dispersing agent solution C, uniformly stirred, the temperature of the reaction kettle is kept at 15 ℃, the stirring speed is 300r/min, and the silver nitrate solution A and the reducing agent solution B are respectively dropwise added into the dispersing agent solution C in a parallel flow feeding mode, wherein the dropwise adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The silver powder obtained has an actual particle diameter D50 of 2.0 μm, a tap density of 6.18g/m 3, a scanning electron microscope image shown in FIG. 7, and good dispersibility, but a wide particle diameter distribution range and low sphericity.
Comparative example 2:
Preparation of spheroid silver powder D2#, and method for preparing the same
Comparative example 2 the silver powder was prepared in substantially the same manner as in example 1 except that a silver colloid was used instead of the neutralizing agent completely, while increasing the amount of reducing agent added, comprising the steps of:
Weighing 1.60kg of silver nitrate solid to prepare 20% silver nitrate solution A; weighing 0.87kg of ascorbic acid as a reducing agent to prepare a reducing agent solution B with the mass concentration of 10%; 0.224kg of polyvinylpyrrolidone was weighed out to prepare a dispersant solution C having a mass concentration of 3.66%.
1.5G of silver colloid with the particle size of 40nm (the silver particle content is 6.0 per mill, and the silver particle has a hydrophilic surface) is weighed and added into the dispersing agent solution C, after the silver colloid is uniformly stirred, the temperature of a reaction kettle is kept at 15 ℃ and the stirring speed is 300r/min, and the silver nitrate solution A and the reducing agent solution B are respectively dropwise added into the dispersing agent solution C in a parallel flow feeding mode, wherein the dropwise adding time is 10min.
Washing with deionized water and ethanol, filtering, drying at 70deg.C for 30min, and sieving with 500 mesh sieve to obtain silver powder. The silver powder obtained had an actual particle diameter D50 of 2.1 μm and a tap density of 6.10g/m 3, and a scanning electron microscope image was shown in FIG. 8, and as shown in FIG. 8, the silver powder had a satisfactory dispersibility and dimensional uniformity, but a low sphericity and crystallinity.
Test example:
The comparison of the performance parameters of the silver powders obtained in each example and comparative example is shown in table 1:
TABLE 1
As can be seen from the results of table 1, in comparative example 1, after the silver colloid is added, in the initial stage of the reaction, on the one hand, the newly formed silver simple substance directly grows on the basis of the silver colloid, on the other hand, the newly formed silver simple substance self-nucleates, and the newly formed silver simple substance self-nucleates simultaneously, so that the size distribution of the silver powder is widened, agglomeration growth between large and small powders is easily formed, and the sphericity and the dispersibility are relatively reduced. The use of silver colloid in comparative example 2 completely replaces the neutralizing agent, avoids the problem of uneven size distribution caused by the simultaneous occurrence of nucleation and growth processes, but reduces the induction effect of the silver colloid with the increase of silver powder size and the decrease of the pH of the reaction solution in the reaction process, and the newly generated silver simple substance cannot be uniformly distributed on the silver core, so that the sphericity and crystallinity of the silver powder are rapidly deteriorated. In specific examples 1 to 6, the preparation of the spheroidal silver powder is sequentially controlled from the particle size range of 0.9 to 3.6 mu m, the obtained silver powder has uniform morphology, good dispersibility and higher tap density, the precise regulation and control of nucleation reaction are verified by adjusting the dosage, the type and the like of the neutralizer, and the graded regulation and control of the nucleation and growth process of the silver powder are realized under the reaction system.
The comparison of the performance parameters of the slurries prepared from the silver powders obtained in example 4 and comparative examples 1 to 2 is shown in Table 2:
TABLE 2
| Sample of | Fineness of | VIS | High height | Wide width of | Ratio of | Line resistor |
| Example silver powder 4# | 3 | 244/109/55 | 11.12 | 26.36 | 0.422 | 1.10 |
| Comparative example silver powder D1#) | 8 | 260/115/70 | 11.02 | 32.50 | 0.34 | 1.14 |
| Comparative example silver powder D2#) | 5 | 210/95/40 | 12.15 | 29.21 | 0.416 | 1.28 |
As shown in the results of table 2, since the silver powder d1# of comparative example has a certain aggregation, the fineness of the silver powder after pulping is larger, and a large amount of small powder exists at the same time, the line width is wider during printing, and the line collection is not facilitated; the comparative example silver powder d2# has a low sphericity, a relatively poor printability due to the high crystallinity of the silver powder, a lower viscosity than the silver powder d1# of example 4# and comparative example, and a high crystallinity results in a poor sintering activity and a large line resistance after printing. Example 4# has good plasticity (larger difference of test viscosity at different rotation speeds) and lower line resistance due to good dispersibility of silver powder, high sphericity and lower fineness of slurry after pulping; compared with the prior art, the spherical silver powder and the preparation method thereof have the advantages that the spherical silver powder has good dispersibility and sphericity, and meanwhile, the silver powder has high activity, and the spherical silver powder has wide application prospect in the field of photovoltaic silver paste.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements could be made by those skilled in the art without departing from the inventive concept, which falls within the scope of the present invention.
Claims (3)
1. The preparation method of the spherical silver powder is characterized by comprising the following steps of:
(1) Preparing a silver nitrate solution, wherein the mass concentration of the silver nitrate is 20%, and the weight of the silver nitrate is 1.60kg;
(2) Preparing a reducing agent solution, wherein the mass concentration of the reducing agent is 10%, the reducing agent is ascorbic acid, and the weight of the ascorbic acid is 0.38kg;
(3) Preparing a dispersing agent solution: weighing 0.224kg of polyvinylpyrrolidone, preparing into a dispersant solution with the mass concentration of 3.66%, adding 0.48kg of ascorbic acid into the dispersant solution as a neutralizing agent, or adding 0.48kg of ascorbic acid and 4g of sodium hydroxide into the dispersant solution as a neutralizing agent, or adding 0.48kg of ascorbic acid and 20g of sodium hydroxide into the dispersant solution as a neutralizing agent;
(4) Under the stirring condition, synchronously dripping the silver nitrate solution in the step (1) and the reducing agent solution in the step (2) into the dispersing agent solution in the step (3) in a parallel flow mode to obtain silver powder slurry;
(5) Separating silver powder in the step (4), washing and drying to obtain spherical-like silver powder;
The stirring speed in the step (4) is 300r/min, and the reaction temperature is 15 ℃;
the dropping time of the silver nitrate solution in the step (4) is 10min; the dropping time of the reducing agent solution in the step (4) is 10min.
2. The method according to claim 1, wherein the drying temperature in the step (5) is 50 to 90 ℃ and the drying time is 20 to 60min.
3. The spherical silver powder produced by the production method according to any one of claims 1 to 2, characterized in that the particle diameter of the silver powder is 3.6 μm and tap density is 6.5g/cm 3; or the grain diameter of the silver powder is 3.1 mu m, and the tap density is 6.5g/cm 3; or the grain diameter of the silver powder is 2.9 mu m, and the tap density is 6.47g/cm 3.
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