CN116237533A - Silver powder for PERC battery front silver paste and preparation method and application thereof - Google Patents
Silver powder for PERC battery front silver paste and preparation method and application thereof Download PDFInfo
- Publication number
- CN116237533A CN116237533A CN202310006328.3A CN202310006328A CN116237533A CN 116237533 A CN116237533 A CN 116237533A CN 202310006328 A CN202310006328 A CN 202310006328A CN 116237533 A CN116237533 A CN 116237533A
- Authority
- CN
- China
- Prior art keywords
- silver powder
- solution
- silver
- mixing
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 20
- 239000004332 silver Substances 0.000 title claims abstract description 20
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract description 18
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract description 18
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 50
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000010902 jet-milling Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 13
- 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 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 241000220479 Acacia Species 0.000 claims description 5
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 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 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 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 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229920000847 nonoxynol Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 244000215068 Acacia senegal Species 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to silver powder for PERC battery front silver paste, a preparation method and application thereof, and relates to the technical field of silver powder manufacturing. The preparation method comprises the following steps: preparing each reaction solution; wherein the concentration of the silver nitrate solution is 1.8-2.4mol/L; mixing a silver nitrate solution with a first pH regulating solution to obtain a first mixed solution; mixing the reduced dispersion liquid with a second pH regulating liquid to obtain a second mixed liquid; adding the first mixed solution into the second mixed solution at a preset speed, adding the surface modifier solution, mixing and stirring to obtain a solid-liquid mixture; centrifuging and washing the solid-liquid mixture to obtain a filter cake; drying and dispersing silver powder: and (3) drying the filter cake, dispersing and stirring, and carrying out jet milling to obtain silver powder. The preparation method adopts the silver nitrate with higher concentration and the reducing agent for reaction, so that the waste water yield is small, the preparation process is simple and controllable, and the prepared silver powder has high sphericity, good dispersibility and high tap density.
Description
Technical Field
The invention relates to the technical field of silver powder manufacturing, in particular to silver powder for PERC battery front silver paste, and a preparation method and application thereof.
Background
Silver powder is a major raw material in the optoelectronic and electronic industries, where it serves the key functions of electrodes and conductive tracks, mainly due to its excellent conductivity. With the rapid development of photovoltaic and electronic industries, the silver powder market also gets a great progress. In the field of conductive silver powder, the silver powder with the particle size of 0.5-3 mu m is mainly prepared by a chemical reduction method, and the chemical reduction method has the advantages of controllable conditions, small equipment investment, simple operation, low cost and the like, and is widely developed.
In the use process of silver powder, the performances such as particle size, morphology, dispersibility and the like of the silver powder are key parameters of the silver powder, particularly in the field of photovoltaic slurry, the performances of the silver powder have great correlation on printing of the slurry, and further the photoelectric conversion efficiency, the welding performance and the cost control are reflected. For example, in the photovoltaic front side silver paste, in order to increase the photoelectric conversion efficiency, it is necessary to increase the light energy absorption area and reduce the aspect ratio of the printed wiring, and thus, the printed wiring becomes narrower. Among them, silver powder having a paste ratio of about 90% is required to have high dispersibility, high bulk density, narrow particle size distribution and a certain wettability on the surface. In order to meet the requirement, the preparation process of most silver powder is complex, the preparation efficiency is low, the cost is high, the industrialized development is severely restricted to a certain extent, and in order to control the reaction process and the performance parameters of the silver powder in the silver powder preparation process more easily, the concentrations of silver nitrate and reducing agent are generally low, which also results in a large amount of wastewater in the silver powder preparation process.
Disclosure of Invention
Aiming at the technical problems, the invention provides the preparation method of the silver powder for the silver paste on the front surface of the PERC battery, which adopts the silver nitrate with higher concentration to react with the reducing agent, so that the waste water yield is small, the preparation process is simple and controllable, and the prepared silver powder has high sphericity, good dispersibility and high tap density.
The invention provides a preparation method of silver powder for PERC battery front silver paste, which comprises the following steps:
preparing a solution: preparing a silver nitrate solution, a reduction dispersion liquid, a first pH regulating liquid, a second pH regulating liquid and a surface modifier solution; the concentration of the silver nitrate solution is 1.8-2.4mol/L;
mixing: mixing the silver nitrate solution with the first pH regulating solution to obtain a first mixed solution; mixing the reduction dispersion liquid with the second pH regulating liquid to obtain a second mixed liquid; adding the first mixed solution into the second mixed solution at a preset speed, adding the surface modifier solution, and mixing and stirring to obtain a solid-liquid mixture;
washing silver powder: centrifuging and washing the solid-liquid mixture to obtain a filter cake;
drying and dispersing silver powder: and drying the filter cake, dispersing and stirring, and jet milling to obtain silver powder.
In order to reduce the generation of wastewater in the preparation process, the inventor adopts a silver nitrate solution with higher concentration as a reaction raw material, and simultaneously constructs the preparation method, and the addition amount of each reaction material is controlled to be matched with the reaction condition and the post-treatment process, so that the silver powder with better performance parameters and meeting the use requirement of PERC front silver paste can be prepared on the premise of using the silver nitrate solution with higher concentration.
In one embodiment, in the step of preparing the solution, the concentration of the silver nitrate solution is 1.96mol/L;
the solute of the reduction dispersion liquid comprises a reducing agent and a dispersing agent, and the concentration of the reducing agent in the reduction dispersion liquid is 0.8-1.5mol/L; the weight ratio of the reducing agent to the dispersing agent is (45-98): 1.
because the silver nitrate solution with higher concentration is used as the reaction raw material, the concentration of the reducing agent is correspondingly increased.
In one embodiment, the reducing agent comprises at least 1 of the following materials: hydroquinone, formaldehyde, glucose, ascorbic acid, glyceraldehyde, or a polyol;
the dispersing agent comprises at least 1 of the following raw materials: acacia, gelatin, polyethylene glycol, polyvinyl alcohol, or polyvinylpyrrolidone.
In one embodiment, the first pH adjusting liquid comprises a pH adjusting agent with a concentration of 4-8mol/L, and the second pH adjusting liquid comprises a pH adjusting agent with a concentration of 1-4 mol/L;
the pH adjuster is independently optionally selected from: sodium hydroxide, ammonia, nitric acid, potassium hydroxide, or sodium dihydrogen phosphate.
In one embodiment, the surface modifier solution includes at least 1 of the following surface modifiers: alkylphenol ethoxylates, fatty alcohol ethoxylates, nonylphenol ethoxylates, unsaturated fatty acids, saturated fatty acids, or sodium dodecylbenzenesulfonate.
In one embodiment, the surface modifier comprises alkylphenol ethoxylates and fatty alcohol ethoxylates, wherein the weight ratio of the alkylphenol ethoxylates to the fatty alcohol ethoxylates is 1:1.
In one embodiment, in the mixing step, the preset speed is 0.6-1.0L/min, the speed of mixing and stirring is 350-450rpm, the temperature of mixing and stirring is 35-45 ℃, and the time of mixing and stirring is 0.3-0.7h;
in the silver powder washing step, the conductivity of the filter cake is less than or equal to 10us/cm.
In one embodiment, in the step of drying and dispersing silver powder, the temperature of drying is 55-65 ℃, the time of drying is 10-14 hours, the speed of dispersing and stirring is 1800-2200rpm, the time of dispersing and stirring is 8-12 minutes, the feeding air flow pressure of air flow crushing is 0.35-0.45MPa, the dispersing air flow pressure of air flow crushing is 0.6-1.0MPa, and the feeding speed of air flow crushing is 8-12kg/h.
The invention also provides the silver powder obtained by the preparation method, wherein the silver powder is spherical silver powder, and the real particle size of the silver powder is 0.5-3 mu m.
The actual particle size is the particle size detected by a scanning electron microscope, the conventional particle size is the particle size obtained by testing by a wet or dry laser particle sizer, and light diffraction can be generated due to different testing principles of the laser particle sizer, so that the detected particle size is larger, and the particle size detected by the laser particle sizer has deviation. The silver powder with the real particle size is prepared by a liquid phase reduction method, and the liquid phase reduction method is difficult to avoid the formation of oxygen bridges due to the fact that the silver powder belongs to a solution system, and the smaller the particle size of the powder to be prepared is, the more easily agglomerates are generated, so that the silver powder with the real particle size is prepared on the basis of the liquid phase reduction method, and the higher difficulty is achieved.
The invention also provides front silver paste for PERC batteries, which is prepared from the silver powder.
The silver powder not only has the real particle size of 0.5-3 mu m, but also has the specific surface area and tap density which meet the requirements for preparing PERC battery front silver paste (the silver powder for preparing PERC battery front silver paste has the specific surface area of 0.4-0.6 and tap density of 5.5-6.5).
Compared with the prior art, the invention has the following beneficial effects:
the silver powder for the PERC battery front silver paste and the preparation method and application thereof, disclosed by the invention, have the advantages that the silver nitrate with higher concentration is adopted for reaction with the reducing agent, the waste water yield is small, the preparation process is simple and controllable, and certain industrialization capacity is realized. The silver powder is spherical silver powder with high sphericity, high dispersivity, high bulk density and narrow particle size distribution, and the real particle size range is 0.5-3 mu m.
Drawings
FIG. 1 is a flow chart showing the preparation of silver powder in example 1;
FIG. 2 is an electron microscopic view of the silver powder of example 1;
FIG. 3 is an electron microscopic view of the silver powder of example 2;
FIG. 4 is an electron microscopic view of the silver powder of comparative example 1;
FIG. 5 is an electron microscopic view of the silver powder of comparative example 2;
FIG. 6 is an electron microscopic view of the silver powder of comparative example 3.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Definition:
the PERC battery provided by the invention comprises: and forming a passivation layer on the back surface of the solar cell, so as to improve the conversion efficiency of the cell.
Front silver paste: refers to silver paste for the front surface of a photovoltaic panel, and the main function is to collect current.
True particle size: refers to the particle size detected by a scanning electron microscope.
The source is as follows:
the reagents, materials and equipment used in the examples are all commercially available sources unless otherwise specified; the test methods are conventional in the art unless otherwise specified.
Example 1
Silver powder for use in PERC cell front silver paste.
1. The preparation method of the silver powder specifically comprises the following steps of:
1. preparing a first pH regulating solution and a second pH regulating solution.
0.02kg of industrial grade nitric acid (65% nitric acid solution by mass) and deionized water are prepared according to the mass ratio of 1:1 to obtain first pH regulating solution, wherein the concentration of the first pH regulating solution is 6.0018mol/L.
Preparing 0.5kg of industrial grade ammonia water (ammonia water solution with the mass percentage of 25 percent) and deionized water according to the mass ratio of 1:4 to obtain second pH regulating solution, wherein the concentration of the second pH regulating solution is 2.8788mol/L.
2. Preparing silver nitrate solution.
1kg of silver nitrate crystals were weighed and dissolved in 3L of deionized water to prepare a silver nitrate solution having a concentration of 1.96mol/L and 0.02kg of a first pH adjusting solution was added thereto, and the solution was stirred to obtain a first mixed solution, and the temperature was maintained at 40 ℃.
3. Preparing a reduction dispersion.
0.58kg of ascorbic acid powder is weighed and dissolved in 4L of deionized water, the concentration of the ascorbic acid is 0.8233mol/L, 0.06kg of acacia water solution is weighed, the mass fraction of the acacia is 10%, the acacia water solution is added into the water solution containing the ascorbic acid, the mixture is stirred and mixed, then 0.5kg of second pH regulating solution is added, a second mixed solution is obtained, and the temperature is kept at 40 ℃.
4. Preparing a surface modifier solution.
1.6g of alkylphenol ethoxylate-21 was weighed, 1.6g of fatty alcohol ethoxylate (AEO-7) was weighed and dissolved in 0.1kg of deionized water, maintaining a temperature of 55 ℃.
5. Mixing.
And (3) transferring the second mixed solution to a 20L glass reaction kettle, starting stirring speed to 400rpm, keeping the temperature of a heating system of the reaction kettle at 40 ℃, adding the first mixed solution into the reaction kettle at a speed of 0.8L/min through a peristaltic pump, immediately adding the surface modifier solution after the liquid adding is finished, and stirring for 0.5h to obtain a solid-liquid mixture.
6. Washing silver powder.
And (3) carrying out solid-liquid separation on the solid-liquid mixture in a centrifugal way, fully stirring and washing a filter cake by using deionized water, carrying out centrifugal treatment, repeatedly washing until the conductivity is less than or equal to 10us/cm, and carrying out centrifugation to obtain the filter cake.
7. Drying and dispersing silver powder:
and (3) drying the filter cake in a vacuum drying oven at 60 ℃ for 12 hours, taking out, stirring for 10 minutes at a speed of 2000rpm by using a continuous stirrer, and adding the obtained pretreated silver powder product into a jet mill for crushing treatment, wherein the jet pressure of a feed inlet is 0.4MPa, the jet pressure of a dispersing disc is 0.8MPa, and the feed speed is 10kg/h, thus obtaining the final silver powder product.
2. Silver powder was detected.
The electron microscopic image of the silver powder prepared in this example is spherical silver powder, as shown in fig. 2.
The specific surface area was measured by nitrogen adsorption: 0.45m 2 /g; tap density is 6.1g/ml;
the particle size distribution is tested by adopting a Markov 3000, absolute ethyl alcohol is used as a solvent, ultrasonic dispersion is carried out for 10min, and a test result D10 is obtained: 1.07 μm, D50:2.06 μm, D90:4.09 μm, D100:7.62 μm;
the burning loss rate is calculated to be 0.82% by a GB/T1773-2008 flake silver powder burning loss calculation method.
The silver powder has good hydrophobicity and is suitable for silver powder for solar PERC battery front silver paste.
Example 2
Silver powder for use in PERC cell front silver paste.
1. The preparation method of the silver powder specifically comprises the following steps:
the difference from example 1 is that in the step of preparing a reduced dispersion, 0.12kg of an aqueous solution of gum arabic was weighed, and the remaining raw materials and the production method were the same as in example 1.
2. Silver powder was detected.
The electron microscopic image of the silver powder prepared in this example is spherical silver powder, as shown in fig. 3.
The specific surface area was measured by nitrogen adsorption: 0.45m 2 /g; tap density is 6.0g/ml;
the particle size distribution is tested by adopting a Markov 3000, absolute ethyl alcohol is used as a solvent, ultrasonic dispersion is carried out for 10min, and a test result D10 is obtained: 0.86 μm, D50:1.49 μm, D90:2.68 μm, D100:5.85 μm;
the burning loss rate is calculated to be 0.79% by a GB/T1773-2008 flake silver powder burning loss calculation method.
The silver powder has good hydrophobicity and is suitable for silver powder for solar PERC battery front silver paste.
Comparative example 1
A silver powder.
1. The preparation method of the silver powder specifically comprises the following steps:
the difference from example 1 was that in the step of preparing the reduced dispersion, polyvinylpyrrolidone K60 was used instead of gum arabic, and the amount of the aqueous polyvinylpyrrolidone K60 added was 0.06kg, wherein the mass fraction of polyvinylpyrrolidone K60 was 10%, and the remaining raw materials and the preparation method were the same as in example 1.
2. Silver powder was detected.
The electron microscopic image of the silver powder prepared in this comparative example is a sphere-like silver powder, as shown in fig. 4.
The specific surface area was measured by nitrogen adsorption: 0.58m 2 /g; tap density is 5.0g/ml;
the particle size distribution is tested by adopting a Markov 3000, absolute ethyl alcohol is used as a solvent, ultrasonic dispersion is carried out for 10min, and a test result D10 is obtained: 0.86 μm, D50:2.00 μm, D90:4.92 μm, D100:13.7 μm;
the burning loss rate is 1.38 percent calculated by a GB/T1773-2008 flake silver powder burning loss calculation method.
Comparative example 2
A silver powder.
1. The preparation method of the silver powder specifically comprises the following steps:
the difference from example 1 is that no surface modifier solution was added, and the remaining raw materials and preparation method were the same as in example 1.
2. Silver powder was detected.
The electron microscopic image of the silver powder prepared in this comparative example is spherical silver powder, as shown in fig. 5.
The specific surface area was measured by nitrogen adsorption: 0.43m 2 /g; tap density is 3.4g/ml;
the particle size distribution is tested by adopting a Markov 3000, absolute ethyl alcohol is used as a solvent, ultrasonic dispersion is carried out for 10min, and a test result D10 is obtained: 1.59 μm, D50:3.27 μm, D90:6.52 μm, D100:16.1 μm;
the burning loss rate is calculated to be 0.96% by a GB/T1773-2008 flake silver powder burning loss calculation method.
Comparative example 3
A silver powder.
1. The preparation method of the silver powder specifically comprises the following steps:
the difference from example 1 is that the silver powder taken out after 12 hours of the drying treatment was directly fed to the jet mill for treatment without stirring with a continuous mixer, and the remaining raw materials and the production method were the same as those of example 1.
2. Silver powder was detected.
The electron microscopic image of the silver powder prepared in this comparative example is spherical silver powder, as shown in fig. 6.
The specific surface area was measured by nitrogen adsorption: 0.46m 2 /g; tap density is 5.60g/ml;
the particle size distribution is tested by adopting a Markov 3000, absolute ethyl alcohol is used as a solvent, ultrasonic dispersion is carried out for 10min, and a test result D10 is obtained: 1.45 μm, D50:2.87 μm, D90:7.65 μm, D100:14.3 μm;
the burning loss rate is calculated to be 0.78% by a GB/T1773-2008 flake silver powder burning loss calculation method.
Experimental example
And carrying out statistics and analysis on the detection results of the silver powder prepared in each example and the comparative example.
The detection results of silver powder prepared in each example and comparative example are counted as follows.
TABLE 1 detection results of silver powder of examples and comparative examples
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Morphology of electron microscope | Spherical shape | Spherical shape | Spheroid shape | Spherical shape | Spherical shape |
| Specific surface area (m) 2 /g) | 0.45 | 0.45 | 0.58 | 0.43 | 0.46 |
| Tap Density (g/ml) | 6.1 | 6.0 | 5.0 | 3.4 | 5.60 |
| D10(μm) | 1.07 | 0.86 | 0.86 | 1.59 | 1.45 |
| D50(μm) | 2.06 | 1.49 | 2.00 | 3.27 | 2.87 |
| D90(μm) | 4.09 | 2.68 | 4.92 | 6.52 | 7.65 |
| D100(μm) | 7.62 | 5.85 | 13.7 | 16.1 | 14.3 |
| Burn loss Rate (%) | 0.82 | 0.79 | 1.38 | 0.96 | 0.78 |
The test data, the scanning electron microscope image and the corresponding conditions with the table can be obtained: in the embodiment, under the same process condition, the dispersion of silver powder can be properly improved by adding the dispersing agent into the reducing agent solution;
the change of the dispersing agent in the reduction dispersion solution in comparative example 1 can cause the particle size of silver powder to show a bipolar differentiation phenomenon, the proportion of small particles in the powder is obviously increased, and the test data D100 is obviously larger;
in comparative example 2, no surface modifier is used, the dispersibility of the silver powder is obviously deteriorated, and the tap density is low, because a hydrophobic layer is not formed on the surface of the reaction silver powder, oxygen bridges are formed on the surface of the silver powder due to moisture in the medium and air in the subsequent washing and drying processes, and hard agglomeration is caused;
in comparative example 3, the particle size distribution of the silver powder obtained is wider and the tap density is slightly lower than that of the example, because the silver powder is in a block shape after being dried, the block needs to be impacted into a small block after entering the jet mill, and then the block is deagglomerated, because the residence time in a dispersion disc is shorter, and the deagglomeration is not completely caused.
The preparation method provided by the embodiment has the characteristics of low cost, small wastewater yield, simplicity in operation, high sphericity, good dispersibility, high tap density and capability of adjusting various performances within a certain range according to requirements.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing silver powder for PERC battery front silver paste, which is characterized by comprising the following steps:
preparing a solution: preparing a silver nitrate solution, a reduction dispersion liquid, a first pH regulating liquid, a second pH regulating liquid and a surface modifier solution; the concentration of the silver nitrate solution is 1.8-2.4mol/L;
mixing: mixing the silver nitrate solution with the first pH regulating solution to obtain a first mixed solution; mixing the reduction dispersion liquid with the second pH regulating liquid to obtain a second mixed liquid; adding the first mixed solution into the second mixed solution at a preset speed, adding the surface modifier solution, and mixing and stirring to obtain a solid-liquid mixture;
washing silver powder: centrifuging and washing the solid-liquid mixture to obtain a filter cake;
drying and dispersing silver powder: and drying the filter cake, dispersing and stirring, and jet milling to obtain silver powder.
2. The method according to claim 1, wherein in the step of preparing the solution, the concentration of the silver nitrate solution is 1.96mol/L;
the solute of the reduction dispersion liquid comprises a reducing agent and a dispersing agent, and the concentration of the reducing agent in the reduction dispersion liquid is 0.8-1.5mol/L; the weight ratio of the reducing agent to the dispersing agent is (45-98): 1.
3. the method of claim 2, wherein the reducing agent comprises at least 1 of the following materials: hydroquinone, formaldehyde, glucose, ascorbic acid, glyceraldehyde, or a polyol;
the dispersing agent comprises at least 1 of the following raw materials: acacia, gelatin, polyethylene glycol, polyvinyl alcohol, or polyvinylpyrrolidone.
4. The method according to claim 1, wherein the first pH adjusting liquid comprises a pH adjusting agent having a concentration of 4 to 8mol/L, and the second pH adjusting liquid comprises a pH adjusting agent having a concentration of 1 to 4mol/L;
the pH adjuster is independently optionally selected from: sodium hydroxide, ammonia, nitric acid, potassium hydroxide, or sodium dihydrogen phosphate.
5. The method of preparation of claim 1, wherein the surface modifier solution comprises at least 1 of the following surface modifiers: alkylphenol ethoxylates, fatty alcohol ethoxylates, nonylphenol ethoxylates, unsaturated fatty acids, saturated fatty acids, or sodium dodecylbenzenesulfonate.
6. The preparation method of claim 5, wherein the surface modifier comprises alkylphenol ethoxylates and fatty alcohol ethoxylates, and the weight ratio of the alkylphenol ethoxylates to the fatty alcohol ethoxylates is 1:1.
7. The method according to claim 1, wherein in the mixing step, the predetermined speed is 0.6 to 1.0L/min, the speed of the mixing and stirring is 350 to 450rpm, the temperature of the mixing and stirring is 35 to 45 ℃, and the time of the mixing and stirring is 0.3 to 0.7h;
in the silver powder washing step, the conductivity of the filter cake is less than or equal to 10us/cm.
8. The method according to claim 1, wherein in the step of drying and dispersing silver powder, the temperature of the drying is 55 to 65 ℃, the time of the drying is 10 to 14 hours, the speed of the dispersing stirring is 1800 to 2200rpm, the time of the dispersing stirring is 8 to 12 minutes, the feed gas flow pressure of the gas flow pulverization is 0.35 to 0.45MPa, the dispersion gas flow pressure of the gas flow pulverization is 0.6 to 1.0MPa, and the feed rate of the gas flow pulverization is 8 to 12kg/h.
9. The silver powder obtained by the production process according to any one of claims 1 to 8, wherein the silver powder is spherical silver powder, and the true particle diameter of the silver powder is 0.5 to 3 μm.
10. A front side silver paste for a PERC battery, characterized by being prepared using the silver powder of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310006328.3A CN116237533A (en) | 2023-01-04 | 2023-01-04 | Silver powder for PERC battery front silver paste and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310006328.3A CN116237533A (en) | 2023-01-04 | 2023-01-04 | Silver powder for PERC battery front silver paste and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116237533A true CN116237533A (en) | 2023-06-09 |
Family
ID=86625308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310006328.3A Pending CN116237533A (en) | 2023-01-04 | 2023-01-04 | Silver powder for PERC battery front silver paste and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116237533A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117358941A (en) * | 2023-12-08 | 2024-01-09 | 长春黄金研究院有限公司 | Preparation method of flower-spherical silver powder with high specific surface area |
-
2023
- 2023-01-04 CN CN202310006328.3A patent/CN116237533A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117358941A (en) * | 2023-12-08 | 2024-01-09 | 长春黄金研究院有限公司 | Preparation method of flower-spherical silver powder with high specific surface area |
| CN117358941B (en) * | 2023-12-08 | 2024-03-01 | 长春黄金研究院有限公司 | Preparation method of flower-spherical silver powder with high specific surface area |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101929961B1 (en) | Precursor Synthetic method for lithium-ion secondary battery cathode active material from waste battery material, and manufacturing method of the cathode active material made by the same | |
| CN1837055B (en) | Indium oxide powder and method for producing same | |
| CN108933239B (en) | Preparation method of lithium manganate coated nickel cobalt lithium manganate positive electrode material | |
| CN1648036A (en) | Method for preparing Li Fe PO4 ball shape powder | |
| JP5907169B2 (en) | Nickel oxide fine powder and method for producing the same | |
| CN116237533A (en) | Silver powder for PERC battery front silver paste and preparation method and application thereof | |
| CN107792891B (en) | Preparation method of nickel cobalt lithium manganate powder | |
| CN107293728B (en) | Method for preparing carbon-coated lithium iron phosphate by using water-soluble starch one-step hydrothermal method | |
| CN114644329B (en) | Hydrothermal synthesis method of nano lithium iron manganese phosphate | |
| CN110604932A (en) | Method for preparing potassium perchlorate powder by using closed-loop circulating spray dryer | |
| CN114420372B (en) | Preparation method of nano silver powder for preparing silver electrode on back of solar cell | |
| KR20150025234A (en) | Method for producing electrode active material agglomerates for lithium secondary battery by spray drying process and the electrode active material particles prepared therefrom | |
| CN109835879B (en) | Preparation method of submicron lithium iron phosphate cathode material | |
| CN110350162B (en) | Multiplying power type nickel-cobalt-aluminum positive electrode material and preparation method and application thereof | |
| JP2011225395A (en) | Nickel oxide fine powder, and method for producing the same | |
| CN215746418U (en) | System for preparing silver powder by continuous formate reduction | |
| CN116393713A (en) | Preparation method of small-particle-size flake silver powder for fine line printing | |
| CN114380281B (en) | Lithium iron phosphate material and preparation method thereof | |
| CN114044544A (en) | Method for preparing wide-particle-size-distribution ternary precursor material by oxidation method | |
| CN112357964A (en) | Preparation method of battery-grade trimanganese tetroxide | |
| CN110182780B (en) | Densification spherical lithium iron phosphate and preparation method thereof | |
| CN113526531A (en) | Method for recovering high-purity submicron lithium carbonate from lithium battery ternary material washing liquid | |
| JP2017188293A (en) | Lithium-nickel-cobalt-aluminum composite oxide powder | |
| CN105817646B (en) | A kind of preparation method of the ball shape silver powder of high-tap density | |
| CN115321564B (en) | Long rod-shaped lithium carbonate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |