CN116100038A - Submicron flake silver powder and preparation method thereof - Google Patents
Submicron flake silver powder and preparation method thereof Download PDFInfo
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- CN116100038A CN116100038A CN202211693788.XA CN202211693788A CN116100038A CN 116100038 A CN116100038 A CN 116100038A CN 202211693788 A CN202211693788 A CN 202211693788A CN 116100038 A CN116100038 A CN 116100038A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 33
- 239000004332 silver Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000003223 protective agent Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000010899 nucleation Methods 0.000 claims abstract description 17
- 230000006911 nucleation Effects 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 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 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 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 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims 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 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 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 3
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 claims description 3
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 3
- 239000001472 potassium tartrate Substances 0.000 claims description 3
- 229940111695 potassium tartrate Drugs 0.000 claims description 3
- 235000011005 potassium tartrates Nutrition 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000011083 sodium citrates Nutrition 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- B22F1/068—Flake-like 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
- H01B1/20—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the technical field of metal powder, and particularly relates to submicron flake silver powder and a preparation method thereof. Adding a protective agent solution into a silver precursor solution, uniformly mixing, adding an acidic solution to adjust the pH value to 0.5-6, and then adding a reducing agent solution to carry out nucleation reaction to obtain a nucleation system; adding alkaline solution into the nucleation system to adjust the pH value to 7-13, and continuing to grow to obtain silver powder dispersion liquid; and carrying out post-treatment on the silver powder dispersion liquid to obtain submicron flake silver powder. The preparation method provided by the invention regulates and controls the concentration, the reaction temperature and the reaction time of each reaction raw material by using the selective reaction solvent, and is used for controlling the stability of nucleation and the uniformity of growth speed, so that the silver powder with uniform particle size distribution and good crystal form is prepared.
Description
Technical Field
The invention belongs to the technical field of metal powder, and particularly relates to submicron flake silver powder and a preparation method thereof.
Background
The micro-nano silver powder is a functional raw material widely applied to the electronic industry, has excellent catalytic performance, magnetic performance, electrical performance and the like, is noble metal powder which is the most widely applied and used in the electronic industry, such as being used for manufacturing electronic paste, conductive paint, electromagnetic shielding material, conductive ink, conductive plastic, conductive ceramic and the like, and is a key material for producing various electronic component products.
The existing preparation methods of micro-nano silver powder are divided into a physical method and a chemical method, and the silver powder prepared by the physical method has complex process and poor performance. So at present, the micro-nano silver powder is mainly prepared by a chemical method, wherein the chemical reduction method, the electrolytic method and the sol-gel method are commonly used. The chemical reduction method is the most commonly used method for preparing the micro-nano silver powder at present, and has the advantages of simple equipment, low production cost, controllable product performance and good repeatability.
However, when the existing chemical reduction method is used for preparing the flake silver powder, the post-treatment is complex, the morphology of the silver powder is not easy to control, and the problems of insufficient uniform particle size distribution of the silver powder and the like can also exist.
Disclosure of Invention
The invention aims to at least solve the problems that when the existing chemical reduction method is used for preparing the flake silver powder, the post-treatment is complex, the morphology of the silver powder is not easy to control, the particle size distribution of the silver powder is not uniform enough and the like.
The aim is achieved by the following technical scheme:
in a first aspect, the present invention provides a method for preparing submicron plate-like silver powder, the method comprising the following preparation steps:
1) Dispersing a silver precursor, a reducing agent and a protecting agent into a solvent to form a silver precursor solution, a reducing agent solution and a protecting agent solution respectively;
wherein the molar ratio among the silver precursor, the reducing agent and the protecting agent is 1 (0.5-4): 1-4; the molar ratio here also refers to the ratio of the amounts of the substances.
2) Adding the protective agent solution into the silver precursor solution, uniformly mixing, adding an acidic solution to adjust the pH value to 0.5-6, and then adding the reducing agent solution for nucleation reaction to obtain a nucleation system;
3) Adding alkaline solution into the nucleation system to adjust the pH value to 7-13, and continuing to grow to obtain silver powder dispersion liquid;
4) And carrying out post-treatment on the silver powder dispersion liquid to obtain submicron flake silver powder.
In some embodiments of the invention, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1 (0.5-1): 1-2.
In some embodiments of the invention, in step 1), the solvent is a mixed solvent of deionized water and polyol, and the mass ratio of deionized water to polyol in the mixed solvent is (0.5-4): 1, preferably (1-2): 1. The solvent is favorable for controlling the stability of nucleation reaction and generating flaky powder with a polyhedral structure.
In some embodiments of the present invention, the deionized water comprises any one of pure water and ultrapure water, and the polyol comprises any one of ethylene glycol and glycerol.
In some embodiments of the invention, in step 1), the molar concentration ratio between the silver precursor solution, the reducing agent solution and the protecting agent solution is (0.2-8): (0.02-2): (0.2 to 4), preferably (0.4 to 4): (0.04-1): (0.4-2), and the molar concentration unit is mol/L.
In some embodiments of the invention, the silver precursor is any one of silver nitrate and silver acetate;
the protective agent is one or two or more of PVA, PVP, sorbitol, sodium citrate, gelatin, gum arabic and BTA, PEG, SDBS; wherein, the protective agent plays a role in controlling the morphology of particles, and plays an important role in the nucleation process.
The reducing agent is at least one of formaldehyde, ascorbic acid, potassium tartrate, hydrazine hydrate, hydrazine carbonate and glucose.
In some embodiments of the invention, the reaction temperature of step 2) and step 3) is 10 to 60 ℃, preferably 15 to 50 ℃, and the reaction time of step 2) is lower than the reaction time of step 3);
specifically, the reaction time in the step 2) is less than or equal to 10min, preferably 2-6 min;
the reaction time of the step 3) is less than or equal to 120min, preferably 60-100 min.
In some embodiments of the present invention, in step 2), the acidic solution comprises an aqueous solution of any one of nitric acid and acetic acid, and the concentration of the acidic solution is 0.02 to 0.5mol/L;
in the step 3), the alkaline solution comprises any one of sodium hydroxide and ammonia water, and the concentration of the alkaline solution is 0.02-3 mol/L.
In some embodiments of the invention, in step 4), the post-treatment comprises centrifugation, washing and drying, wherein the washing comprises washing 3-4 times with one or two or three of ethanol, acetone or deionized water, the drying is vacuum drying, and the vacuum drying comprises controlling the temperature to be 40-90 ℃ and drying for 1-6 hours.
In a second aspect, the present invention provides a submicron plate-like silver powder, said silver powder being produced by the method of the first aspect.
In some embodiments of the present invention, the silver powder comprises platelets having a polyhedral crystal form, and the platelets account for 90wt% or more; wherein the D50 of the sheet is 0.3-1 mu m, and the thickness of the sheet is 50-200 nm;
and the tap density of the silver powder is 4.0-6.0 g/cm 3 。
Wherein the polyhedral flaky powder comprises regular or irregular hexagonal flaky powder.
Therefore, the silver powder with polyhedral crystal forms is prepared, and the particle size distribution of the silver powder is uniform.
In a third aspect, the present invention provides the silver powder prepared by the method of the first aspect or the silver powder of the second aspect as a raw material of the conductive silver paste.
The beneficial effects of the technical scheme disclosed by the invention are mainly shown as follows:
1. according to the preparation method provided by the invention, the selective reaction solvent is used, the concentration and the dosage of each reaction raw material are regulated and controlled, the reaction temperature and the reaction time are better controlled, the stability of the nucleation reaction and the uniformity of the growth speed are better controlled, and the silver powder with the polyhedral crystal form is prepared.
2. The preparation method provided by the invention is not complex in post-treatment for preparing silver powder, and is suitable for mass industrial production
3. The silver powder provided by the invention comprises flaky powder with a polyhedral structure, wherein the flaky powder with the polyhedral structure accounts for more than 90wt%, and the powder can be used as a raw material of conductive silver paste.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
fig. 1 schematically shows a microscopic morphology of the silver powder produced according to example 1 of the present invention.
Fig. 2 schematically shows a microscopic morphology of the silver powder produced according to example 1 of the present invention.
Fig. 3 schematically shows a microscopic morphology of the silver powder produced according to example 5 of the present invention.
Fig. 4 schematically shows a microscopic morphology of the silver powder produced according to example 5 of the present invention.
Fig. 5 schematically shows a microscopic morphology of the silver powder produced according to example 6 of the present invention.
Fig. 6 schematically shows a microscopic morphology of the silver powder produced according to example 6 of the present invention.
Fig. 7 schematically shows a microscopic morphology of the silver powder produced according to example 11 of the present invention.
Fig. 8 schematically shows a microscopic morphology of the silver powder produced according to example 12 of the present invention.
Detailed Description
Chemical name and english abbreviation:
polyvinyl alcohol: PVA; polyvinylpyrrolidone: PVP; phenylpropiotriazole: BTA; polyethylene glycol: PEG; sodium dodecyl benzene sulfonate: SDBS.
When the chemical reduction method is adopted to prepare the flake silver powder in the prior art, the post-treatment is complex, the morphology of the silver powder is not easy to control, and the problem of uneven particle size distribution of the silver powder is likely to exist.
In order to solve the technical problems, the invention provides submicron flake silver powder and a preparation method thereof.
The first aspect of the present invention for achieving the above technical effects provides a method for preparing submicron plate-like silver powder, the method comprising the following preparation steps:
1) Respectively dissolving a silver precursor, a reducing agent and a protective agent into a solvent to form a silver precursor solution, a reducing agent solution and a protective agent solution;
wherein the molar ratio among the silver precursor, the reducing agent and the protecting agent is 1 (0.5-4): 1-4;
2) Adding the protective agent solution into the silver precursor solution, uniformly mixing, adding an acidic solution to adjust the pH value to 0.5-6, and then adding the reducing agent solution for nucleation reaction to obtain a nucleation system;
3) Adding alkaline solution into the nucleation system to adjust the pH value to 7-13, and continuing to grow to obtain silver powder dispersion liquid;
4) And carrying out post-treatment on the silver powder dispersion liquid to obtain submicron flake silver powder.
Illustratively, the molar ratio of the silver precursor to the reducing agent is any one of 1:0.5, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, or any ratio in the range of values.
Illustratively, the molar ratio of the silver precursor to the protective agent is any one of 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, or any ratio in the range of values.
In some embodiments, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1 (0.5-1): 1-2.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:0.75:1.5.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:0.5:1.5.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:0.75:1.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:0.5:1.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:0.5:1.
Illustratively, the molar ratio between the silver precursor, the reducing agent, and the protecting agent is 1:1:1.
Illustratively, in step 2), the pH is adjusted to any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8, 2.0, 2.2, 2.5, 2.8, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.5, 4.8, 5.0, 5.2, 5.5, 5.8, 6.0 or any ratio in the range of values.
Illustratively, in step 3), the pH is adjusted to any one of 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13 or any ratio in the range of values.
In some embodiments, the solvent is a mixed solvent of deionized water and polyol, and the mass ratio of deionized water to polyol in the mixed solvent is (0.5-4): 1.
In some embodiments, the mass ratio between deionized water and polyol in the mixed solvent is preferably (1-2): 1.
Illustratively, the mass ratio between deionized water and polyol in the mixed solvent is any one of 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or any ratio in the range of values.
In some embodiments, the deionized water comprises any one of pure water and ultrapure water, and the polyol comprises any one of ethylene glycol and glycerol. Among them, when glycerol is selected as the polyol, deionized water is used in a relatively large amount when the solvent is prepared due to the high viscosity of glycerol.
In some embodiments, in step 1), the molar concentration ratio between the silver precursor solution, the reducing agent solution, and the protecting agent solution is:
(0.2-8): (0.02-2): (0.2-4). And the solution preparation is carried out at room temperature.
In some embodiments, the molar concentration ratio between the silver precursor solution, the reducing agent solution, and the protecting agent solution is preferably (0.4-4): (0.04-1): (0.4-2), and the molar concentration unit is mol/L.
Illustratively, the molar concentration ratio between the silver precursor solution, the reducing agent solution, and the protecting agent solution is:
any ratio of any of 0.2:1:1, 0.5:1:1, 1:1:1, 1.5:1:1, 2:1:1, 2.5:1:1, 3:1:1, 3.5:1:1, 4:1:1, 4.5:1:1, 5:1:1, 5.5:1:1, 6:1:1, 6.5:1:1, 7:1:1, 7.5:1:1, 8:1:1 or range values).
In some embodiments, the silver precursor is any one of silver nitrate, silver acetate;
the protective agent is one or two or more of PVA, PVP, sorbitol, sodium citrate, gelatin, gum arabic and BTA, PEG, SDBS;
the reducing agent is at least one of formaldehyde, ascorbic acid, potassium tartrate, hydrazine hydrate, hydrazine carbonate and glucose.
In some embodiments, the reaction temperature of step 2) and step 3) is 10 to 60 ℃, preferably 15 to 50 ℃, and the reaction time of step 2) is lower than the reaction time of step 3);
specifically, the reaction time in the step 2) is less than or equal to 10min, preferably 2-6 min;
the reaction time of the step 3) is less than or equal to 120min, preferably 60-100 min.
In some embodiments, in step 2), the acidic solution comprises an aqueous solution of any one of nitric acid and acetic acid, and the concentration of the acidic solution is 0.02-0.5 mol/L.
In some embodiments, in step 3), the alkaline solution comprises an aqueous solution of any one of sodium hydroxide and ammonia water, and the concentration of the alkaline solution is 0.02-3 mol/L.
In some embodiments, in step 4), the post-treatment comprises centrifugation, washing and drying, wherein the washing comprises washing 3-4 times with one or two or three of ethanol, acetone or deionized water, the drying is vacuum drying, and the vacuum drying comprises controlling the temperature to be 40-90 ℃ and drying for 1-6 hours.
In order to achieve the technical effect, the second aspect of the invention provides submicron flake silver powder, wherein the silver powder is prepared by the method in the first aspect.
In some embodiments, the silver powder comprises platelets with polyhedral crystalline forms, and the platelets account for 90wt% or more; wherein the D50 of the sheet is 0.3-1 mu m, and the thickness of the sheet is 50-200 nm;
and the tap density of the silver powder is 4.0-6.0 g/cm 3 。
In a third aspect, the present invention provides the silver powder prepared by the method of the first aspect or the silver powder of the second aspect as a raw material of the conductive silver paste.
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. The chemical reagents, chemical raw materials and the like used in the following examples are all laboratory-used, the purity grade is laboratory grade, and the choice of each reagent and raw material is not limited by manufacturer and model.
Example 1
Discloses a preparation method of submicron flake silver powder, which comprises the following preparation steps:
1) Mixing ultrapure water and glycerin according to a mass ratio of 1:1 to prepare 0.2L of silver nitrate solution, 1.5L of ascorbic acid solution and 1L of LPVP solution with the concentration of 2mol/L and the concentration of 0.2mol/L at room temperature;
2) At room temperature, adding PVP solution into silver nitrate solution, stirring and mixing uniformly, dropwise adding 0.2mol/L nitric acid aqueous solution into the mixed solution, and adjusting the pH value of the system to 2.8; then adding ascorbic acid solution, controlling the reaction temperature to 35 ℃ and carrying out nucleation reaction for 6min;
3) Adding 2mol/L sodium hydroxide aqueous solution into the reaction product of the step 2), adjusting the pH value of the system to 11, maintaining the reaction temperature at 35 ℃, and reacting for 1h to obtain silver powder dispersion liquid;
4) And (3) centrifugally separating the silver powder dispersion liquid to obtain silver colloid, washing the silver colloid with ethanol for 3 times and ultrapure water for 1 time, and then drying in vacuum at 55 ℃ for 3 hours to obtain the flaky silver powder.
Examples 2 to 14
Discloses a preparation method of submicron flake silver powder, wherein the concentration and the dosage of each raw material and the control condition of a reaction system are shown in the following table 1;
table 1 list of silver powder preparation process parameters provided in examples 2 to 14
The silver powder dispersion liquid obtained in examples 1 to 14 was subjected to centrifugal separation, washing and drying to obtain silver powder, and the particle size distribution and tap density of the silver powder are shown in table 2 below:
TABLE 2 particle size distribution and tap Density List
The tap density test method in Table 2 meets the requirements of GB/T5162-2021, and the thickness of the flake silver powder is the distance between two opposite polygonal planes of the same flake powder in the microstructure.
As can be seen from the above-mentioned fig. 1 and 2, the silver powder prepared by the present invention comprises a typical plate-like structure having a polyhedral crystal form, wherein the polyhedral crystal form comprises regular or irregular plates having a hexagonal shape, and as can be seen from fig. 3, 4, 5, 6, 7 and 8, the particle size distribution and thickness of the silver powder are within the scope of the claims of the present invention.
Therefore, the silver powder prepared by the method can be used as a raw material of conductive silver paste, and has a good application prospect.
It is to be understood that the terminology used herein is for the purpose of describing particular example embodiments only, and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises," "comprising," "includes," "including," and "having" are inclusive and therefore specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order described or illustrated, unless an order of performance is explicitly stated. It should also be appreciated that additional or alternative steps may be used.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (10)
1. A method for preparing submicron plate-like silver powder, which is characterized by comprising the following preparation steps:
1) Dispersing a silver precursor, a reducing agent and a protecting agent into a solvent to form a silver precursor solution, a reducing agent solution and a protecting agent solution respectively;
wherein the molar ratio among the silver precursor, the reducing agent and the protecting agent is 1 (0.5-4): 1-4;
2) Adding the protective agent solution into the silver precursor solution, uniformly mixing, adding an acidic solution to adjust the pH value to 0.5-6, and then adding the reducing agent solution for nucleation reaction to obtain a nucleation system;
3) Adding alkaline solution into the nucleation system to adjust the pH value to 7-13, and continuing to grow to obtain silver powder dispersion liquid;
4) And carrying out post-treatment on the silver powder dispersion liquid to obtain submicron flake silver powder.
2. The preparation method according to claim 1, wherein in the step 1), the solvent is a mixed solvent of deionized water and polyol, and the mass ratio of deionized water to polyol in the mixed solvent is (0.5-4): 1, preferably (1-2): 1.
3. The method according to claim 2, wherein the deionized water contains any one of pure water and ultrapure water, and the polyol contains any one of ethylene glycol and glycerol.
4. The method according to claim 1, wherein in step 1), the molar concentration ratio between the silver precursor solution, the reducing agent solution and the protecting agent solution is (0.2 to 8): (0.02-2): (0.2 to 4), preferably (0.4 to 4): (0.04-1): (0.4-2), and the molar concentration unit is mol/L.
5. The preparation method according to claim 4, wherein the silver precursor is any one of silver nitrate and silver acetate;
the protective agent is one or two or more of PVA, PVP, sorbitol, sodium citrate, gelatin, gum arabic and BTA, PEG, SDBS;
the reducing agent is at least one of formaldehyde, ascorbic acid, potassium tartrate, hydrazine hydrate, hydrazine carbonate and glucose.
6. The process according to claim 1, wherein the reaction temperature of step 2) and step 3) is 10-60 ℃, preferably 15-50 ℃, and the reaction time of step 2) is lower than the reaction time of step 3);
specifically, the reaction time in the step 2) is less than or equal to 10min, preferably 2-6 min;
the reaction time of the step 3) is less than or equal to 120min, preferably 60-100 min.
7. The method according to claim 1, wherein in the step 2), the acidic solution contains an aqueous solution of any one of nitric acid and acetic acid, and the concentration of the acidic solution is 0.02 to 0.5mol/L;
in the step 3), the alkaline solution comprises any one of sodium hydroxide and ammonia water, and the concentration of the alkaline solution is 0.02-3 mol/L.
8. The method according to claim 1, wherein in the step 4), the post-treatment comprises centrifugation, washing and drying, the washing comprises washing 3 to 4 times with one or two or three of ethanol, acetone or deionized water, the drying is vacuum drying, and the vacuum drying comprises controlling the temperature to be 40 to 90 ℃ and drying for 1 to 6 hours.
9. A submicron plate-like silver powder, characterized in that said silver powder is produced by the method according to any one of claims 1 to 8.
10. The silver powder according to claim 9, wherein the silver powder comprises platelets having a polyhedral crystal form and the platelets account for 90wt% or more; wherein the D50 of the sheet is 0.3-1 mu m, and the thickness of the sheet is 50-200 nm;
and the tap density of the silver powder is 4.0-6.0 g/cm 3 。
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| CN101569935A (en) * | 2009-06-05 | 2009-11-04 | 中国乐凯胶片集团公司 | Preparation method for flaky micro-silver powder |
| CN103008677A (en) * | 2011-09-27 | 2013-04-03 | 中国钢铁股份有限公司 | Micron flaky silver grains and production method thereof |
| CN106297950A (en) * | 2015-06-11 | 2017-01-04 | 广东银研高新材料股份有限公司 | A kind of conductive silver paste and preparation method thereof |
| CN106694904A (en) * | 2017-02-14 | 2017-05-24 | 贵研铂业股份有限公司 | Preparation method of highly dispersed micron order flake silver powder with large radius-thickness ratio |
| CN110355380A (en) * | 2019-08-13 | 2019-10-22 | 山东建邦胶体材料有限公司 | A kind of preparation method of hexagonal flake micron crystalline substance silver powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101569935A (en) * | 2009-06-05 | 2009-11-04 | 中国乐凯胶片集团公司 | Preparation method for flaky micro-silver powder |
| CN103008677A (en) * | 2011-09-27 | 2013-04-03 | 中国钢铁股份有限公司 | Micron flaky silver grains and production method thereof |
| CN106297950A (en) * | 2015-06-11 | 2017-01-04 | 广东银研高新材料股份有限公司 | A kind of conductive silver paste and preparation method thereof |
| CN106694904A (en) * | 2017-02-14 | 2017-05-24 | 贵研铂业股份有限公司 | Preparation method of highly dispersed micron order flake silver powder with large radius-thickness ratio |
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