CN117324632A - Flake and spherical mixed silver powder and preparation method and application thereof - Google Patents
Flake and spherical mixed silver powder and preparation method and application thereof Download PDFInfo
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- CN117324632A CN117324632A CN202311254081.3A CN202311254081A CN117324632A CN 117324632 A CN117324632 A CN 117324632A CN 202311254081 A CN202311254081 A CN 202311254081A CN 117324632 A CN117324632 A CN 117324632A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 230000001590 oxidative effect Effects 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000003311 flocculating effect Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 18
- 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 claims description 17
- 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 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 9
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 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 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 74
- 229910052709 silver Inorganic materials 0.000 description 39
- 239000004332 silver Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 25
- 238000009826 distribution Methods 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000012798 spherical particle Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 229920003081 Povidone K 30 Polymers 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- 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
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
-
- 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
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses flake and spherical mixed silver powder, a preparation method and application thereof, and belongs to the technical field of conductive metal powder and a preparation method thereof. The preparation method comprises the following steps: s1, respectively preparing a reducing solution, an oxidizing solution and a control agent solution; s2, adding the reducing solution obtained in the step S1 into a reaction kettle, stirring, and then adding an oxidizing solution and a control agent solution; and S3, adding the flocculating solution, stirring, precipitating, cleaning and drying to obtain the flaky and spherical mixed silver powder. The silver powder is mixed with flake silver powder in the proportion of 10-20%, flake diameter of 0.5-2 um, thickness of 10-20 nm, diameter-thickness ratio of 50-100 and particle size of 100-800 nm. The method is simple in the process of simultaneously obtaining the flaky and spherical silver powder, and the silver powder is used for preparing the slurry, so that the slurry has lower resistivity and can be suitable for mass application.
Description
Technical Field
The invention relates to the technical field of conductive metal powder and a preparation method thereof, in particular to flake and spherical mixed silver powder and a preparation method and application thereof.
Background
Silver powder is one of the most widely used noble metal powders in the electronics industry for making conductive pastes, conductive paints, and various electronic pastes. With the development of miniaturization, integration and intellectualization trend of electronic products, the performance requirements of the market on silver powder products are also higher and higher. Silver powder with different morphologies has very different properties under the same use environment.
The current preparation method of silver powder with different morphologies comprises the following steps: 1) And (3) reducing the silver salt solution under an acidic condition by taking the ferrous salt solution as a reducing agent to obtain the mixed silver powder with adjustable flake duty ratio. However, the acid solution is used as a morphology control regulator, so that the morphology of the silver powder flake and sphere is not clear in limitation, and the morphology of the flake and sphere silver particles is easily confused. 2) Adding silver solution and alkaline aqueous solution into the reducing solution, reacting for 30min to obtain silver powder, drying and ball milling to obtain flaky silver powder with higher tap density and specific surface area. The alkaline regulator is selected from one of sodium carbonate, sodium hydroxide and ammonia water. The silver flake is obtained by ball milling, but the silver flake is obtained by ball milling the silver powder after reaction, the process is complex, the specific surface area is large, the filler is small during slurry preparation, and the solid content is difficult to improve. 3) The silver nitrate is reduced by ascorbic acid to obtain flake silver powder, and the reaction rate is controlled by the synergistic effect of nitric acid, an adsorbent and low temperature to obtain the flake silver powder. However, the excessive reducing agent reacts rapidly with subsequent ultrasonic dispersion and standing aging for 1-3 hours, and the rapid mixing of the reducing agent and the oxidizing agent contradicts with the control of the reaction rate, and the obtained flake silver powder has larger diameter. 4) Adding ascorbic acid into silver nitrate solution containing concentrated nitric acid to react to obtain spherical and flaky mixed silver powder. 5) And adding nano-flake silver seed crystal solution serving as crystal nucleus into the reduction base solution, and then adding oxidizing solution to obtain ultrathin flake silver powder. The whole reaction time is longer, the existence of seed crystal is needed, and the efficiency is lower. The current research technology has the defects that the morphology of the flake silver powder is mixed with that of the flake silver powder, or the flake diameter is large and the particle diameter of the spherical particles is large for directly preparing the spheroidal silver powder and the flake silver powder.
Therefore, it is needed to develop a preparation method of flaky and spherical mixed silver powder which can simultaneously obtain two different morphologies and has the characteristics of flaky and spherical silver powder.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the preparation method of the flaky and spherical mixed silver powder, which can obtain the flaky and spherical mixed silver powder in one step, has the advantages of simple process, mild chemical reagent, small particle size of the silver powder and easy collection by flocculation.
The invention also provides the flaky and spherical mixed silver powder obtained by the preparation method.
The invention also provides application of the flaky and spherical mixed silver powder.
The first aspect of the present invention provides a method for producing a plate-like and spherical mixed silver powder, comprising the steps of:
s1, respectively preparing a reducing solution, an oxidizing solution and a control agent solution;
s2, adding the reducing solution obtained in the step S1 into a reaction kettle, stirring, and then adding an oxidizing solution and a control agent solution;
and S3, adding the flocculating solution, stirring, precipitating, cleaning and drying to obtain the flaky and spherical mixed silver powder.
According to the embodiment of the first aspect of the invention, at least the following beneficial effects are achieved:
the invention uses the liquid phase reduction method to obtain the silver powder with the flaky and spherical mixture at the same time, can simultaneously have the characteristics of flaky and spherical silver powder, has the proportion of the flaky silver powder of about 10-20 percent, has simple process, mild chemical reagent and small particle size, and is easy to collect by flocculation.
The invention respectively adds the oxidizing solution and the control solution into the reducing solution in two ways, and the adding speed and the concentration of the control solution are used for adjusting the morphology of the silver particles in the process. The control agent solution is added as a single path, the adding time is related to the adding time of the oxidizing solution, the adding time of the control agent solution influences the proportion of the flaky particles in the synthesized silver powder, the diameter-thickness ratio of the flaky particles and other performances,
according to some embodiments of the invention, in step S1, the reducing liquid comprises a dispersant and a reducing liquid.
According to some embodiments of the invention, in step S1, the concentration of the reducing agent in the reducing solution is 4-10 wt%, for example, may be 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%.
According to some embodiments of the invention, in step S1, the reducing agent comprises at least one of glucose, ascorbic acid and sodium hypophosphite.
Preferably, in step S1, the reducing agent is ascorbic acid.
According to some embodiments of the invention, in step S1, the dispersant comprises at least one of polyacrylic acid, polyvinyl alcohol, polyacrylamide, styrene maleic anhydride, and sodium polyacrylate.
Preferably, in step S1, the dispersing agent is polyvinyl alcohol.
According to some embodiments of the invention, in step S1, the oxidizing liquid comprises a silver salt and a complexing agent.
According to some embodiments of the invention, in step S1, the molar ratio of complexing agent to silver salt in the oxidizing solution is 1: (10-30).
Preferably, in step S1, the molar ratio of complexing agent to silver salt in the oxidizing solution is 1:20.
according to some embodiments of the invention, in step S1, the complexing agent comprises at least one of tartronic acid, tartaric acid, malic acid, maleic acid and fumaric acid.
Preferably, in step S1, the complexing agent is tartaric acid.
According to some embodiments of the invention, in step S1, the silver salt comprises silver nitrate.
According to some embodiments of the invention, in step S1, the control agent in the control agent solution comprises at least one of polyvinylpyrrolidone (PVP), sodium citrate and citric acid.
Preferably, in step S1, the control agent in the control agent solution is PVP-K30.
The control agent solution plays a role in controlling the reaction to generate the flake silver powder, the concentration and the adding speed of the control agent solution can influence parameters such as the duty ratio, the radius-thickness ratio and the like of the flake silver powder, and the control agent is preferably a substance with adsorption effect on silver atom crystal faces.
According to some embodiments of the invention, in step S1, the concentration of the control agent solution is 20 to 40wt%.
According to some embodiments of the invention, in step S2, the oxidizing solution and the control agent solution are added as two separate paths.
The control agent solution is added as a single path, and the feeding time and the concentration influence the ratio of the flaky silver powder in the whole silver powder, the diameter-thickness ratio of the flaky silver powder and other characteristics.
According to some embodiments of the invention, in step S2, the stirring speed is 100-300 r/min.
According to some embodiments of the invention, in step S2, the oxidizing solution is added for 20 to 50 minutes.
Preferably, in step S2, the time for adding the oxidizing solution is 30min.
The adding time refers to the final time required by adding the oxidizing solution into the base solution at a constant speed, for example, the oxidizing solution is added at a constant speed within 20 min.
According to some embodiments of the invention, in step S2, the control agent solution is added for a time period of 40 to 60% of the time period of addition of the oxidizing solution.
Preferably, in step S2, the time for adding the control agent solution is 50% of the time for adding the oxidizing solution, that is, half the time for adding the oxidizing agent is used to finish adding the control agent solution.
According to some embodiments of the invention, in step S2, the control agent solution is added for a period of 8 to 12 minutes.
According to some embodiments of the invention, in step S2, the molar ratio of the reducing agent to silver salt is 1 to 1.1:1.
preferably, in step S2, the molar ratio of the reducing agent to silver salt is 1.05:1.
according to some embodiments of the invention, in step S2, the molar ratio of the control agent to the silver salt is (0.15-0.4): 1.
preferably, in step S2, the molar ratio of the control agent to silver salt is (0.3 to 0.4): 1.
according to some embodiments of the invention, in step S3, the flocculant in the flocculation liquid comprises at least one of palmitic acid, lauric acid and oleic acid.
Preferably, in step S3, the flocculant in the flocculation liquid is lauric acid.
The flocculant mainly has the functions of preventing particle agglomeration, strictly controlling the dosage and preventing excessive coating on the surface of the particles so as to influence the conductivity.
According to some embodiments of the invention, in step S3, the solvent of the flocculation liquid is an alcoholic solution.
According to some embodiments of the invention, in step S3, the mass concentration of the flocculating solution is 1%.
According to some embodiments of the invention, in step S3, the mass ratio of the flocculating solution to the silver salt is (1 to 5): 1.
preferably, in step S3, the mass ratio of the flocculant to silver salt in the flocculation liquid is 1:1.
the second aspect of the present invention provides the plate-like and spherical mixed silver powder prepared by the above-mentioned preparation method, wherein the ratio of the plate-like silver powder in the plate-like and spherical mixed silver powder is 10 to 20%.
According to the embodiment of the second aspect of the invention, at least the following beneficial effects are achieved:
the flaky and spherical mixed silver powder has the characteristics of high diameter-thickness ratio and small particle size, the specific surface area of the flaky silver powder is large, the flaky silver powder is used as a conductive phase filler in the slurry preparation process, the specific surface area of the spherical silver powder is small, and the flaky and spherical mixed silver powder can be filled into the slurry more, so that the conductivity of the slurry can be further optimized by matching the flaky silver powder with the spherical silver powder.
According to some embodiments of the present invention, the plate-like silver powder in the plate-like and spherical mixed silver powder has a plate diameter of 0.5 to 2 μm;
according to some embodiments of the present invention, the plate-like silver powder in the plate-like and spherical mixed silver powder has a thickness of 10 to 20nm.
According to some embodiments of the present invention, the particle size of the spherical silver powder in the plate-shaped and spherical mixed silver powder is 100 to 800nm.
Preferably, the particle diameter of the spherical silver powder in the plate-like and spherical mixed silver powder is 500nm.
The particle diameter refers to a diameter value of spherical particles obtained by measuring the size of the particles by a scale in an SEM image.
According to some embodiments of the present invention, the ratio of the thicknesses of the plate-like silver powder in the plate-like and spherical mixed silver powder is 50 to 100.
Preferably, the ratio of the diameter to the thickness of the plate-like silver powder in the plate-like and spherical mixed silver powder is 80.
The third aspect of the invention provides an application of the flaky and spherical mixed silver powder prepared by the preparation method in preparation of conductive paste.
According to the embodiment of the third aspect of the invention, at least the following beneficial effects are achieved:
in the preparation of the conductive paste, the flaky silver powder is used as the conductive filler, the silver powder is in surface contact with each other, the silver powder can be used as a supporting structure of a conductive phase, and the spheroidal silver particles are in point contact with each other in the conductive phase and can be used for filling gaps between the flaky supports, so that the density of conductive paths is improved, and the resistivity is reduced.
According to some embodiments of the invention, the conductive paste comprises silver paste.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is an SEM image of the plate-like and spherical mixed silver powder obtained in example 1 of the present invention;
FIG. 2 is a graph showing the particle size distribution of the plate-like and spherical mixed silver powder obtained in example 1 of the present invention;
FIG. 3 is an SEM image of the plate-like and spherical mixed silver powder obtained in example 2 of the present invention;
FIG. 4 is an SEM image of the plate-like and spherical mixed silver powder obtained in example 3 of the present invention;
FIG. 5 is an SEM image of the plate-like and spherical mixed silver powder obtained in example 4 of the present invention;
FIG. 6 is an SEM image of the plate-like and spherical mixed silver powder obtained in example 5 of the present invention;
FIG. 7 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 1 of the present invention;
FIG. 8 is a graph showing the particle size distribution of the plate-like and spherical mixed silver powder obtained in comparative example 1 of the present invention;
FIG. 9 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 2 of the present invention;
FIG. 10 is a graph showing the particle size distribution of the plate-like and spherical mixed silver powder obtained in comparative example 2 of the present invention;
FIG. 11 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 3 of the present invention;
FIG. 12 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 4 of the present invention;
FIG. 13 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 5 of the present invention;
FIG. 14 is a graph showing the particle diameter distribution of the plate-like and spherical mixed silver powder obtained in comparative example 5 of the present invention;
FIG. 15 is an SEM image of the plate-like and spherical mixed silver powder obtained in comparative example 6 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, wherein like or similar reference numerals denote like or similar elements or elements having like or similar functions throughout the embodiments. The following examples are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that references to orientation descriptions, such as directions or positional relationships indicated above, below, etc., are based on the orientation or positional relationships shown in the embodiments, are merely for convenience of description of the present invention and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The reagent and the device adopted in the embodiment of the invention comprise:
reagent CAS number:
7761-88-8 parts of silver nitrate;
80-69-3 parts of tartronic acid;
ascorbic acid, 50-81-7;
9002-89-5 parts of polyvinyl alcohol;
PVP-K30，9003-39-8；
sodium citrate, 68-04-2;
palmitic acid, 57-10-3;
oleic acid, 112-80-1.
The equipment used is:
laser particle sizer, dandongbaite;
scanning electron microscope, national instrument quantum;
three-roll mill, QGM-65.
Example 1
The embodiment provides a preparation method of flaky and spherical mixed silver powder, which comprises the following specific preparation method steps:
(1) 3.8g of silver nitrate and 0.135g of tartronic acid are used for dissolving in 72.2g of deionized water to obtain an oxidation solution; using 0.02g polyvinyl alcohol and 1.97g ascorbic acid dissolved in 47.3g deionized water to obtain a reducing solution; 19g PVP-K30 was dissolved in 76g deionized water to give a control agent solution; and (5) standby.
(2) Placing the reducing solution in a reaction kettle, setting the stirring speed to be 250r/min, setting the temperature to be room temperature, simultaneously adding the oxidizing solution and the control agent solution into the reducing solution, controlling the adding time of the oxidizing solution to be 30min, controlling the adding time of the control agent solution to be 15min, and controlling the adding speed to be uniform. After the two solutions are added, adding 11.4g of flocculating solution into the reaction system, and continuously stirring for 5min to obtain spherical and flaky mixed silver powder;
(3) The silver powder obtained was filtered and washed, and dried at 50 c for 2 hours using a vacuum drying oven to obtain about 2.3g of silver powder, the powder microstructure of which is shown in fig. 1. The particle size distribution of the silver powder was measured using a laser particle sizer, with a D10 particle size value of 0.209 μm, a D50 particle size value of 0.792 μm, a D90 particle size value of 1.437 μm, and a D100 value of 3 μm, and the particle size distribution is shown in FIG. 2.
The embodiment also provides an application of the flaky and spherical mixed silver powder in preparing silver paste, which comprises the following steps:
7.5g of silver powder obtained in the example, 0.65g of vinyl chloride-vinyl acetate copolymer, 0.6g of n-butyl ester and 1.25g of polyurethane are used for preparing conductive silver paste, the silver paste is mixed and stirred, a screen printer is used for printing lines with the thickness of 0.5mm multiplied by 100mm, and after baking at 150 ℃ for 1 hour, the test resistivity is 2.01X10 -7 Ω·m。
Example 2
This example provides a method for preparing a plate-like and sphere-like mixed silver powder, which is different from example 1 in that the concentration of the control agent solution PVP is 30%, i.e., 19g PVP-K30 is dissolved in 44.3g deionized water. The microstructure of the synthesized silver powder is shown in fig. 3, and the silver powder is flaky and spherical mixed silver powder.
Example 3
The present example provides a method for producing a plate-like and spherical mixed silver powder, which is different from example 1 in that the time at which the addition of the control liquid was completed was changed to 40% of the time at which the oxidizing liquid was added, i.e., the addition time of the control agent solution was 12 minutes. The microstructure of the synthesized silver powder is shown in fig. 4, and the silver powder is flaky and spherical mixed silver particles.
Example 4
This example provides a method for preparing a plate-like and sphere-like mixed silver powder, which is different from example 1 in that the control agent is replaced with sodium citrate, and the synthesized silver powder has a microscopic morphology as shown in fig. 5, which is a plate-like and sphere-like mixed silver particle.
Example 5
This example provides a method for preparing a plate-like and sphere-like mixed silver powder, which is different from example 1 in that the flocculant is replaced with palmitic acid, and the synthesized silver powder has a microstructure as shown in fig. 6, which is a plate-like and sphere-like mixed silver particle.
Comparative example 1
This comparative example provides a method for producing plate-like and spherical mixed silver powder, which is different from example 1 in that the addition time of the control agent is 20% of the addition time of the oxidizing solution, i.e., the addition of the control agent solution is completed within 6 minutes. The synthesized spherical silver powder has uneven particle size, the flaky silver particles are seriously agglomerated, and the microscopic morphology of the obtained silver powder is shown in figure 7.
The particle size distribution of the silver powder was measured using a laser particle sizer, the particle size distribution of which is shown in FIG. 8, and there was a bimodal case in which the D10 particle size value was 0.021. Mu.m, the D50 value was 0.121. Mu.m, the D90 particle size value was 1.078. Mu.m, the D100 value was 2. Mu.m, the particle size distribution was broad, and the flaky particles occupied more.
The comparative example also provides the use of the above-mentioned plate-like and spherical mixed silver powder for the preparation of silver paste, which has the same procedure as in example 1, and which has a test resistivity of 9.76X10 after preparation of silver paste and firing -7 Omega.m, particle agglomeration results in an undesirable effect of the flake silver powder as a scaffold, resulting in a higher electrical resistance.
Comparative example 2
This comparative example provides a method for producing a plate-like and spherical mixed silver powder, which is different from example 1 in that the control agent is placed in the reaction base liquid in advance, i.e., equivalent to a shorter control agent addition time.
The microscopic morphology of the silver powder obtained after the reaction is shown in fig. 9, the silver particles are in a sheet-like structure and are gathered into a spherical open-cell structure, and no obvious spherical particles appear. The particle size distribution of the silver powder was measured using a laser particle sizer, the particle size distribution is shown in FIG. 10, the D10 particle size value is 1.804 μm, the D50 particle size value is 2.925 μm, the D90 particle size value is 4.949 μm, and the D100 particle size is 10. Mu.m, and aggregation of the flaky silver particles results in a larger particle size of the powder.
The comparative example also provides the use of the above-mentioned plate-like and spherical mixed silver powder for the preparation of silver paste, which has the same procedure as in example 1, and has a test resistivity of 4.58X 10 after preparation and sintering -6 Omega.m, only flaky particles, more voids inside, and no filling of spherical particles, result in higher resistivity of the obtained silver paste.
Comparative example 3
The comparative example provides a method for preparing plate-like and spherical mixed silver powder, which is different from example 1 in that the addition time of the control solution is increased, and the addition time of the control solution is 80% of that of the oxidizer solution, i.e., the control solution is added after 24 minutes.
The microstructure of the synthesized silver particles is shown in fig. 11, the silver particles are in a mixed form of a flake shape and a sphere shape, but the thickness of the flake particles is obviously increased, the size of the sphere particles is also increased, and the flake particles are developed to a polyhedron shape.
The comparative example also provides the use of the above-mentioned plate-like and spherical mixed silver powder for the preparation of silver paste, which has the same procedure as in example 1, and has a test resistivity of 1.03X10 after the preparation of silver paste and sintering -6 Omega.m, the flaky particles and the spherical particles are larger, the sintering activity is lower at the same temperature, and the flaky and spherical particles are difficult to form supporting and filling conductive paths, so that the resistivity of the obtained silver paste is higher.
Comparative example 4
This comparative example provides a method for producing a plate-like and spherical mixed silver powder, which is different from example 1 in that the concentration of the control liquid is lowered, i.e., the content of the control agent PVP-K30 is 7.6g. The addition of the control liquid with low concentration leads to the micro morphology of the synthesized silver particles as shown in fig. 12, and the flaky silver particles are obviously reduced. The dosage of the control agent is reduced, and the steric hindrance capability of the system is reduced in the reaction process, so that spherical particles are easier to generate.
Comparative example 5
This comparative example provides a method for producing a plate-like and spherical mixed silver powder, which differs from example 1 in that the control agent and the oxidizing agent are added together to the reaction base liquid, i.e., only one way. The microstructure of the synthesized silver particles is shown in fig. 13, the particle size distribution of the silver particles is wider, the shape is disordered, and no obvious shape characteristics are provided.
The particle size distribution was measured using a laser particle sizer, and the particle size distribution is shown in FIG. 14, with a D10 value of 0.059 μm, a D50 value of 0.279 μm, a D90 value of 1.364 μm, and a D100 value of 3. Mu.m.
Comparative example 6
This comparative example provides a method for producing a plate-like and spherical mixed silver powder, which is different from example 1 in that an alkaline aqueous ammonia is used as the complexing agent in the oxidizer solution, i.e., the oxidizer solution is an aqueous silver-ammonia solution.
The microscopic morphology of the silver particles synthesized after the reaction is shown in fig. 15, the silver particles are spherical, but obvious agglomeration occurs, the agglomeration is similar to cluster of grapes, and no lamellar structure is generated.
From the above results, it is understood that, compared with comparative examples 1 to 5 and examples, the control agent solution was added as a single route, the addition time was correlated with the addition time of the oxidizing solution, the length of the addition time of the control agent solution affected the ratio of the flaky particles in the synthesized silver powder and the ratio of the diameter to thickness of the flaky particles, and the like, the addition rate of the control agent solution was fast, and silver particles having more mixed morphology in the form of flakes were obtained with less preferable addition time than in the present embodiment, but the particle size distribution of the spherical silver particles was uneven. The addition rate of the control agent continues to increase, even if the control agent is placed in the reaction base solution in advance, a structure in which the flaky silver particles are more flaky but the flaky silver particles are aggregated into a sphere-like shape is obtained. The rate of addition of the control agent is slower than the preferred time of the present protocol, and spherical-like silver particles are obtained. The concentration of the control agent solution is at a higher value, and a lower concentration results in more spheroidal silver particles. The silver particles with disordered morphology can be obtained without using a control agent or adding the control agent and the oxidant together, and the morphology of the silver particles cannot be controlled.
In summary, the spherical and flaky mixed silver powder prepared by the method can simultaneously obtain silver particles with two morphologies by a simple chemical reduction method, the proportion of the flaky silver powder is about 10-20%, the process is simple, the chemical reagent is mild, the particle size of the silver powder is small, and the silver powder is easy to collect by flocculation.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for producing a plate-like and spherical mixed silver powder, characterized by comprising the steps of:
s1, respectively preparing a reducing solution, an oxidizing solution and a control agent solution;
s2, adding the reducing solution obtained in the step S1 into a reaction kettle, stirring, and then adding an oxidizing solution and a control agent solution;
and S3, adding the flocculating solution, stirring, precipitating, cleaning and drying to obtain the flaky and spherical mixed silver powder.
2. The method according to claim 1, wherein in step S1, the reducing liquid includes a dispersant and a reducing liquid; preferably, in the step S1, the concentration of the reducing agent in the reducing solution is 4-10wt%; preferably, the reducing agent includes at least one of glucose, ascorbic acid and sodium hypophosphite; preferably, the dispersant includes at least one of polyacrylic acid, polyvinyl alcohol, polyacrylamide, styrene maleic anhydride, and sodium polyacrylate.
3. The method according to claim 1, wherein in step S1, the oxidizing liquid comprises a silver salt and a complexing agent; preferably, in step S1, the molar ratio of complexing agent to silver salt in the oxidizing solution is 1: (10-30); preferably, the complexing agent comprises at least one of tartronic acid, tartaric acid, malic acid, maleic acid and fumaric acid; preferably, the silver salt comprises silver nitrate.
4. The method of claim 1, wherein in step S1, the control agent in the control agent solution comprises at least one of polyvinylpyrrolidone, sodium citrate, and citric acid; preferably, the concentration in the control agent solution is 20 to 40wt%.
5. The method according to claim 1, wherein in step S2, the oxidizing solution and the control agent solution are added simultaneously as two paths, respectively; preferably, in the step S2, the stirring speed is 100-300 r/min; preferably, in the step S2, the time for adding the oxidizing solution is 20-50 min; preferably, in step S2, the time for adding the control agent solution is 40 to 60% of the time for adding the oxidizing solution.
6. The method according to claim 1, wherein in step S2, the molar ratio of the reducing agent to silver salt is 1 to 1.1:1, a step of; preferably, the molar ratio of the control agent to silver salt is (0.15-0.4): 1.
7. the method of claim 1, wherein in step S3, the flocculant in the flocculation liquid comprises at least one of palmitic acid, lauric acid, and oleic acid; preferably, in the step S3, the mass ratio of the flocculation liquid to the silver salt is (1-5): 1.
8. the plate-like and spherical mixed silver powder produced by the production process according to any one of claims 1 to 7, wherein the ratio of the plate-like silver powder in the plate-like and spherical mixed silver powder is 10 to 20%.
9. The plate-like and spherical mixed silver powder according to claim 8, wherein the plate-like silver powder in the plate-like and spherical mixed silver powder has a plate diameter of 0.5 to 2 μm; preferably, the thickness of the flake silver powder in the flake and spherical mixed silver powder is 10-20 nm; preferably, the particle diameter of the spherical silver powder in the flaky and spherical mixed silver powder is 100-800 nm; preferably, the ratio of the diameter to the thickness of the flake silver powder is 50-100.
10. Use of the flake and sphere mixed silver powder prepared by the preparation method according to any one of claims 1 to 7 for preparing conductive paste.
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