CN117600480A - Spherical superfine silver powder and preparation method and application thereof - Google Patents
Spherical superfine silver powder and preparation method and application thereof Download PDFInfo
- Publication number
- CN117600480A CN117600480A CN202311623656.4A CN202311623656A CN117600480A CN 117600480 A CN117600480 A CN 117600480A CN 202311623656 A CN202311623656 A CN 202311623656A CN 117600480 A CN117600480 A CN 117600480A
- Authority
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- Prior art keywords
- silver powder
- silver
- spherical
- reducing agent
- superfine
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 51
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229930182830 galactose Natural products 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 229930091371 Fructose Natural products 0.000 claims abstract description 5
- 239000005715 Fructose Substances 0.000 claims abstract description 5
- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 claims abstract description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 4
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims abstract description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 23
- 229930195729 fatty acid Natural products 0.000 claims description 23
- 239000000194 fatty acid Substances 0.000 claims description 23
- 150000004665 fatty acids Chemical class 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 10
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 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 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- -1 hydrazides Chemical compound 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical class N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 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
- B22F1/06—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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses spherical superfine silver powder, a preparation method and application thereof, which belong to the technical field of silver powder preparation, wherein the spherical superfine silver powder is prepared by taking silver nitrate as a silver source through a liquid phase reduction method, and a reducing agent comprises one or more of galacturonic acid, galactose, fructose and benzaldehyde. The reducing agent disclosed by the invention has weaker reducibility and can be reduced due to the reduction of the reducibilityThe reaction time is prolonged, and the rate of product generation can be controlled. By using two or more reducing agents for mixing and selecting materials with weaker reducibility, the reaction speed is favorably slowed down, and a window for controlling the growth of silver powder in the following reaction process is increased. The silver powder obtained by the preparation method of the spherical superfine silver powder provided by the invention has high sphericity, very few superfine powder, concentrated particle size distribution of silver powder particles, tap density of 4.0-6.5g/mL, particle size distribution D50-2 mu m and D90-5 mu m; the specific surface area of silver powder is 0.1-0.4m 2 /g。
Description
Technical Field
The invention belongs to the technical field of silver powder preparation, and particularly relates to spherical superfine silver powder, and a preparation method and application thereof.
Background
At present, the superfine silver powder is the most applied in the aspect of electronic paste, and is widely applied to sintered silver paste on rear window glass of automobiles, vacuum fluorescent display screens, thermosensitive devices, pressure sensitive devices, solar cell electrodes and other matrix materials, and the most applied in the electronic paste is silver conductive paste on the front and back surfaces of crystalline silicon solar cells. In addition, the superfine silver powder is also applied to environmental protection materials, antibacterial materials, catalyst materials, decorative materials, optical materials, building materials and the like. The process for stably producing high-quality silver powder in batches is developed in China and has important significance. In recent years, the main preparation methods of ultrafine silver powder are physical methods and chemical methods. Compared with the physical method, the liquid phase reduction method gradually becomes a common method for preparing a large amount of superfine silver powder due to simple preparation process, low energy consumption and easy realization of surface and performance control of silver particles. The production equipment and the formula for preparing the metal powder material by the chemical reduction method belong to core technology for manufacturers.
In the prior art, a silver source is generally prepared into silver salt dissolved in water, the silver salt is dissolved in water and then reacts with a weak reducing agent (glucose, formaldehyde, ascorbic acid, sucrose and the like) to produce micro-nano silver powder, the micro-nano silver powder is filtered and subjected to liquid phase or powder modification, an organic carrier is coated, and the qualified nano silver powder is prepared after drying and pulverization, the technological flow chart is shown in figure 1, and the different schemes in the process are mainly different in that: (1) Silver salts are distinguished by mostly silver nitrate, but silver ammonium complexes are also partly used; (2) The reducing agent may be selected from ascorbic acid, sulfite, alkanolamine, aqueous hydrogen peroxide, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, sodium borohydride, hydroquinone, hydrazine, hydrazides, pyrogallol, glucose, gallic acid salt, formalin, dried sodium sulfate, and rongalite; (3) Some patents describe the difference in the process of the modification step, which requires the addition of the modifier solution only after filtration to form a filter cake, but also the manner in which the modifier is added immediately after reduction. Patent 200510074647.X proposes a liquid phase reduction method, but the reduction performance of the reducing agent (substances of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin) is relatively too strong, so that the reaction speed is too high, the reaction process cannot be controlled, the stability is poor, the uniformity of the particle size of the produced silver powder is not high, and the sphericity is not ideal. Patent 201310429617.0 teaches that controlling the pH and temperature significantly increases the stability of the reduction process, but controlling the temperature and pH alone is not sufficient to fully ensure batch stability of the silver alloy properties.
Disclosure of Invention
The invention aims to provide spherical superfine silver powder, and a preparation method and application thereof, so as to solve the problems in the prior art. According to the invention, the reducing agent with weaker reducibility is selected, and the mixing speed, temperature and pH value of the reaction solution are controlled simultaneously by controlling the reaction speed, so that the batch stability of the synthesized silver powder is improved.
One of the schemes of the invention is as follows:
a method for preparing spherical superfine silver powder comprises the steps of preparing spherical superfine silver powder by a liquid phase reduction method by taking silver nitrate as a silver source, wherein a reducing agent comprises one or more of galacturonic acid, galactose, fructose and benzaldehyde.
Preferably, the ratio of the amounts of the reducing agent to the silver nitrate is (0.5:1) - (0.8-1).
Preferably, the specific preparation method comprises the following steps: the silver source is preferably high-purity silver nitrate (above AR level), the silver nitrate and pure water are prepared into a silver nitrate aqueous solution, a reducing agent and pure water are prepared into a reducing agent aqueous solution, the silver nitrate aqueous solution and the reducing agent aqueous solution are mixed by pumping into a Y-type liquid mixing pipe through a metering pump, wherein the pH value of the silver nitrate aqueous solution and the reducing agent aqueous solution is controlled within 1.5, the temperature is controlled within 30 ℃, the pumping amount of the silver nitrate aqueous solution and the reducing agent aqueous solution is controlled to be in a complete turbulence state, re is more than 15000, the silver nitrate aqueous solution and the reducing agent aqueous solution enter a synthesis tank after the mixing is completed, stirring is continued for 15min (the rotating speed is 100 rpm), and silver powder stirring reaction is carried out for 120min to obtain a suspension; and filtering and washing the silver powder suspension, ending washing and filtering when the conductivity of the filtrate is less than 120 mu m/cm after filtering and washing, taking out a filter cake, adding an alcohol solution of solid fatty acid, stirring for 60-120min, drying for 24-36 h at the temperature of not more than 80 ℃, crushing and grinding after drying to obtain superfine silver powder (primary powder), and separating spherical superfine silver powder by an ultrasonic vibration sieve.
Preferably, the pH of the silver nitrate aqueous solution is 1.2-1.5; the pH of the aqueous solution of the reducing agent is 1.2-1.5.
Preferably, a dispersing agent is further added into the silver nitrate aqueous solution, and more preferably, the dispersing agent is PVP (polyvinylpyrrolidone); preferably, the concentration of the silver nitrate solution is 20-50g/L.
Preferably, the method for mixing the silver nitrate aqueous solution and the reducing agent aqueous solution comprises the following steps: and (3) insulating the silver nitrate aqueous solution and the reducing agent aqueous solution at 20-22 ℃, pumping the silver nitrate aqueous solution and the reducing agent aqueous solution into a Y-type liquid mixing pipe at the speed of 1000-1200mL/min respectively for mixing, and introducing the mixed solution into a reaction kettle for stirring reaction to obtain silver powder suspension.
Preferably, the solid fatty acid accounts for 0.1-0.5% of the Ag mass, the solid fatty acid is dissolved in an alcohol solution, the silver powder filter cake is added into the alcohol solution of the solid fatty acid and is uniformly stirred, and the fatty acid is used as a surfactant to mainly improve the surface state of the silver powder, so that the hydrophilicity is changed into lipophilicity, and the dispersing capability of the silver powder in a subsequent organic solvent is improved.
More preferably, the solid fatty acid is dissolved in ethanol.
The scheme II of the invention is as follows:
a spherical superfine silver powder has tap density of 4.0-6.5g/mL and specific surface area of 0.1-0.4m 2 /g; the particle size distribution is D50 of 1-2 μm and D90 of 3-5 μm.
The third scheme of the invention:
an application of the spherical superfine silver powder in preparing conductive silver paste.
The invention has the beneficial effects that:
the reducing agent disclosed by the invention has weaker reducibility, and the reduction of the reducibility inevitably prolongs the reaction time, so that the production rate of a product can be obviously reduced. The invention also uses the reducing agent with weaker reducibility, which is beneficial to slowing down the reaction speed and increasing the window for controlling the growth of silver powder in the reaction process.
According to the invention, the Y-shaped pipe is used for mixing the silver source and the reducing agent, so that the determination of the relative concentration ratio of reactants can be effectively ensured, the relative concentration ratio can be basically unchanged along with the reaction, the mixing uniformity is remarkably improved, the ratio of the amounts of the silver source and the reducing agent in two liquids can be ensured to be hardly changed along with the reaction, and the batch stability is further ensured. The silver powder obtained by the preparation method of the spherical superfine silver powder provided by the invention has high sphericity, very few superfine powder, concentrated particle size distribution of silver powder particles, tap density of 4.0-6.5g/mL, particle size distribution D50-2 mu m and D90-5 mu m; the specific surface area of silver powder is 0.1-0.4m 2 /g。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for preparing silver powder according to the prior art in the background of the invention;
FIG. 2 is a schematic diagram showing the particle size distribution of the spherical ultrafine silver powder prepared in example 1 of the present invention;
FIG. 3 is an SEM image of the spherical ultrafine silver powder prepared in example 1 of the present invention;
FIG. 4 is an SEM image of the spherical ultrafine silver powder prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM image of the spherical ultrafine silver powder prepared in comparative example 2 of the present invention;
FIG. 6 is an SEM image of the spherical ultrafine silver powder prepared in comparative example 3 of the present invention;
fig. 7 is an SEM scanning electron microscope image of the spherical ultrafine silver powder prepared in comparative example 4 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature of the present invention means 25.+ -. 2 ℃.
Example 1 preparation method of spherical ultrafine silver powder
S1, preparing 10L of 20g/L silver nitrate solution, dropwise adding concentrated nitric acid to adjust the pH value to 1.5, preserving the temperature between 20 ℃ and 22 ℃, taking PVP as a dispersing agent, and adding the PVP into the silver nitrate solution, wherein the concentration of PVP is 0.3g/L; galactose is selected as a reducing agent to prepare 10L of reducing agent solution, the mass ratio of the reducing agent to the silver nitrate is (reducing agent): (silver nitrate) =0.65:1, concentrated nitric acid is used for regulating the pH value to be 1.5, and the temperature is kept between 20 ℃ and 22 ℃;
s2, respectively pumping the silver nitrate aqueous solution and the reducing agent aqueous solution into Y-type liquid mixing pipes, respectively mixing at the speed of 1000mL/min, introducing the mixed liquid into another clean reaction kettle, stirring while introducing the liquid, wherein the stirring speed is 120 revolutions/min, and keeping stirring for 120min after all the liquid is completely introduced to form silver powder suspension;
s3, filtering silver powder suspension, washing the filtered silver powder with deionized water for 5 times until the conductivity of the filtrate is less than 120 mu m/cm, and finishing washing and filtering work;
s4, weighing solid fatty acid accounting for 0.3% of the theoretical total mass of the silver powder, adding the solid fatty acid into 400mL of absolute ethyl alcohol, adding the solid fatty acid into a filter cake after the solid fatty acid is uniformly dispersed, carrying out surface modification, dispersing for 30min by using a double planetary mixer with the effective volume of 5L, and taking out the solid fatty acid after uniform stirring;
s5, drying the modified silver powder liquid at 80 ℃ for 30 hours, crushing and grinding after the drying is finished to obtain superfine silver powder (primary powder), and separating powder meeting the requirements through an ultrasonic vibration sieve to obtain spherical superfine silver powder, wherein the vibration density of the spherical superfine silver powder is 6.48g/mL, and the specific surface area is 0.26m 2 /g; the particle size distribution is schematically shown in FIG. 2, and the particle size is as follows: d50 is 1.48 μm and D90 is 2.75 μm; the SEM image is shown in FIG. 3, and the spherical superfine silver powder prepared by the invention can be seen from FIG. 3The sphericity of the powder is high, and the superfine powder is very little.
5 batches of spherical ultrafine silver powder were continuously prepared again according to the method of example 1, and the vibration density, specific surface area and particle size of the spherical ultrafine silver powder were measured, respectively, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the preparation method of the spherical ultrafine silver powder provided by the invention has high repeatability, and the prepared spherical ultrafine silver powder has stable performance.
Example 2 preparation method of spherical ultrafine silver powder
Meanwhile, example 1 was different only in that galactose was replaced with fructose. The mass ratio of the reducing agent to the silver nitrate is (reducing agent) to (silver nitrate) =0.5:1, the vibration density of the obtained spherical superfine silver powder is 5.9g/mL, and the specific surface area is 0.38m 2 /g; particle size: d50 is 1.21 μm and D90 is 4.35. Mu.m.
Example 3 preparation method of spherical ultrafine silver powder
Meanwhile, in example 1, only galactose was replaced by galactose after galactose and fructose were mixed in a mass ratio of 1:1. The mass ratio of the reducing agent to the silver nitrate is (reducing agent) to (silver nitrate) =0.6:1, the vibration density of the obtained spherical superfine silver powder is 6.32g/mL, and the specific surface area is 0.377m 2 /g; particle size: d50 is 1.19 μm and D90 is 3.82. Mu.m.
Example 4 preparation method of spherical ultrafine silver powder
S1, preparing 10L of 40g/L silver nitrate solution, dropwise adding concentrated nitric acid to adjust the pH value to 1.2, preserving the temperature to 20-22 ℃, taking PVP as a dispersing agent, and adding the PVP into the silver nitrate solution, wherein the concentration of PVP is 0.6g/L; the reducing agent is benzaldehyde, 10L of reducing agent solution is prepared, the mass ratio of the reducing agent to the silver nitrate is (reducing agent) to (silver nitrate) =0.7:1, the pH value is regulated to 1.2 by concentrated nitric acid, and the temperature is kept between 20 ℃ and 22 ℃;
s2, respectively pumping the silver nitrate solution and the reducing agent solution into Y-type liquid mixing pipes, respectively mixing at the speed of 1200mL/min, introducing the mixed liquid into another clean reaction kettle, introducing the liquid while stirring, and keeping stirring for 120min after all the liquid is introduced completely, so as to form silver powder suspension;
s3, filtering the silver powder suspension, washing the filtered silver powder with deionized water for 5 times until the conductivity of the filtrate is less than 60 mu m/cm, and then finishing washing and filtering;
s4, weighing solid fatty acid accounting for 0.2% of the theoretical total mass of the silver powder, adding the solid fatty acid into 800mL of absolute ethyl alcohol, adding the solid fatty acid into a filter cake after the solid fatty acid is uniformly dispersed, carrying out surface modification, dispersing for 45min by using a double planetary mixer with the effective volume of 10L, and taking out the solid fatty acid after uniform stirring;
s5, drying the modified silver powder liquid at 80 ℃ for 30 hours, crushing and grinding after drying to obtain superfine silver powder (primary powder), and separating powder meeting the requirements through an ultrasonic vibration sieve to obtain spherical superfine silver powder. The vibration density of the obtained spherical superfine silver powder is 5.9g/mL, and the specific surface area is 0.418m 2 /g; particle size: d50 is 1.8 μm and D90 is 4.4. Mu.m.
Example 5 preparation method of spherical ultrafine silver powder
S1, preparing 10L of 50g/L silver nitrate solution, dropwise adding concentrated nitric acid to adjust the pH value to 1.3, preserving the temperature to 20-22 ℃, taking PVP as a dispersing agent, and adding the PVP into the silver nitrate solution, wherein the concentration of PVP is 0.75g/L; the reducer is galacturonic acid to prepare 10L reducer solution, and the mass ratio of the reducer solution to the silver nitrate is n (reducer) to n (silver nitrate) =0.8: 1, regulating the pH value to 1.3 by using concentrated nitric acid, and preserving heat at 20-22 ℃;
s2, respectively pumping the silver nitrate solution and the reducing agent solution into Y-type liquid mixing pipes, respectively mixing at the speed of 1200mL/min, introducing the mixed liquid into another clean reaction kettle, introducing the liquid while stirring, and keeping stirring for 120min after all the liquid is introduced completely, so as to form silver powder suspension;
s3, filtering the silver powder suspension, washing the filtered silver powder with deionized water for 5 times until the conductivity of the filtrate is less than 90 mu m/cm, and then finishing the washing and filtering work.
S4, weighing solid fatty acid accounting for 0.4% of the theoretical total mass of the silver powder, adding the solid fatty acid into 900mL of absolute ethyl alcohol, adding the solid fatty acid into a filter cake after the solid fatty acid is uniformly dispersed, carrying out surface modification, dispersing for 45min by using a double planetary mixer with the effective volume of 10L, and taking out the solid fatty acid after uniform stirring;
s5, drying the modified silver powder liquid at 80 ℃ for 30 hours, crushing and grinding after drying to obtain superfine silver powder (primary powder), and separating powder meeting the requirements through an ultrasonic vibration sieve to obtain spherical superfine silver powder. The vibration density of the obtained spherical superfine silver powder is 5.95g/mL, and the specific surface area is 0.35m 2 /g; particle size: d50 is 1.48 μm and D90 is 4.2. Mu.m.
Comparative example 1
The only difference from example 1 is that galactose is replaced with ascorbic acid. The SEM scanning electron microscope of the silver powder is shown in FIG. 4, the vibration density is 4.65g/mL, and the specific surface area is 0.48m 2 /g; particle size: d50 is 1.25 μm and D90 is 5.1. Mu.m.
Comparative example 2
The only difference from example 1 is that galactose is replaced with glucose. SEM scanning electron microscope of the silver powder is shown in FIG. 5, the vibration density is 4.89g/mL, and the specific surface area is 0.52m 2 /g; particle size: d50 is 1.44 μm and D90 is 6.7. Mu.m.
Comparative example 3
The only difference from example 1 is that galactose is replaced with formaldehyde. SEM scanning electron microscope of the silver powder obtained is shown in FIG. 6, the vibration density is 5.95g/mL, and the specific surface area is 0.48m 2 /g; particle size: d50 is 2.23 μm and D90 is 6.4. Mu.m.
Comparative example 4
The difference from example 1 is that the Y-type mixing tube is not used in S2, but the silver nitrate aqueous solution is directly added to the reducing agent aqueous solution. An SEM scanning electron microscope diagram of the silver powder obtained by the preparation is shown in figure 7; vibration density of 6.3g/mL and specific surface area of 0.46m 2 /g; particle size: d50 is 1.5 μm and D90 is 5.9. Mu.m.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. The preparation method of spherical superfine silver powder is characterized in that silver nitrate is used as a silver source to prepare the spherical superfine silver powder through a liquid phase reduction method, and the spherical superfine silver powder is characterized in that the reducing agent comprises one or more of galacturonic acid, galactose, fructose and benzaldehyde.
2. The method for preparing spherical ultrafine silver powder according to claim 1, wherein the ratio of the amounts of the reducing agent and the silver nitrate is (0.5:1) - (0.8-1).
3. The method for preparing spherical ultrafine silver powder according to claim 1, characterized in that the specific preparation method comprises: mixing silver nitrate aqueous solution and reducer aqueous solution, obtaining silver powder suspension after the reaction is completed, filtering, washing, adding the washed filter cake into solid fatty acid alcohol solution, dispersing and stirring to obtain silver powder solution; and drying, crushing and grinding the silver powder liquid to obtain superfine silver powder, and finally separating to obtain spherical superfine silver powder.
4. The method for producing spherical ultrafine silver powder according to claim 2, wherein the pH of the aqueous silver nitrate solution is 1.2 to 1.5; the pH of the aqueous solution of the reducing agent is 1.2-1.5.
5. The method for preparing spherical ultrafine silver powder according to claim 2, wherein the method for mixing the aqueous silver nitrate solution and the aqueous reducing agent solution comprises the steps of: and (3) insulating the silver nitrate aqueous solution and the reducing agent aqueous solution at 20-22 ℃, pumping the silver nitrate aqueous solution and the reducing agent aqueous solution into a Y-type liquid mixing pipe at the speed of 1000-1200mL/min respectively for mixing, and introducing the mixed solution into a reaction kettle for stirring reaction to obtain silver powder suspension.
6. The method for preparing spherical ultrafine silver powder according to claim 2, wherein the solid fatty acid accounts for 0.1 to 0.5% of the mass of Ag.
7. The spherical ultrafine silver powder produced by the production process according to any one of claims 1 to 6, wherein the spherical ultrafine silver powder has a tap density of 4.0 to 6.5g/mL and a specific surface area of 0.1 to 0.4m 2 /g; the particle size distribution is D50 of 1-2 μm and D90 of 3-5 μm.
8. Use of the spherical ultrafine silver powder of claim 7 for preparing conductive silver paste.
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