CN114540881A - Preparation method of micron-sized monodisperse silver powder based on electrochemical deposition method - Google Patents
Preparation method of micron-sized monodisperse silver powder based on electrochemical deposition method Download PDFInfo
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- CN114540881A CN114540881A CN202210172619.5A CN202210172619A CN114540881A CN 114540881 A CN114540881 A CN 114540881A CN 202210172619 A CN202210172619 A CN 202210172619A CN 114540881 A CN114540881 A CN 114540881A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 100
- 239000008139 complexing agent Substances 0.000 claims abstract description 42
- 239000002270 dispersing agent Substances 0.000 claims abstract description 39
- 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 abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000001680 brushing effect Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 229960001124 trientine Drugs 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- 241000978776 Senegalia senegal Species 0.000 claims description 4
- 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 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 4
- 229940074439 potassium sodium tartrate Drugs 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
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-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
- 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
- 230000002378 acidificating effect Effects 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 22
- 238000009826 distribution Methods 0.000 abstract description 18
- 238000005137 deposition process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 6
- 229940071536 silver acetate Drugs 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 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 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- 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
Abstract
The invention relates to a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method. The method comprises the steps of preparing a silver salt solution, a dispersing agent solution, a complexing agent solution and a pH regulator solution by adopting a silver source, a complexing agent, a dispersing agent and a pH regulator respectively; uniformly mixing a silver salt solution, a dispersant solution and a complexing agent solution, stirring until the mixed solution is clarified, and then performing fixed dissolution to obtain an electrolyte system; controlling the pH value of an electrolyte system to be 1-3 or 8-11 by a pH regulator solution at the temperature of 15-70 ℃, and carrying out electrochemical deposition to obtain the micron-sized monodisperse silver powder which is flaky, flower-shaped, dendritic or spheroidal. The invention utilizes the electrochemical deposition method and strictly controls the silver source, the complexing agent and the dispersing agent in the deposition process, and the anode, the cathode, the current density, the distance between the anode and the cathode, the brushing period and the like in the electrochemical deposition process, and can efficiently prepare the superfine silver powder with special shape, narrow particle size distribution and high specific surface area.
Description
Technical Field
The invention relates to a preparation method of monodisperse ultrafine silver powder, in particular to a preparation method of micron monodisperse silver powder based on an electrochemical deposition method.
Background
The superfine silver powder is an important field for the development of new material industry at present, and is widely used in many fields such as solar slurry, electronic slurry industry, electronic component manufacturing, medical and antibacterial materials, electromagnetic shielding, composite materials, catalysts, coatings and the like. With the high-speed innovation and development of electronic, information and microelectronic technologies, environmental protection, precision and miniaturization become the development direction of electronic components, the requirements on superfine silver powder are higher and higher, and especially the higher requirements on the performance indexes such as morphology, conductivity, dispersibility, apparent density and specific surface area are required. Due to the difference of the morphology and the particle size of the silver powder, the arrangement of surface atoms of the crystal structure of the silver powder is correspondingly changed, a large number of surface defects are generated, so that the material has unsaturation and chemical activity, and has small-size effect, surface effect, quantum effect and macroscopic quantum tunneling effect, which are different from macroscopic bulk material and microscopic atoms or molecules, thereby determining the difference of the application value.
At present, a plurality of methods for preparing silver powder at home and abroad mainly comprise a grinding method, an atomization method, an evaporation and condensation method, an electrochemical deposition method, a sol-gel method, a liquid phase reduction method and the like. The superfine silver powder on the market is mainly prepared by a liquid-phase reduction method, mainly takes silver nitrate as a silver source, is reduced by a reducing agent, and is obtained by washing, hydrophobic treatment, drying and other treatments. The reducing agent mainly comprises glucose, ascorbic acid, formaldehyde, hydroxylamine sulfate, hydrazine hydrate, ethanolamine, polyhydric alcohol and the like, wherein the hydrazine hydrate, the hydroxylamine sulfate and the like have high toxicity and over-strong reducing capability, a large amount of gas is generated in the reducing process, a large amount of foam is easily generated in the reaction liquid containing a dispersing agent and in a stirring state, and the product performance is not suitable to be controlled. Formaldehyde is volatile and has strong carcinogenicity and high operation risk. The high-temperature heat loss of the silver powder reduced by the glucose and the ascorbic acid is large, and the performance of the powder is easily influenced. The reduction capability of the ethanolamine and the polyalcohol reducing agents is weak, silver ions can be reduced only at a higher solution temperature, and the incomplete reduction has low yield. In addition, the liquid phase reduction method is simple and controllable, and becomes the mainstream method for preparing micron-sized silver powder at present, but the silver powder prepared by the method is easy to generate larger aggregates, and in order to prevent silver powder particles from agglomerating, a layer of organic matter is usually coated on the surface of the silver powder, and the conductivity of the silver powder can be influenced to a certain extent by the organic matter. Therefore, the exploration of the preparation method and the system of the low-carbon and environment-friendly silver powder has important significance for preparing the micron-sized silver powder.
The electrochemical deposition method plays an important role in powder production and has incomparable advantages compared with other methods: 1) the requirement on raw materials is low (crude silver can be adopted); 2) the preparation process is carried out in a water system; 3) the equipment and the operation are simple, and the maintenance is convenient; 4) the cost is low; 5) the product has high purity, uniform and controllable particle size. However, the process of preparing the micron-sized silver powder by the electrochemical method at present has high energy consumption and high production cost, is difficult to produce in a large scale, and is particularly embodied in that the electrode material (platinum electrode) has high value and small selectable space; the electrolyte system is single, and the concentration range is narrow; the selection of additives such as a complexing agent and the like is small, the adding process is strict, and the analysis technology of the residual additives of the system is lagged during continuous production, so that accurate detection is difficult.
Disclosure of Invention
The invention provides a micron-sized monodisperse silver powder preparation method based on an electrochemical deposition method, aiming at the problems of large process energy consumption, high production cost and difficulty in large-scale production in the existing micron-sized silver powder electrochemical method, namely, the electrochemical deposition method is utilized to strictly control a silver source, a complexing agent, a dispersing agent, an anode, a cathode, current density, an inter-anode-cathode spacing, a brushing period and the like in the deposition process, and superfine silver powder with special shape (flake/flower-shaped/dendritic/spheroidal), narrow particle size distribution and high specific surface area can be efficiently prepared.
A preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing silver salt solution, dispersant solution, complexing agent solution and pH regulator solution by adopting a silver source, a complexing agent, a dispersant and a pH regulator respectively;
(2) uniformly mixing a silver salt solution, a dispersant solution and a complexing agent solution, stirring until the mixed solution is clarified, and then performing fixed dissolution to obtain an electrolyte system;
(3) controlling the pH value of an electrolyte system to be 1-3 or 8-11 by a pH regulator solution at the temperature of 15-70 ℃, and carrying out electrochemical deposition to obtain micron-sized monodisperse silver powder which is flaky, flower-shaped, dendritic or spheroidal;
the solvents of the silver salt solution, the dispersing agent solution, the complexing agent solution and the pH regulator solution in the step (1) are deionized water;
the silver source in the step (1) is one or more of silver nitrate, silver carbonate, silver sulfate and silver oxalate;
the complexing agent in the step (1) is one or more of tartaric acid, ethylenediamine, ammonia water, salicylic acid, triethanolamine, triethylene tetramine, potassium sodium tartrate, sodium citrate, thiourea and sodium thiosulfate; preferably, the complexing agent is a composite complexing agent of two or more;
the dispersant in the step (1) is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, gum arabic, tween, oleic acid and water-soluble polyether; preferably, the dispersant is a composite dispersant of two or more;
the pH regulator in the step (1) is an acidic regulator or an alkaline regulator, and the concentration of the pH regulator is 0.5-5 g/L;
the acid regulator is one or two of nitric acid, acetic acid, formic acid, oxalic acid and citric acid, and the alkaline regulator is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia water and triethylene tetramine;
the concentration of silver salt in the electrolyte system in the step (2) is 5-108 g/L, the concentration of a complexing agent is 3-10 g/L, and the concentration of a dispersing agent is 0.1-3 g/L;
the cathode of the electrochemical deposition in the step (3) is a titanium plate, a silver plate or a stainless steel plate, the anode is a coarse silver plate, the inter-polar distance is 3-20 cm, and the deposition current is 20-1500A/m2The brushing period is 1-20 min/time;
the micron-sized monodisperse silver powder has a particle size of 0.5-10 um and a bulk density of 0.4-2.4 g/cm2And the burning loss is less than or equal to 0.5 percent.
The invention has the beneficial effects that:
(1) the invention adopts an electrochemical deposition method, overcomes the defects that a liquid phase reduction method uses toxic reducing agents such as hydrazine hydrate, hydroxylamine and hydroxylamine sulfate, and also overcomes the defect that the dispersibility of the obtained powder is poor because nitrogen is generated in the reduction process to cause reaction liquid to generate a large amount of foam;
(2) according to the invention, an electrochemical deposition method is utilized, and the silver source, the complexing agent and the dispersing agent, as well as the anode, the cathode, the current density, the distance between the anode and the cathode, the brushing period and the like in the deposition process are strictly controlled, so that the superfine silver powder with special shape (flake/flower/tree-like/sphere-like), narrow particle size distribution and high specific surface area can be efficiently prepared, and the superfine silver powder can be applied to the fields of conductive adhesive, photovoltaic silver paste, low-temperature printing silver paste and the like.
Drawings
FIG. 1 is a scanning electron microscope image and a particle size distribution diagram of the spheroidal silver powder prepared in example 1;
FIG. 2 is a scanning electron microscope image and a particle size distribution diagram of the spheroidal silver powder prepared in example 2;
FIG. 3 is a scanning electron microscope photograph and a particle size distribution chart of the silver flake prepared in example 3;
FIG. 4 is a scanning electron micrograph and a particle size distribution of the silver dendrite powder prepared in example 4;
FIG. 5 is a scanning electron microscope image and a particle size distribution chart of the flower-like silver powder prepared in example 5.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing a silver salt solution (silver nitrate solution), a composite complexing agent solution (mixed solution of triethanolamine and tartaric acid), a composite dispersing agent (mixed solution of polyvinylpyrrolidone and tween in a mass ratio of 5: 1) and a pH regulator (nitric acid) with a solvent (deionized water) respectively to obtain a silver salt solution (silver nitrate solution), a composite complexing agent solution (mixed solution of triethanolamine and tartaric acid), a composite dispersing agent solution (mixed solution of polyvinylpyrrolidone and tween) and a pH regulator solution (nitric acid solution); wherein the concentration of the pH regulator solution (nitric acid solution) is 0.5 g/L;
(2) uniformly mixing a silver salt solution and a dispersing agent solution, then adding a complexing agent solution, uniformly mixing, stirring until the mixed solution is clear and transparent, and fixing the volume to obtain an electrolyte system; wherein the concentration of silver nitrate in the electrolyte system is 5g/L, the concentration of a complexing agent is 10g/L, and the concentration of a dispersing agent is 3 g/L;
(3) controlling the pH value of an electrolyte system to be 1 by a pH regulator solution (a nitric acid solution) at the temperature of 15 ℃, performing electrochemical deposition for 20min, scraping powder, collecting silver powder obtained by deposition after the electrochemical deposition is circulated for 10 times, and sequentially performing suction filtration, water washing and drying on the silver powder to obtain micron-sized monodisperse silver powder, wherein the cathode of the electrochemical deposition is a titanium plate, the anode of the electrochemical deposition is a coarse silver plate, the inter-polar distance is 3cm, and the deposition current is 20A/m2The brushing period is 20 min/time;
the micron-sized monodisperse silver powder obtained in this example was spheroidal in shape, and the scanning electron microscopy pattern and the particle size distribution plot are shown in FIG. 1, D in the particle size distribution501.85um, and a loose packed density of 1.48g/cm2And the burning loss is less than or equal to 0.28 percent.
Example 2: a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing a silver salt solution (silver acetate solution), a complexing agent solution (gum arabic and polyethylene glycol in a mass ratio of 3: 1) and a pH regulator (citric acid) into a solvent (deionized water), a silver salt (silver acetate solution), a complexing agent solution (sodium citrate and salicylic acid mixed solution), a dispersing agent solution (gum arabic and polyethylene glycol mixed solution) and a pH regulator solution (citric acid solution) respectively with the silver salt (silver acetate), the complexing agent (sodium citrate and salicylic acid mixed solution) and the pH regulator solution (citric acid solution); wherein the concentration of the pH regulator solution (citric acid solution) is 2 g/L;
(2) uniformly mixing a silver salt solution and a dispersing agent solution, then adding a complexing agent solution, uniformly mixing, stirring until the mixed solution is clear and transparent, and fixing the volume to obtain an electrolyte system; wherein the concentration of silver salt in the electrolyte system is 10g/L, the concentration of complexing agent is 8g/L, and the concentration of dispersing agent is 1 g/L;
(3) controlling the pH value of an electrolyte system to be 3 by a pH regulator solution (citric acid solution) at the temperature of 20 ℃, scraping powder after electrochemical deposition for 10min, collecting the silver powder obtained by deposition after the electrochemical deposition is circulated for 10 times, and sequentially performing suction filtration, water washing and drying on the silver powder to obtain micron-sized monodisperse silver powder, wherein the cathode of the electrochemical deposition is a silver plate, the anode of the electrochemical deposition is a coarse silver plate, the inter-polar distance is 4cm, and the deposition current is 100A/m2The brushing period is 10 min/time;
the micron-sized monodisperse silver powder obtained in this example was spheroidal in shape, and the scanning electron microscopy image and the particle size distribution diagram, D in the particle size distribution, are shown in FIG. 250Is 3.01um, and the loose packed density is 1.27g/cm2And the burning loss is less than or equal to 0.34 percent.
Example 3: a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing a silver salt solution (silver acetate solution), a composite complexing agent solution (mixed solution of triethanolamine and ethylenediamine), a dispersing agent solution (polyethylene glycol solution) and a pH regulator solution (sodium carbonate solution) by respectively using a solvent (deionized water) and a silver salt (silver acetate), a composite complexing agent (triethanolamine and ethylenediamine), a dispersing agent solution (polyethylene glycol solution) and a pH regulator solution (sodium carbonate solution); wherein the concentration of the pH regulator solution (sodium carbonate solution) is 5 g/L;
(2) uniformly mixing a silver salt solution and a dispersing agent solution, then adding a composite complexing agent solution, uniformly mixing, stirring until the mixed solution is clear and transparent, and fixing the volume to obtain an electrolyte system; wherein the concentration of silver acetate in the electrolyte system is 108g/L, the concentration of a complexing agent is 3g/L, and the concentration of a dispersing agent is 3 g/L;
(3) controlling the pH value of an electrolyte system to be 11 through a pH regulator solution (sodium carbonate solution) at the temperature of 30 ℃, scraping powder after electrochemical deposition is carried out for 1min, collecting silver powder obtained by deposition after electrochemical deposition is circulated for 10 times, and sequentially carrying out suction filtration, water washing and drying on the silver powder to obtain micron-sized monodisperse silver powder, wherein a cathode of the electrochemical deposition is a titanium plate, and an anode of the electrochemical deposition is a titanium plateIs a thick silver plate with a pole spacing of 20cm and a deposition current of 1500A/m2The brushing period is 1 min/time;
the micron-sized silver powder obtained in this example was flake-shaped, and the scanning electron microscopic image and the particle size distribution diagram are shown in FIG. 3, wherein D is the particle size distribution509.47um, loose packed density of 0.62g/cm2And the burning loss is less than or equal to 0.45 percent.
Example 4: a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing a silver salt solution (silver nitrate solution), a complexing agent solution (potassium sodium tartrate solution), a dispersing agent solution (sodium carboxymethyl cellulose solution) and a pH regulator solution (triethylene tetramine solution) by respectively using a solvent (deionized water) and a silver salt (silver nitrate), a complexing agent (potassium sodium tartrate), a dispersing agent (sodium carboxymethyl cellulose solution) and a pH regulator (triethylene tetramine solution); wherein the concentration of the pH regulator solution (triethylene tetramine solution) is 3 g/L;
(2) uniformly mixing a silver salt solution and a dispersing agent solution, then adding a complexing agent solution, uniformly mixing, stirring until the mixed solution is clear and transparent, and fixing the volume to obtain an electrolyte system; wherein the concentration of silver salt in the electrolyte system is 60g/L, the concentration of complexing agent is 10g/L, and the concentration of dispersing agent is 1.5 g/L;
(3) controlling the pH value of an electrolyte system to be 10 by a pH regulator solution (triethylene tetramine solution) at the temperature of 50 ℃, scraping powder after electrochemical deposition for 5min, collecting silver powder obtained by deposition after electrochemical deposition is circulated for 10 times, and sequentially performing suction filtration, water washing and drying on the silver powder to obtain micron-sized monodisperse silver powder, wherein the cathode of the electrochemical deposition is a stainless steel plate, the anode of the electrochemical deposition is a coarse silver plate, the inter-polar distance is 10cm, and the deposition current is 800A/m2The brushing period is 5 min/time;
the micron-sized monodisperse silver powder obtained in this example was dendritic, and the scanning electron microscopy pattern and the particle size distribution plot are shown in FIG. 4, wherein D is the particle size distribution505.95um, loose packed density 0.48g/cm2And the burning loss is less than or equal to 0.43 percent.
Example 5: a preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method comprises the following specific steps:
(1) preparing a silver salt solution (silver oxalate solution), a composite complexing agent solution (salicylic acid and citric acid mixed solution), a composite dispersing agent solution (oleic acid and sodium carboxymethyl cellulose solution) and a pH regulator solution (acetic acid) by respectively using a solvent (deionized water) and a silver salt (silver oxalate), a composite complexing agent (salicylic acid and sodium carboxymethyl cellulose solution) and a pH regulator solution (acetic acid solution); wherein the concentration of the pH regulator solution (acetic acid solution) is 2 g/L;
(2) uniformly mixing a silver salt solution and a composite dispersant solution, then adding a composite complexing agent solution, uniformly mixing, stirring until the mixed solution is clear and transparent, and fixing the volume to obtain an electrolyte system; wherein the concentration of silver oxalate in the electrolyte system is 20g/L, the concentration of a complexing agent is 5g/L, and the concentration of a dispersing agent is 2 g/L;
(3) controlling the pH value of an electrolyte system to be 2 by a pH regulator solution (acetic acid solution) at the temperature of 70 ℃, scraping powder after electrochemical deposition is carried out for 8min, collecting silver powder obtained by deposition after electrochemical deposition is circulated for 10 times, and sequentially carrying out suction filtration, water washing and drying on the silver powder to obtain micron-sized monodisperse silver powder, wherein the cathode of the electrochemical deposition is a titanium plate, the anode of the electrochemical deposition is a coarse silver plate, the inter-polar distance is 15cm, and the deposition current is 700A/m2The brushing period is 8 min/time;
the micron-sized silver powder obtained in this example was flake-shaped, and its scanning electron microscopic image and particle size distribution diagram are shown in FIG. 5, D in the particle size distribution50Is 7.17um, and the loose packed density is 0.52g/cm2And the burning loss is less than or equal to 0.5 percent.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. A preparation method of micron-sized monodisperse silver powder based on an electrochemical deposition method is characterized by comprising the following specific steps:
(1) preparing silver salt solution, dispersant solution, complexing agent solution and pH regulator solution by adopting a silver source, a complexing agent, a dispersant and a pH regulator respectively;
(2) uniformly mixing a silver salt solution, a dispersant solution and a complexing agent solution, stirring until the mixed solution is clarified, and then performing fixed dissolution to obtain an electrolyte system;
(3) controlling the pH value of an electrolyte system to be 1-3 or 8-11 by a pH regulator solution at the temperature of 15-70 ℃, and carrying out electrochemical deposition to obtain the micron-sized monodisperse silver powder which is flaky, flower-shaped, dendritic or spheroidal.
2. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 1, wherein: and (2) the solvents of the silver salt solution, the dispersing agent solution, the complexing agent solution and the pH regulator solution in the step (1) are deionized water.
3. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 2, wherein: the silver source in the step (1) is one or more of silver nitrate, silver carbonate, silver sulfate and silver oxalate.
4. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 1, wherein: the complexing agent in the step (1) is one or more of tartaric acid, ethylenediamine, ammonia water, salicylic acid, triethanolamine, triethylene tetramine, potassium sodium tartrate, sodium citrate, thiourea and sodium thiosulfate.
5. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 1, wherein: the dispersant in the step (1) is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, gum arabic, tween, oleic acid and water-soluble polyether.
6. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 1, wherein: the pH regulator in the step (1) is an acidic regulator or an alkaline regulator, and the solution concentration of the pH regulator is 0.5-5 g/L.
7. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 6, wherein: the acidic regulator is one or more of nitric acid, acetic acid, formic acid, oxalic acid and citric acid, and the alkaline regulator is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia water and triethylene tetramine.
8. The method for preparing micron-sized monodisperse silver powder based on electrochemical deposition method according to claim 1, wherein the method comprises the following steps: in the electrolyte system in the step (2), the concentration of silver salt is 5-108 g/L, the concentration of complexing agent is 3-10 g/L, and the concentration of dispersing agent is 0.1-3 g/L.
9. The method for preparing micron-sized mono-dispersed silver powder based on electrochemical deposition method according to claim 1, wherein: the cathode of the electrochemical deposition in the step (3) is a titanium plate, a silver plate or a stainless steel plate, the anode is a coarse silver plate, the interpolar distance is 3-20 cm, and the deposition current is 20-1500A/m2The brushing period is 1-20 min/time.
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