CN113000855B - Preparation method of micro-nano copper powder - Google Patents
Preparation method of micro-nano copper powder Download PDFInfo
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- CN113000855B CN113000855B CN202110317252.7A CN202110317252A CN113000855B CN 113000855 B CN113000855 B CN 113000855B CN 202110317252 A CN202110317252 A CN 202110317252A CN 113000855 B CN113000855 B CN 113000855B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 185
- 239000012266 salt solution Substances 0.000 claims abstract description 151
- 239000000243 solution Substances 0.000 claims abstract description 138
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 claims abstract description 77
- 239000010949 copper Substances 0.000 claims abstract description 77
- 238000003756 stirring Methods 0.000 claims abstract description 73
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 87
- 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 40
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 238000005485 electric heating Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 6
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- 235000010350 erythorbic acid Nutrition 0.000 claims description 4
- 229940026239 isoascorbic acid Drugs 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 238000009295 crossflow filtration Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229940083542 sodium Drugs 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 28
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 44
- 238000005303 weighing Methods 0.000 description 28
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000010352 sodium erythorbate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid 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
- 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
-
- 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
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
Abstract
The invention discloses a preparation method of micro-nano copper powder, which comprises the following steps: step S10, preparing a reducing solution containing a high molecular surfactant, a first copper salt solution and a second copper salt solution respectively; step S20, heating the reducing solution under the stirring condition, then adding the first copper salt solution into the solution, heating and stirring until elemental copper is generated in the solution, continuously adding the second copper salt solution into the solution, and heating and stirring to obtain a product solution with micro-nano copper powder; and step S30, concentrating, cleaning and drying the product solution to obtain the micro-nano copper powder. The preparation method realizes controllable micro-nano copper particle size, is simple and convenient and easy to realize, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of micro-nano copper powder.
Background
The monodisperse micro-nano copper has excellent physical and chemical properties, including good heat conduction, electric conduction, lubrication, antibiosis and catalysis, and can be used as main or important components of novel electronic paste, lubricating oil modifier, antibiosis material, working catalyst and the like. Taking a main application scenario of electronic paste as an example of a multilayer ceramic capacitor MLCC (a typical passive electronic component), the market size of the global multilayer ceramic capacitor MLCC in 2019 was about 960 hundred million renmins. With the acceleration of 5G construction and the alternation of mobile terminals and communication equipment in the next few years, new energy automobiles and intelligent home appliances are popularized, and the MLCC market is expected to be further expanded, and the 2024 market scale is expected to be increased to about 1200 hundred million yuan. The proportion of the micro-nano metal powder (palladium, silver, nickel, copper and the like) in the structural cost of the MLCC is more than 5 percent (5 percent in the low-capacity type MLCC and 5 to 10 percent in the high-capacity type MLCC). In order to adapt to the recent trend of cost reduction and light weight development of MLCC, the monodisperse micro-nano copper powder is used as an important substitute material of the micro-nano metal powder (palladium, silver and nickel), has huge market scale and development potential, and further improves the specification requirements of the used micro-nano copper powder. The MLCC with the inner electrode thickness of 2-3 microns requires the metal crystal to be spherical or nearly spherical in shape, have the particle size controlled below the micron level, preferably 0.2-0.7 microns, and be uniformly distributed. The metal crystal with the specification is a necessary condition for preparing uniform conductive slurry, can ensure good contact after sintering, and can effectively prevent the defect of no laminated structure caused by large particles penetrating through a ceramic dielectric layer. Wet chemical reduction process to synthesize micro-nano copper powder has been the hot problem in chemical field. Compared with other technical routes, the wet chemical reduction method has the characteristics of less equipment investment, short process flow, low industrial production cost and the like. In the process route, cupric ion salt, cupric oxide, cuprous oxide, cupric hydroxide and the like are generally used as copper sources, potassium borohydride, hydrazine hydrate, polyalcohol, ascorbic acid, sodium hypophosphite and the like are used as reducing agents, a macromolecular surfactant is used for assisting in inhibiting explosive aggregation of copper powder, and the aim of producing micro-nano copper powder with different sizes or morphologies is fulfilled by adjusting parameters such as the feeding ratio, temperature, pH value, mixing process, reaction time and the like of the reaction.
According to published literature data, most of the current synthesis processes cannot accurately control the particle size of micro-nano copper, and the prepared copper powder is difficult to meet the technical requirements of specific application scenes. Therefore, the development of a stable, effective and particle-size-controllable synthesis method of the monodisperse micro-nano copper, which is easy for mass production, has important value.
Disclosure of Invention
The invention mainly aims to provide a preparation method of micro-nano copper powder, and aims to provide a synthesis method with controllable micro-nano copper particle size.
In order to achieve the above purpose, the invention provides a preparation method of micro-nano copper powder, which comprises the following steps:
Step S10, preparing a reducing solution containing a high molecular surfactant, a first copper salt solution and a second copper salt solution respectively;
step S20, heating the reducing solution under the stirring condition, then adding the first copper salt solution into the solution, heating and stirring until elemental copper is generated in the solution, continuously adding the second copper salt solution into the solution, and heating and stirring to obtain a product solution with micro-nano copper powder;
And step S30, concentrating, cleaning and drying the product solution to obtain the micro-nano copper powder.
Optionally, the solvent of the reducing solution, the first copper salt solution, and the second copper salt solution includes at least one of a monohydric alcohol and a polyhydric alcohol, or a mixed solution of at least one of a monohydric alcohol and a polyhydric alcohol with water.
Optionally, the solvents of the reducing solution, the first copper salt solution and the second copper salt solution are monohydric alcohols.
Optionally, the solvent of the reducing solution, the first copper salt solution and the second copper salt solution is ethanol;
In step S20: the mol ratio of the total ethanol to the total copper ions in the reducing solution, the first copper salt solution and the second copper salt solution is (85-500): 1.
Optionally, the copper salt in the first copper salt solution comprises at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate, copper acetylacetonate; and/or the number of the groups of groups,
The copper salt in the second copper salt solution comprises at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate and copper acetylacetonate; and/or the number of the groups of groups,
The first copper salt solution has a copper salt concentration not lower than the copper salt concentration in the second copper salt solution.
Optionally, the copper salt in the first copper salt solution and the second copper salt solution is copper acetate; and/or the number of the groups of groups,
The first copper salt solution has a copper salt concentration comparable to the copper salt concentration in the second copper salt solution.
Optionally, the reducing agent in the reducing solution comprises at least one of ascorbic acid, sodium ascorbate, isoascorbic acid, sodium isoascorbate; and/or the number of the groups of groups,
The surfactant in the reducing solution comprises at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether.
Optionally, the reducing agent in the reducing solution is ascorbic acid, and in step S20, a molar ratio of total ascorbic acid to total copper ions in the reducing solution and the first copper salt solution, the second copper salt solution is (1-20): 1, a step of; and/or the number of the groups of groups,
The surfactant in the reducing solution is polyvinylpyrrolidone, and in step S20, the molar ratio of the total polyvinylpyrrolidone in the reducing solution to the first copper salt solution and the second copper salt solution to the total copper ions is (1-20): 1.
Optionally, in step S20:
the heating condition is any one of water bath, oil bath, electric heating plate and electric heating sleeve, and the reaction temperature of the reaction system is 50-99 ℃; and/or the number of the groups of groups,
The stirring is at least one of magnetic stirring and mechanical stirring; and/or the number of the groups of groups,
The adding rate of the second copper salt solution is 0.5-10 mL/min.
Optionally, in step S30:
the concentration mode comprises at least one of centrifugation, rotary evaporation, reduced pressure distillation and cross-flow filtration; and/or the number of the groups of groups,
The solvent used in the cleaning comprises at least one of methanol, ethanol and water; and/or the number of the groups of groups,
The drying temperature during the drying is 40-90 ℃.
The preparation method of the micro-nano copper is a synthesis method based on a wet chemical reduction technology route, a reducing solution added with a surfactant as a protective agent is used as a main component of a reaction system, a first copper salt solution is added into the reducing solution under the condition of heating and stirring, a seed solution with elemental copper is obtained through heating and stirring reaction, a second copper salt solution is continuously added into the seed solution, copper is further grown on the elemental copper through heating and stirring reaction, so that monodisperse micro-nano copper is prepared, and then a reaction product is separated, washed and dried to obtain the micro-nano copper; the particle size of the micro-nano copper prepared by the method provided by the invention is controllable, and the precise adjustment of the particle size of the micro-nano copper can be realized by adjusting the concentration and volume ratio of the first copper salt solution and the second copper salt solution, the reaction temperature and other technological parameters, so that the particle size distribution is uniform, and the particle size range is 1-1000 nm.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing micro-nano copper according to the present invention;
FIG. 2 is a scanning electron microscope image of micro-nano copper prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of micro-nano copper prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of micro-nano copper prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of micro-nano copper prepared in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image of micro-nano copper prepared in example 5 of the present invention;
FIG. 7 is a scanning electron microscope image of micro-nano copper prepared in example 6 of the present invention;
FIG. 8 is a scanning electron microscope image of micro-nano copper prepared in example 7 of the present invention;
FIG. 9 is an X-ray diffraction pattern of micro-nano copper prepared in example 4 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. 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 be within the scope of the invention.
According to published literature data, most of the current synthesis processes cannot accurately control the particle size of micro-nano copper, and the prepared copper powder is difficult to meet the technical requirements of specific application scenes. Therefore, the development of a stable, effective and particle-size-controllable synthesis method of the monodisperse micro-nano copper, which is easy for mass production, has important value.
The invention provides a preparation method of micro-nano copper powder, and fig. 1 shows an embodiment of the preparation method of micro-nano copper provided by the invention. Referring to fig. 1, in this embodiment, the preparation method of the micro-nano copper includes the following steps:
Step S10, preparing a reducing solution containing a high molecular surfactant, a first copper salt solution and a second copper salt solution respectively;
step S20, heating the reducing solution under the stirring condition, then adding the first copper salt solution into the solution, heating and stirring until elemental copper is generated in the solution, continuously adding the second copper salt solution into the solution, and heating and stirring to obtain a product solution with micro-nano copper powder;
And step S30, concentrating, cleaning and drying the product solution to obtain the micro-nano copper powder.
The preparation method of the micro-nano copper is a synthesis method based on a wet chemical reduction technology route, a reducing solution added with a surfactant as a protective agent is used as a main component of a reaction system, a first copper salt solution is added into the reducing solution under the condition of heating and stirring, a seed solution with elemental copper is obtained through heating and stirring reaction, a second copper salt solution is continuously added into the seed solution, copper is further grown on the elemental copper through heating and stirring reaction, so that monodisperse micro-nano copper is prepared, and then a reaction product is separated, washed and dried to obtain the micro-nano copper; the particle size of the micro-nano copper prepared by the method provided by the invention is controllable, and the precise adjustment of the particle size of the micro-nano copper can be realized by adjusting the concentration and volume ratio of the first copper salt solution and the second copper salt solution, the reaction temperature and other technological parameters, so that the particle size distribution is uniform, and the particle size range is 1-1000 nm.
The solvent used to prepare the reducing solution, the first copper salt solution, and the second copper salt solution is preferably at least one selected from the group consisting of an alcohol solvent and water, and may be an alcohol solvent or water, or a mixed solution of an alcohol solvent and water. Further, the solvent used to formulate the reducing solution, the first copper salt solution, and the second copper salt solution is more preferably a mixed solution comprising at least one of a monohydric alcohol and a polyhydric alcohol, or at least one of a monohydric alcohol and a polyhydric alcohol with water. Still further, the solvent of the reducing solution, the first copper salt solution, and the second copper salt solution is more preferably monohydric alcohol, and particularly preferably ethanol. When the solvents of the reducing solution, the first copper salt solution and the second copper salt solution are all ethanol, the molar ratio of the reducing solution to the total ethanol to the total copper ions in the first copper salt solution and the second copper salt solution in step S20 is (85-500): 1.
The reducing agent in the reducing solution is at least one of a small molecular organic reducing agent and a salt thereof, preferably at least one of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium isoascorbate, and can be any one of the reducing agents or a mixture of two or more of the reducing agents. In a specific embodiment of the present invention, the reducing agent in the reducing solution is preferably any one of the above reducing agents, and further preferably ascorbic acid. When the reducing agent in the reducing solution is ascorbic acid, the molar ratio of the reducing solution to the total ascorbic acid to the total copper ions in the first copper salt solution and the second copper salt solution in step S20 is (1-20): 1.
The surfactant in the reducing solution is a polymer surfactant, preferably at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether, and can be any one of the reducing agents or a mixture of two or more of the reducing agents. In a specific embodiment of the present invention, the surfactant in the reducing solution is preferably any one of the above surfactants, and further preferably polyvinylpyrrolidone model K30. When the surfactant in the reducing solution is polyvinylpyrrolidone, the molar ratio of the reducing solution to the total polyvinylpyrrolidone and the total copper ions in the first copper salt solution and the second copper salt solution in step S20 is (1-20): 1.
In addition, a proper amount of surfactant may be added to the first copper salt solution and/or the second copper salt solution, and specific optional materials of the surfactant are the same as those described above, and are not described herein. When polyvinylpyrrolidone is added to the first copper salt solution and/or the second copper salt solution as a surfactant, the concentration of polyvinylpyrrolidone contained in the reducing solution and the first copper salt solution and the second copper salt solution may be the same or different, and it is only necessary to satisfy that the molar ratio of the reducing solution in step S20 to total polyvinylpyrrolidone and total copper ions in the first copper salt solution and the second copper salt solution is (1 to 20): 1.
The first copper salt solution is used for preparing a seed solution containing elemental copper, the second copper salt solution is used for further carrying out copper growth on the basis of the elemental copper, so that monodisperse micro-nano copper is prepared, a divalent copper source can be selected from copper salts in the first copper salt solution and the second copper salt solution, copper salts containing crystal water or not containing crystal water can be selected, specifically, in some embodiments of the invention, the copper salts in the first copper salt solution comprise at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate and copper acetylacetonate, and the copper salts can be any one of the copper salts or a mixture of two or more of the copper salts; and/or the copper salt in the second copper salt solution comprises at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate and copper acetylacetonate, and can be any one of the copper salts, or can be a mixture of two or more of the copper salts. It will be appreciated that the copper salts in the first and second copper salt solutions may or may not be the same, and in some embodiments of the invention it is preferred that the copper salts in the first and second copper salt solutions are the same, and further preferably are both copper acetate.
On the other hand, the copper salt concentration in the first copper salt solution and the second copper salt solution is not limited, and may be the same or different, or the copper salt concentration in the first copper salt solution is higher than the copper salt concentration in the second copper salt solution, or the copper salt concentration in the first copper salt solution is lower than the copper salt concentration in the second copper salt solution, and the particle size of the micro-nano copper obtained by controlling the concentration and the volume ratio of the first copper salt solution and the second copper salt solution can be adjusted and controlled, which will be described in detail in the following further with reference to specific examples. In some preferred embodiments of the present invention, the copper salt concentration of the first copper salt solution is not lower than the copper salt concentration of the second copper salt solution, and further preferably, the copper salt concentration of the first copper salt solution is equal to the copper salt concentration of the second copper salt solution, so that the regulation and control process is further simplified, and the particle size of the prepared micro-nano copper is more conveniently regulated and controlled by regulating and controlling the volume ratio of the first copper salt solution to the second copper salt solution.
After the preparation of the reducing solution, the first copper salt solution and the second copper salt solution is respectively completed, the reducing solution is stirred under heating conditions, wherein the heating conditions can be any one of water bath, oil bath, electric heating plate and electric heating sleeve, the reaction vessel is a glass reactor with a condensing device, and the reaction temperature of a liquid reaction system in the glass reactor is kept at 50-99 ℃ in the reaction process. When the heating condition is water bath, the temperature interval of the water bath can be set to be 50-99 ℃; when the heating condition is an electric heating plate, the temperature of the electric heating plate can be set to be 70-200 ℃; when the heating condition is an electric heating sleeve, the temperature of the electric heating sleeve can be set to be 70-200 ℃; when the heating condition is an oil bath, the temperature interval of the oil bath may be set to 50 to 180 ℃. In addition, the stirring is at least one of magnetic stirring or mechanical stirring, which may be simple mechanical stirring or magnetic stirring, or may be a combination of mechanical stirring and magnetic stirring, and in some embodiments of the present invention, magnetic stirring is preferred, and the stirring speed of magnetic stirring is more preferred to be 100-2000 r/min.
After the reducing solution is heated to a preset temperature, adding a first copper salt solution into a reaction container under the condition of keeping heating and stirring, and reacting to obtain a seed solution with elemental copper, wherein the reaction time is 1-60 min; then, adding a second copper salt solution into the seed solution as a growth solution, and continuously reacting for 1-30 min under the condition of changing heating and stirring to obtain a product solution with monodisperse micro-nano copper. The second copper salt solution is preferably added slowly, preferably, the adding rate of the second copper salt solution is set to be 0.5-10 mL/min, for example, 0.5mL/min, 2.5mL/min, 4.0mL/min, 5.0mL/min, 8.0mL/min, 10.0mL/min, etc., and the adding form is not limited, and may be one or more of dripping, injection by a syringe pump, injection by a peristaltic pump, etc.
Then, after the reaction is finished, the solid matters in the product solution are concentrated by one or a combination of two or more modes of centrifugation, rotary evaporation, reduced pressure distillation and cross-flow filtration. And then cleaning the concentrated product, wherein the solvent used in the cleaning comprises any one or a mixed solution of two or more of methanol, ethanol and water. And finally, drying the product obtained by cleaning, wherein an electrothermal blowing drying oven, a vacuum drying oven or the like can be adopted in the drying process, and the drying temperature can be set to be 40-90 ℃. Further, in some embodiments of the present invention, the drying process is preferably performed using a vacuum drying oven, which has advantages of high drying efficiency and small influence on the properties of the material to be dried, and the drying temperature is preferably set to 50 to 80 ℃, and more preferably set to 55 to 75 ℃.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 120 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 99mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 5min to obtain a seed solution with elemental copper; adding 1mL of the second copper salt solution prepared in the step (3) into the obtained seed solution by using a peristaltic pump, wherein the adding rate is 4.0mL/min, and continuing to keep the temperature and stir for 10min after the adding is finished, so as to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a speed of 12000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 50nm.
Example 2
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 120 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 4.0mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 5min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 2.0mL/min, and continuing to keep the temperature and stir for 10min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a speed of 11000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 110nm.
Example 3
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 120 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 2.0mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 5min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 3.5mL/min, and continuing to keep the temperature and stir for 6min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a speed of 12000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 150nm.
Example 4
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 120 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 2.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 1.0mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 5min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 2.5mL/min, and continuing to keep the temperature and stir for 5min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a rotating speed of 9000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 240nm.
Example 5
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 110 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 1.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 1.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 50mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 1.5mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 10min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 10.0mL/min, and continuing to keep the temperature and stir for 10min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a rotational speed of 8000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 400nm.
Example 6
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 110 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 1.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 1.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 1.5mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 10min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 5.0mL/min, and continuing to keep the temperature and stir for 10min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at a rotating speed of 7500r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 500nm.
Example 7
(1) Weighing 7.0g of ascorbic acid and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 150mL of ethanol, placing the beaker on a flat heating table with the temperature of 110 ℃, stirring while heating, and obtaining a reducing solution for later use, wherein the temperature of a solution system is 80 ℃ and the magnetic stirring rotating speed is 600r/min until all raw materials are completely dissolved;
(2) Weighing 1.0g of copper acetate monohydrate and 1.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 100mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a first copper salt solution for later use;
(3) Weighing 2.0g of copper acetate monohydrate and 2.0g of polyvinylpyrrolidone K30, placing in a beaker, adding 200mL of ethanol, stirring at room temperature for dissolution, and magnetically stirring at a rotation speed of 600r/min until all raw materials are completely dissolved to obtain a second copper salt solution for later use;
(4) Weighing 1.5mL of a first copper salt solution, rapidly adding the first copper salt solution into the reducing solution prepared in the step (1), keeping the heating and stirring conditions unchanged, and reacting for 10min to obtain a seed solution with elemental copper; adding the second copper salt solution prepared in the step (3) into the obtained seed solution by a peristaltic pump, wherein the adding rate is 0.5mL/min, and continuing to keep the temperature and stir for 10min after the adding is finished to obtain a product solution with monodisperse micro-nano copper;
(5) Transferring the obtained product solution into a centrifuge tube, centrifuging by a high-speed centrifuge at 7000r/min for 5min, and discarding the supernatant after the centrifugation is finished; adding proper amount of ethanol into the centrifugal product, dispersing the product by using ultrasonic waves, and centrifuging again; repeating the centrifugation process for 3-5 times, placing the finally obtained product into a vacuum drying oven, vacuumizing to about-0.1 MPa, setting the temperature to 60 ℃, and drying to obtain the monodisperse micro-nano copper with the particle size of 600nm.
Example 8
The procedure was the same as in example 1, except that the temperature of the solution system was controlled to be 50℃at 60℃at 70℃at 90℃or 99℃in step (1).
The particle size of the prepared monodisperse micro-nano copper is 50nm.
Example 9
The procedure was the same as in example 1, except that the drying temperature in step (5) was set to 40 ℃, 50 ℃, 55 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃,85 ℃ or 90 ℃.
The particle size of the prepared monodisperse micro-nano copper is 50nm.
Fig. 2 to 8 are scanning electron microscope images of the monodisperse micro-nano copper prepared in example 1 to example 7 of the present invention, and fig. 9 is an X-ray diffraction pattern of the monodisperse micro-nano copper prepared in example 4 of the present invention. As can be seen from fig. 2 to 9, the monodisperse nano-copper prepared in the embodiment of the present invention has a uniform particle size distribution, and can achieve precise control of micro-nano-copper particle size, wherein the particle size distribution of the embodiment 1 to the embodiment 4 is more uniform than that of the embodiment 7 to the embodiment 7.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the micro-nano copper powder is characterized by comprising the following steps of:
Step S10, preparing a reducing solution containing a high molecular surfactant, a first copper salt solution and a second copper salt solution respectively;
step S20, heating the reducing solution under the stirring condition, then adding the first copper salt solution into the solution, heating and stirring until elemental copper is generated in the solution, continuously adding the second copper salt solution into the solution, and heating and stirring to obtain a product solution with micro-nano copper powder;
s30, concentrating, cleaning and drying the product solution to obtain micro-nano copper powder;
wherein the solvents of the reductive solution, the first copper salt solution and the second copper salt solution are ethanol;
The reducing agent in the reducing solution comprises at least one of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium isoascorbic acid;
The copper salt concentration of the first copper salt solution is not lower than the copper salt concentration of the second copper salt solution;
In step S20: the mol ratio of the total ethanol to the total copper ions in the reducing solution, the first copper salt solution and the second copper salt solution is (85-500): 1.
2. The micro-nano copper powder according to claim 1, wherein the solvent of the reducing solution, the first copper salt solution, and the second copper salt solution includes at least one of a monohydric alcohol and a polyhydric alcohol, or a mixed solution of at least one of a monohydric alcohol and a polyhydric alcohol with water.
3. The method for preparing micro-nano copper powder according to claim 2, wherein the solvent of the reducing solution, the first copper salt solution and the second copper salt solution is monohydric alcohol.
4. The method for preparing micro-nano copper powder according to claim 1, wherein the copper salt in the first copper salt solution comprises at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate, and copper acetylacetonate; and/or the number of the groups of groups,
The copper salt in the second copper salt solution comprises at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, copper formate and copper acetylacetonate.
5. The method for preparing micro-nano copper powder according to claim 4, wherein copper salts in the first copper salt solution and the second copper salt solution are copper acetate; and/or the number of the groups of groups,
The first copper salt solution has a copper salt concentration comparable to the copper salt concentration in the second copper salt solution.
6. The method for preparing micro-nano copper powder according to claim 1, wherein the surfactant in the reducing solution comprises at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether.
7. The method of producing micro-nano copper powder according to claim 6, wherein the reducing agent in the reducing solution is ascorbic acid, and in step S20, a molar ratio of total ascorbic acid to total copper ions in the reducing solution and the first copper salt solution and the second copper salt solution is (1 to 20): 1, a step of; and/or the number of the groups of groups,
The surfactant in the reducing solution is polyvinylpyrrolidone, and in step S20, the molar ratio of the total polyvinylpyrrolidone in the reducing solution to the first copper salt solution and the second copper salt solution to the total copper ions is (1-20): 1.
8. The method for preparing micro-nano copper powder according to claim 1, wherein in step S20:
the heating condition is any one of water bath, oil bath, electric heating plate and electric heating sleeve, and the reaction temperature of the reaction system is 50-99 ℃; and/or the number of the groups of groups,
The stirring is at least one of magnetic stirring and mechanical stirring; and/or the number of the groups of groups,
The adding rate of the second copper salt solution is 0.5-10 mL/min.
9. The method for preparing micro-nano copper according to claim 1, wherein in step S30:
the concentration mode comprises at least one of centrifugation, rotary evaporation, reduced pressure distillation and cross-flow filtration; and/or the number of the groups of groups,
The solvent used in the cleaning comprises at least one of methanol, ethanol and water; and/or the number of the groups of groups,
The drying temperature during the drying is 40-90 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036309A (en) * | 2003-06-25 | 2005-02-10 | Toda Kogyo Corp | Silver ultrafine particle colloid, and its production method |
| CN102764898A (en) * | 2012-08-09 | 2012-11-07 | 深圳市圣龙特电子有限公司 | method for preparing ultrafine copper powder for electronic paste |
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN103737013A (en) * | 2013-12-20 | 2014-04-23 | 宁夏东方钽业股份有限公司 | Method for preparing nanometer spherical copper powder |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
| CN108031861A (en) * | 2017-12-18 | 2018-05-15 | 中国科学院深圳先进技术研究院 | Metal nano material and preparation method thereof |
| CN110451568A (en) * | 2019-09-17 | 2019-11-15 | 中国科学技术大学先进技术研究院 | A kind of caesium tungsten bronze nano-powder and the preparation method and application thereof |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130230717A1 (en) * | 2011-09-02 | 2013-09-05 | Washington University In St. Louis | Copper nanostructures and methods for their preparation |
| US9700940B2 (en) * | 2012-09-27 | 2017-07-11 | Lockheed Martin Corporation | Metal nanoparticles formed around a nucleus and scalable processes for producing same |
-
2021
- 2021-03-23 CN CN202110317252.7A patent/CN113000855B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036309A (en) * | 2003-06-25 | 2005-02-10 | Toda Kogyo Corp | Silver ultrafine particle colloid, and its production method |
| CN102764898A (en) * | 2012-08-09 | 2012-11-07 | 深圳市圣龙特电子有限公司 | method for preparing ultrafine copper powder for electronic paste |
| CN103170647A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Method for forming copper nanometer sheet through self-assembly |
| CN103737013A (en) * | 2013-12-20 | 2014-04-23 | 宁夏东方钽业股份有限公司 | Method for preparing nanometer spherical copper powder |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
| CN108031861A (en) * | 2017-12-18 | 2018-05-15 | 中国科学院深圳先进技术研究院 | Metal nano material and preparation method thereof |
| CN110451568A (en) * | 2019-09-17 | 2019-11-15 | 中国科学技术大学先进技术研究院 | A kind of caesium tungsten bronze nano-powder and the preparation method and application thereof |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
Non-Patent Citations (3)
| Title |
|---|
| 刘卫.《经皮给药纳米技术》.北京：中国医药科学技术出版社,2020,202. * |
| 宁远涛.《铂》.北京：冶金工业出版社,2010,480. * |
| 晶核生长法制备纳米铜粒子;刘伟;《中国粉体技术》;20040331;31-32 * |
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