CN116372175B - Preparation method of graphene coated nano copper particle composite material - Google Patents
Preparation method of graphene coated nano copper particle composite material Download PDFInfo
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- CN116372175B CN116372175B CN202310371265.1A CN202310371265A CN116372175B CN 116372175 B CN116372175 B CN 116372175B CN 202310371265 A CN202310371265 A CN 202310371265A CN 116372175 B CN116372175 B CN 116372175B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 150
- 239000010949 copper Substances 0.000 title claims abstract description 150
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000012265 solid product Substances 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 95
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 ethylene, propylene, butylene, acetylene Chemical group 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- 238000010309 melting process Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000005276 aerator Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002356 single layer 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F2009/065—Melting inside a liquid, e.g. making spherical balls
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a graphene-coated nano copper particle composite material, which comprises the following steps: a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper; b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene. Compared with the prior art, the preparation method provided by the invention adopts specific process steps, realizes better overall interaction, has high efficiency and good yield, and the obtained graphene coated nano copper particle composite material has high quality, fewer defects and fewer adhesion on the surface of copper powder, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a graphene-coated nano copper particle composite material.
Background
The rapid development of modern industrial technology places higher demands on the combination of strength, electrical and thermal conductivity of the material. Copper has been widely focused on due to its good electrical conductivity, thermal conductivity and ductility, but copper has limited its application due to its low strength, low wear resistance and high temperature variability. Graphene is a nanomaterial consisting of carbon atoms and having a hexagonal two-dimensional lattice structure, and has a monolayer thickness of only 0.34nm, and is the thinnest, highest-strength, toughest, and most excellent heat transfer and conductivity nanomaterial discovered so far, and has been known as an excellent reinforcement of a metal matrix composite since it was discovered. And combining the advantages of graphene and copper, and combining the graphene serving as a reinforcing phase with a copper matrix to prepare the high-strength high-electric-conductivity high-heat-conductivity composite material meeting industrial development.
The graphene is easy to agglomerate, the wettability between the graphene and the copper matrix is poor, the two problems seriously affect the interface bonding strength of the composite material, and how to coat the graphene on copper powder is a problem to be solved. The current technical means for obtaining graphene/copper-based composite materials can be classified into two main types, namely, graphene and copper powder are physically mixed, and composite powder is obtained after a series of treatments, such as: ball milling, wet mixing and electrostatic adsorption, wherein the ball milling method is easy to damage the original structure of graphene, which is unfavorable for the conductivity and mechanical property of the composite material; the wet mixing method and the electrostatic adsorption method are complex in process, long in time consumption, unfavorable for mass production and limited in dispersion effect. The other is to perform in-situ growth of graphene after copper powder treatment, and the technical route well solves the problem of graphene dispersibility.
Patent CN105965025A adds multichannel gas circuit in traditional powder process device atomizing chamber outside, adds step by step temperature regulating device and material deceleration device in the atomizing chamber inside, and apparatus for producing schematic diagram is shown with reference to FIG. 1, realizes that graphite alkene is at the normal position cladding growth of copper powder particle surface. And patent CN113996782A adopts carbon source gas as atomizing medium to atomize copper liquid, so that the carbon source gas is catalyzed and decomposed to obtain graphene and is attached to the surface of copper powder formed by atomization, and the schematic diagram of a production device is shown in fig. 2, so that the composite material of the graphene coated copper powder is obtained. However, both methods are based on the gas atomization powder process technology, and the generated graphene coated copper composite material is cooled from top to bottom and settled.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a graphene-coated nano copper particle composite material, which is obviously different from the traditional preparation method based on the gas atomization powder preparation technology, and has the advantages of high efficiency and good yield, and the obtained graphene-coated nano copper particle composite material has high quality, few defects of graphene on the surface of copper powder and less adhesion.
The invention provides a preparation method of a graphene-coated nano copper particle composite material, which comprises the following steps:
a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper;
b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene.
Preferably, the purity of the pure copper raw material in step a) is greater than 99.90%.
Preferably, the crucible in step a) is a graphite crucible; the height of the crucible is 0.5 m-1.5 m, and the inner diameter is 100 mm-300 mm.
Preferably, the heating and melting process in the step a) is specifically:
Placing pure copper raw materials into a crucible in a reaction furnace, vacuumizing the furnace body to below 10Pa, then introducing inert gas or hydrogen for protection into the furnace body, inflating to the pressure of 0.05-0.09 MPa in the furnace, heating the crucible, and heating until the pure copper raw materials are melted to obtain the molten copper.
Preferably, the temperature of the heating and melting in step a) is 1000 ℃ to 1700 ℃.
Preferably, the mixed gas containing hydrocarbon gas in the step b) is a mixed gas of hydrocarbon gas and auxiliary gas;
the hydrocarbon gas is selected from one or more of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, propyne, butyne natural gas and liquefied petroleum gas;
The auxiliary gas is hydrogen and/or inert gas;
The volume fraction of the hydrocarbon gas in the mixed gas containing the hydrocarbon gas is 0.1-2%.
Preferably, the flow rate of the gas introduced in the step b) is 1000sccm to 200000sccm.
Preferably, the way of introducing in step b) is by introducing from a high temperature resistant conduit inserted into the bottom of the crucible above the copper bath or from the bottom of the crucible.
Preferably, the size of the bubbles formed in the molten copper by the gas distribution means in step b) is 1 μm to 100 μm.
Preferably, the separation process in step b) is specifically:
Continuously collected solid products pass through an air classifier, the graphene coated nano copper particle composite material with higher density is discharged from the bottom of the classifier, and the graphene with lower density is discharged from the top of the classifier.
The invention provides a preparation method of a graphene-coated nano copper particle composite material, which comprises the following steps: a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper; b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene. Compared with the prior art, the preparation method provided by the invention adopts specific process steps, realizes better overall interaction, has high efficiency and good yield, and the obtained graphene coated nano copper particle composite material has high quality, fewer defects and fewer adhesion on the surface of copper powder, and has wide application prospect.
In addition, the preparation method provided by the invention can simultaneously realize the production of byproducts such as graphene, hydrogen and the like, thereby improving the economy of the whole production process.
Drawings
FIG. 1 is a schematic diagram of a production apparatus of patent CN 105965025A;
FIG. 2 is a schematic diagram of a production device of patent CN 113996782A;
FIG. 3 is a schematic view of an aerator according to an embodiment of the present invention;
Fig. 4 is a TEM of the graphene-coated copper material provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a graphene-coated nano copper particle composite material, which comprises the following steps:
a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper;
b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene.
Firstly, putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper.
In the present invention, the purity of the pure copper raw material is preferably more than 99.90%. The source of the pure copper raw material is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the crucible is preferably a graphite crucible; the height of the crucible is preferably 0.5m to 1.5m, more preferably 1m, and the inner diameter is preferably 100mm to 300mm, more preferably 200mm.
In the present invention, the heating and melting process is preferably specifically:
Placing pure copper raw materials into a crucible in a reaction furnace, vacuumizing the furnace body to below 10Pa, then introducing inert gas or hydrogen for protection into the furnace body, inflating to the pressure of 0.05-0.09 MPa in the furnace, heating the crucible, and heating until the pure copper raw materials are melted to obtain molten copper;
More preferably:
placing pure copper raw materials into a crucible in a reaction furnace, vacuumizing the furnace body to 2 Pa-8 Pa, then introducing inert gas into the furnace body for protection, inflating to 0.05 MPa-0.08 MPa, heating the crucible, and heating until the pure copper raw materials are melted, thus obtaining the molten copper.
In the present invention, the inert gas is preferably one or more selected from helium, neon, argon and nitrogen, more preferably nitrogen. The sources of the inert gas and the hydrogen gas are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the temperature of the heating and melting is preferably 1000 ℃ to 1700 ℃, more preferably 1300 ℃ to 1500 ℃; at the same time, the subsequent inflation process maintains the above temperature.
After the metal copper liquid is obtained, the mixed gas containing hydrocarbon gas is introduced into the obtained metal copper liquid, bubbles are formed in the metal copper liquid through a gas distribution device, the bubbles break when moving to the surface of the metal copper liquid, solid products are collected, and then the graphene-coated nano copper particle composite material and graphene are respectively obtained after separation and purification.
In the present invention, the mixed gas containing a hydrocarbon gas is preferably a mixed gas of a hydrocarbon gas and an assist gas; wherein the hydrocarbon gas is preferably selected from one or more of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, propyne, butyne natural gas and liquefied petroleum gas, more preferably methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene or propyne; the auxiliary gas is preferably hydrogen and/or an inert gas, more preferably hydrogen; the sources of the hydrocarbon gas and the assist gas are not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the volume fraction of the hydrocarbon gas in the mixed gas containing the hydrocarbon gas is preferably 0.1% to 2%, more preferably 0.1% to 1%.
In the present invention, the flow rate of the gas is preferably 1000sccm to 200000sccm, more preferably 1000sccm to 4000sccm.
In the invention, the mode of the feeding is preferably that a high-temperature-resistant guide pipe inserted into the bottom of the crucible from the upper part of the copper liquid or the bottom of the crucible.
In the present invention, the gas distribution means is preferably an aerator, as shown in fig. 3; the end of the air outlet of the two air inlet modes is provided with the aerator, and the invention is not particularly limited to the end.
In the present invention, the size of the bubbles formed in the molten metal by the gas distribution means is preferably 1 μm to 100. Mu.m, more preferably 5 μm to 50. Mu.m.
In the invention, bubbles break when travelling to the surface of the metal copper liquid, and the process of collecting solid products is preferably specifically as follows:
After the gas leaves with the generated solid product, the gas is separated by a collecting device, and the solid product is continuously collected.
In the present invention, the separation process is preferably specifically:
Continuously collected solid products pass through an air classifier, the graphene coated nano copper particle composite material with higher density is discharged from the bottom of the classifier, and the graphene with lower density is discharged from the top of the classifier.
The purification process is not particularly limited, and the technical schemes of metal pickling, jet milling, high-temperature purification and the like which are well known to those skilled in the art can be adopted.
The invention provides a method for producing a high-strength and high-conductivity graphene coated nano copper particle composite material; mixing hydrocarbon gas and auxiliary gas, introducing the mixture into molten copper liquid, bubbling the gas in the molten copper liquid, carrying out mass transfer and heat transfer, enabling the heated temperature of the hydrocarbon gas to reach a decomposition temperature, simultaneously fully contacting the hydrocarbon gas with the copper liquid for catalytic reaction, carrying out in-situ pyrolysis on the surface of copper to generate graphene, coating the graphene, and then blowing out the liquid level along with the gas; meanwhile, the pressure above the copper liquid is smaller, so that the copper liquid is facilitated to evaporate, hydrocarbon gas can be cracked on the surface of copper steam, and the graphene-coated copper composite material is generated and then leaves the reactor along with the gas; and collecting the solid product to obtain the graphene coated nano copper particle composite material. The method is obviously different from the traditional production method based on the gas atomization powder preparation technology, has high efficiency and good yield, and the obtained graphene coated nano copper particle composite material has high quality, few defects and less adhesion of graphene on the surface of copper powder; in addition, by-products such as graphene, hydrogen and the like can be obtained by the production method, so that the economy of the whole production process is improved.
The invention provides a preparation method of a graphene-coated nano copper particle composite material, which comprises the following steps: a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper; b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene. Compared with the prior art, the preparation method provided by the invention adopts specific process steps, realizes better overall interaction, has high efficiency and good yield, and the obtained graphene coated nano copper particle composite material has high quality, fewer defects and fewer adhesion on the surface of copper powder, and has wide application prospect.
In addition, the preparation method provided by the invention can simultaneously realize the production of byproducts such as graphene, hydrogen and the like, thereby improving the economy of the whole production process.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
The graphene coated nano copper particle composite material is prepared according to the following steps:
Putting 90kg of pure copper raw material with purity of 99.91% into a graphite crucible with height of 1.0m and inner diameter of 200mm in a reaction furnace, vacuumizing the furnace body to 8Pa, then introducing inert gas nitrogen into the furnace body, and stopping charging after the pressure in the furnace rises to 0.05 MPa; heating the crucible, and heating until copper is melted to obtain molten metal copper liquid; controlling the temperature of the copper liquid to be 1300 ℃; a high-temperature resistant guide pipe is inserted from the upper part of the copper liquid, mixed gas of methane and hydrogen is introduced, the position of an air outlet of the guide pipe is close to the bottom of the crucible, and the inflow rate of the mixed gas is 1000sscm; in the mixed gas, the volume fraction of methane is 0.1%; forming bubbles in the copper liquid by the mixed gas through an aerator, wherein the bubble size is 50 mu m, and the bubbles are broken when travelling to the surface of molten metal copper; the gas leaves the reactor with the generated solid product, and the gas is separated by a collecting device to obtain hydrogen; continuously collecting and separating solid products (discharging the graphene-coated nano copper particle composite material with heavier density from the bottom of the classifier through the air classifier, discharging the graphene with lighter density from the top of the classifier), and purifying to obtain the graphene-coated nano copper particle composite material and graphene respectively.
According to detection, the graphene-coated nano copper particle composite material obtained in the example 1 accounts for 99% (mass ratio) of the collected solid product; the transmission electron microscope of the graphene-coated nano copper particle composite material is shown in fig. 4.
Example 2
The graphene coated nano copper particle composite material is prepared according to the following steps:
Putting 90kg of pure copper raw material with purity of 99.92% into a graphite crucible with height of 1.0m and inner diameter of 200mm in a reaction furnace, vacuumizing the furnace body to 5Pa, then introducing inert gas nitrogen into the furnace body, and stopping charging after the pressure in the furnace is raised to 0.06 MPa; heating the crucible, and heating until copper is melted to obtain molten metal copper liquid; controlling the temperature of the copper liquid to be 1400 ℃; a high-temperature resistant guide pipe is inserted from the upper part of the copper liquid, mixed gas of methane and hydrogen is introduced, the position of an air outlet of the guide pipe is close to the bottom of the crucible, and the inflow rate of the mixed gas is 2000sscm; in the mixed gas, the volume fraction of methane is 0.5%; forming bubbles in the copper liquid by the mixed gas through an aerator, wherein the bubble size is 50 mu m, and the bubbles are broken when travelling to the surface of molten metal copper; the gas leaves the reactor with the generated solid product, and the gas is separated by a collecting device to obtain hydrogen; continuously collecting and separating solid products (discharging the graphene-coated nano copper particle composite material with heavier density from the bottom of the classifier through the air classifier, discharging the graphene with lighter density from the top of the classifier), and purifying to obtain the graphene-coated nano copper particle composite material and graphene respectively.
According to detection, the graphene-coated nano copper particle composite material obtained in the example 2 accounts for 95% (mass ratio) of the collected solid product.
Example 3
The graphene coated nano copper particle composite material is prepared according to the following steps:
Putting 90kg of pure copper raw material with purity of 99.93% into a graphite crucible with height of 1.0m and inner diameter of 200mm in a reaction furnace, vacuumizing the furnace body to 2Pa, then introducing inert gas nitrogen into the furnace body, and stopping charging after the pressure in the furnace is raised to 0.08 MPa; heating the crucible, and heating until copper is melted to obtain molten metal copper liquid; controlling the temperature of the copper liquid to be 1500 ℃; a high-temperature resistant guide pipe is inserted from the upper part of the copper liquid, mixed gas of methane and hydrogen is introduced, the position of an air outlet of the guide pipe is close to the bottom of the crucible, and the inflow rate of the mixed gas is 4000sscm; in the mixed gas, the volume fraction of methane is 1%; forming bubbles in the copper liquid by the mixed gas through an aerator, wherein the bubble size is 50 mu m, and the bubbles are broken when travelling to the surface of molten metal copper; the gas leaves the reactor with the generated solid product, and the gas is separated by a collecting device to obtain hydrogen; continuously collecting and separating solid products (discharging the graphene-coated nano copper particle composite material with heavier density from the bottom of the classifier through the air classifier, discharging the graphene with lighter density from the top of the classifier), and purifying to obtain the graphene-coated nano copper particle composite material and graphene respectively.
According to detection, the graphene-coated nano copper particle composite material obtained in the example 3 accounts for 90% (mass ratio) of the collected solid product.
Example 4
The preparation method provided in example 3 was used, with the difference that: the mixed gas is introduced from the bottom of the crucible instead (the mixed gas also forms bubbles in the copper liquid through the aerator), and other conditions are unchanged.
According to detection, the graphene-coated nano copper particle composite material obtained in example 4 accounts for 88% (mass ratio) of the collected solid product.
Example 5
The preparation method provided in example 3 was used, with the difference that: the pore diameter of the air hole on the aerator is adjusted to be small, so that the size of the formed air bubble is 5 mu m, and other conditions are unchanged.
According to detection, the graphene-coated nano copper particle composite material obtained in the example 5 accounts for 80% (mass ratio) of the collected solid product.
Comparative example 1
The graphene coated nano copper particle composite material is prepared according to the following steps:
Putting 90kg of pure copper raw material with purity of 99.93% into a graphite crucible with height of 1.0m and inner diameter of 200mm in a reaction furnace, vacuumizing the furnace body to 2Pa, then introducing inert gas nitrogen into the furnace body, and stopping charging after the pressure in the furnace rises to 0.1 MPa; heating the crucible, and heating until copper is melted to obtain molten metal copper liquid; controlling the temperature of the copper liquid to be 1500 ℃; a high-temperature resistant guide pipe is inserted from the upper part of the copper liquid, mixed gas of methane and hydrogen is introduced, the position of an air outlet of the guide pipe is close to the bottom of the crucible, and the inflow rate of the mixed gas is 4000sscm; in the mixed gas, the volume fraction of methane is 1%; the mixed gas forms bubbles in the copper liquid, the bubble size is 50 mu m, and the bubbles break when travelling to the surface of molten metal copper; the gas leaves the reactor with the generated solid product, and the gas is separated by a collecting device to obtain hydrogen; continuously collecting and separating solid products (discharging the graphene-coated nano copper particle composite material with heavier density from the bottom of the classifier through the air classifier, discharging the graphene with lighter density from the top of the classifier), and purifying to obtain the graphene-coated nano copper particle composite material and graphene respectively.
According to detection, the graphene-coated nano copper particle composite material obtained in the comparative example 1 accounts for 20% (mass ratio) of the collected solid product.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The preparation method of the graphene-coated nano copper particle composite material is characterized by comprising the following steps of:
a) Putting pure copper raw materials into a crucible in a reaction furnace, and heating and melting to obtain molten copper; the heating and melting process specifically comprises the following steps:
Placing pure copper raw materials into a crucible in a reaction furnace, vacuumizing the furnace body to below 10Pa, then introducing inert gas or hydrogen for protection into the furnace body, inflating to the pressure of 0.05-0.09 MPa in the furnace, heating the crucible, and heating until the pure copper raw materials are melted to obtain molten copper;
b) And c), introducing the mixed gas containing hydrocarbon gas into the metal copper liquid obtained in the step a), forming bubbles in the metal copper liquid through a gas distribution device, cracking the bubbles when the bubbles travel to the surface of the metal copper liquid, collecting a solid product, and separating and purifying the solid product in sequence to obtain the graphene-coated nano copper particle composite material and the graphene.
2. The method of claim 1, wherein the purity of the pure copper feedstock in step a) is greater than 99.90%.
3. The method of claim 1, wherein the crucible in step a) is a graphite crucible; the height of the crucible is 0.5 m-1.5 m, and the inner diameter is 100 mm-300 mm.
4. The method according to claim 1, wherein the temperature of the heating and melting in step a) is 1000 ℃ to 1700 ℃.
5. The method according to claim 1, wherein the mixed gas containing hydrocarbon gas in the step b) is a mixed gas of hydrocarbon gas and assist gas;
the hydrocarbon gas is selected from one or more of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, propyne, butyne natural gas and liquefied petroleum gas;
The auxiliary gas is hydrogen and/or inert gas;
The volume fraction of the hydrocarbon gas in the mixed gas containing the hydrocarbon gas is 0.1-2%.
6. The method according to claim 1, wherein the flow rate of the inlet in the step b) is 1000sccm to 4000sccm.
7. The method according to claim 1, wherein the way of introducing in step b) is introducing from a refractory conduit inserted into the bottom of the crucible above the copper bath or introducing from the bottom of the crucible.
8. The method according to claim 1, wherein the size of bubbles formed in the molten copper by the gas distribution means in step b) is 1 μm to 100 μm.
9. The preparation method according to claim 1, wherein the separation process in step b) is specifically:
Continuously collected solid products pass through an air classifier, the graphene coated nano copper particle composite material with higher density is discharged from the bottom of the classifier, and the graphene with lower density is discharged from the top of the classifier.
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| JPH04259313A (en) * | 1991-02-07 | 1992-09-14 | Dowa Mining Co Ltd | Production of spherical powder of high purity copper |
| CN108059153A (en) * | 2018-02-05 | 2018-05-22 | 苏州第元素纳米技术有限公司 | A kind of synthesizer and its method for preparing graphene |
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