CN112176316A - Method for preparing graphene/metal composite powder - Google Patents
Method for preparing graphene/metal composite powder Download PDFInfo
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- CN112176316A CN112176316A CN201910602706.8A CN201910602706A CN112176316A CN 112176316 A CN112176316 A CN 112176316A CN 201910602706 A CN201910602706 A CN 201910602706A CN 112176316 A CN112176316 A CN 112176316A
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Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
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- 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
-
- 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]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
The application discloses a method for preparing graphene/metal composite powder, and belongs to the field of metal-based composite materials. The method comprises the following steps: and heating the carbon-containing free radicals obtained by hot wire cracking and metal powder in a fluidized bed for reaction, cooling, and growing graphene on the fluidized metal powder. According to the method, a hot wire-fluidized bed chemical vapor deposition technology is adopted, so that the high-activity carbon-containing free radicals are fully contacted with fluidized metal powder, graphene grows at a relatively low temperature, good gas-solid contact is formed, the metal powder is prevented from being bonded, and the coverage rate and uniformity of the graphene coating layer are improved. In addition, the method does not need to use a dispersing agent, and is beneficial to improving the quality and the purity. The graphene/metal composite powder prepared by the method has the advantages of high graphene coverage rate, uniform distribution, low impurity content, uniform and stable overall performance and capability of obtaining single-layer graphene.
Description
Technical Field
The application relates to a method for preparing graphene/metal composite powder, belonging to the field of metal-based composite materials.
Background
Graphene is a new carbonaceous material with a two-dimensional honeycomb lattice structure formed by close packing of carbon atoms, can be as thin as a single atom, and has many unprecedented properties, such as ultrahigh room temperature electron mobility (15000 cm)2V · s, 10 times or more the theoretical value of silicon), high thermal conductivity (theoretical value: 4800-5300W/(m.K)), high thermal stability, and high Young's modulus (theoretical value: 1.0Tpa), for molecules (air, argon, helium, etc.) and ions (Cl)-1、Mg2+Etc.) good barrier properties and a low electronic work function, their use in composite materials is becoming increasingly appreciated. The Chemical Vapor Deposition (CVD) method related to graphene is a method of forming a graphene thin film by catalytic cracking and self-assembly of a gaseous carbon source at a high temperature on a substrate of transition metal (copper, nickel, iron, cobalt, gold, etc.) and alloy (cobalt-nickel, gold-nickel, copper-nickel, nickel-molybdenum, etc.). The CVD method has become the main process for growing and preparing large-area and high-quality graphene, and the growth with copper and nickel as the substrate is the most representative.
However, high-quality graphene grows on the surface of metal powder by a thermal CVD method, and due to the fact that the temperature is too high (about 1000 ℃), copper powder is bonded in the growing process to form a porous copper material, and the heat conduction performance is obviously reduced. In the existing CVD technology, the Plasma Enhanced Chemical Vapor Deposition (PECVD) is a graphene growth technology that uses high-activity plasma as a carbon source, which can realize growth of graphene at low temperature and reduce adhesion of copper powder or nickel powder to a certain extent. However, the PECVD technique has two disadvantages: one is that copper powder particles or nickel powder particles are piled together in the growth process like a thermal CVD method, and good gas-solid contact is difficult to form, so that the method can not realize uniform growth of graphene on the surface of the copper powder or nickel powder; secondly, the plasma has a serious etching effect on the grown graphene, so that the quality of the graphene is poor. The patent application of Tianjin university "a method for preparing graphene/copper composite material by loading solid carbon source on the surface of copper powder by impregnation" (CN 105081312A) is to impregnate solid carbon source PMMA loaded on the surface of flaky copper powder and grow graphene in situ on the surface of copper sheet to prepare graphene/copper powder composite material, however, the method needs to use organic solvent which is not friendly to environment. The patent application of Tianjin university "method for preparing graphene/copper composite material by catalyzing solid carbon source in situ on the surface of copper powder" (CN 104874803A) prepares copper-polymethyl methacrylate powder which is uniformly dispersed by ball milling, and then prepares graphene/copper composite powder by catalytically reducing polymethyl methacrylate into graphene in a tube furnace, however, the graphene grown in the method has defects. Therefore, the research and development of the technology for in-situ growth of high-quality graphene on the surface of the powder are of great significance.
Disclosure of Invention
According to one aspect of the present application, a method for preparing graphene/metal composite powder is provided, which adopts a hot filament-fluidized bed chemical vapor deposition (HF-FBCVD) technique to allow a high-activity carbon-containing radical to fully contact with a fluidized metal powder, so that graphene grows at a relatively low temperature, not only can good gas-solid contact be formed, but also adhesion of the metal powder can be avoided, thereby facilitating improvement of coverage rate and coverage uniformity of a graphene coating layer. In addition, the method can realize highly uniform dispersion of graphene without using a dispersing agent, thereby being beneficial to improving the quality and purity of the graphene/metal composite powder.
The method for preparing the graphene/metal composite powder is characterized by comprising the following steps:
and heating the carbon-containing free radicals obtained by hot wire cracking and metal powder in a fluidized bed for reaction, cooling, and growing graphene on the fluidized metal powder.
Optionally, the method comprises: and growing graphene on the surface of the metal powder in situ.
Alternatively, the method is carried out using a hot wire-fluidized bed chemical vapor deposition technique.
Optionally, the graphene/metal composite powder is a graphene-coated metal powder.
Optionally, the metal powder is fluidized by introducing a fluidizing gas into the fluidized bed.
Optionally, the fluidizing gas is selected from at least one of hydrogen, argon, nitrogen, helium and krypton.
Preferably, the fluidizing gas is argon and/or hydrogen.
Optionally, the flow rate of the fluidizing gas is 100-10000 sccm.
Optionally, the metal is selected from at least one of transition metals and alloys.
Optionally, the metal powder is selected from transition metal powder or alloy powder.
Optionally, the transition metal is selected from at least one of copper, nickel, iron, cobalt, and gold.
Optionally, the alloy is selected from at least one of a cobalt-nickel alloy, a gold-nickel alloy, a copper-nickel alloy, and a nickel-molybdenum alloy.
Alternatively, the particle size of the metal powder is 1nm to 1000 μm, preferably 5nm to 300 μm, and more preferably 8nm to 100 μm.
Alternatively, the particle size of the metal powder is 1nm to 1000 μm, preferably 20nm to 800 μm, and more preferably 25nm to 550 μm.
Optionally, the particle size of the metal powder is 10nm to 920 μm.
In the context of the present application, the term "particle size" generally refers to the average particle size, unless otherwise indicated.
Optionally, the purity of the metal powder is 99-99.99%.
Preferably, the purity of the metal powder is 99.5-99.99%.
Optionally, the carbon-containing radical is obtained in a manner comprising: obtained by heating and decomposing a gas-phase carbon source.
In the context of the present application, the term "carbon-containing radical" encompasses both an active radical containing an activated carbon atom and a single activated carbon atom, depending on the molecular structure of the gas-phase carbon source employed.
Optionally, the gas phase carbon source is selected from at least one of methane, ethane, propane, ethylene, propylene, acetylene, and propyne.
Optionally, the flow rate of the gas-phase carbon source is 1-8000 sccm.
Preferably, the flow rate of the gas-phase carbon source is 1-1000 sccm.
In one embodiment, the gas phase carbon source has a flow rate of ≧ 1sccm and <200 sccm.
In one embodiment, the flow rate of the gas phase carbon source is 200sccm or more and 300sccm or less.
Optionally, the temperature for cracking the gas-phase carbon source under the hot wire is 1000-2200 ℃.
Optionally, the hot wire is made of at least one of refractory metals.
Optionally, the hot wire is selected from at least one of tantalum wire, tungsten wire, and molybdenum wire.
Optionally, the hot wire has a helical structure.
In one embodiment, the hot wire is a helically structured filament made from at least one of the refractory metals tantalum, tungsten, and molybdenum.
Optionally, the carbon-containing radicals are introduced into the fluidized bed by a carrier gas.
Optionally, the carrier gas is selected from at least one of hydrogen, argon, nitrogen, helium, and krypton.
Optionally, the reaction is performed under vacuum.
Preferably, the reaction is at 10-3～102Pa.
Optionally, the reaction temperature is 400-1000 ℃, preferably 450-850 ℃.
Optionally, the temperature of the reaction is 400-850 ℃.
Optionally, the reaction time is 0.1-1 hour, preferably 0.2-0.5 hour.
In one embodiment, the reaction time is 0.1 hours or more and 0.5 hours or less.
In one embodiment, the time of the reaction is >0.5 hours and ≦ 1 hour.
Optionally, after the reaction, cooling to 20-40 ℃.
Preferably, after the reaction, the temperature is reduced to 25-35 ℃.
Optionally, the temperature reduction is performed in a natural cooling manner.
Optionally, the cooling down is performed in a rapid cooling manner.
Optionally, the cooling rate is 20-300 ℃/min.
Optionally, the cooling rate is 20-200 ℃/min.
Optionally, the upper limit of the rate of cooling is selected from 300 ℃/min, 280 ℃/min, 260 ℃/min, 240 ℃/min, 220 ℃/min, 200 ℃/min, 180 ℃/min, 160 ℃/min, 140 ℃/min, 120 ℃/min, 100 ℃/min, 80 ℃/min, 60 ℃/min, 50 ℃/min, 40 ℃/min or 30 ℃/min, and the lower limit is selected from 20 ℃/min, 30 ℃/min, 40 ℃/min, 50 ℃/min, 60 ℃/min, 80 ℃/min, 100 ℃/min, 120 ℃/min, 140 ℃/min, 160 ℃/min, 180 ℃/min, 200 ℃/min, 220 ℃/min, 240 ℃/min, 260 ℃/min or 280 ℃/min.
Preferably, the cooling rate is 50-200 ℃/min.
In one embodiment, the cooling comprises: and continuously introducing the fluidizing gas, stopping introducing the carbon-containing free radicals, and stopping heating the fluidized bed to reduce the temperature of the fluidized bed to room temperature to obtain the graphene/metal composite powder.
According to the method, the growth of the graphene on the metal powder is mainly completed in the process of cooling. In this regard, control of the cooling rate is an important condition for graphene growth. When the cooling rate is too slow, too little carbon is precipitated and graphene may not be formed; when the temperature reduction rate is too fast, too much carbon is precipitated, which may result in too thick graphene layer or uneven distribution.
According to the method, the number of layers of the obtained graphene can be correspondingly adjusted by controlling the degree of reaction of the carbon-containing free radicals and the metal powder (for example, changing the reaction time or the flow of a gas-phase carbon source), so that the graphene-coated metal powder in which the graphene coating layer is a single-layer or multi-layer graphene (for example, 2 to 20 layers) can be prepared.
In particular, single-layer graphene, whose raman characterization I is enabled by the methods described herein, can be prepared2D/IGGreater than or equal to 1.25.
Optionally, the method comprises the steps of:
a1) adding metal powder into a fluidized bed, and vacuumizing;
b1) introducing fluidizing gas into the fluidized bed to fluidize the metal powder;
c1) heating the fluidized bed to a reaction temperature;
d1) cracking a gas-phase carbon source into carbon-containing free radicals through a hot wire, and introducing the carbon-containing free radicals into a fluidized bed;
e1) reacting the carbon-containing free radicals with fluidized metal powder at a reaction temperature, cooling, and growing graphene on the surface of the fluidized metal powder to obtain the graphene/metal composite powder;
or
a2) Adding metal powder into a fluidized bed, and vacuumizing;
b2) cracking a gas-phase carbon source into carbon-containing free radicals through a hot wire, and introducing the carbon-containing free radicals into a fluidized bed;
c2) introducing fluidizing gas into the fluidized bed to fluidize the metal powder;
d2) heating the fluidized bed to a reaction temperature;
e2) reacting the carbon-containing free radicals with fluidized metal powder at a reaction temperature, cooling, and growing graphene on the surface of the fluidized metal powder to obtain the graphene/metal composite powder.
In a specific embodiment, the method comprises the steps of:
1) placing the metal powder in a fluidized bed, vacuumizing, and introducing fluidizing gas into the fluidized bed to fluidize the metal powder in the fluidized bed;
2) introducing a gas-phase carbon source into a hot wire device below the fluidized bed, and fully cracking the gas-phase carbon source at high temperature into carbon-containing free radicals;
3) introducing carbon-containing radicals into the fluidized bed with a carrier gas;
4) reacting the fluidized metal powder with carbon-containing free radicals at low temperature;
5) and optionally, rapidly cooling the metal powder to prepare the metal powder/graphene composite material with the surface coated with the graphene.
According to another aspect of the present application, a graphene/metal composite powder is provided, which has high graphene coverage rate, uniform distribution, low impurity content, and uniform and stable overall performance.
The graphene/metal composite powder is characterized by being prepared by the method.
Optionally, the graphene/metal composite powder is a graphene-coated metal powder.
Optionally, the thickness of the graphene coating layer of the graphene/metal composite powder is 0.3-3 nm, and preferably 0.3 nm.
Optionally, the coverage rate of the graphene coating layer of the graphene/metal composite powder is 95-100%.
Optionally, the coverage rate of the graphene coating layer of the graphene/metal composite powder is greater than or equal to 95%, preferably greater than or equal to 98%, and more preferably 100%.
Optionally, the graphene coating layer of the graphene/metal composite powder is single-layer graphene or multi-layer graphene, for example, 2 to 20 layers of graphene.
Optionally, the graphene coating layer of the graphene/metal composite powder is single-layer graphene, and raman characterization I2D/IGGreater than or equal to 1.25.
Optionally, the carbon content of the graphene/metal composite powder is less than 1%.
Preferably, the carbon content of the graphene/metal composite powder is 0.001-0.7%.
The graphene/metal composite powder is uniformly dispersed, and the granularity of the graphene/metal composite powder is almost the same as that of the corresponding metal powder; the contained graphene is high in quality, few or no in defects, and can be single-layer graphene.
The method described in this application combines hot filament CVD technology with fluidized bed technology-hot filament-fluidized bed chemical vapor deposition (HF-FBCVD) technology. In the fluidized bed, the particles are in a fluidized state under the action of high-speed airflow, so that good gas-solid contact can be realized; the high-activity carbon-containing free radical obtained by the hot wire technology is used as a carbon source, so that the metal powder can be in all-dimensional contact with the high-activity carbon-containing free radical in a fluidized state, and the coating growth of high-quality graphene on the surface of the metal powder (such as copper powder and nickel powder) is realized.
The beneficial effects that this application can produce include:
1) according to the method for preparing the graphene/metal composite powder, a hot wire-fluidized bed chemical vapor deposition technology is adopted, so that the high-activity carbon-containing free radicals are fully contacted with the fluidized metal powder, the graphene grows at a relatively low temperature, good gas-solid contact can be formed, the metal powder can be prevented from being bonded, and the coverage rate and the coverage uniformity of a graphene coating layer can be improved.
2) According to the method for preparing the graphene/metal composite powder, the graphene can be highly uniformly dispersed without using a dispersing agent, so that the quality and the purity of the graphene/metal composite powder are improved.
3) The graphene/metal composite powder is high in graphene coverage rate, uniform in distribution, low in impurity content, uniform and stable in overall performance, and capable of obtaining single-layer graphene.
Drawings
Fig. 1 shows raman spectrum measurement results of a graphene/copper composite powder sample 1 in example 1 of the present application.
Fig. 2 is a raman spectrum measurement result of the graphene/nickel composite powder sample 5 in example 5 of the present application.
Fig. 3 is a TEM photograph of a graphene/nickel composite powder sample 5 in example 5 of the present application.
Fig. 4 is SEM photographs of the graphene/copper composite powder sample 1 and the copper powder material in example 1 of the present application, in which (a) is a SEM photograph of graphene-coated copper powder and (B) is a SEM photograph of virgin copper powder.
Detailed Description
As previously mentioned, the present application relates to a method of preparing a graphene-coated metal powder. According to the method, a hot wire-fluidized bed chemical vapor deposition method is adopted, and carbon-containing free radicals are used as reaction raw materials, so that high-quality graphene coated with metal powder can be prepared. Therefore, the application provides a method for preparing high-quality graphene on powder in situ based on a hot wire-fluidized bed chemical vapor deposition technology and a preparation technology for preparing high-quality graphene on the surface of the powder.
The present inventors have conducted extensive and intensive studies for a long time to coat high-quality graphene on the surface of a powder such as copper powder/nickel powder by using a hot filament-fluidized bed chemical vapor deposition (HF-FBCVD) technique. Specifically, a hot wire-fluidized bed chemical vapor deposition growth technology is adopted, argon, hydrogen and the like are used as fluidizing gas, and the metal powder is in a fluidized state in a fluidized bed by optimizing the flow and pressure of the fluidizing gas; by optimizing the power supply power, current and hot wire structure of the hot wire, the hot wire is utilized to crack methane (2200 ℃) to generate carbon-containing free radicals, the carbon-containing free radicals are conveyed into the fluidized bed through carrier gas, the metal powder is in all-dimensional contact with the high-activity carbon-containing free radicals in a fluidized state, and the graphene is formed on the surface of the metal powder through rearrangement under the catalysis of the metal powder. On this basis, the inventors have completed the present application.
More specifically, the present application employs hot wire-fluidized bed chemical vapor deposition growth techniques. The hot wire (2200 ℃) is utilized to crack a gas phase carbon source to generate high-activity carbon-containing free radicals, and then the high-activity carbon-containing free radicals are sent into a fluidization cavity through a carrier gas to be rearranged on the surface of metal medium powder in the cavity to form graphene. The temperature of the fluidization cavity is controlled below 850 ℃ and is far lower than the melting point of metal, and the difficult problem of metal powder adhesion in the technology of preparing graphene by CVD is effectively solved in a fluidization state. In addition, the metal powder and the high-activity carbon-containing free radicals form all-around contact in a fluidized state, so that the problem of poor gas-solid contact caused by standing and stacking of the metal powder in the traditional CVD method is solved. Therefore, the graphene coating layer with high quality can be uniformly grown on the surface of the metal powder.
The method can effectively overcome the defects of the existing technology for coating the metal powder with the graphene and preparing the metal powder, such as the defects that the metal powder is easy to bond, impurities such as a dispersing agent are easy to mix, the graphene has defects and the like.
Compared with a thermal CVD technology, the method has the advantages that a hot wire technology is adopted to ensure that a gas-phase carbon source is cracked into carbon-containing free radicals by using a hot wire at high temperature, and the metal powder is ensured to react with the carbon-containing free radicals in a fluidized state under the catalytic action of the metal powder, so that good gas-solid contact is formed, and the graphene full coverage on the surface of the metal powder is realized. In addition, compared with a preparation method adopting a gas-phase carbon source in a CVD furnace, the method does not add a dispersing agent in the preparation process, can prepare high-quality and uniformly-dispersed graphene/metal composite powder in a fluidized state, and has higher purity and quality.
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were purchased commercially, wherein the purity of each metal powder was 99.9%; the copper-nickel powder is purchased from Shanghai Seawa materials science and technology Limited, and the mass ratio of copper to nickel is 4: 1.
The analysis method in the examples of the present application is as follows:
the carbon content of the graphene/metal composite powder sample was measured using a high-frequency infrared carbon-sulfur analyzer (model: CS844, available from LECO).
The Raman spectrum of the graphene/metal composite powder sample was measured by using a confocal micro-Raman spectrometer (model: Renishaw inVia Reflex, available from Reflex corporation).
The morphology of the graphene/metal composite powder sample was observed using a scanning electron microscope (model: FEI Quanta FEG250, available from FEI corp., usa).
The thickness of the coating layer of the graphene/metal composite powder sample was measured using a transmission electron microscope (model: Tecnai F20, available from FEI, USA).
The experimental procedures, in which specific conditions are not specified in the examples of the present application, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless otherwise indicated, percentages and parts herein are by weight.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present application. The preferred methods and materials described herein are exemplary only.
Example 1 graphene/copper composite powder sample 1
1) 10g of atomized copper powder (particle size 40 μm) was added to the fluidized bed, vacuum was applied to 5Pa, and then fluidizing gas, argon gas, was introduced into the fluidized bed at a flow rate of 4000sccm to fluidize the copper powder.
2) The fluidized bed is heated to 800 ℃ with a heating rate of 20 ℃/min.
3) Methane enters a hot wire device at a flow rate of 20sccm, is heated by a molybdenum heating wire, obtains carbon-containing free radicals after methane cracking at 2200 ℃, and enters a fluidized bed along with carrier gas argon.
4) And (3) keeping the temperature of the fluidized bed at 800 ℃ for 0.5 hour, continuously introducing the fluidizing gas argon at 4000sccm, closing methane until the temperature of the fluidized bed is reduced to 25 ℃, and reducing the temperature at a speed of 100 ℃/min to obtain the copper powder with the surface coated with graphene, namely the graphene/copper composite powder sample 1.
Example 2 graphene/nickel composite powder sample 2
1) 20g of nickel powder (particle size 10nm) is added into a fluidized bed, and the fluidized bed is vacuumized to 3 Pa.
2) Methane is led into a hot wire device at the flow rate of 50sccm, and is heated by a tantalum heating wire, so that carbon-containing free radicals after methane cracking are obtained at the temperature of 2200 ℃, and enter a fluidized bed along with argon gas as a carrier gas.
3) And (3) introducing fluidizing gas argon into the fluidized bed, and fluidizing the nickel powder by adjusting the mass flow meter to ensure that the flow of the argon is 2000 sccm. The fluidized bed was heated to 750 ℃ at a rate of 20 ℃/min.
4) And (3) keeping the temperature of the fluidized bed at 750 ℃ for 0.3 hour, continuously introducing the fluidized gas argon at 2000sccm, closing the methane until the temperature of the fluidized bed is reduced to 30 ℃, and reducing the temperature at a rate of 50 ℃/min to obtain the nickel powder with the surface coated with the graphene, namely the graphene/nickel composite powder sample 2.
Example 3 graphene/copper-nickel composite powder sample 3
1) 30g of copper-nickel powder (with the particle size of 30nm) is added into a fluidized bed, and the fluidized bed is vacuumized to 8 Pa.
2) Methane enters a hot wire device at the flow rate of 100sccm, is heated by a molybdenum heating wire, obtains carbon-containing free radicals after methane cracking at the temperature of 2200 ℃, and enters a fluidized bed along with carrier gas argon.
3) Fluidizing gas argon gas was introduced into the fluidized bed, and the flow rate of argon gas was adjusted to 1000sccm by adjusting the mass flow meter, so that the copper-nickel powder was fluidized. The fluidized bed was heated to 650 ℃ at a rate of 20 ℃/min.
4) And (3) keeping the temperature of the fluidized bed at 650 ℃ for 0.3 hour, continuously introducing the argon of the fluidizing gas at 1000sccm, closing the methane until the temperature of the fluidized bed is reduced to 30 ℃, and reducing the temperature at a rate of 20 ℃/min to obtain the copper-nickel powder with the surface coated with the graphene, namely the graphene/copper-nickel composite powder sample 3.
Example 4 graphene/copper composite powder sample 4
1) 40g of copper powder (particle size: 10 μm) was charged into a fluidized bed and evacuated to 5 Pa.
2) Ethylene enters a hot filament device at a flow rate of 10sccm, is heated by a molybdenum heating wire to obtain carbon-containing free radicals after ethylene cracking at 2200 ℃, and enters a fluidized bed along with carrier gas argon.
3) Fluidizing gas argon gas was introduced into the fluidized bed, and the flow rate of argon gas was adjusted to 3000sccm by adjusting the mass flow meter, so that the copper powder was fluidized. The fluidized bed was heated to 700 ℃ at a rate of 10 ℃/min.
4) Keeping the temperature of the fluidized bed at 700 ℃ for 0.5 hour, continuing introducing the fluidizing gas argon at 3000sccm, closing ethylene until the temperature of the fluidized bed is reduced to 25 ℃, and reducing the temperature at a rate of 100 ℃/min to obtain the copper powder with the surface coated with graphene, namely the graphene/copper composite powder sample 4.
Example 5 graphene/nickel composite powder sample 5
1) 50g of nickel powder (particle size 100 μm) was charged into a fluidized bed and evacuated to 5 Pa.
2) Methane enters a hot wire device at 200sccm, is heated by a molybdenum heating wire, obtains carbon-containing free radicals after methane cracking at 2000 ℃, and enters a fluidized bed along with carrier gas argon.
3) And (3) introducing fluidizing gas hydrogen into the fluidized bed, and fluidizing the copper powder by adjusting the mass flow meter to ensure that the flow of the hydrogen is 300 sccm. The fluidized bed was heated to 750 ℃ at a rate of 12 ℃/min.
4) And (3) keeping the temperature of the fluidized bed at 750 ℃ for 1 hour, continuously introducing the liquefied gas hydrogen at 300sccm, closing the methane, rapidly cooling the fluidized bed to 30 ℃ at a cooling rate of 20 ℃/min, and obtaining the nickel powder with the surface coated with the graphene, namely the graphene/nickel composite powder sample 5.
Example 6 characterization of graphene/Metal composite powder samples
The result of quantitative elemental analysis showed that the carbon content of the graphene/copper composite powder sample 1 prepared in example 1 was 0.003%. The carbon content of the graphene/metal composite powder samples 2 to 4 prepared in the embodiments 2 to 4 is similar to that of the sample 1, and the specific numerical values thereof are slightly different. The carbon content of the graphene/nickel composite powder sample 5 prepared in example 5 was 0.64%.
The graphene/metal composite powder samples 1 to 5 prepared in examples 1 to 5 were characterized by raman spectroscopy. The raman spectroscopy measurement results of the graphene/copper composite powder sample 1 in example 1 are shown in fig. 1. From fig. 1, it can be confirmed that graphene is obtained. Specifically, in fig. 1, a typical characteristic peak of graphene is located at a wave number of 2700cm-1Nearby 2D peak and wave number 1580cm-1Nearby G peak. From the intensity ratio (I) of the 2D peak and the G peak2D/IG) A single layer graphene can be determined to be prepared for 1.6. In addition, no Raman spectrum was observed at a wavenumber of 1350cm-1And the nearby D peak indicates that the prepared graphene has high quality. Raman spectrum and method for graphene/metal composite powder sample 2-4Sample 1 was similar, with slightly different peak intensities and intensity ratios. The Raman spectrum of the graphene/nickel composite powder sample 5 is shown in FIG. 2, and the intensity ratio (I) of the 2D peak and the G peak is shown2D/IG) The preparation of multilayer graphene can be determined to be 1.02. Further, the Transmission Electron Microscope (TEM) results of the graphene/nickel composite powder sample 5 are shown in fig. 3, and it can be seen from fig. 3 that the sample contains about 10 layers of graphene, and the thickness of the graphene is about 3 nm.
The shapes of the graphene/metal composite powder samples 1 to 5 prepared in the above examples 1 to 5 were observed by a Scanning Electron Microscope (SEM). The typical sample is graphene/copper composite powder sample 1, and the SEM result is shown in fig. 4. As can be seen from fig. 4, the particle size of the graphene/copper composite powder sample 1 was about 40 μm, similar to that of the copper powder raw material, and the dispersion was uniform. SEM pictures of the graphene/metal composite powder samples 2-5 are similar to those of the sample 1, and the particle sizes are correspondingly different.
The coverage rate of the graphene coating layer of the graphene/metal composite powder sample 1-5 is determined by the following steps: for each sample, a plurality of sampling points are randomly selected, Raman spectrum measurement is carried out on each sampling point to judge whether the point is coated with graphene or not, and a calculation result is obtained through statistical analysis on the basis. Taking the graphene/copper composite powder sample 1 as a typical representative, wherein 20 sampling points are selected, and the Raman spectrum measurement result shows that the 20 points all show a characteristic peak 2D peak and a characteristic peak G peak representing graphene, so that the coverage rate of the graphene coating layer of the sample is 100%. The coverage rate of the graphene coating layers of the graphene/metal composite powder samples 2-5 is similar to that of the sample 1, and is within the range of 95-100%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing graphene/metal composite powder is characterized by comprising the following steps:
and heating the carbon-containing free radicals obtained by hot wire cracking and metal powder in a fluidized bed for reaction, cooling, and growing graphene on the fluidized metal powder.
2. The method according to claim 1, wherein the metal powder is fluidized by introducing a fluidizing gas into a fluidized bed;
preferably, the fluidizing gas is selected from at least one of hydrogen, argon, nitrogen, helium and krypton;
preferably, the metal is selected from at least one of transition metals and alloys;
further preferably, the transition metal is selected from at least one of copper, nickel, iron, cobalt and gold;
further preferably, the alloy is selected from at least one of a cobalt-nickel alloy, a gold-nickel alloy, a copper-nickel alloy, and a nickel-molybdenum alloy;
preferably, the particle size of the metal powder is 1nm to 1000 μm.
3. The method of claim 1, wherein the carbon-containing radicals are obtained by: obtained by heating and decomposing a gas-phase carbon source;
preferably, the gas-phase carbon source is selected from at least one of methane, ethane, propane, ethylene, propylene, acetylene, and propyne;
preferably, the hot wire is selected from at least one of tantalum wire, tungsten wire and molybdenum wire.
4. The method of claim 1 wherein the carbon-containing radicals are introduced into the fluidized bed by a carrier gas;
preferably, the carrier gas is selected from at least one of hydrogen, argon, nitrogen, helium and krypton.
5. The method of claim 1, wherein the reaction is carried out under vacuum;
preferably, the reaction temperature is 400-1000 ℃;
preferably, the reaction time is 0.1-1 hour.
6. The method according to claim 1, wherein after the reaction, the temperature is reduced to 20-40 ℃;
preferably, the temperature reduction is carried out in a natural cooling mode;
preferably, the temperature reduction is carried out in a rapid cooling mode;
preferably, the cooling rate is 20-300 ℃/min.
7. The method of claim 1, wherein the graphene is single-layer graphene, Raman characterization I2D/IGGreater than or equal to 1.25.
8. The method according to any one of claims 1 to 7, comprising the steps of:
a1) adding metal powder into a fluidized bed, and vacuumizing;
b1) introducing fluidizing gas into the fluidized bed to fluidize the metal powder;
c1) heating the fluidized bed to a reaction temperature;
d1) cracking a gas-phase carbon source into carbon-containing free radicals through a hot wire, and introducing the carbon-containing free radicals into a fluidized bed;
e1) reacting the carbon-containing free radicals with fluidized metal powder at a reaction temperature, cooling, and growing graphene on the surface of the fluidized metal powder to obtain the graphene/metal composite powder; or
a2) Adding metal powder into a fluidized bed, and vacuumizing;
b2) cracking a gas-phase carbon source into carbon-containing free radicals through a hot wire, and introducing the carbon-containing free radicals into a fluidized bed;
c2) introducing fluidizing gas into the fluidized bed to fluidize the metal powder;
d2) heating the fluidized bed to a reaction temperature;
e2) reacting the carbon-containing free radicals with fluidized metal powder at a reaction temperature, cooling, and growing graphene on the surface of the fluidized metal powder to obtain the graphene/metal composite powder.
9. A graphene/metal composite powder characterized by being prepared by the method of any one of claims 1 to 8.
10. The graphene/metal composite powder according to claim 9, wherein the graphene coating layer of the graphene/metal composite powder has a thickness of 0.3 to 3 nm;
preferably, the coverage rate of the graphene coating layer of the graphene/metal composite powder is 95-100%;
preferably, the graphene coating layer of the graphene/metal composite powder is single-layer graphene, and Raman representation I2D/IGGreater than or equal to 1.25;
preferably, the carbon content of the graphene/metal composite powder is less than 1%.
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|---|---|---|---|---|
| CN114226719A (en) * | 2021-11-12 | 2022-03-25 | 深圳前海石墨烯产业有限公司 | Graphene manganese-copper-based damping material powder, alloy damping material, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764545A (en) * | 2011-09-02 | 2014-04-30 | 贝克休斯公司 | Method to generate and disperse nanostructures in a composite material |
| CN105483641A (en) * | 2015-12-28 | 2016-04-13 | 哈尔滨工业大学 | Preparing method of copper-base electric contact material enhanced by in-situ grown graphene |
| WO2017219945A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Graphene dispersion method and graphene composite material |
| CN109112504A (en) * | 2017-06-26 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene/copper composite material and its preparation and application |
| CN109722641A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Diamond/graphene composite heat conduction film and preparation method thereof and cooling system |
-
2019
- 2019-07-05 CN CN201910602706.8A patent/CN112176316A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764545A (en) * | 2011-09-02 | 2014-04-30 | 贝克休斯公司 | Method to generate and disperse nanostructures in a composite material |
| CN105483641A (en) * | 2015-12-28 | 2016-04-13 | 哈尔滨工业大学 | Preparing method of copper-base electric contact material enhanced by in-situ grown graphene |
| WO2017219945A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Graphene dispersion method and graphene composite material |
| CN109112504A (en) * | 2017-06-26 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene/copper composite material and its preparation and application |
| CN109722641A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Diamond/graphene composite heat conduction film and preparation method thereof and cooling system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114226719A (en) * | 2021-11-12 | 2022-03-25 | 深圳前海石墨烯产业有限公司 | Graphene manganese-copper-based damping material powder, alloy damping material, preparation method and application |
| CN114226719B (en) * | 2021-11-12 | 2023-10-03 | 深圳前海石墨烯产业有限公司 | Graphene manganese copper-based damping material powder, alloy damping material, preparation method and application |
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