CN110371955A - A kind of preparation method of graphene-metallic composite - Google Patents
A kind of preparation method of graphene-metallic composite Download PDFInfo
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- CN110371955A CN110371955A CN201910660089.7A CN201910660089A CN110371955A CN 110371955 A CN110371955 A CN 110371955A CN 201910660089 A CN201910660089 A CN 201910660089A CN 110371955 A CN110371955 A CN 110371955A
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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
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1031—Alloys containing non-metals starting from gaseous compounds or vapours of at least one of the constituents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
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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
- C23C16/56—After-treatment
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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
- C01B2204/22—Electronic properties
Abstract
The invention discloses a kind of preparation methods of graphene-metallic composite, comprising the following steps: (1) using raw metal as substrate, deposits graphene using chemical meteorology deposition method, obtain the raw metal that surface is deposited with graphene layer；(2) oxidation polishes technique: the raw metal for being deposited with graphene layer being heated under oxidizing atmosphere, so that the graphene layer is uniform, obtains graphene-metal composite raw material；(3) it by graphene-metal composite raw material, is sintered after accumulation or ordered stacks, the graphene-metallic composite is made.The present invention polishes process due to having carried out oxidation to the graphene film for being deposited on metal surface, eliminate the graphene " isolated island " that vapour deposition process deposition graphene film unavoidably generates, retain complete regular graphene layer, to improve graphene-metallic composite electric conductivity.
Description
Technical field
The invention belongs to graphene composite material fields, more particularly, to a kind of system of graphene-metallic composite
Preparation Method.
Background technique
Thermal conductivity (5000W/m) and excellent mechanical characteristic (the up to tensile strength of 130GPa of the graphene because of its superelevation
And the Young's modulus of 1.0TPa or more) etc., it is a kind of ideal two-dimentional reinforced phase in field of compound material, by graphene
It is combined in the substrates such as aluminium, titanium, copper, it is contemplated that available high-strength light, the composite wood for having both the functional characteristics such as conductive, thermally conductive
Material.
In graphene-metallic composite, graphene is generally grown using chemical vapour deposition technique metal surface, is then adopted
Graphene-block of metallic material is prepared with vacuum hot-pressing process.Its electric conductivity still needs to be further increased.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of graphene-metallic composites
Preparation method remove " isolated island " of the graphene film grown in metal surface its object is to polish technique by oxidation,
The integrality of the graphite film of deposition is improved, to improve graphene-metallic composite electric conductivity of preparation, is thus solved existing
Some graphenes-metallic composite electric conductivity technical problem to be improved.
To achieve the above object, according to one aspect of the present invention, a kind of system of graphene-metallic composite is provided
Preparation Method, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
(2) oxidation polishes technique: by the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere
Heating obtains graphene-metal composite raw material so that the graphene layer is uniform；
(3) graphene-metal composite raw material that will be obtained in step (2) is sintered after accumulation or ordered stacks, is made described
Graphene-metallic composite.
Preferably, the preparation method of the graphene-metallic composite, the oxidizing atmosphere are preferably air atmosphere
Lower progress, temperature is at 150 to 220 DEG C, and preferably 200 DEG C, heating time 1-20min.
Preferably, the preparation method of the graphene-metallic composite, the raw metal are metal foil；Metal
Type is preferably the simple substance or alloy of copper, nickel.
Preferably, the preparation method of the graphene-metallic composite, step (1) are described heavy using chemical vapor
Area method deposits graphene, specifically:
By sheet metal foil to hang in deposit cavity, graphene is deposited on copper foil two sides；Or
Metal foil will be wrapped in continuous roll-to-roll mode by deposit cavity, deposit graphene in copper foil surface.
Preferably, the preparation method of the graphene-metallic composite, step (1) are described heavy using chemical vapor
Area method deposits graphene, specifically:
By packaged copper foil in continuous roll-to-roll mode by deposit cavity, graphene is deposited in copper foil surface.
Step (2) heats the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere, specifically
Are as follows:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 200 DEG C, and growth has graphene
Copper foil slow transits through heating zone, speed 15-300mm/min.
Preferably, the preparation method of the graphene-metallic composite, step (1) deposit graphene process are as follows: take out
Vacuum, plasma polishing copper foil, copper foil annealing grow graphene, rapid cooling.
Preferably, the preparation method of the graphene-metallic composite, the plasma polishing copper foil process gas
Body atmosphere is argon gas and hydrogen, and the argon flow is 20-400sccm, and the hydrogen flowing quantity is 20-100sccm；
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 20-400sccm, hydrogen flowing quantity 20-
100sccm；
Annealing temperature: 500 DEG C to 1050 DEG C；
Annealing time: 2min to 40min；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 10-100sccm, hydrogen flowing quantity 20-
100sccm, argon flow 0-400sccm；
Growth temperature: 600 DEG C to 1050 DEG C；
Growth time: 2min to 40min；
The rapid cooling process is that copper foil is quickly drawn to low-temperature region from heating zone, is carried out under vacuum conditions cold
But.
Preferably, the preparation method of the graphene-metallic composite, step (3) specifically:
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
Preferably, the preparation method of the graphene-metallic composite, the sintering process are vacuum heating-press sintering
Or alternating current impression sintering.
Preferably, the preparation method of the graphene-metallic composite, its vacuum degree of the vacuum heating-press sintering exist
1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；Sintering temperature is 850-1100 DEG C, keeps the temperature 20-120min,
With pressure head pressure maintaining furnace cooling.
The alternating current impression is sintered its vacuum degree in 1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；It burns
Junction temperature is 850-1100 DEG C, 20-120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, due to being deposited on gold
The graphene film of metal surface has carried out oxidation and has polished process, and it is inevitable to eliminate vapour deposition process deposition graphene film
The graphene " isolated island " of generation retains complete regular graphene layer, to improve graphene-metallic composite electric conductivity
Energy.
Detailed description of the invention
Fig. 1 is that present invention oxidation polishes process principle figure；
Fig. 2 is graphene-metallic composite Resistivity testing result report that the embodiment of the present invention 1 provides；
Fig. 3 is graphene-metallic composite Resistivity testing result report that the embodiment of the present invention 2 provides；
Fig. 4 is graphene-metallic composite Resistivity testing result report that comparative example provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below each other it
Between do not constitute conflict and can be combined with each other.
The preparation method of graphene metallic composite provided by the invention, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
The raw metal is metal foil；Metal species are preferably the simple substance or alloy of copper, nickel.Copper, nickel metallic substrates compared with
For be suitble to graphene growth, using the graphene layer of chemical meteorology deposition method depositing homogeneous.
Deposition graphene is sent out using chemical vapor deposition specifically:
By sheet metal foil to hang in deposit cavity, graphene is deposited on copper foil two sides；Or
Metal foil will be wrapped in continuous roll-to-roll mode by deposit cavity, deposit graphene in copper foil surface.
Deposit graphene process are as follows: it vacuumizes, plasma polishing copper foil, copper foil annealing, grows graphene, it is rapidly cold
But.
The plasma polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 20-
400sccm, the hydrogen flowing quantity are 20-100sccm.It is polished, is penetrated using the radio-frequency coil in chemical vapor depsotition equipment
Frequency power 30-100W, preferably 50W or so.
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 20-400sccm, hydrogen flowing quantity 20-
100sccm；
Annealing temperature: 600 DEG C to 1050 DEG C；
Annealing time: 2min to 40min；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 10-100sccm, hydrogen flowing quantity 20-
100sccm, argon flow 0-400sccm；
Growth temperature: 600 DEG C to 1050 DEG C；
Growth time: 2min to 40min；
The rapid cooling process is that copper foil is quickly drawn to low-temperature region from heating zone, is carried out under vacuum conditions cold
But.
In continuous roll-to-roll mode by deposit cavity, deposit cavity is a vitreosil pipe, respectively connected feed end
And discharge end, copper foil reach discharge end by quartz ampoule from feed end.Quartz ampoule about 1.5m long, front end (close to feed end) installation
There is radio-frequency coil, there is tube furnace in middle section, is heating zone, rear end (close to discharge end) is cooling down area.Annealing, the life of graphene
Long and cooling is disposably completed in the vacuum chamber of equipment, so each stage is in pipelined process, time synchronization；Annealing,
Growth and cooling time, depending on speed of the copper foil from feed end to discharge end.Therefore continuous roll-to-roll growth graphene energy
The preparation yield of significant increase graphene, reduces cost.
(2) oxidation polishes technique: by the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere
Heating obtains graphene-metal composite raw material so that the graphene layer is uniform；
The oxidizing atmosphere is preferably to carry out under air atmosphere, and temperature is at 150 to 220 DEG C, and preferably 200 DEG C, heating time
For 1-20min.Concrete operations are preferred are as follows:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 200 DEG C, and growth has graphene
Copper foil slow transits through heating zone, and speed is about 15-300mm/min, is 1-20min in the time in heating zone.
Inevitably occur in the graphene layer of raw metal surface deposition due to the randomness of deposition in step (2)
The free graphite alkene fragment of multilayer island shape, as shown in Figure 1, this free graphene fragment causes to bring graphene thickness not
Uniformly, so that graphene layer property is inconsistent, it will affect the electric conductivity with copper after compound.We have found that this free graphite alkene
Fragment is oxidized easily, and is heated under 150 to 220 DEG C of air atmosphere, and this incomplete island shape graphene layer can be by oxygen
Melt, and the graphene layer of regular deposition then due to form stable structure this oxidizing atmosphere and under the conditions of and be not easy by oxygen
Change, therefore by accurately controlling oxidizing condition, may make the oxidation of free graphite alkene isolated island to polish, retain complete regular graphene
Layer, to improve graphene-metallic composite electric conductivity.
(3) graphene-metal composite raw material that will be obtained in step (2) is sintered after accumulation or ordered stacks, is made described
Graphene-metallic composite.
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
The sintering process is that vacuum heating-press sintering or alternating current impression are sintered；
Its vacuum degree of the vacuum heating-press sintering is in 1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；It burns
Junction temperature is 850-1100 DEG C, 20-120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
The alternating current impression is sintered its vacuum degree in 1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；It burns
Junction temperature is 850-1100 DEG C, 20-120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
The preferred alternating current impression sintering of sintering process, can be with Fast Sintering bulk graphene-metallic composite.
The following are embodiments:
Embodiment 1
A kind of preparation method of graphene metallic composite, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
The raw metal is web-like copper foil；
Using chemical vapor deposition graphene specifically:
By packaged copper foil in continuous roll-to-roll mode by deposit cavity, graphene is deposited in copper foil surface.
Deposit graphene process are as follows: it vacuumizes, plasma polishing copper foil, copper foil annealing, grows graphene, it is cooling.It is whole
A process flow is synchronously completed in the same cavity with pipeline system, copper foil be about 150mm/min speed from cavity
It passes through, the time in heating zone is about 2min.
The plasma polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 400sccm, institute
Stating hydrogen flowing quantity is 100sccm.It is polished using the radio-frequency coil in chemical vapor depsotition equipment, radio-frequency power 100W.
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 400sccm, hydrogen flowing quantity 100sccm；
Annealing temperature: 1050 DEG C；Time 2min
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 100sccm, hydrogen flowing quantity 100sccm,
Argon flow is 400sccm；
Growth temperature: 1050 DEG C；
The cooling process is that copper foil is drawn to low-temperature region from heating zone, is cooled down under vacuum conditions.
(2) oxidation polishes technique: by the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere
Heating obtains graphene-metal composite raw material so that the graphene layer is uniform；
The oxidizing atmosphere is to carry out under air atmosphere, 220 DEG C of temperature.Concrete operations are as follows:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 220 DEG C, and growth has graphene
Copper foil slow transits through heating zone 300mm, and speed is about 15mm/min, and the time by heating zone is about 20min.
(3) the web-like graphene-metal composite raw material obtained in step (2) is cut into equal with hot pressing die internal diameter
Disk, accumulation or ordered stacks after be sintered, the graphene-metallic composite is made.
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
The sintering process is vacuum heating-press sintering；Vacuum degree is evacuated to 10Pa；Pressure head given pressure is between 30MPa；Add
Heat keeps the temperature 120min, with pressure head pressure maintaining furnace cooling to 1050 DEG C.
Embodiment 2
A kind of preparation method of graphene metallic composite, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
The raw metal is web-like copper foil；
Using chemical vapor deposition graphene specifically:
By packaged copper foil in continuous roll-to-roll mode by deposit cavity, graphene is deposited in copper foil surface.
Deposit graphene process are as follows: it vacuumizes, plasma polishing copper foil, copper foil annealing, grows graphene, it is cooling.It is whole
A process flow is synchronously completed in the same cavity with pipeline system, and copper foil is worn from cavity with the speed for being about 80mm/min
It crosses, the time in heating zone is about 20min.
The plasma polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 200sccm, institute
Stating hydrogen flowing quantity is 40sccm.It is polished using the radio-frequency coil in chemical vapor depsotition equipment, radio-frequency power 50W.
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 200sccm, hydrogen flowing quantity 40sccm；
Annealing temperature: 900 DEG C；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 40sccm, hydrogen flowing quantity 40sccm, argon
Throughput is 200sccm；
Growth temperature: 900 DEG C；
The cooling process is that copper foil is drawn to low-temperature region from heating zone, is cooled down under vacuum conditions.
(2) oxidation polishes technique: by the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere
Heating obtains graphene-metal composite raw material so that the graphene layer is uniform；
The oxidizing atmosphere is to carry out under air atmosphere, 200 DEG C of temperature.Concrete operations are as follows:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 200 DEG C, and growth has graphene
Copper foil slow transits through heating zone 300mm, and speed is about 50mm/min, and the time by heating zone is about 6min.
(3) the web-like graphene-metal composite raw material obtained in step (2) is cut into equal with hot pressing die internal diameter
Disk, accumulation or ordered stacks after be sintered, the graphene-metallic composite is made.
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
The sintering process is vacuum heating-press sintering；Vacuum degree is evacuated to 10Pa；Pressure head given pressure is between 30MPa；Add
Heat keeps the temperature 120min, with pressure head pressure maintaining furnace cooling to 1050 DEG C.
Embodiment 3
A kind of preparation method of graphene metallic composite, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
The raw metal is sheet copper foil；
Deposition graphene is sent out using chemical vapor deposition specifically:
By sheet copper foil to hang in deposit cavity, graphene is deposited on copper foil two sides.
Deposit graphene process are as follows: it vacuumizes, plasma polishing copper foil, copper foil annealing, grows graphene, it is rapidly cold
But.Successively sequence is completed in the same cavity for entire process flow.
The plasma polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 20sccm, institute
Stating hydrogen flowing quantity is 20sccm.It is polished using the radio-frequency coil in chemical vapor depsotition equipment, radio-frequency power 30W.
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 20sccm, hydrogen flowing quantity 20sccm；
Annealing temperature: 600 DEG C；
Annealing time: 40min；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 10sccm, hydrogen flowing quantity 20sccm, argon
Throughput is 0sccm；
Growth temperature: 600 DEG C；
Growth time: 40min；
The rapid cooling process is that copper foil is quickly drawn to low-temperature region from heating zone, is carried out under vacuum conditions cold
But.
(2) oxidation polishes technique: by the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere
Heating obtains graphene-metal composite raw material so that the graphene layer is uniform；
The oxidizing atmosphere is preferably to carry out under air atmosphere, and 150 DEG C of temperature, 15min.Concrete operations are as follows:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 150 DEG C, and growth has graphene
Sheet copper foil is placed on heating zone and keeps 15min, is then drawn to low-temperature region, is cooled to room temperature taking-up.
(3) the flake graphite alkene-metal composite raw material obtained in step (2) is cut into equal with hot pressing die internal diameter
Disk, accumulation or ordered stacks after be sintered, the graphene-metallic composite is made.
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
Vacuum degree is evacuated to 5Pa；Pressure head given pressure is in 50MPa；1000 DEG C are heated to, 120min is kept the temperature, with pressure head pressure maintaining
Furnace cooling.
Comparative example
A kind of preparation method of graphene metallic composite, comprising the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene
The raw metal of layer；
The raw metal is web-like copper foil；
Using chemical vapor deposition graphene specifically:
By packaged copper foil in continuous roll-to-roll mode by deposit cavity, graphene is deposited in copper foil surface.
Deposit graphene process are as follows: it vacuumizes, plasma polishing copper foil, copper foil annealing, grows graphene, it is cooling.It is whole
A process flow is synchronously completed in the same cavity with pipeline system, and copper foil is worn from cavity with the speed for being about 80mm/min
It crosses, the time in heating zone is about 20min.
The plasma polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 400sccm, institute
Stating hydrogen flowing quantity is 40sccm.It is polished using the radio-frequency coil in chemical vapor depsotition equipment, radio-frequency power 50W.
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 400sccm, hydrogen flowing quantity 40sccm；
Annealing temperature: 1000 DEG C；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 40sccm, hydrogen flowing quantity 40sccm, argon
Throughput is 400sccm；
Growth temperature: 1000 DEG C；
The cooling process is that copper foil is drawn to low-temperature region from heating zone, is cooled down under vacuum conditions.
(2) the web-like graphene-metal composite raw material obtained in step (1) is cut into equal with hot pressing die internal diameter
Disk, accumulation or ordered stacks after be sintered, the graphene-metallic composite is made.
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-Metals composite is sintered into
Material.
The sintering process is vacuum heating-press sintering；Vacuum degree is evacuated to 10Pa；Pressure head given pressure is in 30MPa；It is heated to
1050 DEG C, 120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
Embodiment 1,2 and graphene-copper of comparative example preparation meet the survey monitoring of material commission China and survey to its resistivity
Test result such as following table, test report are shown in Fig. 2,3,4:
Testing result shows that preparation method according to the invention, graphene-carbon/carbon-copper composite material of preparation, resistivity is more not
Graphene-the carbon/carbon-copper composite material for polishing technique preparation through oxidation has significantly improved.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene-metallic composite, which comprises the following steps:
(1) using raw metal as substrate, graphene is deposited using chemical meteorology deposition method, surface is obtained and is deposited with graphene layer
Raw metal；
(2) oxidation polishes technique: the raw metal for being deposited with graphene layer obtained in step (1) is added under oxidizing atmosphere
Heat obtains graphene-metal composite raw material so that the graphene layer is uniform；
(3) graphene-metal composite raw material that will be obtained in step (2) is sintered after accumulation or ordered stacks, the graphite is made
Alkene-metallic composite.
2. the preparation method of graphene-metallic composite as described in claim 1, which is characterized in that the oxidizing atmosphere
Preferably being carried out under air atmosphere, temperature is at 150 to 220 DEG C, and preferably 200 DEG C, heating time 1-20min.
3. the preparation method of graphene-metallic composite as described in claim 1, which is characterized in that the raw metal
For metal foil；Metal species are preferably the simple substance or alloy of copper, nickel.
4. the preparation method of graphene-metallic composite as described in claim 1, which is characterized in that step (1) is described to adopt
Graphene is deposited with chemical meteorology deposition method, specifically:
By sheet metal foil to hang in deposit cavity, graphene is deposited on copper foil two sides；Or
Metal foil will be wrapped in continuous roll-to-roll mode by deposit cavity, deposit graphene in copper foil surface.
5. the preparation method of graphene-metallic composite as claimed in claim 4, which is characterized in that step (1) is described to adopt
Graphene is deposited with chemical meteorology deposition method, specifically:
By packaged copper foil in continuous roll-to-roll mode by deposit cavity, graphene is deposited in copper foil surface.
Step (2) heats the raw metal for being deposited with graphene layer obtained in step (1) under oxidizing atmosphere, specifically:
Stopping vacuumizes roll-to-roll equipment, is connected to atmospheric environment, and furnace temperature is maintained at 200 DEG C, and growth has the copper foil of graphene
Slow transit through heating zone, speed 15-300mm/min.
6. the preparation method of graphene-metallic composite as described in claim 1, which is characterized in that step (1) deposits stone
Black alkene process are as follows: vacuumize, plasma polishing copper foil, copper foil annealing, grow graphene, rapid cooling.
7. the preparation method of graphene-metallic composite as claimed in claim 6, which is characterized in that the plasma
Polishing copper foil process gases atmosphere is argon gas and hydrogen, and the argon flow is 20-400sccm, and the hydrogen flowing quantity is 20-
100sccm；
Its annealing conditions includes:
Atmosphere: argon gas and hydrogen mixed gas atmosphere, argon flow 20-400sccm, hydrogen flowing quantity 20-100sccm；
Annealing temperature: 600 DEG C to 1050 DEG C；
Annealing time: 2min to 40min；
Its growth conditions includes:
Atmosphere: methane, argon gas and hydrogen mixed gas atmosphere, methane flow 10-100sccm, hydrogen flowing quantity 20-
100sccm, argon flow 0-400sccm；
Growth temperature: 600 DEG C to 1050 DEG C；
Growth time: 2min to 40min；
The rapid cooling process is that copper foil is quickly drawn to low-temperature region from heating zone, is cooled down under vacuum conditions.
8. the preparation method of graphene-metallic composite as described in claim 1, which is characterized in that step (3) is specific
Are as follows:
By the graphene-metal composite raw material ordered stacks, orthotropy graphene-metallic composite is sintered into.
9. the preparation method of graphene-metallic composite as claimed in claim 8, which is characterized in that the sintering process
It is sintered for vacuum heating-press sintering or alternating current impression.
10. the preparation method of graphene-metallic composite as claimed in claim 9, which is characterized in that the vacuum hotpressing
Its vacuum degree is sintered in 1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；Sintering temperature is 850-1100 DEG C,
20-120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
The alternating current impression is sintered its vacuum degree in 1Pa to 10Pa；Pressure head given pressure is in 30MPa between 50MPa；Sintering temperature
Degree is 850-1100 DEG C, 20-120min is kept the temperature, with pressure head pressure maintaining furnace cooling.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111069611A (en) * | 2019-12-23 | 2020-04-28 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN112867377A (en) * | 2020-12-16 | 2021-05-28 | 苏州驭奇材料科技有限公司 | Heat-conducting wave absorber and preparation method and application thereof |
| CN113355058A (en) * | 2021-06-04 | 2021-09-07 | 上海交通大学 | Two-dimensional carbon-metal configuration composite material and preparation method and application thereof |
| CN114472522A (en) * | 2022-01-26 | 2022-05-13 | 重庆墨希科技有限公司 | Method and device for preparing high-conductivity graphene metal composite material with assistance of plasma |
| WO2023019484A1 (en) * | 2021-08-18 | 2023-02-23 | 中车工业研究院有限公司 | Composite material for improving metal conductivity and preparation method therefor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344132A (en) * | 2011-07-08 | 2012-02-08 | 中国科学院上海微***与信息技术研究所 | Method for thinning grapheme layer by layer |
| WO2013172792A1 (en) * | 2012-05-17 | 2013-11-21 | National University Of Singapore | Methods of growing uniform, large-scale, multilayer graphene films |
| CN104649259A (en) * | 2015-02-06 | 2015-05-27 | 北京大学 | Large monocrystal graphene and preparation method thereof |
| CN108950683A (en) * | 2017-05-24 | 2018-12-07 | 北京大学 | A kind of high mobility N doping large single crystal graphene film and preparation method thereof |
| CN109811175A (en) * | 2019-03-26 | 2019-05-28 | 重庆大学 | A kind of graphene-method of manufacturing carbon/carbon-copper composite material |
-
2019
- 2019-07-22 CN CN201910660089.7A patent/CN110371955B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344132A (en) * | 2011-07-08 | 2012-02-08 | 中国科学院上海微***与信息技术研究所 | Method for thinning grapheme layer by layer |
| WO2013172792A1 (en) * | 2012-05-17 | 2013-11-21 | National University Of Singapore | Methods of growing uniform, large-scale, multilayer graphene films |
| CN104649259A (en) * | 2015-02-06 | 2015-05-27 | 北京大学 | Large monocrystal graphene and preparation method thereof |
| CN108950683A (en) * | 2017-05-24 | 2018-12-07 | 北京大学 | A kind of high mobility N doping large single crystal graphene film and preparation method thereof |
| CN109811175A (en) * | 2019-03-26 | 2019-05-28 | 重庆大学 | A kind of graphene-method of manufacturing carbon/carbon-copper composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111069611A (en) * | 2019-12-23 | 2020-04-28 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN111069611B (en) * | 2019-12-23 | 2021-07-30 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN112867377A (en) * | 2020-12-16 | 2021-05-28 | 苏州驭奇材料科技有限公司 | Heat-conducting wave absorber and preparation method and application thereof |
| CN113355058A (en) * | 2021-06-04 | 2021-09-07 | 上海交通大学 | Two-dimensional carbon-metal configuration composite material and preparation method and application thereof |
| WO2023019484A1 (en) * | 2021-08-18 | 2023-02-23 | 中车工业研究院有限公司 | Composite material for improving metal conductivity and preparation method therefor |
| CN114472522A (en) * | 2022-01-26 | 2022-05-13 | 重庆墨希科技有限公司 | Method and device for preparing high-conductivity graphene metal composite material with assistance of plasma |
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