CN102674321A - Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof - Google Patents

Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof Download PDF

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CN102674321A
CN102674321A CN2011100569733A CN201110056973A CN102674321A CN 102674321 A CN102674321 A CN 102674321A CN 2011100569733 A CN2011100569733 A CN 2011100569733A CN 201110056973 A CN201110056973 A CN 201110056973A CN 102674321 A CN102674321 A CN 102674321A
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graphene
foam
dimensional
grapheme foam
mesh network
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CN102674321B (en
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任文才
成会明
陈宗平
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Institute of Metal Research of CAS
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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
    • 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
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to a graphene-based novel material and a chemical vapor deposition preparation technology thereof, in particular to graphene foam with a three dimensional fully connected network and a macroscopic quantity preparation method thereof. The method is suitable for a mass preparation of the graphene foam with high qualities. Three dimensional connected graphene can grow by catalytic cracking of carbon source gases on the surface of a three dimensional porous metal through the chemical vapor deposition technology, and a porous foam-shaped graphene three dimensional macroscopic body can be obtained after a porous metal base is removed by dissolving subsequently. According to the graphene foam with the three dimensional fully connected network and the macroscopic quantity preparation method thereof, a simple template replication method is used for preparing the three dimensional connected graphene macroscopic body, and the method has the advantages that the operation is simple and convenient, the rate of production is high, and the adjustment and control of the structure are easy. The graphene foam forms the fully connected network in a seamless connection mode, has a low density, a high porosity and specific surface area and excellent capabilities of charge conduction and heat conduction and establishes a foundation for applications of graphene in fields of electric conduction, thermally conductive composite materials, electromagnetic shielding, wave absorbing, catalysis, sensing and energy storage materials and the like.

Description

A kind of grapheme foam and magnanimity preparation method thereof with three-dimensional full-mesh network
Technical field:
The present invention relates to graphene-based novel material and chemical vapor deposition (CVD) technology of preparing thereof, be specially a kind of grapheme foam and magnanimity preparation method thereof, be suitable for preparing in a large number high-quality Graphene macroscopic body with three-dimensional full-mesh network.
Background technology:
Graphene is the bi-dimensional cellular shape crystalline structure by the tightly packed one-tenth of monolayer carbon atom, is the basic structural unit that makes up other dimension raw material of wood-charcoal material (zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).The unique crystalline structure of Graphene makes it have excellent electricity, calorifics and mechanical property, like its electronic mobility under the room temperature up to 200,000cm 2/ Vs, thermal conductivity is expected the acquisition widespread use in fields such as multi-functional nanometer electronic device, nesa coating, matrix material, catalytic material, energy storage material, field emmision material, gas sensor and atmosphere storage up to 5300W/mk.In order to fully utilize numerous excellent specific properties of Graphene, a large amount of preparations of high quality Graphene and the monolithic Graphene is assembled into multi-functional macroscopic body material will becomes most important.After the study group of Univ Manchester UK in 2004 adopts tape stripping method (or micromechanics is peeled off method) to separate the Graphene that obtains stable existence first; A lot of methods that prepare Graphene are grown up successively, comprise that SiC matrix surface epitaxial growth method, chemical oxidation are peeled off method, high-energy ultrasonic solution is peeled off method and chemical Vapor deposition process.Owing to relatively simply prepare process; And output is bigger; Chemical oxidation is peeled off the Graphene that method makes and has been widely used in matrix material and has been assembled into various two-dimentional macroscopic body structures, like superpower Graphene paper material, the graphene film of flexible and transparent conductive etc.But these matrix materials and nacrostructure have relatively poor electric property; Be owing to graphite raw material in the chemical stripping process is peeled off by strong oxidation on the one hand; The Graphene that obtains has a large amount of textural defect and relatively poor conductive capability; Be because the Graphene that the chemical stripping method makes has less size on the other hand, have very big contact resistance when being assembled into nacrostructure between sheet and the sheet.Recently people have been developed the Graphene transparent conductive film that the CVD method is successfully prepared large-area high-quality, show than adopt the more excellent electrically conducting transparent performance of film of chemical stripping method Graphene preparation.But as growth substrate, the Graphene output of preparation is lower, and can only obtain the graphene film of two dimensional surface, can only satisfy the application of Graphene in fields such as electron device and nesa coatings with flush type metals such as tinsels for the CVD method at present.
Three-dimensional body is material the most general existence and application form in the human lives.Except that two-dimensional film, the porous materials such as foam, sponge with three-dimensional net structure are another kind of important macroscopic bodies, multiple physics and chemical properties such as the high conduction that it can compound material, heat conduction, HS, low density, high gas permeability.Timber, cork, sponge, coral, bone are the common macroscopic body materials with network structure of nature.Development of modern science and technology makes polymkeric substance, metal, pottery, glass etc. also can be made into foam materials, and has obtained practical application in gas delivery, water purification, catalysis, energy storage, heat exchange, heat insulation, noise reduction, damping, human lives's such as explosion-proof every aspect.Compare with two-dimentional graphene film, three-dimensional Graphene network material has extremely low density and high porosity, except that can making full use of the excellent electricity of Graphene, calorifics, mechanical property, can also utilize the big characteristics of its specific surface area.So develop a kind of grapheme foam and magnanimity preparation method thereof with three-dimensional net structure; Can expand the rerum natura and the application space of Graphene; Will greatly promote the application of Graphene, have huge industrial application background and vast market prospect in fields such as conduction, heat-conductive composite material, thermal management materials, electromagnetic shielding, suction ripple, catalysis, sensing and energy storage materials.
Summary of the invention:
The object of the present invention is to provide a kind of grapheme foam and magnanimity preparation method thereof with three-dimensional full-mesh network; Give full play to the application of excellent properties with the expansion Graphene of Graphene; It is lower to solve the Graphene output that exists in the prior art; And can only obtain the problems such as graphene film of two dimensional surface, have easy and simple to handle, cost is low, productive rate is high and be easy to the characteristics of structure regulating.
Technical scheme of the present invention is:
A kind of grapheme foam and magnanimity preparation method thereof with three-dimensional full-mesh network; This method adopts the CVD technology to grow the Graphene of three-dimensional communication at three-dimensional porous metal form surface catalysis cracking carbon-source gas, and follow-up dissolving removed the Graphene macroscopic body that can obtain a kind of three-dimensional full-mesh of porous foam shape after the metal porous substrate.Concrete steps are following:
(1) chemical vapor deposition growth of Graphene: with porous metal is template, adopts chemical gaseous phase depositing process at foamed metal surface growth one deck graphene film, and its mean thickness is 0.34-5nm;
(2) coating of high molecular polymer resist: the Graphene surface having grown evenly applies one deck high molecular polymer, destroys in subsequent disposal to prevent the Graphene network;
(3) dissolving of foamed metal template: the porous metal form cage is removed in the lysate dissolving with porous metal such as acid or iron(ic)chloride;
(4) removal of high molecular polymer resist: the high molecular polymer resist dissolving that will cover Graphene network surface with organic molten Ji is removed.
Among the present invention, the porous metal template that is adopted is nickel foam, foam copper, foam iron or foam cobalt etc., and its pore size distribution is at 50-200PPI, and preferable range is 90-120PPI; Area density is 50-1000g/m 2, preferable range is 250-400g/m 2
Among the present invention, the porous metal template that is adopted can be put into reaction zone through the mode of curling, to realize the magnanimity preparation of large-area three-dimensional full-mesh Graphene network.
Among the present invention; The CVD cracking carbon source that is adopted is one or more of hydrocarbon polymer methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone, carbon monoxide; The carbon source flow velocity is the 1-100 ml/min, and preferable range is the 2-20 ml/min.Carrier gas is hydrogen or is the gas mixture of hydrogen and rare gas element that wherein hydrogen volume is than >=1/10, and the carrier gas overall flow rate is the 1-5000 ml/min, and preferable range is the 100-1000 ml/min.
Among the present invention, the number of plies of Graphene can be controlled through carbon source concentration.
Among the present invention, the CVD growth temperature is 500-1100 ℃, and preferable range is 700-1000 ℃; Growth time is 1-60 minute, and preferable range is 2-15 minute; It is 10-600 ℃/minute that reaction finishes postcooling speed, and preferable range is 50-200 ℃/minute.
Among the present invention, adopt one or more high molecular polymers that the Graphene network is consolidated protection, prevent that the Graphene network from destroying in the process of dissolving porous metal skeleton.These high molecular polymers are one or more of polymethylmethacrylate, Vilaterm, PS, Vestolen PP 7052.
Among the present invention, the lysate of the metal that defoams is one or more of sulfuric acid, hydrochloric acid, nitric acid, ferric chloride in aqueous solution, and concentration is at 0.1-5mol/L, and preferable range is 0.5-3mol/L; The solubilizing reaction temperature is at 0-100 ℃, and preferable range is 20-80 ℃.
Among the present invention, adopt organic solvent to remove the high molecular polymer resist, the organic solvent of employing is one or more of ketones such as acetone, ethyl lactate, ethylene dichloride, trieline, chloroform, hydrochloric ether, halohydrocarbon, aromatic hydrocarbons reagent.Solvent temperature is at 0-200 ℃, and preferable range is 25-100 ℃.
To be Graphene constitute the network structure of three-dimensional full-mesh with the mode of seamless link to the grapheme foam that the present invention obtains, and density is 0.1mg/cm 3-100mg/cm 3, porosity is 60%-99.9%, specific surface area is 130-2600m 2/ g, specific conductivity is 0.5S/cm-1000S/cm.
The invention has the beneficial effects as follows:
1, the present invention the three-dimensional full-mesh network of a kind of Graphene novel material-have is proposed grapheme foam and simple CVD template to realize the magnanimity preparation of grapheme foam.
2, the Graphene in the grapheme foam that obtains of the present invention constitutes the network of a full-mesh with a kind of mode of seamless link; The charge-conduction and the thermal conduction capability that make this grapheme foam macroscopic body have low density, high porosity, high-specific surface area, excellence are for Graphene is laid a good foundation in the application in fields such as conduction, heat-conductive composite material, thermal management materials, electromagnetic shielding, suction ripple, catalysis, sensing and energy storage material.
3, the present invention have easy and simple to handle, cost is low and be easy to the characteristics of structure regulating, is expected the high-quality grapheme foam of scale operation.
4, the density of the grapheme foam of the three-dimensional full-mesh of the present invention's acquisition can be low to moderate 0.1mg/cm 3, porosity can be up to 99.9%, and specific surface area reaches as high as 2600m 2/ g, specific conductivity can reach more than the 1000S/cm.
Description of drawings:
Fig. 1 is the experimental installation synoptic diagram of CVD method growth grapheme foam.Among the figure, 1 gas inlet; 2 porous metal; 3 thermopairs; 4 pneumatic outlets.
Fig. 2 is the stereoscan photograph of the nickel foam of the surperficial coating graphite alkene in CVD growth back; Wherein, (a) be the low power stereoscan photograph; (b-d) be the high power stereoscan photograph.
Fig. 3 is the sign with grapheme foam of three-dimensional full-mesh network.Wherein, (a) be the optical photograph of grapheme foam; (b) be the stereoscan photograph of grapheme foam; (c) be the low power transmission electron microscope photo of grapheme foam; (d) be the high power transmission electron microscope photo of grapheme foam; (e) be the resonance laser Raman spectroscopy of grapheme foam.
Fig. 4 is the average number of plies of Graphene of the CVD growth variation tendency with methane concentration, and the Graphene number of plies that the methane concentration of employing obtains more greatly is thick more.
Fig. 5 (a)-(b) is the influence of the variation of the average number of plies of Graphene to thickness, quality, density and the specific surface area of grapheme foam; Wherein, Fig. 5 (a) figure is the average number of plies relation curve of thickness, quality and Graphene; Fig. 5 (b) figure is the average number of plies relation curve of density, specific surface area and Graphene.
Embodiment:
Through embodiment and accompanying drawing the present invention is detailed further below.
Embodiment 1
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Nickel foam 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With nickel foam (70 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) be positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 1000 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 1000 ℃ of post-heat-treated 10 minutes; After accomplishing, thermal treatment feeds the mixed gas (gas flow rate is respectively methane 5 ml/min, hydrogen 200 ml/min and argon gas 500 ml/min) of methane, hydrogen and argon gas; Begin the Graphene of growing; Growth time is 5 minutes; Speed with 100 ℃ minutes behind the growth ending is cooled off fast, obtains the nickel foam of surperficial coating graphite alkene, and the mean thickness of graphene film is about 1.7nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the nickel foam surface that the surface is coated with Graphene; Put into the 3mol/L hydrochloric acid soln in baking under 180 ℃ of temperature after 30 minutes, under 80 ℃ of temperature, react 3 hours with dissolving nickel foam template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 70 millimeters * 300 millimeters * 0.2 millimeter, the graphene-structured continuous whole does not have breakage, has better quality; About 5 layers of the average numbers of plies, the density of grapheme foam is about 5mg/cm 3, porosity is about 99.7%, and specific surface area is about 520m 2/ g, specific conductivity is about 10S/cm.
Embodiment 2
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Nickel foam 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With nickel foam (70 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) be positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 1000 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 1000 ℃ of post-heat-treated 10 minutes; After accomplishing, thermal treatment feeds the mixed gas (gas flow rate is respectively methane 2 ml/min, hydrogen 200 ml/min and argon gas 500 ml/min) of methane, hydrogen and argon gas; Begin the Graphene of growing; Growth time is 5 minutes; Cool off fast with 100 ℃/minute speed behind the growth ending, obtain the nickel foam of surperficial coating graphite alkene, the mean thickness of graphene film is about 1nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the nickel foam surface that the surface is coated with Graphene; Put into the 3mol/L hydrochloric acid soln in baking under 180 ℃ of temperature after 30 minutes, under 80 ℃ of temperature, react 3 hours with dissolving nickel foam template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 70 millimeters * 300 millimeters * 0.1 millimeter, the graphene-structured continuous whole does not have breakage, has better quality; About 3 layers of the average numbers of plies, the density of grapheme foam is about 6mg/cm 3, porosity is about 99.6%, and specific surface area is about 850m 2/ g, specific conductivity is about 7S/cm.
Embodiment 3
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Nickel foam 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With nickel foam (70 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) be positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 900 ℃ of post-heat-treated 10 minutes; After accomplishing, thermal treatment feeds the mixed gas (gas flow rate is respectively methane 5 ml/min, hydrogen 200 ml/min and argon gas 500 ml/min) of methane, hydrogen and argon gas; Begin the Graphene of growing; Growth time is 5 minutes; Cool off fast with 100 ℃/minute speed behind the growth ending, obtain the nickel foam of surperficial coating graphite alkene, the mean thickness of graphene film is about 1.7nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the nickel foam surface that the surface is coated with Graphene; Put into the 3mol/L hydrochloric acid soln in baking under 180 ℃ of temperature after 30 minutes, under 80 ℃ of temperature, react 3 hours with dissolving nickel foam template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 70 millimeters * 300 millimeters * 0.2 millimeter; The graphene-structured continuous whole does not have breakage, has better quality, about 5 layers of the average numbers of plies.The density of grapheme foam is about 5mg/cm 3, porosity is about 99.7%, and specific surface area is about 520m 2/ g, specific conductivity is about 8S/cm.
Embodiment 4
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Foam copper 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With foam copper (70 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) be positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 1000 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 1000 ℃ of post-heat-treated 10 minutes; After accomplishing, thermal treatment feeds the mixed gas (gas flow rate is respectively methane 5 ml/min, hydrogen 200 ml/min and argon gas 500 ml/min) of methane, hydrogen and argon gas; Begin the Graphene of growing; Growth time is 10 minutes; Speed with 100 ℃ minutes behind the growth ending is cooled off fast, obtains the nickel foam of surperficial coating graphite alkene, and the mean thickness of graphene film is about 0.34nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the foam copper surface that the surface is coated with Graphene; After drying by the fire 30 minutes under 180 ℃ of temperature, put into the mixing solutions (concentration of iron(ic)chloride and hydrochloric acid is 1mol/L) of iron(ic)chloride and hydrochloric acid, under 80 ℃ of temperature, react 3 hours with dissolving foam copper template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 70 millimeters * 300 millimeters * 0.05 millimeter, the graphene-structured continuous whole does not have breakage, has better quality; About 1 layer of the average number of plies, the density of grapheme foam is about 4mg/cm 3, porosity is about 99.8%, and specific surface area is about 2600m 2/ g, specific conductivity is about 5S/cm.
Embodiment 5
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Nickel foam 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With nickel foam (1000 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) curling is positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 1000 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 1000 ℃ of post-heat-treated 10 minutes; After accomplishing, thermal treatment feeds the mixed gas (gas flow rate is respectively methane 5 ml/min, hydrogen 200 ml/min and argon gas 500 ml/min) of methane, hydrogen and argon gas; Begin the Graphene of growing; Growth time is 5 minutes; Speed with 100 ℃ minutes behind the growth ending is cooled off fast, obtains the nickel foam of surperficial coating graphite alkene, and the mean thickness of graphene film is for being about 1.7nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the nickel foam surface that the surface is coated with Graphene; Put into the 3mol/L hydrochloric acid soln in baking under 180 ℃ of temperature after 30 minutes, under 80 ℃ of temperature, react 3 hours with dissolving nickel foam template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 1000 millimeters * 300 millimeters * 0.2 millimeter, the graphene-structured continuous whole does not have breakage, has better quality; About 5 layers of the average numbers of plies, the density of grapheme foam is about 5mg/cm 3, porosity is about 99.7%, and specific surface area is about 520m 2/ g, specific conductivity is about 10S/cm.
Embodiment 6
At first, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growth Graphene; Horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4; Nickel foam 2 places horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, with real-time monitoring temperature of reaction.With nickel foam (70 millimeters * 300 millimeters * 1.2 millimeters, its pore size distribution is about 110PPI, area density is about 300g/m 2) be positioned over horizontal Reaktionsofen (75 millimeters of boiler tube diameters, 300 millimeters of reaction zone length) middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); In the atmosphere of hydrogen and argon gas, be heated to 10000 ℃ (hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min in the heat-processed, and heat-up rate is 33 ℃/minute), treat that furnace temperature rises to 1000 ℃ of post-heat-treated 10 minutes; Thermal treatment is brought ethanol (wherein, the flow velocity of argon gas is 50 ml/min, and ethanol is positioned over constant temperature in 0 ℃ Meng Shi wash bottle) into by the mode of argon gas bubbling after accomplishing; Feed hydrogen simultaneously as buffer gas (gas flow rate is 200 ml/min); Begin the Graphene of growing, growth time is 5 minutes, cools off fast with 100 ℃/minute speed behind the growth ending; Obtain the nickel foam of surperficial coating graphite alkene, the mean thickness of graphene film is about 1.7nm.
Then; The ethyl lactate solution (polymethylmethacrylate accounts for 4wt%) of polymethylmethacrylate (PMMA) is added drop-wise to the nickel foam surface that the surface is coated with Graphene; Put into the 3mol/L hydrochloric acid soln in baking under 180 ℃ of temperature after 30 minutes, under 80 ℃ of temperature, react 3 hours with dissolving nickel foam template.PMMA dissolves under 55 ℃ of temperature with acetone and removes, and finally obtains having the grapheme foam of three-dimensional networks.
Sem, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown; Gained grapheme foam complete copy the pattern and the structure of foamed metal template; Be of a size of 70 millimeters * 300 millimeters * 0.2 millimeter, the graphene-structured continuous whole does not have breakage, has better quality; About 5 layers of the average numbers of plies, the density of grapheme foam is about 5mg/cm 3, porosity is about 99.7%, and specific surface area is about 520m 2/ g, specific conductivity is about 10S/cm.
As shown in Figure 1, an end of gas inlet 1 is provided with four mass flowmeters among the figure, and optionally control feeds gases such as argon gas, helium, hydrogen, methane, ethane or carbon monoxide.Liquid carbon source (like ethanol, methyl alcohol, benzene, toluene or hexanaphthene etc.) places 0 ℃ Meng Shi wash bottle, brings into through the gas mixture bubbling of argon gas or argon gas and helium.
As shown in Figure 2, the stereoscan photograph of the nickel foam of surperficial coating graphite alkene can be found out from CVD growth back, nickel foam through CVD reaction back coated with uniform one deck graphene film, this layer graphene film does not evenly have damaged continuously.
As shown in Figure 3, can find out from the sign of grapheme foam, adopt the size of this method gained grapheme foam can reach 170 * 220mm 2, stereoscan photograph shows that network does not evenly have breakage continuously in the grapheme foam, and transmission electron microscope photo shows that the Graphene number of plies comprises individual layer and minority layer, and the resonance laser Raman spectroscopy shows that Graphene has very high quality (D mould intensity is almost nil).
As shown in Figure 4, can find out with the variation tendency of methane concentration that from the average number of plies of Graphene of CVD growth the average number of plies of Graphene can be controlled through the methane concentration of regulating the CVD reaction.
As shown in Figure 5, can find out the influence of thickness, quality, density and the specific surface area of grapheme foam from the variation of the average number of plies of Graphene, adopt this method gained grapheme foam to have extremely low density and (be low to moderate 3mg/cm 3) and high specific surface area (up to 850m 2/ g).
The above results shows that the present invention has realized a kind of Graphene novel material with a kind of method of simple CVD template duplicating---have the magnanimity preparation of the grapheme foam of three-dimensional full-mesh network, have easy and simple to handle, cost is low and be easy to the characteristics of structure regulating.In such three-dimensional macro body; Graphene constitutes the network of a full-mesh with a kind of mode of seamless link; The charge-conduction and the thermal conduction capability that make this grapheme foam macroscopic body have low density, high porosity, high-specific surface area, excellence are for the application of Graphene in fields such as conduction, heat-conductive composite material, thermal management materials, electromagnetic shielding, suction ripple, catalysis, sensing and energy storage materials lays the foundation.

Claims (10)

1. grapheme foam with three-dimensional full-mesh network is characterized in that: to be Graphene constitute the network structure of three-dimensional full-mesh with the mode of seamless link to grapheme foam, and density is 0.1mg/cm 3-100mg/cm 3, porosity is 60%-99.9%, specific surface area is 130-2600m 2/ g, specific conductivity is 0.5S/cm-1000S/cm.
2. described magnanimity preparation method of claim 1 with grapheme foam of three-dimensional full-mesh network; It is characterized in that: this method adopts chemical vapour deposition technique at three-dimensional porous metal form surface catalysis cracking carbon-source gas; Grow the Graphene of three-dimensional communication; Follow-up dissolving except that after the metal porous substrate obtains having the grapheme foam of three-dimensional full-mesh network.
3. according to the described magnanimity preparation method of claim 2, it is characterized in that concrete steps are following with grapheme foam of three-dimensional full-mesh network:
(1) chemical vapor deposition growth of Graphene: with porous metal is template, adopts chemical gaseous phase depositing process at foamed metal surface growth one deck graphene film;
(2) coating of high molecular polymer resist: the Graphene surface having grown evenly applies one deck high molecular polymer, destroys in subsequent disposal to prevent the Graphene network;
(3) dissolving of foamed metal template: the porous metal form cage is removed in the lysate dissolving with porous metal;
(4) removal of high molecular polymer resist: the high molecular polymer resist dissolving that will cover Graphene network surface with organic molten Ji is removed.
4. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; The porous metal template that adopts is nickel foam, foam copper, foam iron or foam cobalt etc., and its pore size distribution is at 50-200PPI, and area density is 50-1000g/m 2
5. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; In the chemical vapour deposition reaction process; Carbon source is one or more of hydrocarbon polymer methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone, carbon monoxide, and the carbon source flow velocity is the 1-100 ml/min.
6. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; In the chemical vapour deposition reaction process; Carrier gas is hydrogen or is the gas mixture of hydrogen and rare gas element that wherein hydrogen volume is than >=1/10, and the carrier gas overall flow rate is the 1-2000 ml/min.
7. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; Chemical vapor deposition growth Graphene temperature is 500-1100 ℃, and growth time is 1-60 minute, and it is 5-600 ℃/minute that reaction finishes postcooling speed.
8. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; Adopt one or more high molecular polymers that the Graphene network is consolidated protection; Prevent that the Graphene network from destroying in the process of dissolving porous metal skeleton, said high molecular polymer is one or more of polymethylmethacrylate, Vilaterm, PS, Vestolen PP 7052.
9. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; The lysate of porous metal is one or more of sulfuric acid, hydrochloric acid, nitric acid, ferric chloride in aqueous solution; Concentration is at 0.1-5mol/L, and the solubilizing reaction temperature is at 0-100 ℃.
10. according to claim 2 or 3 described magnanimity preparing methods with grapheme foam of three-dimensional full-mesh network; It is characterized in that; After removing the porous metal skeleton; Remove the high molecular polymer resist with organic solvent, the organic solvent of employing is one or more of ketone, hydrochloric ether, halohydrocarbon, aromatic hydrocarbons reagent, and solvent temperature is at 0-200 ℃.
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