CN102674321B - 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 PDFInfo
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- CN102674321B CN102674321B CN201110056973.3A CN201110056973A CN102674321B CN 102674321 B CN102674321 B CN 102674321B CN 201110056973 A CN201110056973 A CN 201110056973A CN 102674321 B CN102674321 B CN 102674321B
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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
- C23C16/01—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
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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
- C23C16/04—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
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
Technical field:
The present invention relates to graphene-based novel material and chemical vapour deposition (CVD) technology of preparing thereof, be specially a kind of grapheme foam and the preparation in macroscopic quantity method thereof with three-dimensional full-mesh network, be suitable for preparing high-quality graphene macroform in a large number.
Background technology:
Graphene is by the bi-dimensional cellular shape crystalline structure of the tightly packed one-tenth of monolayer carbon atom, is the basic structural unit building other dimension Carbon Materials (zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).The crystalline structure of Graphene uniqueness makes it have excellent electricity, calorifics and mechanical property, if its electronic mobility under room temperature is up to 200,000cm
2/ Vs, thermal conductivity, up to 5300W/mk, is expected to obtain 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.In order to fully utilize numerous excellent specific properties of Graphene, a large amount of preparation of high-quality graphene and monolithic graphite alkene is assembled into multi-functional macroscopic body material and will becomes most important.After the study group of Univ Manchester UK in 2004 adopts tape stripping method (or micromechanics stripping method) to be separated the Graphene obtaining stable existence first, the method much preparing Graphene is grown up successively, comprises SiC matrix surface epitaxial growth method, chemical oxidation stripping method, high-energy ultrasonic solution stripping method and chemical Vapor deposition process.Due to relatively simple preparation process, and output is larger, the Graphene that chemical oxidation stripping method obtains has been widely used in matrix material and has been assembled into various two-dimentional macroscopic body structure, as the graphene film etc. of superpower graphene paper material, flexible and transparent conductive.But these matrix materials and macrostructure have poor electric property, because in chemical stripping process, graphite raw material is oxidized stripping strongly on the one hand, the Graphene obtained has a large amount of textural defect and poor conductive capability, be that the Graphene obtained due to chemical stripping method has less size on the other hand, be assembled between macrostructure time slice and sheet and there is very large contact resistance.Nearest people have developed the transparent graphene conductive film that CVD method successfully prepares large-area high-quality, show the electrically conducting transparent performance more excellent than the film adopting chemical stripping method Graphene to prepare.But current CVD method is using planar metal such as tinsels as growth substrate, and the Graphene output of preparation is lower, and can only obtain the graphene film of two dimensional surface, can only meet the application of Graphene in the field such as electron device and nesa coating.
Three-dimensional body is the existence the most general in human lives of material and application form.Except two-dimensional film, having the porous materials such as the foam of three-dimensional net structure, sponge is another kind of important macroscopic body, and it can the multiple process based prediction model such as high connductivity, heat conduction, high strength, low density, high gas permeability of compound material.Timber, cork, sponge, coral, bone are the common macroscopic body materials with network structure of nature.The development of modern science and technology makes polymkeric substance, metal, pottery, glass etc. also can be made into foam materials, and obtains practical application in the every aspect of gas delivery, Water warfare, catalysis, energy storage, heat exchange, heat insulation, noise reduction, damping, the human lives such as explosion-proof.Compared with two-dimensional graphene film, three-dimensional grapheme network material has extremely low density and high porosity, except can making full use of the electricity of Graphene excellence, calorifics, mechanical property, can also utilize the feature that its specific surface area is large.So develop a kind of grapheme foam and the preparation in macroscopic quantity method thereof with three-dimensional net structure, the physical property of easily extensible Graphene and application space, greatly will promote 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, there are huge industrial application background and wide market outlook.
Summary of the invention:
The object of the present invention is to provide a kind of grapheme foam and the preparation in macroscopic quantity method thereof with three-dimensional full-mesh network, give full play to the excellent properties of Graphene and the application of expansion Graphene, solve the Graphene output existed in prior art lower, and the problem such as the graphene film that can only obtain two dimensional surface, have easy and simple to handle, cost is low, productive rate is high and be easy to the feature of structure regulating.
Technical scheme of the present invention is:
A kind of grapheme foam and preparation in macroscopic quantity method thereof with three-dimensional full-mesh network, the method adopts CVD technology to grow the Graphene of three-dimensional communication at three-dimensional porous metal form surface catalysis cracking carbon-source gas, the follow-up molten graphene macroform except obtaining a kind of three-dimensional full-mesh of porous foam shape after metal foraminous substrate.Concrete steps are as follows:
(1) chemical vapor deposition growth of Graphene: take porous metal as template, adopt chemical gaseous phase depositing process at foamed metal surface growth one deck graphene film, its mean thickness is 0.34-5nm;
(2) coating of high molecular polymer protective layer: evenly apply one deck high molecular polymer at the graphenic surface grown, destroys in subsequent disposal to prevent graphene mesh network;
(3) dissolving of foamed metal template: dissolve removing porous metal form cage with the lysate of the porous metal such as acid or iron(ic) chloride;
(4) removal of high molecular polymer protective layer: the high molecular polymer protective layer covering Graphene network surface is dissolved removal by organic molten Ji.
In the present invention, the porous metal template adopted is nickel foam, foam copper, foamed 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.
In the present invention, the porous metal template adopted puts into reaction zone by curling mode, to realize the preparation in macroscopic quantity of large-area three-dimensional full-mesh Graphene network.
In the present invention, the CVD cracking carbon source adopted be hydrocarbon polymer methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone, carbon monoxide one or more, carbon source flow velocity is 1-100 ml/min, and preferable range is 2-20 ml/min.Carrier gas is hydrogen or the gas mixture for hydrogen and rare gas element, and wherein hydrogen volume compares >=1/10, and carrier gas overall flow rate is 1-5000 ml/min, and preferable range is 100-1000 ml/min.
In the present invention, the number of plies of Graphene can be controlled by carbon source concentration.
In the present invention, CVD growth temperature is 500-1100 DEG C, and preferable range is 700-1000 DEG C; Growth time is 1-60 minute, and preferable range is 2-15 minute; It is 10-600 DEG C/min that reaction terminates rear speed of cooling, and preferable range is 50-200 DEG C/min.
In the present invention, adopt one or more high molecular polymers to carry out consolidation protection to Graphene network, prevent Graphene network from destroying in the process of dissolving porous metal skeleton.These high molecular polymers be polymethylmethacrylate, polyethylene, polystyrene, polypropylene one or more.
In the present invention, the lysate of the metal that defoams be sulfuric acid, hydrochloric acid, nitric acid, ferric chloride in aqueous solution one or more, concentration is at 0.1-5mol/L, and preferable range is 0.5-3mol/L; Solubilizing reaction temperature is at 0-100 DEG C, and preferable range is 20-80 DEG C.
In the present invention, adopt organic solvent to remove high molecular polymer protective layer, the organic solvent of employing be the ketones such as acetone, ethyl lactate, ethylene dichloride, trieline, chloroform, hydrochloric ether, halohydrocarbon, aromatic hydrocarbons reagent one or more.Solvent temperature is at 0-200 DEG C, and preferable range is 25-100 DEG C.
The grapheme foam that the present invention obtains is the network structure that Graphene forms three-dimensional full-mesh in a seamless fashion, and density is 0.1mg/cm
3-100mg/cm
3, porosity is 60%-99.9%, and 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 proposes the grapheme foam of the three-dimensional full-mesh network of a kind of graphene new material-have and simple CVD template to realize the preparation in macroscopic quantity of grapheme foam.
2, the Graphene in the grapheme foam that obtains of the present invention is formed the network of a full-mesh in a kind of mode of seamless link, this grapheme foam macroscopic body is made to have low density, high porosity, high-specific surface area, excellent charge-conduction and thermal conduction capability, 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 is laid a good foundation.
3, the present invention have easy and simple to handle, cost is low and be easy to the feature 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 up to 99.9%, and specific surface area reaches as high as 2600m
2/ g, specific conductivity can reach more than 1000S/cm.
Accompanying drawing illustrates:
Fig. 1 is the experimental installation schematic diagram of CVD growing graphene foam.In figure, 1 gas inlet; 2 porous metal; 3 thermopairs; 4 pneumatic outlets.
Fig. 2 is the stereoscan photograph that CVD grows the nickel foam of rear surface coating graphite alkene; Wherein, (a) is low power stereoscan photograph; (b-d) be high power stereoscan photograph.
Fig. 3 is the sign of the grapheme foam with three-dimensional full-mesh network.Wherein, (a) optical photograph that is grapheme foam; B stereoscan photograph that () is grapheme foam; C low power transmission electron microscope photo that () is grapheme foam; D high power transmission electron microscope photo that () is grapheme foam; E resonance laser Raman spectroscopy that () is grapheme foam.
Fig. 4 is the variation tendency of the average number of plies of Graphene with methane concentration of CVD growth, and the Graphene number of plies that the methane concentration of employing obtains more greatly is thicker.
The change that Fig. 5 (a)-(b) is the average number of plies of Graphene is on the impact of the thickness of grapheme foam, quality, density and specific surface area; 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:
The present invention is described in further detail below by embodiment and accompanying drawing.
Embodiment 1
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, nickel foam 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By nickel foam, (70 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 1000 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 1000 DEG C of postheat treatment 10 minutes; 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 is passed into after thermal treatment completes, start growing graphene, growth time is 5 minutes, cool fast with the speed of 100 DEG C minutes after growth terminates, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, dry at 180 DEG C of temperature after 30 minutes and put into 3mol/L hydrochloric acid soln, at 80 DEG C of temperature, react 3 hours to dissolve nickel foam template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 70 millimeters × 300 millimeters × 0.2 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 5 layers, 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
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, nickel foam 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By nickel foam, (70 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 1000 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 1000 DEG C of postheat treatment 10 minutes; 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 is passed into after thermal treatment completes, start growing graphene, growth time is 5 minutes, cool fast with the speed of 100 DEG C/min after growth terminates, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, dry at 180 DEG C of temperature after 30 minutes and put into 3mol/L hydrochloric acid soln, at 80 DEG C of temperature, react 3 hours to dissolve nickel foam template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 70 millimeters × 300 millimeters × 0.1 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 3 layers, 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
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, nickel foam 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By nickel foam, (70 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 900 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 900 DEG C of postheat treatment 10 minutes; 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 is passed into after thermal treatment completes, start growing graphene, growth time is 5 minutes, cool fast with the speed of 100 DEG C/min after growth terminates, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, dry at 180 DEG C of temperature after 30 minutes and put into 3mol/L hydrochloric acid soln, at 80 DEG C of temperature, react 3 hours to dissolve nickel foam template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 70 millimeters × 300 millimeters × 0.2 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 5 layers.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
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, foam copper 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By foam copper, (70 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 1000 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 1000 DEG C of postheat treatment 10 minutes; 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 is passed into after thermal treatment completes, start growing graphene, growth time is 10 minutes, cool fast with the speed of 100 DEG C minutes after growth terminates, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, at 180 DEG C of temperature, dry the mixing solutions (concentration of iron(ic) chloride and hydrochloric acid is 1mol/L) putting into iron(ic) chloride and hydrochloric acid after 30 minutes, at 80 DEG C of temperature, react 3 hours to dissolve foam copper template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 70 millimeters × 300 millimeters × 0.05 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 1 layer, 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
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, nickel foam 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By nickel foam, (1000 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be curlingly positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 1000 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 1000 DEG C of postheat treatment 10 minutes; 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 is passed into after thermal treatment completes, start growing graphene, growth time is 5 minutes, cool fast with the speed of 100 DEG C minutes after growth terminates, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, dry at 180 DEG C of temperature after 30 minutes and put into 3mol/L hydrochloric acid soln, at 80 DEG C of temperature, react 3 hours to dissolve nickel foam template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 1000 millimeters × 300 millimeters × 0.2 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 5 layers, 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
First, as shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, nickel foam 2 is placed in horizontal Reaktionsofen high-temperature zone, and thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor temperature of reaction in real time.By nickel foam, (70 millimeters × 300 millimeters × 1.2 millimeters, its pore size distribution is about 110PPI, and area density is about 300g/m
2) be positioned over horizontal Reaktionsofen (boiler tube diameter 75 millimeters, reaction zone length 300 millimeters) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); Be heated to 10000 DEG C (in heat-processed, hydrogen and argon gas flow velocity are respectively 200 and 500 ml/min, and heat-up rate is 33 DEG C/min) in the atmosphere of hydrogen and argon gas, treat that furnace temperature rises to 1000 DEG C of postheat treatment 10 minutes; Ethanol is brought into (wherein by the mode of bubbling argon after thermal treatment completes, the flow velocity of argon gas is 50 ml/min, ethanol is positioned over constant temperature in the Meng Shi wash bottle of 0 DEG C), pass into hydrogen as buffer gas (gas flow rate is 200 ml/min) simultaneously, start growing graphene, growth time is 5 minutes, cools fast after growth terminates with the speed of 100 DEG C/min, obtain the nickel foam of Surface coating Graphene, 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 Surface coating has Graphene, dry at 180 DEG C of temperature after 30 minutes and put into 3mol/L hydrochloric acid soln, at 80 DEG C of temperature, react 3 hours to dissolve nickel foam template.PMMA acetone dissolves removing at 55 DEG C of temperature, finally obtains the grapheme foam with three-dimensional networks.
Scanning electronic microscope, transmission electron microscope and resonance laser Raman spectroscopy are observed and are shown, the gained grapheme foam complete copy morphology of foamed metal template, be of a size of 70 millimeters × 300 millimeters × 0.2 millimeter, graphene-structured is continuous whole without damaged, there is better quality, the average number of plies about 5 layers, 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, in figure, one end of gas inlet 1 is provided with four mass flowmeters, optionally controls to pass into the gases such as argon gas, helium, hydrogen, methane, ethane or carbon monoxide.Liquid carbon source (as ethanol, methyl alcohol, benzene, toluene or hexanaphthene etc.) is placed in the Meng Shi wash bottle of 0 DEG C, is brought into by the gas mixture bubbling of argon gas or argon gas and helium.
As shown in Figure 2, grow the stereoscan photograph of the nickel foam of rear surface coating graphite alkene as can be seen from CVD, nickel foam reacts the evenly coated one deck graphene film in rear surface through CVD, and this layer graphene film uniformly continous is without breakage.
As shown in Figure 3, as can be seen from the sign of grapheme foam, the size of the method gained grapheme foam is adopted to reach 170 × 220mm
2, stereoscan photograph shows that in grapheme foam, network uniformly continous is without breakage, and transmission electron microscope photo shows that the Graphene number of plies comprises individual layer and minority layer, and resonance laser Raman spectroscopy shows that Graphene has very high quality (D mould intensity is almost nil).
As shown in Figure 4, as can be seen from the average number of plies of Graphene of CVD growth with the variation tendency of methane concentration, the average number of plies of Graphene can be controlled by the methane concentration regulating CVD react.
As shown in Figure 5, as can be seen from impact on the thickness of grapheme foam, quality, density and specific surface area of the change of the average number of plies of Graphene, adopt the 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, the present invention, with a kind of method of simple CVD template duplicating, achieves a kind of graphene new material---there is the preparation in macroscopic quantity of the grapheme foam of three-dimensional full-mesh network, have easy and simple to handle, cost is low and be easy to the feature of structure regulating.In such three-dimensional macro body, Graphene is formed the network of a full-mesh in a kind of mode of seamless link, this grapheme foam macroscopic body is made to have low density, high porosity, high-specific surface area, excellent charge-conduction and thermal conduction capability, 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 (7)
1. have a preparation in macroscopic quantity method for the grapheme foam of three-dimensional full-mesh network, it is characterized in that: grapheme foam is the network structure that Graphene forms three-dimensional full-mesh in a seamless fashion, density is 0.1mg/cm
3-100mg/cm
3, porosity is 60%-99.9%, and specific surface area is 130-2600m
2/ g, specific conductivity is 0.5S/cm-1000S/cm; The described preparation method with the grapheme foam of three-dimensional full-mesh network is: adopt chemical vapour deposition technique at three-dimensional porous metal form surface catalysis cracking carbon-source gas, grow the Graphene of three-dimensional communication, evenly apply one deck high molecular polymer at the graphenic surface grown, destroy in subsequent disposal to prevent graphene mesh network; Follow-up molten except after metal foraminous substrate, then with organic solvent, the high molecular polymer protective layer covering Graphene network surface is dissolved removal, obtain the grapheme foam with three-dimensional full-mesh network;
The described preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network, concrete steps are as follows:
(1) chemical vapor deposition growth of Graphene: take porous metal as template, adopts chemical gaseous phase depositing process at foamed metal surface growth one deck graphene film;
(2) coating of high molecular polymer protective layer: evenly apply one deck high molecular polymer at the graphenic surface grown, destroys in subsequent disposal to prevent graphene mesh network; Described high molecular polymer is one or more in polymethylmethacrylate, polyethylene, polystyrene and polypropylene;
(3) dissolving of foamed metal template: dissolve removing porous metal form cage with the lysate of porous metal;
(4) removal of high molecular polymer protective layer: the high molecular polymer protective layer covering Graphene network surface is dissolved removal with organic solvent.
2. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1, it is characterized in that, the porous metal template adopted is nickel foam, foam copper, foamed iron or foam cobalt, and its pore size distribution is at 50-200PPI, and area density is 50-1000g/m
2.
3. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1, it is characterized in that, in chemical vapour deposition reaction process, carbon source be hydrocarbon polymer methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone, carbon monoxide one or more, carbon source flow velocity is 1-100 ml/min.
4. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1, it is characterized in that, in chemical vapour deposition reaction process, carrier gas is hydrogen or the gas mixture for hydrogen and rare gas element, wherein hydrogen volume is than >=1/10, and carrier gas overall flow rate is 1-2000 ml/min.
5. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1, it is characterized in that, chemical vapor deposition growth Graphene temperature is 500-1100 DEG C, and growth time is 1-60 minute, and it is 5-600 DEG C/min that reaction terminates rear speed of cooling.
6. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1, it is characterized in that, the lysate of porous metal be sulfuric acid, hydrochloric acid, nitric acid, ferric chloride in aqueous solution one or more, concentration is at 0.1-5mol/L, and solubilizing reaction temperature is at 0-100 DEG C.
7. according to the preparation in macroscopic quantity method with the grapheme foam of three-dimensional full-mesh network according to claim 1; it is characterized in that; after removing porous metal skeleton; high molecular polymer protective layer is removed with organic solvent; adopt organic solvent be ketone, hydrochloric ether, halohydrocarbon, aromatic hydrocarbons reagent one or more, solvent temperature is at 0-200 DEG C.
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