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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 239000006260 foam Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 26
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000011241 protective layer Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000006166 lysate Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000011232 storage material Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000010076 replication Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 54
- 229910052786 argon Inorganic materials 0.000 description 27
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000007726 management method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Carbon And Carbon Compounds (AREA)
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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