CN108602046A

CN108602046A - Graphene-Carbon Hybrid Foam

Info

Publication number: CN108602046A
Application number: CN201680072981.8A
Authority: CN
Inventors: 阿茹娜·扎姆; 张博增
Original assignee: Nanotek Instruments Inc
Current assignee: Nanotek Instruments Inc
Priority date: 2015-12-28
Filing date: 2016-12-09
Publication date: 2018-09-28
Anticipated expiration: 2036-12-09
Also published as: JP7038659B2; CN108602046B; JP2019507715A; KR102584293B1; WO2017116657A1; KR20180102557A

Abstract

Provide a kind of integral type 3D graphene carbon hybrid foams being made of multiple holes and hole wall, wherein these hole walls contain by the chemically combined single layer of carbon material or few layer graphene piece, with the carbon material and graphene weight ratio from 1/100 to 1/2, wherein there are these few layer graphene pieces 2 10 stacked graphene plane layers, these graphene planes to have the interplanar spacing d from 0.3354nm to 0.40nm₀₀₂And these graphene films contain the non-protogenous grapheme material with the substantially raw graphite alkene material of zero % non-carbon elements or with 0.01% to 25% non-carbon element by weight, wherein the non-protogenous graphene be selected from graphene oxide, redox graphene, fluorinated graphene, chlorination graphene, bromination graphene, iodate graphene, hydrogenation graphene, nitridation graphene, doped graphene, chemical functionalization graphene, or combinations thereof.Additionally provide the method for producing the hybrid foam, the product containing the hybrid foam and its application.

Description

Graphene-carbon hybrid foam

Cross reference to related applications

This application claims the U.S. Patent Application No. 14/998,356 and 14/998 that each comfortable 28 days December in 2015 submits, 357 priority, these patent applications are incorporated herein by quoting mode.

Technical field

Present invention relates in general to the fields of carbon graphite foam, and relate more specifically to herein referred to as integral type 3D The porous graphite material of the new model of graphene-carbon hybrid foam, its production method, containing its product and operate the production The method of product.

Background technology

There are five types of unique crystal structures, including diamond, fullerene (0-D nano-graphites material), carbon to receive for known carbon tool Mitron or carbon nano-fiber (1-D nano-graphites material), graphene (2-D nano-graphites material) and graphite (3-D graphite materials). Carbon nanotube (CNT) refers to the tubular structure grown with single wall or multi wall.Carbon nanotube (CNT) and carbon nano-fiber (CNF) tool There is the diameter of several nanometers to hundreds of nanometers of the order of magnitude.Its longitudinal, hollow-core construction assigns the unique machinery of material, electricity and chemistry Characteristic.CNT or CNF is one-dimensional nano carbon or 1-D nano-graphite materials.

Early in 2002, our research group opened up the exploitation of grapheme material and associated production technique：(1) B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates [nanoscale graphite alkene plate] ", U.S. Patent number 7,071,258 (07/04/2006), the application submitted on October 21 in 2002；(2) B.Z.Jang et al. " Process for Producing Nano-scaled Graphene Plates [method for producing nanoscale graphite alkene plate] ", United States Patent (USP) Application number 10/858,814 (06/03/2004)；(3) B.Z.Jang, A.Zhamu and J.Guo, " Process for Producing Nano-scaled Platelets and Nanocomposites are [multiple for producing nanoscale platelet and nanometer The method of condensation material] ", U.S. Patent Application No. 11/509,424 (08/25/2006).

Single-layer graphene film is made of the carbon atom for occupying two-dimentional hexagoinal lattice.Multi-layer graphene is by more than one graphite The platelet that alkene plane is constituted.Individual single-layer graphene film and multi-layer graphene platelet are collectively referred to herein as nano-graphene piece Brilliant (NGP) or grapheme material.NGP includes the graphene of raw graphite alkene (substantially 99% carbon atom), low-level oxidation (by weight Gauge<5% oxygen), graphene oxide (oxygen by weight >=5%), micro- fluorinated graphene (by weight<5% fluorine), The graphene of fluorinated graphene (fluorine by weight >=5%), the graphene of other halogenations and chemical functionalization.

It has been found that NGP has a series of uncommon physics, chemistry and mechanical property.For example, it was discovered that graphene is shown The highest inherent strength and highest thermal conductivity of all current materials.Although the actual electronic for not envisioning graphene applies (example Such as, instead of Si as the trunk in transistor) occur in the following 5-10, but its as the Nano filling in composite material with And the application of the electrode material in energy storage device is at hand.The availability of a large amount of machinable graphene films is for successfully developing Composite material, energy and the other application of graphene are vital.

Our research group finds graphene [B.Z.Jang and W.C.Huang, " Nano-scaled at first Graphene Plates [nanoscale graphite alkene plate] ", the U.S. Patent Application No. 10/274,473 that October 21 in 2002 submits, It is now U.S. Patent number 7,071,258 (07/04/2006)].Recently, we review production NGP and NGP nanocomposites Method [Bor Z.Jang and A Zhamu, " Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites:A Review [the processing of nano-graphene platelet (NGP) and NGP nanocomposites：It is comprehensive State] ", 43 (2008) 5092-5101 of J.Materials Sci. [material science magazine]].Four kinds of main existing skills are followed Art method produces NGP.The advantages of summarizing them as follows and disadvantage：

To the summary of the production of isolated nano-graphene plate or piece (NGP)

Method 1：The chemistry of graphene oxide (GO) is formed and reduction

First method (Fig. 1) needs natural with intercalator and oxidant (for example, respectively concentrated sulfuric acid and nitric acid) processing Graphite powder is to obtain graphite intercalation compound (GIC) or actually graphite oxide (GO).[William S.Hummers, Jr. etc. People, Preparation of Graphitic Oxide [preparation of graphite oxide], Journal of the American Chemical Society [American Chemical Society], page 1958,1339] before intercalation or oxidation, graphite has about Spacing (L between the graphene planes of 0.335nm_d=1/2d₀₀₂=0.335nm).In the case of intercalation and oxidation processes, graphite Spacing increases to the typically greater than value of 0.6nm between alkene.This is the first expansion that graphite material is undergone during the chemical route Stage.Then use the graphene layer of thermal shock exposure method or the supersound process auxiliary based on solution puffing (exfoliation) Method makes gained GIC or GO be subjected to further expanding (commonly referred to as puffing).

In thermal shock exposure method, so that GIC or GO is exposed to high temperature (typically 800 DEG C -1,050 DEG C) and continue short time period (typically 15 to 60 seconds) are so that GIC or GO is puffing or expansion is to form the graphite of puffing or further expansion, the graphite allusion quotation Type in the form of " graphite worm " being made of graphite flake still interconnected amongst one another.This thermal shock program can generate The graphite flake or graphene film of separation, but usually most of graphite flake keeps interconnection.Typically, it is then ground using air Mill, mechanical shearing or supersound process in water make puffing graphite or graphite worm be subjected to thin slice separating treatment.Therefore, method 1 substantially needs three different programs：First expansion (oxidation or intercalation), further expansion (or " puffing ") and separation.

In the partition method based on solution, expansion or puffing GO powder is dispersed in water or alcohol solution, its warp is made It is ultrasonically treated.It is important to note that, in these methods, (that is, in the first expansion after the intercalation of graphite and oxidation Afterwards) and typically supersound process is used (after the second expansion) after the thermal shock exposure of gained GIC or GO.It is alternative Ground, makes the GO powder being dispersed in water be subjected to ion exchange or interminable purifying procedure, and mode is so that being present in interplanar sky Between in ion between repulsive force surpass the Van der Waals force between graphene, cause graphene layer to detach.

In the presence of with the relevant several main problems of this conventional chemical production method：

(1) this method is needed using a large amount of several undesirable chemicals, such as sulfuric acid, nitric acid and potassium permanganate or Sodium chlorate.

(2) chemical treating process needs long intercalation and oxidization time, typically 5 hours to 5 days.

(3) during this prolonged intercalation or oxidation process, strong acid (will by " corrode it and enter the path of graphite " Graphite is converted into the carbon dioxide lost in the process) and consume a large amount of graphite.Lose the immersion of 20%-50% by weight Graphite material in strong acid and oxidant is not uncommon for.

(4) heat is puffing needs high temperature (typically 800 DEG C -1,200 DEG C), and is therefore highly energy intensive method.

(5) heat-and the puffing method of solution-induction are required for very cumbersome washing and purification step.For example, typically making 1 gram of GIC is washed and recycled with the water of 2.5kg, generates the waste water for largely needing proper treatment.

(6) in heat-and puffing method the two of solution-induction, products therefrom is GO platelets, these GO platelets are subjected to Further electronation processing is to reduce oxygen content.Typically, or even after reduction, the conductivity of GO platelets is still far below primary The conductivity of graphene.In addition, reducing program often refers to use toxic chemical, such as hydrazine.

(7) in addition, the range for the intercalation solution amount being retained in after draining on thin slice can be molten from 20 to 150 parts by weight The parts by weight of graphite flakes (pph) of liquid/100, and more typically about 50 to 120pph.During high temperature puffing, protected by thin slice The remaining intercalation species that stay, which decompose, generates various undesirable sulfur-bearings and containing nitrogen compound (such as NO_xAnd SO_x).Stream Go out object and need expensive regulation program, so as not to unfavorable environment influence.

The present invention is in order to overcome the problems, such as the limitation of above-outlined or and carry out.

Method 2：The direct formation of primary nano-graphene platelet

In 2002, our research team was successfully from the partially carbonized or graphite obtained by polymer or pitch precursor Isolate single layer and multi-layer graphene piece [B.Z.Jang and W.C.Huang, " Nano-scaled in the polymerization carbon of change Graphene Plates [nanoscale graphite alkene plate] ", the U.S. Patent Application No. 10/274 that on October 21st, 2002 submits, 473；It is now U.S. Patent number 7,071,258 (07/04/2006)].Mack et al. [" Chemical manufacture of Nanostructured materials [the chemistry manufacture of nano structural material] " U.S. Patent numbers 6,872,330 (2005 3 The moon 29)] a kind of method is developed, this method is related to potassium melt intercalation graphite and the graphite of gained K- intercalations is made to be connect with alcohol It touches, produces the violent expanded graphite containing NGP.This method must carefully be carried out in vacuum or in extremely dry glove box environment, because Pure alkali metals such as potassium and sodium are extremely sensitive to moisture and have explosion danger.This method is unsuitable for mass production NGP.This hair It is bright to be carried out to overcome the limitation of above-outlined.

Method 3：Epitaxial growth and chemical vapor deposition of the nano-graphene piece on mineral crystal surface

The ultra-thin stone of epitaxial growth and the acquisition of laser desorption-ionization technology in substrate based on thermal decomposition can be passed through The small-scale production of black alkene piece.[Walt A.DeHeer,Claire Berger,Phillip N.First,“Patterned Thin film graphite devices and method for making same [patterned film graphite device and its Preparation method] " U.S. Patent number 7,327,000B2 (on June 12nd, 2003)].Graphite with only one or several atomic layers Epitaxial film has technology and scientific importance due to its characteristic feature and as the very high potential of device substrate.However, these Method is unsuitable for the isolated graphene film of mass production and is used for composite material and stored energy application.The present invention is in order to overcome above-outlined Limitation and carry out.

It is in form of film (typically thickness for producing<Another method of graphene 2nm) is catalytic chemical vapor Sedimentation.Catalysis CVD is related to appropriate hydrocarbon gas (such as C₂H₄) catalytic decomposition on the surfaces Ni or Cu to be to form single layer or few layer stone Black alkene.It, will be via the decomposing hydrocarbon gas molecule acquisition at a temperature of 800 DEG C -1,000 DEG C in the case where Ni or Cu are catalyst Carbon atom is deposited directly on Cu foils surface or is precipitate on Ni foils surface from Ni-C solid solution states, to form single layer or few layer Graphene (being less than 5 layers) piece.The CVD method of Ni- or Cu- catalysis is not suitable for depositing more than 5 graphene planes (typically< 2nm), more than 5 graphene planes, Ni or Cu layers below cannot provide any catalytic effect again.CVD graphene films are very Expensive.

Method 4：Method from bottom to top (by small molecule synthesizing graphite alkene)

Yang et al. [" Two-dimensional Graphene Nano-ribbons [two-dimensional graphene nanobelt] ", J.Am.Chem.Soc. [American Chemical Society] 130 (2008) 4216-17] use following methods composition length for most 12nm's Nano-graphene piece, this method is with Isosorbide-5-Nitrae-two iodo- 2, the Suzuki-Miyaura of 3,5,6- tetraphenyls-benzene and 4- bromophenylboronic acids Coupling starts.Gained hexaphenyl benzene derivatives are further derivatized is fused into small graphene film with ring.This is to produce pole so far The slow method of small graphene film.The present invention carries out to overcome the limitation of above-outlined.

Therefore, there is an urgent need to a kind of graphene production method, this method needs the undesirable chemicals of decrement (or all eliminate these chemicals), the process time shortened, the energy expenditure of reduction, reduction graphene degree of oxidation, subtract Less or the undesirable chemical species eliminated enter exhaust system (such as sulfuric acid) or enter air (such as SO₂And NO₂) outflow Amount.This method should be able to generate more primary (aoxidize and damage and is less), more conductive and bigger/broader graphene film.In addition, Should be able to foaming structure easily be made in these graphene films.

Our nearest research has produced a kind of nano-graphene platelet isolated for the production of no chemicals formula Method, this method are novel, because of the method that it does not follow the foundation of the production nano-graphene platelet of above-outlined.This Outside, this method has the practicability of enhancing, because its cost efficient, and novel grapheme material is provided (notable In the case that the environment of reduction influences).In addition, as disclosed herein, we are by graphene without the production of chemicals formula and stone The formation of black alkene-carbon hybrid foam is combined into a single operation.

In order to limit the purpose of claims hereof, NGP or grapheme material include that single layer and multilayer are (typically small In 10 layers) raw graphite alkene, graphene oxide, redox graphene (RGO), graphene fluoride, graphene chloride, Graphene bromide, graphene iodide, hydrogenation graphene, nitridation graphene, chemical functionalization graphene, doped graphene Discrete piece/the platelet of (such as being adulterated by B or N).Raw graphite alkene has substantially 0% oxygen.RGO typically has by weight The oxygen content of gauge 0.001%-5%.Graphene oxide (including RGO) can have the oxygen of 0.001%-50% by weight. In addition to raw graphite alkene, all grapheme materials all have by weight the non-carbon element of 0.001%-50% (such as O, H, N, B, F, Cl, Br, I etc.).These materials are referred to herein as non-protogenous grapheme material.Graphene-carbon foam of the present invention can be with Method containing primary or non-protogenous graphene and the present invention allows this flexibility.

To the summary of the production of grapheme foam

In general, foam or foamed material are made of hole (or abscess) and hole wall (solid material).This some holes can be mutual Even to form open celled foam.Hole wall of the grapheme foam by hole and containing grapheme material is constituted.In the presence of production grapheme foam Three kinds of main methods：

First method is hydrothermal reduction graphene oxide hydrogel, which typically relates to graphene oxide (GO) aqueous suspension be sealed in autoclave and under high pressure (tens of or hundreds of atm), in typically 180 DEG C of -300 DEG C of models It encloses and the GO suspension is heated into extended period (typically 12-36 hours) at interior temperature.The useful reference text of the method It offers and provides herein：Y.Xu et al. " Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process [via the graphene hydrogel of the self assembly of one step hydro thermal method] " ACS Nano [ACS nanometers] 2010,4,4324-4330.In the presence of several main problems associated with the method：(a) high pressure requirement makes it be for industry Unpractical method of large-scale production.First, the method cannot carry out on a continuous basis.(b) it is difficult to (if not It executes if possible) to the aperture of gained porous structure and the control of porosity level.(c) the reduction-oxidation graphite obtained by change Do not have flexibility (for example, the material cannot be made into film shape) in terms of the shape and size of alkene (RGO) material.(d) party Method is related to using the GO (for example, 2mg/mL=2g/L=2kg/kL) for suspending super low concentration in water.Removing non-carbon element (in the case of most 50%), it can only generate less than grapheme material (RGO)/1000 liter suspension of 2kg.In addition, actually The 1000 liters of reactors that must endure as high temperature and high pressure condition can not possibly be operated.It is clear that there is no more for mass production Hole graphene-structured can scalable process.

Second method is to be catalyzed CVD method based on template auxiliary type, and this method is related to sacrificing graphene CVD deposition In template (such as Ni foams).Grapheme material meets the shape and size of Ni foaming structures.Then fallen using etchant etching Ni foams leave the monoblock graphene skeleton of substantially open celled foam.The useful bibliography of the method provides herein： Zongping Chen et al., " Three-dimensional flexible and conductive interconnected Graphene networks grown by chemical vapour deposition [pass through chemical vapor deposition growth Three-dimension flexible and conductive interconnection graphene network] ", Nature Materials [nature material], 10 (in June, 2011) 424-428.There are problems that it is associated with such method several：(a) catalysis CVD is inherently slowly, height consumes Energy and expensive method；(b) it is dirty that etchant, which is typically highly undesirable chemicals and gained etching solution containing Ni, The source of dye.It is extremely difficult and expensive to recycle or recycle the Ni metals of dissolving from etchant solutions.(c) when Ni steeps The shape and size of grapheme foam are maintained to be challenging without damaging cell wall when foam is etched.Gained graphene Foam is typically highly brittle and frangible.(d) it may be tired cvd precursor gas (such as hydrocarbon) to be transferred to inside metal foam Difficult, lead to uneven texture, because certain points of sacrificial metal foam inside may be that cvd precursor gas is inaccessible.

The third method for producing grapheme foam also utilizes expendable material (such as colloid granules of polystyrene, PS), should Expendable material is coated with graphene oxide sheet using self-assembly method.For example, Choi et al. prepares the graphite of chemical modification in two steps Alkene (CMG) paper：Stand alone type PS/ is manufactured by the aqueous soliquid of the mixing of vacuum filter CMG and PS (2.0 μm of PS spheres) CMG films then remove PS pearls to generate 3D macropores.[B.G.Choi et al., " 3D Macroporous Graphene Frameworks for Supercapacitors with High Energy and Power Densities are [for having The 3D macropore graphenes frame of high-energy and the ultracapacitor of power density] ", ACS Nano [ACS nanometers], 6 (2012) 4020-4028.] Choi et al. manufactures the free-standing PS/CMG paper of well-ordering by filtering, the manufacture is negatively charged to be prepared separately CMG colloids and positively charged PS suspension start.The mixture of CMG colloids and PS suspension is scattered in controlled pH In solution under (=2), two of which compound surface charge having the same (zeta potential value for CMG be+13 ± 2.4mV simultaneously And be+68 ± 5.6mV for PS).When pH is increased to 6, the CMG (± 3.7mV of zeta potential=- 29) and PS spheres (zeta potential=+ 51 ± 2.5mV) it is assembled due to electrostatic interaction and hydrophobic character between them, and these then pass through filtering technique One chemical conversion PS/CMG composite papers.The method also has the shortcomings that several：(a) the method is needed to graphene oxide and PS Both particles carry out very cumbersome chemical treatment.(b) removing PS by toluene also causes macroporous structure to die down.(c) toluene is It the chemicals of height control and extremely must carefully handle.(d) aperture is typically excessive (such as several μm), for It is too big for many useful applications.

Each art methods clearly indicated that for producing grapheme foam or technique described above all have mainly Defect.It is highly conductive, mechanically steady based on graphite for mass production that therefore, the purpose of the present invention is to provide a kind of The cost-efficient method of the foam (exactly, integral type 3D graphenes-carbon hybrid foam) of alkene.The method is not related to making With the disagreeableness chemicals of environment.The method makes it possible to flexible design and control porosity level and aperture.

It is a further object to provide a kind of method for producing graphene-carbon hybrid foam, these graphite Alkene-carbon hybrid foam is shown and those of ordinary graphite or carbon foam be comparable or thermal conductivity, conductivity, the springform of bigger Amount and/or intensity.

Another purpose again of the present invention is to provide the hybrid foam of (a) based on raw graphite alkene, and the foam is substantially complete Only contain carbon and preferably there is mesoscale pore diameter range (2-50nm) in portion；And (b) non-protogenous grapheme foam (is fluorinated stone Black alkene, chlorination graphene, nitridation graphene etc.), contain by weight at least 0.001% (typically by weight from 0.01% to 25% and most typically from 0.1% to 20%) non-carbon element, these foams can be used in a variety of applications.

It is a further object to provide the products (such as device) of graphene-carbon foam containing the present invention and behaviour Make the method for these products.

Invention content

It is directly mixed by graphite material particle and polymer beads production integral type 3D graphenes-carbon the present invention provides a kind of The method of miscellaneous foam.The method is shockingly simple.This method includes：

(a) by multiple graphite material particles and multiple solid polymer support materials in the impact room of energy impact equipment Particle is mixed to form mixture；

(b) with certain frequency and intensity by the energy impact equipment operation for a period of time, the time is enough from the graphite material These graphene films are simultaneously transferred to the surface of solid polymer support material granule in the impact room by material stripping graphene film Inside generate graphene coating or graphene insertion polymer beads；(for example, the percussion device is when operated by kinetic energy Polymer beads are assigned, these polymer beads are impinged upon on graphite particle surface/edge and by graphene film in turn from through hitting The graphite particle stripping hit.The graphene film of these strippings is adhered on the surface of these polymer beads.This is referred to herein as " directly shift " process, it is intended that graphene film from graphite particle be directly transferred to the surface of polymer beads and not by any the Tripartite's entity mediates.)

(c) from polymer beads that impact room recycling graphene coats or that graphene is embedded in and by these graphenes Coating or graphene insertion polymer beads are consolidated into desired shape (this consolidation of graphene-polymer hybrid structure Step can be simple as only coating graphene or embedded particle packing is at the compacting step of desired shape)；And

(d) this shape of graphene-polymer hybrid structure is made to be pyrolyzed with by polymer thermal transition pore-forming and carbon or graphite, The carbon or graphite combination graphene film are to form integral type 3D graphenes-carbon hybrid foam.

In certain alternate embodiments, multiple impact beads or medium are added to the impact room of the energy impact equipment In.Simultaneously graphene film is removed from it in surface/edge of these shock ball impact graphite particles accelerated by percussion device.These Graphene film is temporarily diverted to the surface of these impact beads.The impact bead of these carrying graphenes subsequently impinges polymer beads Above and by the graphene film carried it is transferred on the surface of these polymer beads.This event sequence is referred to herein as " indirectly Transfer " process.In some embodiments of the indirect branch process, step (c) includes actuating solenoid with by impact bead or medium It is detached with graphene coating or graphene insertion polymer beads.

Solid polymeric material particle may include have from 10nm to 10mm the plastics or rubber bead of diameter or thickness, Pellet, sphere, line, fiber, long filament, disk, band or stick.Preferably, the diameter or thickness be from 100nm to 1mm, and it is more excellent Selection of land is from 200nm to 200 μm.Solid polymer can be selected from the solid particle of the following terms：Thermoplastic, thermosetting property tree Fat, rubber partly penetrate network polymer (semi-penetrating network polymer), penetrate network polymer, day Right polymer, or combinations thereof.In embodiment, solid polymer before the step (d) by fusing, etch or be dissolved in solvent In be partially removed in.

In certain embodiments, which is selected from natural graphite, synthetic graphite, height-oriented pyrolytic graphite, stone Black fiber, Graphite Nano Fiber, fluorographite, graphite oxide, chemical modification graphite, expanded graphite, recompression expanded graphite, Expanded graphite, carbonaceous mesophase spherules, or combinations thereof.Preferably, the graphite material contain before the mixing step (a) previously from It is not exposed to chemistry or non-intercalation and the unoxidized graphite material of oxidation processes.

We are unexpectedly observed that a variety of percussion devices can be used for putting into practice the present invention.For example, the energy impact equipment Can be vibrator, planetary ball mill, high-energy mills, basket-type grinder, stirring ball mill (agitator Ball mill), low temperature ball mill (cryo ball mill), ball mill, tumbling ball mill (tumbler ball Mill), continuous ball mill, agitating ball mill (stirred ball mill), pressurization ball mill, refrigeration grinding machine, vibrating screen, Pearl grinder, nano-beads grinder, ultrasound pulp grinder (ultrasonic homogenizer mill), centrifugal planetary Mixer, vacuum ball mill or resonance sound mixer (resonant acoustic mixer).

In order to form the carbon component of gained graphene-carbon hybrid foam, can select with high carbon yield or charcoal yield (example As by weight>30%) polymer beads.Carbon yield be polymer architecture by converting heat at solid carbon phase rather than Become the weight percent of a part for escaping gas.High carbon yield polymer can be selected from phenolic resin, poly furfuryl alcohol, poly- third Alkene nitrile, polyimides, polyamide, polyoxadiazoles, polybenzoxazole, polybenzoxazole, polythiazole, polybenzothiozole, polyphenyl And dithiazole, poly- (to phenylene vinylidene), polybenzimidazoles, polyphenyl and diimidazole, its copolymer, the blending of its polymer Object, or combinations thereof.

If wishing that polymer can contain compared with low carbon content (higher graphene ratio) in graphene-carbon hybrid foam There is the low-carbon yield polymer selected from the following terms：Polyethylene, polypropylene, polybutene, polyvinyl chloride, makrolon, acrylonitrile- Butadiene (ABS), polyvinyl alcohol, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), polyphenylene oxide (PPO), gathers polyester Methyl methacrylate (PMMA), its copolymer, its blend polymer, or combinations thereof.

It may be noted that when being heated at a temperature of 300 DEG C -2,500 DEG C, these polymer (high carbon yield and low-carbons Yield) it is converted to carbon material, which is preferentially nucleated in graphene film adjacent edges.Such carbon material is used for bridged graphite Gap between alkene piece, to form the electrical conductance path of interconnection.In other words, gained graphene-carbon hybrid foam is by carbon knot The integral type 3D networks of the graphene film of conjunction are constituted, to allow to continuously transmit electronics harmony between graphene film or structural domain Sub (quantization lattice vibration) and without interruption.When further being heated at a temperature of higher than 2,500 DEG C, in conjunction with the carbon of graphene It can mutually be graphitized, precondition is that the carbon phase is " soft carbon " or graphitisable.In this case, conductivity and thermal conductivity Both rates further increase.

Therefore, in certain embodiments, the step of pyrolysis is included in from 200 DEG C to 2, by the polymerization at a temperature of 500 DEG C Object carbonization is to obtain the graphene film of carbon combination.Optionally, the graphene film which combines can then from 2,500 DEG C to 3, It is graphitized at a temperature of 200 DEG C to obtain the graphene film of graphite combination.

It is noted that the pyrolysis of polymer is due to those escaping gas molecules such as CO₂And H₂The release of O and be inclined to In the formation for leading to resulting polymers carbon phase mesoporous.However, if the polymer is not restricted in carbonization, this pores also has There is the high tendency for becoming to cave in.Surprisingly, it was found that the graphene film of wrapping polymer beads can limit carbon pores wall It shrinks and caves in, while some carbon species also penetrate into the gap between graphene film, wherein these species are by graphene film It is combined together.The aperture of gained 3D integral type grapheme foams and pore volume (porosity level) depend on starting polymer ruler Very little and polymer carbon yield, and pyrolysis temperature is depended in lesser degree.

In certain preferred embodiments, consolidation step includes by the polymer beads pressure of a large amount of these graphenes coating In fact at desirable shape.For example, squeezed and be compressed in cavity body of mould by the particle for coating a large amount of graphene, it can To be readily formed the green compact of compacting.Can quickly heat and melt the polymer, the mild compression green compact with by heat come Slightly together by polymer particles fuse, it and is quickly cooled down to cure the green compact.Then make the green compact that this is consolidated through heated Solution processing (polymer carbonization and optionally graphitization).

In some alternate embodiments, consolidation step includes melting these polymer beads to be wherein dispersed with stone to be formed The Mixing of Polymer Melt object is configured to desirable shape by the Mixing of Polymer Melt object of black alkene piece, and by the shape It is solidified into graphene-polymer composite construction.This shape can be stick, (film or thick film, width or narrow, monolithic are in scroll to film Formula), fiber (short long filament or continuous length long filament), plate, ingot casting, the shape of any rule or strange shape.Then it is pyrolyzed this Graphene-polymer compound shape.

Alternatively, which may include that polymer beads dissolving is wherein dispersed with stone to be formed in a solvent The polymer solution mixture is configured to desirable shape by the polymer solution mixture of black alkene piece, and it is molten to remove this Agent by the shape to be solidified into graphene-polymer composite construction.Then this composite construction is pyrolyzed to form porous structure.

The consolidation step may include melt polymer particle with formed wherein be dispersed with graphene film polymer melt it is mixed Close object, and by the mixture be extruded into rod-like form or sheet form, the mixture is spun into fibers form, by the mixture It is sprayed into powder type or the mixture is cast into ingot casting form.

In some embodiments, which includes wherein being dispersed with polymer beads dissolving to be formed in a solvent The polymer solution mixture of graphene film, and the solution mixture is extruded into rod-like form or sheet form, this is molten Liquid mixture is spun into fibers form, which is sprayed into powder type or the solution mixture is cast into ingot casting shape Formula, and remove solvent.

In a particular embodiment, the polymer solution mixture is sprayed to generate graphene-polymer composite coating Or film, so that the coating or film is pyrolyzed (carbonization or carbonization and graphitization).

Preferably, which may include that the polymer beads for coating graphene are compacted into the porous of macroscopic pores It gives birth to green compact and then infiltrates or impregnate this some holes with the other carbon source material selected from the following terms：Asphalt, coal tar drip Blueness, aromatics organic material (such as naphthalene or other pitch derived objects), monomer, organic polymer, or combinations thereof.The organic polymer Contain the high carbon yield polymer selected from the following terms：Phenolic resin, poly furfuryl alcohol, polyacrylonitrile, polyimides, polyamide, It is polyoxadiazole, polybenzoxazole, polybenzoxazole, polythiazole, polybenzothiozole, polyphenyl and dithiazole, poly- (to phenylene Asia Vinyl), polybenzimidazoles, polyphenyl and diimidazole, its copolymer, its blend polymer, or combinations thereof.It is applied when making graphene When the infiltration life green compact of the polymer beads covered is subjected to pyrolysis, these species become other carbon source, if it is desired in hybrid foam If the carbon for having higher amount.

The present invention also provides a kind of integral type 3D graphenes-carbon hybrid foams being made of multiple holes and hole wall, wherein These hole walls contain by the chemically combined single layer of carbon material or few layer graphene piece, with from 1/200 to 1/2 carbon material with Graphene weight ratio, wherein these few layer graphene pieces have 2-10 stacked graphene plane layer, these graphene planes tool Interplanar spacing d just like the slave 0.3354nm to 0.36nm by X-ray diffraction measurement₀₀₂, and these single layers or few layer stone Black alkene piece contains with the substantially raw graphite alkene material of zero % non-carbon elements or with by weight 0.001% to 35% The non-protogenous grapheme material of (preferably 0.01% to 25%) non-carbon element, wherein the non-protogenous graphene are selected from graphite oxide Alkene, redox graphene, fluorinated graphene, chlorination graphene, bromination graphene, iodate graphene, hydrogenation graphene, nitridation Graphene, chemical functionalization graphene, or combinations thereof.The multiple single layers or few layer graphene for surrounding following polymer beads can be with It overlaps each other to form the stacking of graphene film.The stacking can have be more than 5nm, and in some cases be more than 10nm or The even greater than thickness of 100nm.

Integral type 3D graphenes-carbon hybrid foam typically has from 0.001g/cm³To 1.7g/cm³Density and from 50m²/ g to 3,000m²The specific surface area of/g.In a preferred embodiment, these hole walls contain the graphene planes of stacking, these Graphene planes have the interplanar spacing d such as the slave 0.3354nm to 0.40nm as measured by X-ray diffraction₀₀₂。

For oily recycle (for example, oil is separated from water), which preferably has by weight from 1% To the oxygen content of 25% (more preferably 1%-15% and most preferably 1%-10%).If starting material is graphite oxide, Or if carbonization treatment in mild oxidation environment at a temperature of 300 DEG C -1,500 DEG C (preferably not more than 1,000 DEG C) It carries out and without subsequent graphitization, this may be implemented.Surprisingly, it was found that highly porous with this property Graphene-carbon foam can be absorbed from oil-aqueous mixtures up to its own weight 500% oil.

For thermal management applications, graphene-carbon hybrid foam is preferably by making the graphite flake that carbon combines (in carbonization Graphitization processing is subjected under compressive stress afterwards) to manufacture.This is conducive to the orientation and again of graphene film or graphene-structured domain Group (merge, grow etc.).As a result, graphene-carbon foam piece or film show the per unit proportion at least thermal conductivity of 200W/mK Rate and/or per unit proportion are not less than the conductivity of 2,000S/cm.

In embodiment, hole wall contains raw graphite alkene and 3D solid graphenes-carbon foam has from 0.001g/cm³ To 1.7g/cm³Density or average pore size from 2nm to 50nm.In embodiment, these hole walls contain non-original selected from the group below Raw grapheme material, the group are made of the following terms：Graphene oxide, redox graphene, fluorinated graphene, chlorination graphite Alkene, bromination graphene, iodate graphene, hydrogenation graphene, nitridation graphene, chemical functionalization graphene, and combinations thereof, and The wherein described solid graphene foam contains the non-carbon element content by weight in 0.01% to 20% range.In other words, Non-carbon element may include the element selected from the following terms：Oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen or boron.In a particular embodiment, Hole wall contains fluorinated graphene and solid graphene foam contains the fluorine content by weight from 0.01% to 20%.Another In a embodiment, hole wall contains graphene oxide and the solid graphene foam contains by weight from 0.01% to 20% Oxygen content.In embodiment, solid graphene-carbon hybrid foam has from 200m²/ g to 2,000m²The specific surface area of/g or From 0.01g/cm³To 1.5g/cm³Density.

It is noted that limitation is not present to the shape or size of graphene-carbon hybrid foam of the present invention.Preferred In embodiment, by solid graphene-carbon hybrid foam be made continuous length roll film (roll sheet) form (continuous foam piece Volume), which has is not larger than the thickness of 10cm and at least 1 meter long, preferably at least not less than 100nm 2 meters, further preferably at least 10 meters and most preferably at least 100 meters of length.This sheet volume is produced by roll to roll It is raw.There is no the foams based on graphene for the prior art that piece roll form is made.It does not find previously or suggests to have to use In the roll to roll of the grapheme foam (based on primary or non-protogenous) of production continuous length.

For the application based on heat management or conductivity, graphene-carbon foam preferably has is less than 1% by weight Oxygen content or non-carbon content, and there are hole wall the graphene planes stacked, these graphene planes to have less than 0.35nm's Spacing, per unit the proportion at least thermal conductivity of 250W/mK, and/or per unit proportion are not less than the electricity of 2,500S/cm between graphene Conductance.

In another preferred embodiment, there is graphene-carbon hybrid foam the oxygen for being less than 0.01% by weight to contain Amount or non-carbon content, and the hole wall contains the graphene planes of stacking, and these graphene planes have less than 0.34nm's Spacing, per unit the proportion at least thermal conductivity of 300W/mK, and/or per unit proportion are not less than the electricity of 3,000S/cm between graphene Conductance.

In another preferred embodiment again, graphene-carbon hybrid foam has is not more than 0.01% by weight Oxygen content or non-carbon content, and the hole wall contains the graphene planes of stacking, and these graphene planes, which have, to be less than Spacing between the graphene of 0.336nm, no more than 0.7 inlay latitude of emulsion value, per unit the proportion at least thermal conductivity of 350W/mK and/ Or per unit proportion is not less than the conductivity of 3,500S/cm.

In further preferred embodiment, grapheme foam has the hole wall containing the graphene planes stacked, this A little graphene planes have spacing between the graphene less than 0.336nm, inlay latitude of emulsion value, per unit than great no more than 0.4 It is more than the conductivity of 4,000S/cm in the thermal conductivity, and/or per unit proportion of 400W/mK.

In a preferred embodiment, these hole walls contain the graphene planes of stacking, these graphene planes, which have, to be less than Spacing and latitude of emulsion value is inlayed between the graphene of 0.337nm less than 1.0.In a preferred embodiment, which shows Go out the degree of graphitization not less than 80% (preferably no less than 90%) and/or inlays latitude of emulsion value less than 0.4.Preferably implementing In example, hole wall contains the 3D networks of interconnection graphene planes.

In a preferred embodiment, solid graphene-carbon hybrid foam contains the middle ruler with the aperture from 2nm to 50nm Spend hole.Solid graphene foam is formed into containing micrometer grade hole (1-500 μm).

The present invention also provides a kind of oil removing or the device of separation oil, 3D graphenes-carbon which contains the present invention is mixed Miscellaneous foam is as the element for absorbing oil.It additionally provides a kind of except solvent or the device of separation solvent, the device contain the 3D graphite Alkene-element of the carbon hybrid foam as lyosoption.

The present invention also provides one kind for from oil-aqueous mixtures (such as oil spilling water (oil-spilled water) or come From the waste water of oil-sand) the oily method of separation.This approach includes the following steps：(a) it includes that integral type graphene-carbon mixes bubble to provide The element of the absorption oil of foam；(b) oil-aqueous mixtures are made to be contacted with the element, which absorbs oil from the mixture；And (c) it recalls the element from the mixture and extracts the oil from the element.Preferably, this method includes another step (d)：Repetition makes With the element.

In addition, that the present invention provides one kind is organic molten for detaching from solvent-water mixture or from multi-solvent mixture The method of agent.This approach includes the following steps：(a) offer includes the absorption organic solvent of integral type graphene-carbon hybrid foam Element；(b) multi-solvent of the element with organic solvent-aqueous mixtures or containing the first solvent and at least the second solvent is made to mix Object contacts；(c) this element is allowed from the mixture to absorb the organic solvent or from least second solvent absorption first solvent； And (d) element is recalled from the mixture and extract the organic solvent or the first solvent from the element.Preferably, this method packet Include another step (e)：Reuse the element.

Description of the drawings

Fig. 1 shows that the flow chart for the most frequently used art methods for producing highly oxidized NGP, this method need cumbersome Chemical oxidation/intercalation, flushing and high temperature puffing program.

Fig. 2 (A) shows the flow chart of the method for producing integral type 3D graphenes-carbon hybrid foam of the present invention.

Polymer thermal induction is converted to the schematic diagram of carbon by Fig. 2 (B), which is combined together to form 3D by graphene film Graphene-carbon hybrid foam.The consolidated structure of the polymer beads of graphene coating is converted to highly porous structure.

The SEM image of the integral structure of Fig. 3 (A) 3D graphenes-carbon hybrid foam.

The SEM image of the integral structure of Fig. 3 (B) another kind 3D graphenes-carbon hybrid foam.

The graphite of 3D integral types graphene-carbon foam, mesophase pitch source that Fig. 4 (A) is produced by the method for the invention The heat conductivity value relative to proportion of foam and Ni foam formwork auxiliary type CVD grapheme foams.

The heat conductivity value of the GO grapheme foams of Fig. 4 (B) 3D graphenes-carbon foam and hydrothermal reduction.

Fig. 5 3D graphenes-carbon hybrid foam and raw graphite alkene foam with foaming agent (by being cast and then being carried out Be heat-treated and prepare) heat conductivity value, the function plotting as final (maximum) heat treatment temperature.

The conductivity value of the GO grapheme foams of Fig. 6 3D graphenes-carbon foam and hydrothermal reduction.

The oil mass that every gram of integral type 3D graphenes-carbon hybrid foam of Fig. 7 is absorbed, as with about 98% porosity level Foam in the function of oxygen content draw (from oil-aqueous mixtures separation oil).

The oil mass that every gram of integral type 3D graphenes-carbon hybrid foam of Fig. 8 is absorbed, the function as porosity level are drawn (it is assumed that oxygen content is identical).

Fig. 9 absorbs the chloroform amount from chloroform-aqueous mixtures, and the function as degree of fluorination is drawn.

The schematic diagram (2 examples) of Figure 10 heat spreader structures.

Specific implementation mode

It is directly mixed by graphite material particle and polymer beads production integral type 3D graphenes-carbon the present invention provides a kind of The method of miscellaneous foam.

As Fig. 2 (A) is schematically shown, this method is with by multiple graphite material particles and multiple solid polymer support materials Material particle mixing is started with forming mixture, which is closed in energy impact equipment (for example, vibrator, planet Formula ball mill, high-energy mills, basket-type grinder, stirring ball mill, low temperature ball mill, ball mill, tumbling ball mill, Continuous ball mill, agitating ball mill, pressurization ball mill, refrigeration grinding machine, vibrating screen, pearl grinder, nano-beads grinder, ultrasound Equal pulp grinder, centrifugal planetary mixer, vacuum ball mill or resonance sound mixer) impact room in.When operated, this Energy impact device assigns kinetic energy to solid particle contained therein, to allow polymer beads with high intensity and high-frequency It impinges upon in graphite particle.

Under typical operating conditions, such crash causes to remove graphene film from graphite material and by these stones Black alkene piece is transferred on the surface of solid polymer support particle.These graphene films wrap polymer beads in impact room Portion forms graphene coating or graphene insertion polymer beads.This is referred to herein as " directly transfer " process, it is intended that stone Black alkene piece is directly transferred to the surface of polymer beads from graphite particle and is not mediated by any third party entity.

Alternatively, multiple impact beads or medium can be added in the impact room of the energy impact equipment.Pass through Percussion device accelerate these impact beads impinged upon on surface/edge of graphite particle with kinetic energy, with advantageous angle, with from Graphite particle removes graphene film.These graphene films are temporarily diverted to the surface of these impact beads.These carrying graphenes Impact bead then collides with polymer spherolite and is transferred to the graphene film carried the surface of these polymer beads.This thing Part sequence is referred to herein as " indirect branch " process.These events are occurred with very high frequency and therefore most of polymer Particle is typically covered in less than one hour by graphene film.In some embodiments of the indirect branch process, step (c) It is detached with the polymer beads that coat impact bead or medium with graphene or graphene is embedded in including actuating solenoid.

This method then include from impact room recycling graphene coat or graphene be embedded in polymer beads and by this A little graphene coatings or graphene insertion polymer beads are consolidated into the graphene-polymer composite junction of desired shape Structure.This consolidation step can be walked such as the compacting that only coat graphene or embedded particle machinery is piled into desirable shape It is rapid simple like that.Alternatively, this consolidation step may need to melt these polymer beads is wherein dispersed with graphite to be formed The polymer substrate of alkene piece.Such graphene-polymer structure can be in any true form or size (fiber, stick, plate, circle The shape or strange shape of cylinder or any rule).

Then be pyrolyzed the graphene-polymer pressing entity or composite construction with by the polymer thermal transition at carbon or graphite, The carbon or graphite combination graphene film are to form integral type 3D graphenes-carbon hybrid foam, as shown in Fig. 3 (A) and Fig. 3 (B).

In order to form the carbon component of gained graphene-carbon hybrid foam, can select with high carbon yield or charcoal yield (example As by weight>30% polymer is converted to solid carbon phase；Rather than become a part for escaping gas) polymer Particle.High carbon yield polymer can be selected from phenolic resin, poly furfuryl alcohol, polyacrylonitrile, polyimides, polyamide, polyoxadiazoles, Polybenzoxazole, polybenzoxazole, polythiazole, polybenzothiozole, polyphenyl and dithiazole, poly- (to phenylene vinylidene), Polybenzimidazoles, polyphenyl and diimidazole, its copolymer, its blend polymer, or combinations thereof.When pyrolysis, these polymer Particle become porous, as shown in the bottom part of Fig. 2 (B).

If wish in graphene-carbon hybrid foam compared with low carbon content (relative to carbon ratio example graphene ratio higher) and Lower foam density, then polymer contain selected from the following terms low-carbon yield polymer：Polyethylene, polypropylene, poly- fourth Alkene, polyvinyl chloride, makrolon, acrylonitrile-butadiene (ABS), polyester, polyvinyl alcohol, polyvinylidene fluoride (PVDF), poly- four Vinyl fluoride (PTFE), polyphenylene oxide (PPO), polymethyl methacrylate (PMMA), its copolymer, its blend polymer or its Combination.When pyrolysis, the particle of these polymer becomes porous, as shown in the middle section of Fig. 2 (B).

When being heated at a temperature of 300 DEG C -2,500 DEG C, these polymer (two kinds of high carbon yield and low-carbon yield) turn It is melted into carbon material, which is preferentially nucleated in graphene film adjacent edges.Such carbon material bridged graphite alkene piece naturally Between gap, to form the electrical conductance path of interconnection.In fact, gained graphene-carbon hybrid foam is combined by carbon The integral type 3D networks of graphene film are constituted, and allow to continuously transmit electronics and phonon (amount between graphene film or structural domain Sonization lattice vibration) and without interruption.When further being heated at a temperature of higher than 2,500 DEG C, carbon phase can become to be graphitized, To further increase both conductivity and thermal conductivity.If graphitization time is more than 1 hour, the amount of non-carbon element is also reduced to Typically it is less than 1% by weight.

It is noted that organic polymer typically contains a large amount of non-carbon element, these elements can be via heat treatment To reduce or eliminate.In this way, the pyrolysis of polymer causes escaping gas molecule such as CO₂And H₂The formation and release of O, this leads Cause the formation of resulting polymers carbon phase mesoporous.However, (being released in non-carbon element if the polymer is not restricted in carbonization When carbon structure may shrink), then this pores also has the high tendency for becoming to cave in.It has been unexpectedly discovered that wrapping polymer The graphene film of particle can limit carbon hole wall collapse.At the same time, between some carbon species also penetrate between graphene film In gap, wherein graphene film is combined together by these species.The aperture and pore volume (hole of gained 3D integral type grapheme foams Gap rate is horizontal) depend primarily on the carbon yield of starting polymer size and the polymer.

Graphite material as graphene film source can be selected from natural graphite, synthetic graphite, height-oriented pyrolysis stone Ink, graphite fibre, Graphite Nano Fiber, fluorographite, graphite oxide, chemical modification graphite, expanded graphite, recompression it is puffing Graphite, expanded graphite, carbonaceous mesophase spherules, or combinations thereof.About this point, exist associated several with the method for the present invention A in addition unexpected element：

(1) graphene film can be removed by using individual polymer beads from natural graphite, without using heavier and Harder impact bead (common zirconium dioxide or steel ball such as in ball mill).The graphene film of stripping is transferred directly to Polymer particle surface and securely wrap polymer beads.

(2) it is also surprising that shock polymer beads can be all from the known electrographite with amorphous carbon surface layer As carbonaceous mesophase spherules (MCMB) remove graphene film.

(3) by means of harder impact bead, the also stone of the carbon atom of the peelable internal structure for constituting carbon or graphite fibre Black alkene sample plane and by these planar transfers to polymer particle surface.This never teaches or suggests in the prior art.

(4) the present invention provides it is a kind of shockingly it is simple, quickly, can scale, environmental-friendly and cost-efficient side Method, this method avoid the relevant all defects of art methods substantially with production graphene film.Graphene film is stood It is transferred to polymer beads and wraps these polymer beads, then easily convert it into integral type 3D graphenes- Carbon hybrid foam.

It is noted that if starting graphite is oxidizing to a certain degree (for example, to 2%- by weight is contained intentionally 15% oxygen), then the hole wall that can assign graphene-carbon hybrid foam wishes the hydrophily of degree.Alternatively, if permitted Perhaps carbonization treatment occurs in low-level oxidation environment, then can oxygen-containing functional group be attached to carbon phase.These features make it possible to lead to The selectively absorbing oily from oil-aqueous mixtures is crossed to be separated from water oil.In other words, such graphene-carbon hybrid foam material Can from water oil recovery, to help clean up oil spilling river, lake or ocean.Oily absorptive capacity is typically foam itself Weight from 50% to 500%.This is very useful material for environmental protection purpose.

If it is desired to high conductivity or thermal conductivity, then graphite material can be selected from non-intercalation and unoxidized graphite material Material, the graphite material be previously never exposed to chemistry or oxidation processes before being positioned in impact room.Alternatively or additionally Ground can make graphene-carbon foam be subjected to the graphitization processing at a temperature of higher than 2,500 DEG C.Resulting materials are particularly useful In thermal management applications (for example, for manufacturing fin radiator, heat exchanger or heat diffuser).

It is noted that can make graphene-carbon foam during and/or after graphitization processing through compressed.This behaviour It allows us to adjust graphene film orientation and porosity.

X-ray diffraction pattern is obtained with the X-ray diffractometer radiated equipped with CuKcv.The displacement of diffraction maximum and broadening make It is calibrated with silica flour reference substance.Use Mering formula, d₀₀₂=0.3354g+0.344 (1-g) is calculated by X-ray pattern and is graphitized Spend g, wherein d₀₀₂It is the interlayer spacing of graphite or graphene crystal in terms of nm.Only work as d₀₀₂Equal to or less than about 0.3440nm When, the formula is just effective.With the d higher than 0.3440nm₀₀₂Grapheme foam wall reflect as interval base to increase graphite Between alkene spacing oxygen-containing or fluorine-containing functional group (such as graphene molecules plane surface or-F on edge ,-OH,>O and-COOH) Presence.

Can be used for characterizing graphene foam wall and ordinary graphite crystal in stack and the graphene planes that combine have Another structure index of sequence degree is " inlaying the latitude of emulsion ", and by the rocking curve of (002) or (004) reflection, (X-ray diffraction is strong Degree) full width at half maximum (FWHM) indicate.This degree of order characterization graphite or graphene crystalline size (or crystallite dimension), crystal boundary and other lack Sunken amount and preferred degree of grain alignment.The almost ideal monocrystalline of graphite is characterized by having the exhibition of inlaying of 0.2-0.4 Angle value.Our graphene wall it is most of have in the range of this 0.2-0.4 inlay latitude of emulsion value (if with not less than 2, 500 DEG C of heat treatment temperature (HTT) produces).However, if HTT is between 1,500 DEG C and 2,500 DEG C, then some values exist In the range of 0.4-0.7；And if HTT is between 300 DEG C and 1,500 DEG C, then some values are in the range of 0.7-1.0.

Use the further investigation table of the combination of SEM, TEM, selected diffraction, X-ray diffraction, AFM, Raman spectroscopy and FTIR By several huge graphene planes, (wherein length/width is typically bright graphene foam wall>>20nm, more typically>> 100nm, usually>>1 μm, and in many cases>>10 μm, or even>>100 μm) it constitutes.If final heat treatment temperature Less than 2,500 DEG C, these huge graphene planes often not only by Van der Waals force (such as in conventional graphite microcrystal that Sample) but also stack and combine along thickness direction (crystallography c- axis directions) by covalent bond.In these cases, it is desirable to no It is limited by theory, but Raman and FTIR spectrum method research seem to indicate that sp²(leading) and sp³(weak but presence) electron configuration It coexists, rather than just the conventional sp in graphite²。

Integral type 3D graphenes-carbon hybrid foam is made of multiple holes and hole wall, and wherein these hole walls, which contain, passes through carbon The single layer or lack layer graphene piece, with the carbon material and graphene weight ratio from 1/100 to 1/2 that materials chemistry combines, wherein These few layer graphene pieces have 2-10 stacked graphene plane layer, these graphene planes, which have, such as passes through X-ray diffraction The interplanar spacing d of the slave 0.3354nm to 0.36nm measured₀₀₂, and these single layers or few layer graphene piece contain with base The raw graphite alkene material of this upper zero % non-carbon element has 0.01% to 25% non-carbon element by weight (more typically< 15%) non-protogenous grapheme material, wherein the non-protogenous graphene are selected from graphene oxide, redox graphene, fluorination Graphene, chlorination graphene, bromination graphene, iodate graphene, hydrogenation graphene, nitridation graphene, chemical functionalization graphite Alkene, or combinations thereof.The multiple single layers or few layer graphene for surrounding following polymer beads can overlap each other to form graphene The stacking of piece.The stacking can have the thickness for being more than 5nm, and being more than 10nm or even greater than 100nm in some cases.

Integral type 3D graphenes-carbon hybrid foam typically has from 0.001g/cm³To 1.7g/cm³Density, from 50m²/ g to 3,000m²Specific surface area, the per unit proportion at least thermal conductivity of 200W/mK, and/or per unit proportion of/g be not small In the conductivity of 2,000S/cm.In a preferred embodiment, these hole walls contain the graphene planes of stacking, these graphenes Plane has the interplanar spacing d such as the slave 0.3354nm to 0.40nm as measured by X-ray diffraction₀₀₂。

Many graphene films can edge-to-edge be integrally combined formula graphene entity each other by covalent bond.Those do not merge Piece or shorter merging piece free end between gap combined by the carbon phase by polymer conversion.Due to these uniquenesses Chemical composition (including oxygen or fluorine content etc.), form, crystal structure (including spacing between graphene) and structure feature (such as take Chemical bonding between Xiang Du, few defects, graphene film and very close to each other and do not have substantially along graphene planes direction Have interruption), graphene-carbon hybrid foam has the only of outstanding thermal conductivity, conductivity, mechanical strength and rigidity (elasticity modulus) Spy's combination.

Thermal management applications

Features described above and characteristic so that integral type 3D graphenes-carbon hybrid foam is applied and biology doctor for various engineering Learn the ideal element of application.For example, merely for heat management purpose, graphene-carbon foam can be used in applying below：

A) compressible and with high heat conductance graphene-carbon hybrid foam is preferably suited as thermal interfacial material (TIM), which can be embodied between heat source and heat diffuser or between heat source and radiator.

B) hybrid foam may be used as heat diffuser in itself due to its high heat conductance.

C) hybrid foam is since (induction of exhibiting high surface hole is big for its high heat diffusion capabilities (high heat conductance) and high heat-dissipation ability Amount cross-ventilation micron or nanochannel) and may be used as radiator or dissipation of heat material.

D) light weight is (in 0.001g/cm³With 1.8g/cm³Between adjustable low-density), per unit proportion or per unit The high heat conductance of phsyical density and high structural intergrity (graphene film passes through carbon combination) are so that this hybrid foam is for resistance to With the ideal material of heat exchanger.

Heat management or dissipation of heat device based on graphene-carbon hybrid foam include heat exchanger, radiator (such as wing formula dissipate Hot device), heat pipe, high conductance plug-in unit, thin or thick conductibility plate (between radiator and heat source), hot interfacial medium (or hot boundary Plane materiel material, TIM), thermoelectricity or Peltier (Peltier) coldplate etc..

Heat exchanger is the device for the heat transfer between one or more fluids；One or more fluids for example exist The gas and liquid individually flowed in different channels.These fluids are separated typically via solid wall to prevent from mixing.The present invention Graphene-carbon hybrid foam material be ideal material for such wall, precondition is that the foam is not to allow fluid mixed The complete open celled foam closed.The method of the present invention makes it possible to produce both trepanning and closed-cell foam structure.High surface pore area So that the heat exchange between two or more fluids is significantly faster.

Heat exchanger be widely used in refrigeration system, air-conditioning unit, heater, power station, chemical plant, petrochemical plant, Oil plant, natural gas processing and sewage disposal.The known example of heat exchanger is seen in internal combustion engine, and wherein cycle engine is cold But agent flows through radiator coil, dynamic by these coil pipes, this sky for cooling down the coolant and heating entrance with Airflow Gas.Solid wall (such as constituting the solid wall of radiator coil) is usually made of high thermal conductivity material such as Cu and Al.With more The grapheme foam of the present invention of high heat conductance or more high-specific surface area is the excellent replacement of such as Cu and Al.

There are the commercially available heat exchangers of many types：Shell and tube exchanger, plate heat exchanger, lamella heat exchanger, thermal insulation Wheeled heat exchanger (adiabatic wheel heat exchanger), plate-fin heat exchanger, pillow plate heat exchanger (pillow Plate heat exchanger), fluid heat exchanger, waste heat recovery unit, dynamic scraped surface heat exchanger (dynamic Scraped surface heat exchanger), phase-change heat-exchanger, direct contact heat transfer device and micro-channel heat exchanger.This Each thermal conductivity and specific surface area that the exception of the foamed material of the present invention can be utilized high in the heat exchanger of a little types.

The solid graphene foam of the present invention can be used in radiator.For dissipation of heat purpose, radiator is used extensively In electronic device.Central processing in portable microelectronic device (such as laptop, tablet computer and smart phone) Unit (CPU) and battery are well known heat sources.Typically, make metal or graphite object (such as Cu foils or graphite foil) and hot surface It contacts and this object is helped heat diffusion to outer surface or extraneous air (mainly by conduction and convection current and compared with little Cheng Pass through radiation on degree).In most cases, thin thermal interfacial material (TIM) heat source hot surface and heat diffuser or dissipate Mediation is played between the thermal diffusion surface of hot device.

Radiator is usually made of high conductance material structure, which has one or more flat Surface to ensure to thermally contact with there is the good of component to be cooled, and with a series of pectinations or aliform protruding portion with increase with The surface of air contacts, and therefore increases rate of heat dispation.Radiator can be used with fan combination to increase the sky on radiator Flow of air rate.Radiator can have multiple fins (extension or surface outstanding) to improve heat transfer.With finite quantity Space electronic device in, shape/arrangement of fin must be optimised so that heat transfer density maximizes.Alternatively or Additionally, embedded cavity (being inverted fin) in the region that can be formed between adjacent fins.These cavitys are effective in by heat It is extracted in radiator from multiple heat main bodys.

Typically, integrated radiator includes heat collection component (core or base portion) and integral with the heat collection component (base portion) At least one dissipation of heat component (such as one or more fin) to form fin radiator.These fins and the core are natural Ground connects or integration is integrally formed together, without use the external adhesive applied or mechanical fasteners device by these Fin is connected to the core.Thermal-arrest base portion has the surface thermally contacted with heat source (such as LED), and heat is collected from this heat source, and It is dissipated heat into air by these fins.

As illustrative example, Figure 10 provides the schematic diagram of two kinds of radiators：300 and 302.The first contains thermal-arrest structure Part (or base component) 304 and the multiple fins or dissipation of heat component (such as fin 306) for being connected to the base component 304.It is aobvious Show that base component 304 has the heat collecting surface 314 for being intended to thermally contact with heat source.Display dissipation of heat component or fin 306 at least have There is heat dissipation surface 320.

Particularly useful embodiment is integral type radial direction radiator 302, which includes radial fin radiator component, The component includes：(a) base portion 308, the base portion include heat collecting surface 318；And (b) by the base portion 308 support or with the base The integral multiple parallel plane fin members (such as two examples 310,312) spaced apart in portion, wherein these are flat Face fin members (such as 310) include at least one heat dissipation surface 322.Multiple parallel plane fin members are preferably equidistant Spaced apart.

The present invention high flexibility and elastic graphene-carbon hybrid foam itself be good thermal interfacial material and It is also highly effective thermal diffusion component.In addition, this high conductance foam is also used as electronic device cooling and is used for Enhance the plug-in unit of the heat abstraction from small chip to radiator.Because being to be primarily upon by the space that high conductance material occupies, institute It is to utilize the high conductance path that can be embedded into heating element with more efficient design.It is disclosed herein elastic and highly conductive Solid graphene foam fully meet these requirements.

It is thick that high resiliency and high-termal conductivity so that solid graphene-carbon hybrid foam of the present invention becomes good conductibility Plate, the slab have be placed in be used as thermal transfer interface it is cold to improve between heat source and cold flow fluid (or any other radiator) But performance.In such arrangement, heat source is cooling under thick grapheme foam plate, rather than is in direct contact with cooling fluid next cold But.The slab of grapheme foam can significantly improve the heat between heat source and cooling fluid by conducting hot-fluid in the best way Transfer.Other pump power and extra heat transfer table area are not needed.

Solid graphene foam is also the outstanding material for constructing heat pipe.Heat pipe utilizes two-phase working fluid or coolant It evaporates and condenses to transmit the heat removal devices of amount of heat, there are very small temperature differences between hot interface and cold interface It is different.Conventional heat pipe is made of following item：Hollow tube is sealed made of heat-conducting metal such as Cu or Al；And make working fluid from Evaporator is back to the liquid-sucking core (wick) of condenser.Pipe containing working fluid (such as water, methanol or ammonia) saturated liquid and Both steams, every other gas are excluded.However, both Cu and Al be easy to aoxidize or corrode, and therefore its performance with The time relatively quickly degrades.In contrast, solid graphene foam be it is chemically inert and without these oxidation or Etching problem.Heat pipe for electronic device heat management can have solid graphene foam big envelope and liquid-sucking core, be made using water For working fluid.It can use graphene/methanol if heat pipe needs operate under the freezing point less than water, and graphene/ Ammonia heat pipe can be used for the electronic device cooling in space.

Peltier coldplate is worked based on Peltier effect with by applying electric current connecing in two different electric conductors Heat flux is generated between chalaza.This effect is commonly used in cooling electronic unit and small instrument.In practice, many such junctions It can be with arranged in series the effect is increased to the required amount of being heated or cooled.Solid graphene foam can be used for improving heat Transfer efficiency.

Filtering and fluid absorb application

Solid graphene foam can be made into containing microcosmic hole (<2nm) or the middle ruler with the aperture from 2nm to 50nm Spend hole.Solid graphene-carbon hybrid foam is formed into containing micrometer grade hole (1-500 μm).It is based only upon the hole well controlled Diameter, graphene-carbon foam of the present invention can be the abnormal filtering materials filtered for air or water.

In addition, graphene hole wall chemistry and carbon phase chemistry can be independently controlled with by the official of not same amount and/or type It can roll into a ball and assign one or both of graphene film and carbon binder phase (for example, such as being reflected by the percentage of O, F, N, H in foam ).In other words, while to both chemical functional groups at the different loci in aperture and internal structure or independent control provides Unexampled flexibility or highest degree of freedom, these graphene-carbon in terms of design and manufacture graphene-carbon hybrid foam mix Foam shows many unexpected characteristics, synergistic effect and certain unique combination for being typically considered to mutually exclusive characteristic (for example, certain part of structure is hydrophobic and other parts are hydrophilic；Or foaming structure be not only hydrophobicity but also It is lipophilic).If water is by material or exclusion, then it is assumed that this surface or material are hydrophobic, and are placed in hydrophobic Water droplet on property surface or material will form big contact angle.If surface or material are for oil with strong affinity and for water Do not have, then it is assumed that the surface or material are lipophilic.The method of the present invention allows to carry out essence to hydrophobicity, hydrophily and lipophile Really control.

The present invention also provides a kind of oil removing, the device of separation oil or oil recovery, which contains the 3D graphite of the present invention Alkene-carbon hybrid foam is as the element for absorbing oil or separation oil.Additionally provide a kind of device for removing solvent or detaching solvent, the dress It sets and contains the 3D graphenes-element of the carbon hybrid foam as lyosoption.

The use of graphene of the present invention-carbon hybrid foam as the major advantage for the element for absorbing oil is its structural intergrity. Since graphene film is by the chemically combined viewpoint of carbon material, gained foam will not be disintegrated after the absorption oil operation repeated. In contrast, it has been found that the absorption oil based on graphene prepared by hydrothermal reduction, vacuum assisted filtration or freeze-drying Element absorb oil 2 or 3 times after can be disintegrated.Only without anything (in addition to oily initial contact before it is existing Weak Van der Waals force) graphene film of these separation originally is kept together.Once these graphene films are wetting by the oil, then they It is no longer able to restore to the original shape for the element for absorbing oil.

Another major advantage of the technology of the present invention is can to absorb most up to its own weight in design and manufacture The oil of 400 times of amount but still the flexibility in terms of maintaining the element of the absorption oil of its planform (and without notable expansion).This amount Depending on the ratio pore volume of foam, which can mainly pass through the amount and stone of starting vector polymer beads before the heat treatment Ratio between the amount of black alkene piece controls.

The present invention also provides one kind from oil-aqueous mixtures (such as oil spilling water or from the waste water of oil-sand) separation/recovery The method of oil.This approach includes the following steps：(a) element for the absorption oil for including integral type graphene-carbon hybrid foam is provided； (b) oil-aqueous mixtures are made to be contacted with the element, which absorbs oil from the mixture；And (c) this is recalled from the mixture It absorbs the element of oil and extracts the oil from the element.Preferably, this method includes another step (d)：Reuse the element.

In addition, that the present invention provides one kind is organic molten for detaching from solvent-water mixture or from multi-solvent mixture The method of agent.This approach includes the following steps：(a) offer includes the absorption organic solvent of integral type graphene-carbon hybrid foam Element；(b) multi-solvent of the element with organic solvent-aqueous mixtures or containing the first solvent and at least the second solvent is made to mix Object contacts；(c) this element is allowed from the mixture to absorb the organic solvent or from least second solvent absorption first solvent； And (d) element is recalled from the mixture and extract the organic solvent or the first solvent from the element.Preferably, this method packet Include another step (e)：Reuse the element of the lyosoption.

Following instance is used to illustrate some details of the optimal mode about the practice present invention and should not be solved It is interpreted as limiting the scope of the invention.

Example 1：Graphene-carbon foam is produced by flake graphite via the solid polymer support based on polypropylene powder

In an experiment, by 1kg polypropylene (PP) pellet, 50 grams of flake graphites, 50 mesh (average grain diameter 0.18mm；A Sibai Li Tan companies (Asbury Carbons), New Jersey Asbury (Asbury NJ)) and 250 grams of magnetic steel balls be placed in high energy In balling mill container.Ball mill is operated at 300 rpm 2 hours.It removes container cover and removes stainless steel ball via magnet.Hair Existing polymer carrier materials are coated with black graphene layer.Carrier material is placed in 50 mesh sieve above and is removed unprocessed a small amount of Shape graphite.

Then coated carrier material sample is immersed in tetrachloro-ethylene 24 hours at 80 DEG C, to dissolve PP and allow Graphene film disperses in organic solvent.After solvent removal, recycling isolated graphene film powder, (most of is few layer stone Black alkene).Then remaining coated carrier material is compacted, to form raw green compact, then sealing it in cavity body of mould Crucible in be heat-treated 2 hours at 350 DEG C and then at 600 DEG C to generate graphene-carbon foam.

In individual experiment, the identical batch of PP pellets and exfoliated graphite particles (not hitting steel ball) is placed in identical High energy ball mill container in, and the ball mill is operated into the identical period under the same conditions.By result with by hitting The result that ball auxiliary operation obtains is compared.Most of the isolated graphene film isolated from PP particles after PP dissolvings is single layer Graphene.Thus graphene-carbon foam of method production has higher porosity level (lower phsyical density).

Although polypropylene (PP) is used to be used as example herein, the carrier material for graphene-carbon hybrid foam production It is not limited to PP.It can be any polymer (thermoplastic, thermosetting plastics, rubber, wax, adhesive, colloid, You Jishu Fat etc.), precondition, which is the polymer, can be made particulate form.It is noted that the thermosetting property being uncured or partially cured Resin (such as based on epoxides and imido oligomer or rubber) can be made under room temperature or lower (such as low temperature) Particle form.Therefore or even partially cured thermosetting resin particles may be used as polymer support.

Example 2：Use expanded graphite (thickness>It 100nm) is used as graphene source and uses ABS as polymeric solid supports The graphene of particle-carbon hybrid foam

In an experiment, 16 are placed in together with 5 grams of expanded graphites using 100 grams of ABS pellets as solid carrier material particle In the plastic containers of ounce.The container is placed in sound mixed cell (Resodyn Acoustic mixer companies) and processes 30 Minute.After processing, it is found that carrier material has a thin layer carbon.The small sample of carrier material is placed in acetone and is subjected to Ultrasonic energy is to accelerate the dissolving of ABS.It is washed four times using filter filtering solution appropriate and with other acetone.After washing Later, filtrate is 2 hours dry in the vacuum drying oven for being set in 60 DEG C.The sample by light microscope inspection and is sent out It is now graphene.Remaining pellet is squeezed out to generate graphene-polymer piece (1mm is thick), is then carbonized in difference Graphene-carbon foam sample is prepared at temperature and contractive condition.

Example 3：By carbonaceous mesophase spherules (MCMB is as graphene source material) and polyacrylonitrile (PAN) fiber (as solid Body carrier granular) production graphene-carbon hybrid foam

In an example, by 100 grams of PAN fiber sections (2mm long, as carrier granular), 5 grams of MCMB (Taiwan China Steel chemical limited liability company (China Steel Chemical Co., Taiwan)) and 50 grams of zirconium oxide beads be placed in vibration In ball mill and process 2 hours.After the completion of the process, the oscillating mill is then opened, and it was found that carrier material has The black coating of graphene film.The zirconia particles with visibly different size and color are removed manually.Then by graphene The PAN fiber of coating is compacted and is melted together to form several composite membrane.These films are made to be subjected to following heat treatment：250 2 hours and 2 hours (under an argon atmosphere) at 1,000 DEG C (indoors in air), at 350 DEG C 1 hour at DEG C, to obtain Obtain graphene-carbon foam layer.Then half carbonized foams layer is heated to 2,850 DEG C and remains 0.5 small at this temperature When.

Example 4：Phenolic resin cured particle is as polymer support in refrigeration grinding machine

In being tested at one, by 10 grams of phenolic resin particles together with 0.25 gram of HOPG powder derived from graphitization polyimides End and magnetic stainless steel impacting body are placed in SPEX grinders sample retainer (SPEX Sample Prep companies, new pool together Western state Mai Ta is at (Metuchen, NJ)) in.Identical experiment is carried out, but sample retainer does not contain any impacting body ball.These mistakes Journey carries out in " hothouse " of 1% humidity, to reduce the condensation on water to finished product.By 10-120 points of SPEX grinders operation Clock.After operation, the content of sample retainer is classified (to work as use by removing remnants HOPG powder and impacting body ball When) come recycle graphene coating resin particle.

Digit optical microscope and scanning electron microscope are used (with or without the use of impacting body ball) in both cases (SEM) the two checks the resin particle of gained graphene coating.Observe the thickness of the graphene film of wrapping resin particle with grinding It grinds the operating time and increases and assume identical operation duration, impacting body auxiliary operation generates thicker graphite ene coatings.

The resin particle of a large amount of graphene coatings is compressed to form raw green compact, then infiltrates it with a small amount of asphalt. Individually, under the conditions of comparable, but pitch infiltration is not attempted, to prepare the raw pressure of the another kind of resin particle of graphene coating Base.Then both pressing entities is made to be subjected to identical pyrolysis processing.

Example 5：Natural graphite particles as graphene source, polyethylene (PE) or 6/6 pearl of nylon as solid carrier particle, And the impact bead of ceramics or bead as addition

In an experiment, by the PE of 0.5kg or nylon beads (as solid carrier material), 50 grams of natural graphite (graphene films Source) and 250 grams of Zirconium oxide powders (impact bead) be placed in the container of planetary ball mill.Ball mill is operated 4 at 300 rpm Hour.It removes container cover and zirconium oxide bead (size and weight are different from the PE pearls of graphene coating) is removed by vibrating screen.Hair Existing polymer carrier materials particle is coated with black graphene layer.Carrier material is placed in 50 mesh sieve above and is removed a small amount of undressed Flake graphite.In individual experiment, using bead as impact bead；Other ball milling operation conditions keep identical.

The PE pellets that a large amount of graphene is coated and the nylon beads of a large amount of graphene coating are individually in cavity body of mould Middle compacting, and briefly heat under the fusing point higher than PE or nylon and be then quickly cooled down to form two kinds of raw green compacts. For comparative purposes, two kinds of corresponding pressing entities are prepared by a large amount of uncoated PE pellets and a large amount of uncoated nylon beads. Then this 4 kinds of pressing entities is made to be subjected to pyrolysis (by heating indoor these pressing entities from 100 DEG C to 650 DEG C).These results Very unexpectedly.It was found that the pressing entity of the polymer beads of graphene coating is converted to graphene-carbon hybrid foam structure, this The size that a little structures have and the size (3cm × 3cm × 0.5cm) of initial pressing entity are comparable.The SEM of these structures is checked Show that carbon phase is present in the adjacent edges of graphene film and these carbon phases are for graphene film to be combined together.What carbon combined Graphene film forms the skeleton that there is the graphene-carbon in the hole being contained therein to mix hole wall, this some holes is used for by initial polymerization The space that composition granule occupies, as Fig. 2 (A) is schematically shown.

In contrast, two kinds of pressing entities from uncoated pellet or pearl are shunk and essentially becoming has for initial compacting Two kinds of carbon solid slugs of the volume of the about 15%-20% of body volume.The solid slug of these high shrinkages is actually non-porous Carbon material；They are not foamed materials.

Example 6：Micron order rubber grain is as solid polymer support particle

Experiment is started with preparing micron order rubber grain.By obtaining first using homogenizer 1 minute at ambient conditions Base hydrogen dimethylamino base-siloxane polymer (20g) and dimethyl silicone polymer (polymer of vinyl-dimethyl base sealing end) (30g) Mixture.Add Tween 80 (Tween 80) (4.6g) and by mixture homogenization 20 seconds.Add platinum-divinyl tetramethyl two It silicone complex (0.5g, in 15g methanol) and is mixed 10 seconds.This mixture is added in 350g distilled water simultaneously And obtain stable latex by being homogenized 15 minutes.The latex is heated to 60 DEG C and continues 15 hours.Then the latex is used Anhydrous sodium sulfate (20g) go emulsification and by vacuum filter, be washed with distilled water and be dried in vacuo at 25 DEG C and obtain silicon Ketone rubber grain.The particle diameter distribution of gained rubber grain is 3-11 μm.

In an example, 10 grams of rubber grains, 2 grams of natural graphites and 5 grams of zirconium oxide beads are placed in vibrator And it processes 2 hours.After the completion of the process, the oscillating mill is then opened, and it was found that rubber grain is coated with graphene The black coating of piece.Zirconia particles are removed manually.Then by the rubber grain of graphene coating and by weight 5% oil Pitch (as adhesive) mixes and mechanical ramming is together to form several composite sheet.Then make these composite sheets in pipe Following heat treatment is subjected in formula stove：1 hour at 350 DEG C, 2 hours and 1 hour at 1,000 DEG C at 650 DEG C, to obtain Graphene-carbon foam layer.

Example 7：The preparation of fluorinated graphene foam

In exemplary program, pass through chlorine trifluoride steam fluorinated graphene-carbon impurity in sealing autoclave reactor Piece, to generate fluorinated graphene-carbon hybrid film.Allow the duration of different fluorination times to realize different degree of fluorination. Then fluorinated graphene-carbon foam piece is individually immersed in the container respectively containing chloroform-aqueous mixtures.We observe It arriving, the amount for the chloroform that these foam pieces selectively absorb chloroform and absorbed from water increases with degree of fluorination, until Fluorine content reaches by weight 7.3% (Fig. 9).

Example 8：The preparation of graphene oxide foam and nitridation grapheme foam

Several graphenes prepared in example 3-carbon foam is immersed into 30%H₂O₂Continue 2-48 hours in aqueous solution Period, these foams had the oxygen content of 2%-25% by weight to obtain graphene oxide (GO) foam.

Some GO foam samples are mixed with the urea of different proportion, and by these mixtures at microwave reactor (900W) Middle heating 0.5 to 5 minute.Product is washed with deionized several times and is dried in vacuo.The product obtained is nitridation stone Black alkene foam.Nitrogen content is from 3% to 17.5 weight %, as measured by elemental analysis.

It is noted that the different functionalizations processing of graphene-carbon hybrid foam is for various purposes.For example, oxidation stone Black alkene-carbon hybrid foam structure is as the oil in oil-aqueous mixtures (i.e. oil is sprinkled upon waterborne and then mixes) Absorbent be particularly effective.In this case, integral type 3D graphenes (oxygen of 0%-15% by weight)-carbon foam Structure is not only hydrophobicity but also lipophilic (Fig. 7 and Fig. 8).If water is by material or exclusion, then it is assumed that this surface or material Material is hydrophobic, and the water droplet being placed on hydrophobic surface or material will form big contact angle.If surface or material There is strong affinity for oil and do not have for water, then it is assumed that the surface or material are lipophilic.

O, the different content of F, and/or N is but also graphene-carbon hybrid foam of the present invention can absorb difference from water Organic solvent or a kind of organic solvent is separated from the mixture of multi-solvents.

Comparison example 1：Via the carbonization of the graphene and graphene-polymer composite material of Hummer methods

According to Hummers methods, by preparing graphite oxide with sulfuric acid, nitrate and permanganate oxidation graphite flake [U.S. Patent number 2,798,878, July 9 nineteen fifty-seven].When reacting completion, pours the mixture into deionized water and filter. Graphite oxide is repeatedly washed in 5% HCl solution to remove most sulfate ion.Then repeatedly with deionized water Ground washing sample is until the pH of filtrate is neutrality.Slurry is spray-dried and continues 24 in the vacuum drying oven that is stored at 60 DEG C Hour.The interlayer spacing of gained layered graphite oxide is determined as about 0.73nm by Debey-Scherrer X-ray technologies (7.3A).Then the sample of the material is transferred to and is redefined for continuing in 650 DEG C of stove 4 minutes for puffing, and 4 hours are heated in 1200 DEG C of inert atmosphere stove to generate the low-density powder being made of few layer of redox graphene (RGO). Via N2 adsorption BET measurement table areas.Then by the powder respectively with ABS, PE, PP and nylon pellet with the load of 1%-25% Amount is horizontal dry-mixed, and is compounded using 25mm double screw extruders, to form composite material sheet.Then by these composite woods Tablet is pyrolyzed.

Comparison example 2：Single-layer graphene oxide (GO) piece is prepared by carbonaceous mesophase spherules (MCMB) and then by GO pieces Generate grapheme foam layer

Carbonaceous mesophase spherules (MCMB) are by Kao-hsiung China Steel chemical inc (China Steel Chemical Co., Kaohsiung, Taiwan) supply.This material has about 2.24g/cm³Density and about 16 μm in It is worth grain size.With acid solution (4:1:Sulfuric acid, nitric acid and the potassium permanganate of 0.05 ratio) 48- is continued to (10 grams) progress intercalations of MCMB 96 hours.When reacting completion, pours the mixture into deionized water and filter.Repeatedly washing is inserted in 5% solution of HCl The MCMB of layer is to remove most sulfate ion.Then with deionized water repeatedly washing sample until filtrate pH it is not low In 4.5.Then slurry is made to be subjected to being ultrasonically treated lasting 10-100 minutes to produce GO suspension.TEM and atomic force microscope are ground Study carefully and show that most GO pieces are single-layer graphenes when oxidation processes are more than 72 hours, and when oxidised between be small from 48 When by 72 hours when, be two layers or three layer graphenes.

For 48-96 hours oxidation processes, GO pieces contained the oxygen ratio of by weight about 35%-47%.GO pieces are hanged It floats in water.Just sodium bicarbonate (5%-20% by weight) is added to as chemical foaming agent in suspension before casting. Then suspension is cast on glass surface.It casts several sample, some samples contain foaming agent and some are not contained Foaming agent.After the liquid is removed, gained GO films have the thickness that can change from about 10 to 500 μm.Then make to have or do not have There are the several GO diaphragms of foaming agent to be subjected to being related to heat treatment 1-5 hours of 80 DEG C -500 DEG C of heating temperature, generates graphite Alkene foaming structure.

Comparison example 3：The preparation of raw graphite alkene foam (0% oxygen)

Recognize that high defects count works to reduce the conductive possibility of single graphene planes in GO pieces, we It is more highly thermally conductive to determine whether research can cause to have using raw graphite alkene piece (non-oxide and anaerobic, non-halogenated and halogen-free etc.) The grapheme foam of rate.Raw graphite alkene piece is come by using direct ultrasonic processing technique (it is puffing to be also referred to as liquid phase in this field) Production.

In typical program, will be milled to about 20 μm or smaller size of 5 grams of graphite flakes be dispersed in 1,000mL go from Sub- water (contains by weight 0.1% dispersant, comes from E.I.Du Pont Company (DuPont)FSO to be suspended in) Liquid.Using the ultrasound energy level (Branson S450 ultrasonic generators) of 85W for the puffing of graphene film, separation and size Reduction continues 15 minutes to 2 hours periods.Gained graphene film is from not oxidized and be anaerobic and to be relatively free of The raw graphite alkene of defect.There is no other non-carbon elements.

To chemical foaming agent (N, the N- dinitroso five of not same amount (relative to grapheme material 1%-30% by weight) Methenamine or 4,4 '-oxygen are bis- (benzene sulfonyl hydrazide)) it is added in the suspension containing raw graphite alkene piece and surfactant. Then suspension is cast on glass surface.It casts several sample, including uses and be just introduced into suspension before casting In CO₂The manufactured sample as physical blowing agent.After the liquid is removed, gained graphene film have can from about 10 to The thickness of 100 μm of variations.Then the heat treatment that these graphene films are subjected at a temperature of 80 DEG C -1,500 DEG C is made to continue 1-5 small When, generate grapheme foam.

Comparison example 4：CVD grapheme foams on Ni foam formworks

The program is adapted from the program disclosed in following discloses document：Chen, Z et al. " Three-dimensional flexible and conductive interconnected graphene networks grown by chemical Vapour deposition [graphene network is interconnected by the three-dimension flexible and conductibility of chemical vapor deposition growth] ", Nat.Mater. [nature material] 10,424-428 (2011).Nickel foam is selected (to there is the porous of the 3D nickel holders being connected with each other Structure) as grapheme foam growth template.In short, by decomposing CH at 1,000 DEG C under ambient pressure₄Carbon is drawn Enter in nickel foam, and then graphene film is deposited on the surface of nickel foam.Due to the thermal expansion between nickel and graphene The difference of coefficient forms ripple and wrinkle on graphene film.In order to recycle (separation) grapheme foam, it is necessary to etch away Ni frames Frame.Passing through hot HCl (or FeCl₃) before solution etches away nickel skeleton, poly- (metering system is deposited on the surface of graphene film Sour methyl esters) (PMMA) thin layer as supporter to prevent graphene network from caving in during nickel etches.Careful by hot acetone After removing PMMA layers, frangible grapheme foam sample is obtained.The use of PMMA supporting layers is for preparing the only of grapheme foam It is important for vertical film；The grapheme foam sample of serious distortion and deformation is only obtained in the case of no PMMA supporting layers Product.This be not environment friendly and can not scale cumbersome technique.

Comparison example 5：Ordinary graphite foam from the carbon foam based on pitch

Asphalt powder, particle or spherolite are placed in the aluminum die with desired final foam shape.It uses Mitsubishi ARA-24 mesophase pitch.Sample is evacuated to less than 1 support and is then heated to about 300 DEG C of temperature.This When, vacuum is discharged into blanket of nitrogen and then applies the pressure of up to 1,000psi.Then the temperature of system is increased to 800℃.This is carried out with the rate of 2 DEG C/min.Temperature is kept at least 15 minutes to realize immersion and be then shut off stove power supply And be cooled to room temperature with about 1.5 DEG C/min of rate, it is released stress with the rate of about 2psi/min.Final foam temperature It is 630 DEG C and 800 DEG C.During cooling cycle, pressure is gradually released to atmospheric conditions.Then foam is warm under a nitrogen blanket Processing to 1050 DEG C (carbonizations) and then be heat-treated in argon gas in a separate operation in graphite crucible 2500 DEG C with 2800 DEG C (graphitizations).

Comparison example 6：The grapheme foam of graphene oxide from hydrothermal reduction

In order to compare, graphene hydrogel (SGH) sample of self assembly is prepared by one step hydro thermal method.In typical program In, 2mg/mL uniform alumina graphite that SGH can easily by that will be sealed in the autoclave of Teflon (Teflon) lining Alkene (GO) water-borne dispersions heat 12h to prepare at 180 DEG C.Contain about 2.6% (by weight) graphene film and 97.4% The SGH of water has about 5 × 10^-3The conductivity of S/cm.At 1,500 DEG C after dry and heat treatment, gained grapheme foam shows Go out about 1.5 × 10^-1The conductivity of S/cm, the Conductivity Ratio by carry out at the same temperature heat treatment production graphite of the present invention The conductivity of alkene foam is 2 times low.

Example 9：The Thermal test and mechanical test of various grapheme foams and ordinary graphite foam

It is machined for the sample machine from various conventional carbon or grapheme foam material to measure the sample of thermal conductivity.In Between the range of bulk thermal conductivities of foam in asphalt phase source be from 67W/mK to 151W/mK.The density of sample is from 0.31- 0.61g/cm³.When considering weight, the specific heat conductance of the foam of the asphalt source is every proportion (or per phsyical density) about 67/ 0.31=216 and 151/0.61=247.5W/mK.

With 0.51g/cm³The compressive strength of sample of averag density to be measured as 3.6MPa and compression modulus tested Amount is 74MPa.In contrast, with comparable phsyical density graphene of the present invention-carbon foam sample compressive strength and Compression modulus is 6.2MPa and 113MPa respectively.

Fig. 4 (A) shows 3D graphenes-carbon foam, the graphite foam in mesophase pitch source and Ni foam formwork auxiliary types The heat conductivity value relative to proportion of CVD grapheme foams.These data clearly illustrate following unexpected result：

1) assume that phsyical density is identical, graphite foam and Ni foam formwork auxiliary type CVD stones with mesophase pitch source Both black alkene is compared, and the 3D integral types graphene-carbon foam produced by the method for the invention shows notable higher thermal conductivity.

2) in view of following viewpoint, this is quite unexpected：CVD graphenes be never exposed to oxidation and should be with me Graphene-carbon hybrid foam compare and show the substantially primary graphene of high thermal conductivity.The carbon phase of hybrid foam is total There is low-crystallinity (some are amorphous carbon) on body, and therefore there is much lower thermal conductivity compared with individual graphene Or conductivity.However, when carbon phase couples with graphene film to form the integral structure generated by the method for the invention, gained is mixed Miscellaneous foam shows the thermal conductivity compared to complete raw graphite alkene foam.Mix bubble using this paper graphene-carbon produced These abnormal high heat conductivity value let us that foam is observed are very surprised.This may be due to following observation result：Originally lonely Vertical graphene film is combined by carbon phase now, to provide the bridge for not interrupting transmission for electronics and phonon.

3) the ratio conductance values of hybrid foam material of the present invention show value of the per unit proportion from 250 to 500W/mK；But It is that those of other kinds of foamed material is typically lower than per unit proportion 250W/mK.

4) a series of thermal conductivity of the foam in 3D graphenes-carbon foams and a series of raw graphite alkene source is summarized in Fig. 5 Rate data, the two are drawn relative to final (maximum) heat treatment temperature.In two kinds of material, thermal conductivity is with final HTT Monotonously increase.However, the method for the present invention makes it possible to cost efficient and environmentally friendly production performance is more than primary stone Graphene-carbon foam of black alkene foam.This is another unexpected result.

5) Fig. 4 (B) shows the heat conductivity value of the hybrid foam of the present invention and the GO grapheme foams of hydrothermal reduction.Fig. 6 shows Go out the conductivity value of the GO grapheme foams of 3D graphenes-carbon foam and hydrothermal reduction.These data further support following see Point：It is assumed that the amount of solid material is identical, graphene-carbon foam of the invention is inherently largely conduction, reflects electronics With the successional importance of phonon transportation route.Gap between carbon phase bridged graphite alkene piece or interruption.

Example 10：The characterization of various grapheme foams and ordinary graphite foam

It (crystal structure and is taken using the internal structure of graphene-carbon foam of several series of X-ray diffraction studies To).The X-ray diffraction curve of natural graphite typically shows the peak at about 2 θ=26 °, corresponding to about 0.3345nm's Spacing (d between graphene₀₀₂).The graphene wall of hybrid foam material is shown typically from 0.3345nm to 0.40nm but more allusion quotation Type it is up to the d of 0.34nm₀₀₂Spacing.

The heat treatment temperature for 2,750 DEG C of foaming structure under compression continue 1 it is small in the case of, d₀₀₂Spacing It is reduced to about 0.3354nm, it is identical as the spacing of graphite monocrystalline.In addition, with high intensity the second diffraction maximum corresponding to from (004) occur at 2 θ=55 ° of the X-ray diffraction of plane.(004) peak intensity on identical diffraction curve is relative to (002) Intensity or I (004)/I (002) ratio, are the good instructions of the crystal perfection degree and preferred orientation degree of graphene planes.For All graphite materials being heat-treated at a temperature of less than 2,800 DEG C, (004) peak be it is being not present or relatively weak, I (004)/ I (002) ratio<0.1.Be heat-treated at 3,000 DEG C -3,250 DEG C graphite material (such as height-oriented pyrolytic graphite, HOPG I (004))/I (002) ratios are in the range of 0.2-0.5.In contrast, to continue one with 2,750 DEG C of final HTT small When the grapheme foam for preparing show 0.78 I (004)/I (002) ratios and 0.21 and inlay latitude of emulsion value, instruction hole wall is Actually perfect graphene monocrystalline with good preferred orientation degree (if preparing under compressive force).

The full width at half maximum (FWHM) that " inlaying the latitude of emulsion " value is reflected from (002) in X-ray diffraction intensity curve obtains.This degree of order Index characterization graphite or graphene crystalline size (or crystallite dimension), the amount of crystal boundary and other defect and preferred crystal grain The degree of orientation.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays latitude of emulsion value.When with not less than 2,500 DEG C final heat treatment temperature come when producing, some in our grapheme foam have in the range of this 0.3-0.6 Inlay latitude of emulsion value.

It is the general introduction of some prior results below：

1) generally, addition impact bead helps speed up the process that graphene film is removed from graphite particle.However, the option It needs to detach these impact beads after the polymer beads that graphene coating is made.

2) when without using impact bead (for example, ceramics, glass, metal ball etc.), with more soft polymer particle (such as rubber Glue, PVC, polyvinyl alcohol, latex particle) it compares, harder polymer beads (such as PE, PP, nylon, ABS, polystyrene, height Impact-resistant polystyrene etc. and its filler enhanced form) more it can remove graphene film from graphite particle.

3) in the case of no external impact bead added, softer polymer beads are tended to produce with by weight The graphene coating of the graphene (mainly single-layer graphene film) of meter 0.001% to 5% or embedded particle, and it is harder Polymer drops tend to produce with by weight 0.01% to 30% graphene (mainly single layer and few layer graphene Piece) graphene coating particle, it is assumed that identical 1 hour operating time.

4) in the case where impact bead is added in outside, all polymer drops can support by weight from 0.001% to about 80% graphene film (mainly lack layer graphene,<10 layers, if being by weight more than 30% graphene film).

5) compared with its counterpart produced by conventional prior method, graphene of the invention-carbon hybrid foam Material typically shows notable higher structural intergrity (for example, compressive strength, elasticity and resilience) and higher thermal conductivity Rate and conductivity.

6) it is important to note that, whole art methods for producing graphite foam or grapheme foam seem only to carry For having in about 0.2g/cm³-0.6g/cm³In the range of phsyical density macrocellular foam, for most of intended application Aperture is typically too big (such as from 20 to 300 μm).In contrast, having the present invention provides generation can be down to 0.001g/cm³ With may be up to 1.7g/cm³Density grapheme foam method.Aperture can from it is microcosmic (<2nm) through mesoscale (2- 50nm), and it is maximum to macro-scale (such as from 1 to 500 μm) variation.Designing different types of graphene-carbon foam side This flexibility in face and versatility level are that unexampled and any art methods mismatch.

7) method of the invention also allow to need in response to various applications (for example, from the water of oily pollution oil recovery, will have Solvent detaches with water or other solvents, radiates) and to chemical composition (for example, F, O and N content etc.) into accommodating and flexible Control.

In short, we successfully developed it is a kind of absolutely new, novel, unexpected and visibly different High conductance graphene-carbon hybrid foam material, device and related methods of production.The chemical composition of such new foamed material The % of fluorine and other non-carbon elements (oxygen), structure (crystal perfection, crystallite dimension, defects count etc.), crystal orientation, form, Production method and characteristic are fundamentally different from and are clearly distinguishable from the graphite foam in mesophase pitch source, CVD graphite The grapheme foam of the foam in alkene source and hydrothermal reduction from GO.

Claims

1. a kind of integral type 3D graphenes-carbon hybrid foam, is made of multiple holes and hole wall, passes through wherein the hole wall contains The chemically combined single layer of carbon material or few layer graphene piece, with the carbon material and graphene weight ratio from 1/200 to 1/2, Described in few layer graphene piece there is 2-10 stacked graphene plane layer, these graphene planes by X-ray with such as being spread out Penetrate the interplanar spacing d of the slave 0.3354nm to 0.40nm of measurement₀₀₂, and the single layer or few layer graphene piece contain and have Substantially the raw graphite alkene material of zero % non-carbon elements or the non-protogenous with 0.001% to 25% non-carbon element by weight Grapheme material, wherein the non-protogenous graphene is selected from graphene oxide, redox graphene, fluorinated graphene, chlorination Graphene, bromination graphene, iodate graphene, hydrogenation graphene, nitridation graphene, doped graphene, chemical functionalization graphite Alkene, or combinations thereof.

2. integral type 3D graphenes-carbon hybrid foam as described in claim 1, wherein the 3D grapheme foams have from 0.005g/cm³To 1.7g/cm³Density, from 50m²/ g to 3,200m²The specific surface area of/g, per unit proportion at least 200W/mK Thermal conductivity, and/or per unit proportion be not less than 2,000S/cm conductivity.

3. integral type 3D graphenes-carbon hybrid foam as described in claim 1, wherein the hole wall contains raw graphite alkene simultaneously And the 3D graphenes-carbon hybrid foam has from 0.01g/cm³To 1.7g/cm³Density or average hole from 2nm to 50nm Diameter.

4. integral type 3D graphenes-carbon hybrid foam as described in claim 1, wherein the hole wall contains non-protogenous graphene Material and the wherein described foam contain the non-carbon element content by weight in 0.01% to 20% range, and described non- Carbon includes the element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen or boron.

5. integral type 3D graphenes-carbon hybrid foam as described in claim 1, wherein the hole wall contains fluorinated graphene simultaneously And the solid graphene foam contains the fluorine content by weight from 0.01% to 15%.

6. 3D graphenes-carbon hybrid foam as described in claim 1, wherein the hole wall contains graphene oxide and described Solid graphene foam contains the oxygen content by weight from 0.01% to 20%.

7. 3D graphenes-carbon hybrid foam as described in claim 1, wherein the foam has from 200m²/ g to 3,000m²/ The specific surface area of g or from 0.1g/cm³To 1.2g/cm³Density.

8. 3D graphenes-carbon hybrid foam as described in claim 1, the 3D graphenes-carbon hybrid foam be in have from It the continuous length roll film form of the thickness of 100nm to 10cm and at least 2 meters of length and is produced by roll to roll.

9. 3D graphenes-carbon hybrid foam as described in claim 1, wherein the foam has is less than 1% by weight Oxygen content or non-carbon content, and the hole wall has spacing, per unit proportion at least 250W/ between the graphene less than 0.35nm The thermal conductivity, and/or per unit proportion of mK is not less than the conductivity of 2,500S/cm.

10. 3D graphenes-carbon hybrid foam as described in claim 1 is less than by weight wherein the foam has 0.01% oxygen content or non-carbon content, and the hole wall contains the graphene planes of stacking, and these graphene planes have Spacing, per unit the proportion at least thermal conductivity of 300W/mK, and/or per unit proportion are not less than between graphene less than 0.34nm The conductivity of 3,000S/cm.

11. 3D grapheme foams as described in claim 1, wherein the foam has the oxygen for being not more than 0.01% by weight Content or non-carbon content, and the hole wall contains the graphene planes of stacking, and these graphene planes, which have, is less than 0.336nm Graphene between spacing, per unit the proportion at least thermal conductivity of 350W/mK, and/or per unit proportion not less than 3,500S/cm Conductivity.

12. 3D graphenes-carbon hybrid foam as described in claim 1, wherein the foam has containing the graphene stacked The hole wall of plane, spacing, per unit proportion are more than 400W/mK between these graphene planes have the graphene less than 0.336nm Thermal conductivity, and/or per unit proportion be more than 4,000S/cm conductivity.

13. 3D graphenes-carbon hybrid foam as described in claim 1, wherein these hole walls contain the graphene planes of stacking, These graphene planes with spacing between the graphene less than 0.337nm and inlay latitude of emulsion value less than 1.0.

14. 3D graphenes-carbon hybrid foam as described in claim 1, wherein the hole wall contains interconnection graphene planes 3D networks.

15. 3D graphenes-carbon hybrid foam as described in claim 1 has wherein the foam contains from 2nm to 50nm The mesoscale hole in aperture.

16. the device of a kind of oil removing or separation oil, contains 3D graphenes as described in claim 1-carbon hybrid foam conduct Absorb the element of oil.

17. a kind of device for removing solvent or detaching solvent, contains 3D graphenes-carbon hybrid foam as described in claim 1 As lyosoption or the element of separation solvent.

18. a kind of method for detaching oil and water the described method comprises the following steps：

A. the element for absorbing oil is provided, the element for absorbing oil includes integral type 3D graphenes-carbon as described in claim 1 Hybrid foam；

B. oil-aqueous mixtures are made to be contacted with the element, the element absorbs oil from the mixture；

C. it recalls the element from the mixture and extracts the oil from the element；And

D. the element is reused.

19. a kind of method for the Separation of Organic from solvent-water mixture or from multi-solvent mixture, the method packet Include following steps：

A. the element for absorbing organic solvent or detaching solvent is provided, the element includes integral type 3D as described in claim 1 Graphene-carbon hybrid foam；

B. make the element and organic solvent-aqueous mixtures or the multi-solvent mixture containing the first solvent and at least the second solvent Contact；

C. allow the element from the mixture absorb the organic solvent or separation first solvent with it is described at least Second solvent；

D. it recalls the element from the mixture and extracts the organic solvent or the first solvent from the element；And

E. the element is reused.

20. a kind of heat management device contains 3D integral types graphene as described in claim 1-carbon hybrid foam as heat Diffusion or heat-dissipation member.

21. heat management device as claimed in claim 20, which contains the device selected from the following terms：Heat exchanger, heat dissipation Conductibility plate, thermal diffusion component between device, heat pipe, high conductance plug-in unit, radiator and heat source, dissipation of heat component, hot interface Medium or thermoelectricity or Peltier cooling device.

22. a kind of method that integral type 3D graphenes-carbon hybrid foam directly being produced by graphite material, the method includes：

(a) by multiple graphite material particles and multiple solid polymer support material granules in the impact room of energy impact equipment Mixing is to form mixture；

(b) with certain frequency and intensity by the energy impact equipment operation for a period of time, the time is enough from the graphite material The graphene film is simultaneously transferred to the surface of the solid polymer support material granule with described by material stripping graphene film Graphene coating or graphene insertion polymer beads are generated inside impact room；

(c) from the impact room polymer beads that the graphene coats or graphene is embedded in are recycled and by the graphene Coating or graphene insertion polymer beads are consolidated into the graphene-polymer composite construction of desired shape；And

(d) the graphene-polymer composite construction of the shape is made to be pyrolyzed with by the polymer thermal transition pore-forming and carbon or stone Ink, the carbon or graphite form the integral type 3D graphenes-carbon hybrid foam in conjunction with the graphene film.

23. method as claimed in claim 22, plurality of impact bead or medium are added to the energy impact equipment In the impact room.

24. method as claimed in claim 23, wherein step (c) include actuating solenoid with by these impact beads or medium and this A little graphene coatings or graphene insertion polymer beads separation.

25. method as claimed in claim 22, wherein the solid polymeric material particle includes having from 10nm to 10mm Diameter or the plastics or rubber bead of thickness, pellet, sphere, line, fiber, long filament, disk, band or stick.

26. method as claimed in claim 25, wherein the diameter or thickness are from 100nm to 1mm.

27. method as claimed in claim 22, wherein the solid polymer is selected from the solid particle of the following terms：Thermoplasticity Plastics, thermosetting resin, rubber, partly penetrate network polymer, penetrate network polymer, natural polymer, or combinations thereof.

28. method as claimed in claim 22, wherein the solid polymer before step (d) by fusing, etching or Dissolving is partially removed in a solvent.

29. method as claimed in claim 22, wherein the graphite material is selected from natural graphite, synthetic graphite, height-oriented Pyrolytic graphite, graphite fibre, Graphite Nano Fiber, fluorographite, graphite oxide, chemical modification graphite, expanded graphite, press again The expanded graphite of contracting, expanded graphite, carbonaceous mesophase spherules, or combinations thereof.

30. method as claimed in claim 22, wherein the energy impact equipment are vibrator, planetary ball mill, height Can grinder, basket-type grinder, stirring ball mill, low temperature ball mill, ball mill, tumbling ball mill, continuous ball mill, Agitating ball mill, pressurization ball mill, refrigeration grinding machine, vibrating screen, pearl grinder, nano-beads grinder, ultrasound pulp grinder, Centrifugal planetary mixer, vacuum ball mill or resonance sound mixer.

31. method as claimed in claim 22, wherein the graphite material includes before the mixing step previously never It is exposed to chemistry or non-intercalation and the unoxidized graphite material of oxidation processes.

32. method as claimed in claim 22 is gathered wherein the solid polymer contains the high carbon yield selected from the following terms Close object：Phenolic resin, poly furfuryl alcohol, polyacrylonitrile, polyimides, polyamide, polyoxadiazoles, polybenzoxazole, Ju Ben Bing bis- Evil Azoles, polythiazole, polybenzothiozole, polyphenyl and dithiazole, poly- (to phenylene vinylidene), polybenzimidazoles, polyphenyl and two miaows Azoles, its copolymer, its blend polymer, or combinations thereof.

33. method as claimed in claim 22 is gathered wherein the solid polymer contains the low-carbon yield selected from the following terms Close object：Polyethylene, polypropylene, polybutene, polyvinyl chloride, makrolon, acrylonitrile-butadiene (ABS), polyester, polyvinyl alcohol, Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), polyphenylene oxide (PPO), polymethyl methacrylate (PMMA), its copolymerization Object, its blend polymer, or combinations thereof.

34. method as claimed in claim 22, wherein the pyrolysis step is included in from 200 DEG C to 2, at a temperature of 500 DEG C The polymer be carbonized to obtain graphene-carbon foam or the polymer that is carbonized at a temperature of from 200 DEG C to 2,500 DEG C With obtain graphene-carbon foam and then from 2,500 DEG C to 3,200 DEG C the graphitization graphene-carbon foam to obtain stone Graphene-carbon foam of inkization.

35. method as claimed in claim 22, wherein the consolidation step includes melting the polymer beads to form it In be dispersed with the Mixing of Polymer Melt object of graphene film, the Mixing of Polymer Melt object be configured to desirable shape simultaneously And the shape is solidified into graphene-polymer composite construction.

36. method as claimed in claim 22, wherein the consolidation step includes that the polymer beads are dissolved in solvent In be wherein dispersed with the polymer solution mixture of graphene film to be formed, by the polymer solution mixture be configured to wish The shape of prestige and the solvent is removed so that the shape is solidified into the graphene-polymer composite construction.

37. method as claimed in claim 22, wherein the consolidation step includes the polymer particles for coating the graphene Grain is configured to the compound shape selected from the following terms：Stick, piece, film, fiber, powder, ingot casting or block form.

38. method as claimed in claim 22, wherein the consolidation step includes the polymer particles for coating the graphene Grain is compacted into the porous raw green compact with macroscopic pores and is then infiltrated or impregnated with the other carbon source material selected from the following terms The hole：Asphalt, coal tar asphalt, aromatic organic material, monomer, organic polymer, or combinations thereof.

39. method as claimed in claim 38 is gathered wherein the organic polymer contains the high carbon yield selected from the following terms Close object：Phenolic resin, poly furfuryl alcohol, polyacrylonitrile, polyimides, polyamide, polyoxadiazoles, polybenzoxazole, Ju Ben Bing bis- Evil Azoles, polythiazole, polybenzothiozole, polyphenyl and dithiazole, poly- (to phenylene vinylidene), polybenzimidazoles, polyphenyl and two miaows Azoles, its copolymer, its blend polymer, or combinations thereof.

40. method as claimed in claim 22, wherein the consolidation step include it is by a large amount of graphene coating or The polymer beads of graphene insertion are configured to compacting object.

41. method as claimed in claim 40, wherein the compact body is in the form of selected from the following terms：Stick, piece, Film, fiber, powder, ingot casting or block.