CN103213980A - Preparation method of three-dimensional graphene or composite system thereof - Google Patents
Preparation method of three-dimensional graphene or composite system thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of three-dimensional graphene or a composite system thereof. The preparation method comprises the steps of: by taking a transition metal elementary substance and/or a compound containing a transition metal element as raw materials, preparing a three-dimensional porous metal catalyst template through high-temperature reduction; growing the three-dimensional graphene by utilizing a chemical vapor phase deposition method to obtain the three-dimensional graphene with a catalyst framework; furthermore, etching the three-dimensional graphene with the catalyst framework to obtain three-dimensional graphene powder; and furthermore, compositing the three-dimensional graphene powder with metal, a macromolecular material, a biomolecular material and the like to form a composite material system. The preparation method is simple in technique, capable of fast and massively preparing high-quality and high-density three-dimensional graphene or composite material thereof, and has wide application prospects on the aspects of water treatment, biomedicines, energy generation and conversion and energy accumulation devices, static resistance, thermal management, heat conduction and dissipation, sensors, electromagnetic shielding, wave absorption, catalysis and the like.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, relate in particular to the preparation method of the three-dimensional Graphene of a kind of high quality or its compound system.
Background technology
Graphene is that the monolayer carbon atom is with sp
2Form is piled up the cellular two dimensional crystal that forms.Graphene has big specific surface area and excellent electricity, calorifics and mechanical property.Since Graphene is found, developed and multiple preparation method, comprise that mechanically peel method, SiC or metal single crystal surface epitaxial growth method, chemical oxidation are peeled off method, intercalation is peeled off method and chemical vapor deposition (CVD) method etc.Wherein being considered to the most potential method has chemical oxidation to peel off method and CVD method.Peel off method by chemical oxidation, people prepare paper delivery shape grapheme material, Graphene flexible transparent conductive film and three-dimensional porous body material, yet, peel off the Graphene body material of method preparation based on chemical oxidation and introduced non-carbon functional group and defective, greatly reduced the conductivity of Graphene owing to preparation process.Comparatively speaking, the CVD method is a kind of method of synthetic high quality Graphene.But the CVD method is many at present is substrate with the catalyst film, obtains the graphene film of two dimensional surface, though be suitable for the application of electron device and transparent conductive film, is difficult to satisfy the requirement that magnanimity is used.
The tridimensional network that the graphene film that three-dimensional Graphene is based on two dimension is cross-linked to form by the space, except the proper property with two-dimentional Graphene, three-dimensional graphite is in space heat conduction, and conduction and magnanimity high quality prepare the aspect and have special advantages.2011, it was the three-dimensional Graphene of masterplate that Cheng Huiming group of Shenyang metal institute makes with the nickel foam, and this three-dimensional Graphene and silicon rubber compound system have shown excellent electroconductibility and mechanical property.Afterwards, three-dimensional Graphene has caused extensive interest and concern.At present, three-dimensional Graphene is many to be the template preparation with the nickel foam, is template with the nickel foam, and the three-dimensional Graphene of CVD growth has improved the energy density and the power density of electrical condenser as the electrode of ultracapacitor; As the gas sensing passage, the sensitivity of ppb level is arranged; As electrochemical electrode, embody high electro catalytic activity and be lower than 10
-9Mol concentration Electrochemical Detection ability.But nickel foam has the network hole of hundreds of micron, and the Graphene volume density that grows on this template is very low, has limited the requirement of its magnanimity preparation.
Summary of the invention
The object of the present invention is to provide the novel preparation method of a kind of three-dimensional Graphene or its compound system, it can realize high-density, quick, a large amount of preparations of high-quality three-dimensional Graphene or its matrix material, thus overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
The preparation method of a kind of three-dimensional Graphene or its compound system, comprise: the compound of getting transition metal simple substance and/or containing transition metal is a raw material, through high temperature reduction, prepare three-dimensional porous metal catalyst template, utilize chemical Vapor deposition process growing three-dimensional Graphene, obtain to have the three-dimensional Graphene of catalyst backbone.
Aforementioned three-dimensional porous metal catalyst template cording has three-dimensional cross-linked structure, and its aperture is 100 nm-100 μ m.
The aperture of contained hole is 100 nm-500 μ m in the Graphene of aforementioned band catalyst backbone.
As one of the scheme that can implement, this method also can comprise: transition metal simple substance and/or the compound that contains transition metal are filled in the macropore foamed metal template, behind high temperature reduction, obtain three-dimensional porous metal catalyst template.
The aperture of aforementioned macropore foamed metal catalyst contained hole is 100 nm-500 μ m.
The described compound that contains transition metal can be selected from but be not limited to transition metal oxide, transition metal salt or its hydrate, and described transition metal can be selected from but be not limited to Fe, Cu, Co, Ni, Pt or Ru.
Wherein, for the transition metal salt hydrate, it can be obtained anhydrous transition metal salt or directly carry out high temperature reduction in 50-300 ℃ of oven dry or the microwave heating water that decrystallizes.
As one of embodiment preferred comparatively, described high temperature reduction is to carry out in temperature is 100-1000 ℃ reducing atmosphere, and described reducing atmosphere mainly is made up of hydrogen or hydrogen and rare gas element.
As one of application scheme more specifically, described reducing atmosphere is that argon gas and the hydrogen of 0-500:10-1000 is formed by throughput ratio mainly.
As one of embodiment preferred comparatively, the processing condition of described chemical Vapor deposition process comprise: growth temperature is 400-1200 ℃, and growth time is 30 s-2 h, and growth pressure is 1 torr-800 torr.
Postscript, in aforesaid chemical vapor deposition processes, the carbon source of being introduced comprises solid phase, the liquid and gas carbon source, wherein, solid-phase carbon source can be selected from but be not limited to polymethylmethacrylate, polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyvinyl alcohol, polyethylene, polyoxyethylene glycol, polymkeric substance such as polydimethylsiloxane, glucose, sucrose, fructose, carbohydrate such as Mierocrystalline cellulose and decolorizing carbon and composition thereof; Phase carbon source can be selected from but be not limited to methyl alcohol, ethanol, propyl alcohol, aromatic hydrocarbon and composition thereof; The gas phase carbon source optional from but be not limited to methane, acetylene, ethene, ethane, propane, carbon monoxide, carbonic acid gas and composition thereof.
As one of embodiment preferred comparatively, this method also comprises: the three-dimensional Graphene that has catalyst backbone is carried out etching processing, obtain three-dimensional Graphene powder, wherein, the etching solution that adopts of etching processing can be selected the solution that contains any one or two or more mixture in sulfuric acid, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, ammonium persulphate and the Marble reagent that concentration is 0.05-6 M for use.
As one of embodiment preferred comparatively, in aforementioned etching processing process, also adopt high molecular polymer that three-dimensional Graphene is protected, described high molecular polymer comprises polymethylmethacrylate, polyethylene, polystyrene or polypropylene.
As one of embodiment preferred comparatively, this method also can comprise: get three-dimensional Graphene at least with metallic particles, metal oxide, metal-salt, polymkeric substance and biomolecules in any one is compound, form three-dimensional Graphene compound system, wherein, described composite methods comprises physical mixed, in-situ chemical reaction mixing, galvanic deposit or electrochemical reaction.
Wherein, the contained metallic element of described metallic particles, metal oxide or metal-salt can comprise Au, Ag, Fe, Cu, Co, Ni, Pt, Mn or Ru;
Described polymkeric substance can be selected from but be not limited to polyaniline, polypyrrole, Polythiophene, Resins, epoxy, silicon rubber, polyethylene, polypropylene, polyvinyl chloride, high density polyethylene(HDPE), polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, resol, polymethylmethacrylate, polymeric amide, rubber resin, polyoxyethylene glycol, polycarbonate, polyimide, nylon etc.;
Described biomolecules can be selected from but be not limited to albumen, amino acid, sugar, enzyme biomolecules etc.
Compared with prior art, the present invention has following advantage at least: the preparation method of this three-dimensional Graphene or its compound system can realize quick, a large amount of preparations of three-dimensional Graphene or its matrix material, and the three-dimensional Graphene that obtains has hole little (100 nm-100 μ m), and density is big (can be greater than 100 mg/cm
3), high conduction advantages such as (specific conductivity are 1-50 S/cm), this three-dimensional Graphene and compound system thereof be in water treatment, biological medicine, energy produces and transforms and energy storage device, antistatic, heat management, heat conduction and heat radiation, transmitter, electromagnetic shielding is inhaled aspects such as ripple and catalysis and is had wide practical use.
Description of drawings
Figure 1A-Fig. 1 C is respectively the optics picture and the SEM figure of the embodiment of the invention 1 three-dimensional Graphene sample that obtains;
Fig. 2 is the Raman figure of the embodiment of the invention 1 three-dimensional Graphene sample that obtains;
Fig. 3 is the optics picture of the embodiment of the invention 4 three-dimensional Graphene that obtains and PDMS compound system;
Fig. 4 is the SEM figure of the embodiment of the invention 7 three-dimensional Graphene that obtains and ferric oxide compound system.
Embodiment
As previously mentioned, in view of the deficiencies in the prior art, the invention provides the novel preparation method of a kind of three-dimensional Graphene or its matrix material.
Generalized saying, method of the present invention is that to adopt the self-control small catalyst will make maybe that small catalyst is filled in the macropore foamed metal be template, utilize the CVD method to prepare high-density, high-quality three-dimensional Graphene powder is compounded to form compound system with metallic particles, metal oxide, metal-salt, polymkeric substance or biomolecules etc. then.
Say that further as one of feasible specific embodiments, preparation method of the present invention can comprise:
With transition metal simple substance, oxide compound, salt or its hydrate be raw material (promptly, presoma), transition salt hydrate heating, drying or microwave heating decrystallized obtain anhydrous transition metal salt after the water treatment or above presoma is filled in the macropore foamed metal masterplate, under hot environment and suitable atmosphere, reduce the final three-dimensional cross-linked metal catalyst template that obtains.Adopt chemical Vapor deposition process to prepare high-quality three-dimensional Graphene powder then, with metallic particles, metal oxide and polymer formation compound system.
The present invention obtains three-dimensional Graphene and has good conductivity, specific surface area is big, characteristics such as density height, and this three-dimensional Graphene and compound system thereof are in water treatment, biological medicine, energy produces and transforms and energy storage device, and is antistatic, heat management, heat conduction and heat radiation, transmitter, electromagnetic shielding is inhaled aspects such as ripple and catalysis and is had wide practical use.
Below in conjunction with some preferred embodiments technical scheme of the present invention is further described.
One, the preparation of the three-dimensional Graphene of high quality:
Embodiment 1:The 5g copper powder is joined polymethylmethacrylate (PMMA:4%) sample is put into silica tube, and feed argon gas 15 min.Tube furnace is raised to 900 ℃, and atmosphere is: hydrogen: 200 sccm, argon gas: 100 sccm; Air pressure remains on: 10 torr.After treating that growth finishes, logical argon gas 200 sccm cool off up to silica tube.The good sample of will growing is again put into 1M FeCl
3Carry out etching in the/0.1M HCl solution, obtain three-dimensional Graphene.
Embodiment 2:5 g nickel powders are added to polymethylmethacrylate (PMMA:4%) sample is put into silica tube, and feed argon gas 15 min.Tube furnace is raised to 900 ℃, and atmosphere is: hydrogen: 200 sccm, argon gas: 100 sccm; Air pressure remains on: 10 torr.After treating that growth finishes, logical argon gas 200sccm cools off up to silica tube.The good sample of will growing is again put into 1M FeCl
3Carry out etching in the/0.1M HCl solution, obtain three-dimensional Graphene.
Embodiment 3:The nickelous chloride of 20g is put in the tube furnace, and 600 ℃ keep 10 min, and atmosphere is: hydrogen: 300 sccm, argon gas: 100 sccm.Tube furnace is raised to 1000 ℃ again, keeps 10 min in the time of 1000 ℃, this moment, atmosphere was: methane: 30 sccm, hydrogen: 200 sccm, argon gas: 200 sccm.The silica tube taking-up is cooled to room temperature.Use 1M FeCl
3/ 0.1M HCl carries out etching, finally obtains three-dimensional high quality Graphene sample.
Two, the preparation of the three-dimensional Graphene compound system of high quality:
Embodiment 4: 1 g PDMS prepolymer and 0.1 g solidifying agent mixing, the three-dimensional Graphene of 20 mg is soaked in the mixed solution, the 25 ℃ of degassing 2 h, 80 ℃ solidify 8 h, obtain the compound system of silicon rubber and three-dimensional Graphene.
Embodiment 5:Resins, epoxy and curing agent mixture 2 ml add in the three-dimensional Graphene network structure of 10 mg, and behind 80 ℃ of vacuum outgas 2 h, 120 ℃ solidify 6 h and get Resins, epoxy and three-dimensional graphene composite material matrix material.
Embodiment 6:After soaking 2 h in immersing the three-dimensional Graphene of 10 mg in 1 ml aniline solution or pyrroles or the thiophene solution, the Graphene after soaking is joined 1 ml, 0.1 M FeCl
3In the solution, reaction 24 h under the room temperature, product successively pass through after the deionised water and behind the ethanol thorough washing, 60 ℃ of vacuum-dryings obtain polyaniline or polypyrrole or Polythiophene and three-dimensional Graphene combination product.
Embodiment 7The three-dimensional Graphene of 10 mg is immersed 1M FeCl
3In the solution, soak 1 h after, lyophilize, at 600 ℃, the 1h that anneals under the argon gas atmosphere obtains three-dimensional Graphene/Fe
2O
3Compound system.
More than explanation, and the embodiment shown on drawing can not be resolved the design philosophy of the present invention surely of exceeding.Holding the identical the knowledgeable of knowing in technical field of the present invention can be with technical thought of the present invention with various form improvement change, and such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (10)
1. the preparation method of a three-dimensional Graphene or its compound system, it is characterized in that, comprise: the compound of getting transition metal simple substance and/or containing transition metal is a raw material, through high temperature reduction, prepare three-dimensional porous metal catalyst template, utilize chemical Vapor deposition process growing three-dimensional Graphene, obtain to have the three-dimensional Graphene of catalyst backbone.
2. the preparation method of three-dimensional Graphene according to claim 1 or its compound system, it is characterized in that, this method also comprises: transition metal simple substance and/or the compound that contains transition metal are filled in the macropore foamed metal template, behind high temperature reduction, obtain three-dimensional porous metal catalyst template.
3. the preparation method of three-dimensional Graphene according to claim 1 and 2 or its compound system, it is characterized in that, the described compound that contains transition metal comprises transition metal oxide or transition metal salt or its hydrate, and described transition metal comprises Fe, Cu, Co, Ni, Pt or Ru.
4. the preparation method of three-dimensional Graphene according to claim 1 and 2 or its compound system, it is characterized in that, described high temperature reduction is to carry out in temperature is 100-1000 ℃ reducing atmosphere, and described reducing atmosphere mainly is made up of hydrogen or hydrogen and rare gas element.
5. the preparation method of three-dimensional Graphene according to claim 4 or its compound system is characterized in that, described reducing atmosphere is that argon gas and the hydrogen of 0-500:10-1000 is formed by throughput ratio mainly.
6. the preparation method of three-dimensional Graphene according to claim 1 or its compound system, it is characterized in that, the processing condition of described chemical Vapor deposition process comprise: growth temperature is 400-1200 ℃, and growth time is 30 s-2 h, and growth pressure is 1 torr-800 torr.
7. the preparation method of three-dimensional Graphene according to claim 1 or its compound system, it is characterized in that, this method also comprises: the three-dimensional Graphene that has catalyst backbone is carried out etching processing, obtain three-dimensional Graphene powder, wherein, the etching solution that adopts of etching processing comprises the solution that contains any one or two or more mixture in sulfuric acid, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, ammonium persulphate and the Marble reagent that concentration is 0.05-6 M.
8. the preparation method of three-dimensional Graphene according to claim 7 or its compound system; it is characterized in that; in the etching processing process; also adopt high molecular polymer that three-dimensional Graphene is protected, described high molecular polymer comprises polymethylmethacrylate, polyethylene, polystyrene or polypropylene.
9. the preparation method of three-dimensional Graphene according to claim 7 or its compound system, it is characterized in that, this method also comprises: get three-dimensional Graphene at least with metallic particles, metal oxide, metal-salt, polymkeric substance and biomolecules in any one is compound, form three-dimensional Graphene compound system, wherein, described composite methods comprises physical mixed, in-situ chemical reaction mixing, galvanic deposit or electrochemical reaction.
10. the preparation method of three-dimensional Graphene according to claim 9 or its compound system is characterized in that,
The contained metallic element of described metallic particles, metal oxide or metal-salt comprises Au, Ag, Fe, Cu, Co, Ni, Pt, Mn or Ru;
Described polymkeric substance comprises polyaniline, polypyrrole, Polythiophene, Resins, epoxy, silicon rubber, polyethylene, polypropylene, polyvinyl chloride, high density polyethylene(HDPE), polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, resol, polymethylmethacrylate, polymeric amide, rubber resin, polyoxyethylene glycol, polycarbonate, polyimide or nylon;
Described biomolecules comprises albumen, amino acid, sugar or enzyme biomolecules.
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