CN103213980B - The preparation method of three-dimensional grapheme or its compound system - Google Patents
The preparation method of three-dimensional grapheme or its compound system Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of three-dimensional grapheme or its compound system, comprise: get transition metal simple substance and/or be raw material containing the compound of transition metal, through high temperature reduction, prepare three-dimensional porous metal catalyst template, utilize chemical Vapor deposition process growing three-dimensional Graphene, obtain the three-dimensional grapheme with catalyst backbone.Further, also can etching processing with the three-dimensional grapheme of catalyst backbone, obtain three-dimensional grapheme powder.Further, also three-dimensional grapheme powder and metal, macromolecular material, biomolecules material etc. are compounded to form composite system.Present invention process is simple, can realize high quality, density three-dimensional Graphene or its matrix material quick, prepare in a large number, in water treatment, biological medicine, energy produces and transforms and energy storage device, antistatic, heat management, heat conduction and heat radiation, sensor, electromagnetic shielding, inhales the aspect such as ripple and catalysis and has wide application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, particularly relate to the preparation method of a kind of high quality three-dimensional grapheme or its compound system.
Background technology
Graphene is that monolayer carbon atom is with sp
2form piles up the cellular two dimensional crystal formed.Graphene has large specific surface area and excellent electricity, calorifics and mechanical property.Since Graphene is found, develop multiple preparation method, comprise mechanically peel method, SiC or metal single crystal surface epitaxial growth method, chemical oxidation stripping method, intercalation stripping method and chemical vapour deposition (CVD) method etc.Wherein be considered to most potential method and have chemical oxidation stripping method and CVD.By chemical oxidation stripping method, people prepare paper-like grapheme material, Graphene flexible transparent conductive film and three-dimensional porous body material, but, the Graphene body material prepared based on chemical oxidation stripping method is non-carbon functional group and defect because preparation process introduces, and greatly reduces the conductivity of Graphene.Comparatively speaking, CVD is a kind of method of synthesizing high-quality graphene.But current CVD method is substrate mainly with catalyst film, obtain the graphene film of two dimensional surface, although be suitable for the application of electron device and transparent conductive film, be difficult to the requirement meeting magnanimity application.
Three-dimensional grapheme is the tridimensional network be cross-linked to form by space based on the graphene film of two dimension, and except the proper property with two-dimensional graphene, three-dimensional graphite is in space heat conduction, and conduction and magnanimity high quality are prepared aspect and had unique advantage.2011, it was the three-dimensional grapheme of masterplate that Cheng Huiming group of Shenyang metal institute obtains with nickel foam, and this three-dimensional grapheme and silicon rubber compound system show excellent electroconductibility and mechanical property.Afterwards, three-dimensional grapheme causes interest and concern widely.At present, three-dimensional grapheme is Template preparation mainly with nickel foam, take nickel foam as template, and the three-dimensional grapheme of CVD growth, as the electrode of ultracapacitor, improves energy density and the power density of electrical condenser; As gas sensing passage, there is the sensitivity of ppb level; As electrochemical electrode, embody high electro catalytic activity and lower than 10
-9mol concentration Electrochemical Detection ability.But nickel foam has the network hole of hundreds of micron, very low with the Graphene volume density that this template grows, limit the requirement of its preparation in macroscopic quantity.
Summary of the invention
The object of the present invention is to provide the novel processing step of a kind of three-dimensional grapheme or its compound system, it can realize high-density, high-quality three-dimensional grapheme or its matrix material quick, prepare in a large number, thus overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
The preparation method of a kind of three-dimensional grapheme or its compound system, comprise: get transition metal simple substance and/or be raw material containing the compound of transition metal, through high temperature reduction, prepare three-dimensional porous metal catalyst template, utilize chemical Vapor deposition process growing three-dimensional Graphene, obtain the three-dimensional grapheme with catalyst backbone.
Aforementioned three-dimensional porous metal catalyst template cording has three-dimensional cross-linked structure, and its aperture is 100 nm-100 μm.
In the Graphene of aforementioned strip catalyst backbone, the aperture of contained hole is 100 nm-500 μm.
As one of scheme that can implement, the method also can comprise: by transition metal simple substance and/or be filled in macrocellular foam metal form containing the compound of transition metal, after high temperature reduction, obtains three-dimensional porous metal catalyst template.
The aperture of aforementioned macrocellular foam metal catalyst contained hole is 100 nm-500 μm.
The described compound containing 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 transition metal salt hydrate, it can be dried or the microwave heating water that decrystallizes obtains Anhydrous transition metal-salt or directly carry out high temperature reduction at 50-300 DEG C.
As one of comparatively preferred embodiment, described high temperature reduction is carry out in the reducing atmosphere of 100-1000 DEG C in temperature, and described reducing atmosphere forms primarily of hydrogen or hydrogen and rare gas element.
As more specifically one of application scheme, described reducing atmosphere is argon gas and the hydrogen composition of 0-500:10-1000 primarily of throughput ratio.
As one of comparatively preferred embodiment, the processing condition of described chemical Vapor deposition process comprise: growth temperature is 400-1200 DEG C, 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 introduced comprises solid phase, 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, the polymkeric substance such as polydimethylsiloxane, glucose, sucrose, fructose, the carbohydrates and decolorizing carbon and composition thereof such as Mierocrystalline cellulose; Phase carbon source can be selected from but be not limited to methyl alcohol, ethanol, propyl alcohol, aromatic hydrocarbon and composition thereof; 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 comparatively preferred embodiment, the method also comprises: carry out etching processing to the three-dimensional grapheme with catalyst backbone, obtain three-dimensional grapheme powder, wherein, it is the solution of any one or two or more mixtures in the sulfuric acid of 0.05-6 M, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, ammonium persulphate and Marble reagent that the etching solution that etching processing adopts can be selected containing concentration.
As one of comparatively preferred embodiment, in aforementioned etch processes, also adopt high molecular polymer to protect three-dimensional grapheme, described high molecular polymer comprises polymethylmethacrylate, polyethylene, polystyrene or polypropylene.
As one of comparatively preferred embodiment, the method also can comprise: get three-dimensional grapheme at least with any one compound in metallic particles, metal oxide, metal-salt, polymkeric substance and biomolecules, form three-dimensional grapheme compound system, wherein, the method for described compound comprises physical mixed, in-situ chemical reaction mixing, galvanic deposit or electrochemical reaction.
Wherein, contained by described metallic particles, metal oxide or metal-salt, metallic element 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, epoxy resin, 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 at least has following advantages: the preparation method of this three-dimensional grapheme or its compound system can realize three-dimensional grapheme or its matrix material quick, prepare in a large number, and the three-dimensional grapheme that obtains has hole little (100 nm-100 μm), density (can be greater than 100 mg/cm greatly
3), the advantage such as high connductivity (specific conductivity is 1-50 S/cm), this three-dimensional grapheme and compound system thereof in water treatment, biological medicine, energy produces and transforms and energy storage device, antistatic, heat management, heat conduction and heat radiation, sensor, electromagnetic shielding, inhales the aspect such as ripple and catalysis and has wide practical use.
Accompanying drawing explanation
Figure 1A-Fig. 1 C be respectively the embodiment of the present invention 1 obtain the optics picture of three-dimensional grapheme sample and SEM figure;
Fig. 2 be the embodiment of the present invention 1 obtain three-dimensional grapheme sample Raman figure;
Fig. 3 be the embodiment of the present invention 4 obtain the optics picture of three-dimensional grapheme and PDMS compound system;
Fig. 4 be the embodiment of the present invention 7 obtain three-dimensional grapheme and ferric oxide compound system SEM scheme.
Embodiment
As previously mentioned, in view of the deficiencies in the prior art, the invention provides the novel processing step of a kind of three-dimensional grapheme or its matrix material.
Generally, method of the present invention be adopt self-control small catalyst maybe self-control small catalyst is filled in macrocellular foam metal be template, utilize CVD method to prepare high-density, high-quality three-dimensional grapheme powder, is then compounded to form compound system with metallic particles, metal oxide, metal-salt, polymkeric substance or biomolecules etc.
Further say, 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 for raw material (namely, presoma), transition salt hydrate heating, drying or microwave heating are decrystallized after water treatment and obtain Anhydrous transition metal-salt or above presoma is filled in macrocellular foam metal matrix, reduce under hot environment and suitable atmosphere, the final three-dimensional cross-linked metal catalyst template obtained.Then chemical Vapor deposition process is adopted to prepare high-quality three-dimensional grapheme powder, with metallic particles, metal oxide and polymer formation compound system.
Three-dimensional grapheme that the present invention obtains has good conductivity, specific surface area is large, density high, and this three-dimensional grapheme and compound system thereof are in water treatment, biological medicine, energy produces and transforms and energy storage device, antistatic, heat management, heat conduction and heat radiation, sensor, electromagnetic shielding, inhales the aspect such as ripple and catalysis and has wide practical use.
Below in conjunction with some preferred embodiments, technical scheme of the present invention is further described.
one, the preparation of high quality three-dimensional grapheme:
embodiment 1:5g copper powder is joined polymethylmethacrylate (PMMA:4%) and sample is put into silica tube, and pass into argon gas 15 min.Tube furnace is raised to 900 DEG C, atmosphere is: hydrogen: 200 sccm, argon gas: 100 sccm; Air pressure remains on: 10 torr.After waiting to grow, logical argon gas 200 sccm is until silica tube cooling.Again the sample grown is put into 1M FeCl
3etch in/0.1M HCl solution, obtain three-dimensional grapheme.
embodiment 2:5 g nickel powders are added to polymethylmethacrylate (PMMA:4%) sample is put into silica tube, and pass into argon gas 15 min.Tube furnace is raised to 900 DEG C, atmosphere is: hydrogen: 200 sccm, argon gas: 100 sccm; Air pressure remains on: 10 torr.After waiting to grow, logical argon gas 200sccm is until silica tube cooling.Again the sample grown is put into 1M FeCl
3etch in/0.1M HCl solution, obtain three-dimensional grapheme.
embodiment 3:put in tube furnace by the nickelous chloride of 20g, 600 DEG C keep 10 min, and atmosphere is: hydrogen: 300 sccm, argon gas: 100 sccm.Again tube furnace is raised to 1000 DEG C, 1000 DEG C time, keep 10 min, now atmosphere is: methane: 30 sccm, hydrogen: 200 sccm, argon gas: 200 sccm.Silica tube is taken out and is cooled to room temperature.Use 1M FeCl
3/ 0.1M HCl etches, and finally obtains three-dimensional high-quality graphene sample.
two, the preparation of high quality three-dimensional grapheme compound system:
embodiment 4: 1 g PDMS prepolymer and 0.1 g solidifying agent mix, and are soaked in mixed solution by 20 mg three-dimensional graphemes, 25 DEG C of degassed 2 h, and 80 DEG C of solidification 8 h, obtain the compound system of silicon rubber and three-dimensional grapheme.
embodiment 5:epoxy resin and curing agent mixture 2 ml add in 10 mg three-dimensional grapheme network structures, and after 80 DEG C of vacuum outgas 2 h, 120 DEG C of solidification 6 h obtain epoxy resin and three-dimensional graphene composite material matrix material.
embodiment 6:10 mg three-dimensional graphemes are immersed in 1 ml aniline solution or pyrroles or thiophene solution after soaking 2 h, the Graphene after soaking is joined 1 ml 0.1 M FeCl
3in solution, react 24 h under room temperature, product is successively after deionized water and after ethanol fully washs, and 60 DEG C of vacuum-drying obtains polyaniline or polypyrrole or Polythiophene and three-dimensional grapheme combination product.
embodiment 710 mg three-dimensional graphemes are immersed 1M FeCl
3in solution, after soaking 1 h, lyophilize, at 600 DEG C, anneal under argon gas atmosphere 1h, obtains three-dimensional grapheme/Fe
2o
3compound system.
More than illustrate, and the embodiment shown on drawing, the design philosophy surely of the present invention that is limited can not be resolved.Hold in technical field of the present invention identical know the knowledgeable can by technical thought of the present invention with various form improvement change, such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (9)
1. a preparation method for three-dimensional grapheme or its compound system, is characterized in that, comprising:
Get transition metal simple substance and/or be raw material containing the compound of transition metal, be carry out high temperature reduction in the reducing atmosphere of 100-1000 DEG C in temperature, prepare three-dimensional porous metal catalyst template, the wherein said compound containing transition metal is selected from transition metal oxide or transition metal salt or its hydrate;
Recycle three-dimensional porous metal catalyst template, with chemical Vapor deposition process growing three-dimensional Graphene, obtain the three-dimensional grapheme with catalyst backbone;
And carry out etching processing to the three-dimensional grapheme with catalyst backbone, obtain three-dimensional grapheme powder, the hole in described three-dimensional grapheme powder is 100nm-100 μm, and density is greater than 100mg/cm
3, specific conductivity is 1-50S/cm.
2. the preparation method of three-dimensional grapheme according to claim 1 or its compound system, it is characterized in that, the method also comprises: by transition metal simple substance and/or be filled in macrocellular foam metal form containing the compound of transition metal, after high temperature reduction, obtain three-dimensional porous metal catalyst template.
3. the preparation method of three-dimensional grapheme according to claim 1 and 2 or its compound system, is characterized in that, described transition metal is selected from Fe, Cu, Co, Ni, Pt or Ru.
4. the preparation method of three-dimensional grapheme according to claim 1 and 2 or its compound system, is characterized in that, described reducing atmosphere forms primarily of hydrogen or hydrogen and rare gas element.
5. the preparation method of three-dimensional grapheme according to claim 4 or its compound system, is characterized in that, described reducing atmosphere is argon gas and the hydrogen composition of 0-500:10-1000 primarily of throughput ratio.
6. the preparation method of three-dimensional grapheme 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 DEG C, and growth time is 30s-2h, and growth pressure is 1torr-800torr.
7. the preparation method of three-dimensional grapheme according to claim 1 or its compound system, it is characterized in that, it is the solution of any one or two or more mixtures in the sulfuric acid of 0.05-6M, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, ammonium persulphate and Marble reagent that the etching solution that etching processing adopts comprises containing concentration.
8. the preparation method of three-dimensional grapheme according to claim 1 or its compound system, it is characterized in that, the method also comprises: get three-dimensional grapheme at least with any one compound in metallic particles, metal oxide, metal-salt, polymkeric substance and biomolecules, form three-dimensional grapheme compound system, wherein, the method for described compound comprises physical mixed, in-situ chemical reaction mixing, galvanic deposit or electrochemical reaction.
9. the preparation method of three-dimensional grapheme according to claim 8 or its compound system, is characterized in that,
Contained by described metallic particles, metal oxide or metal-salt, metallic element comprises Au, Ag, Fe, Cu, Co, Ni, Pt, Mn or Ru;
Described polymkeric substance comprises polyaniline, polypyrrole, Polythiophene, epoxy resin, 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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