CN103215469B - Porous graphene, Graphene/porous metal composite material and their preparation method - Google Patents
Porous graphene, Graphene/porous metal composite material and their preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of novel porous graphene or Graphene/porous metal composite material and preparation method thereof.Described method comprises: by metal-powder and/or the blended rear blade coating film forming of metal-oxide powder, under reducing atmosphere after high temperature reduction, form three-dimensional porous metal base; And adopt chemical Vapor deposition process growing graphene to obtain Graphene/porous metal composite material.This material as graphene composite material, can have broad application prospects.The preparation of this porous graphene or Graphene/porous metal composite material has original and positive scientific meaning.
Description
Technical field
The invention belongs to graphene composite material technical field, be specifically related to a kind of porous graphene, Graphene/porous metal composite material and their preparation method.
In the present invention, prepare three-dimensional porous metallic membrane by a kind of method of novelty, and it can be used as substrate, obtain high-quality by the method for vapour deposition, Graphene/porous metal composite material that the number of plies is adjustable.The invention still further relates to porous metal film prepared by the different multi-element metal substrate of molten carbon amounts, use principle of dynamics, select suitable temperature of reaction and time to obtain the adjustable Graphene/porous metal composite material of the number of plies.
Technical background
Graphene from being successfully separated, just because the physical property of its excellence causes the broad interest of scientific circles.As electroconductibility best material in the world, the electronic movement velocity in Graphene reaches 1/300 of the light velocity, considerably beyond the conduction of velocity of electronics in general conductor.According to the electroconductibility of its excellence, it is made also to have huge application potential at microelectronic.Grapheme material or a kind of excellent properties-correcting agent in addition, using Graphene as electro-conductive material and various material compound, is applied to new energy field as photovoltaic, energy storage field as lithium ion battery and ultracapacitor, in the fields such as heat radiation, conduction.Due to its highly conc, high-specific surface area, be applicable to as electrode materials auxiliary agent.At present, research and the preparation of Graphene concentrate on low-dimensional Graphene mostly, and especially two-dimensional film graphene film aspect, needs further exploration in the research of three-dimensional grapheme.And the preparation of three-dimensional porous Graphene and matrix material thereof is especially owing to being limited by the restriction of perforated substrate, aperture cannot adjust, complicated process of preparation, and porosity is low.How to prepare aperture adjustable, the simple high-quality three-dimensional porous Graphene of technique and three-dimensional graphene composite material become problem in urgent need to solve.The product that the present invention obtains can be applied to energy storage, photovoltaic, heat radiation numerous areas of Denging, has vast potential for future development.
Summary of the invention
On the one hand, the invention provides a kind of preparation method of Graphene/porous metal composite material, described method comprises:
By metal-powder and/or metal-oxide powder blended, carry out shaping after forming the powder that mixes, carry out high temperature reduction under reducing atmosphere, form three-dimensional porous metal base;
Adopt chemical Vapor deposition process growing graphene in described three-dimensional porous metal base, obtain Graphene/porous metal composite material.
In a preferred embodiment, the preparation method of described Graphene/porous metal composite material also comprises: metal-powder and oxide powder thereof are carried out ground and mixed.
In a preferred embodiment, the preparation method of described Graphene/porous metal composite material also comprises: in the powder mixed, add binding agent, obtain perforated substrate by forming method.
In embodiments of the present invention, described metal-powder is selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and their combinations thereof.The oxide compound of described metal-powder is selected from the oxide compound of above-mentioned metal-powder.
In embodiments of the present invention, described forming method comprises: Mechanical pressing method, spread coating, spin-coating method and their combination.
In embodiments of the present invention, described high temperature reduction carries out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 DEG C, and the reduction reaction time is between 0.1 hour-20 hours.
In embodiments of the present invention, the carbon source that described chemical Vapor deposition process adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas adopted is hydrogen.
In a preferred embodiment, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate, at 0.5-20 DEG C/min, is heated to temperature of reaction 700-1500 DEG C, constant temperature 1-240 minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
Controlling rate of temperature fall is after completion of the reaction 10-50 DEG C/min, is cooled to room temperature.
On the other hand, the invention provides Graphene/porous metal composite material that above-mentioned preparation method obtains.
Another aspect, the invention provides a kind of preparation method of porous graphene, and described method comprises:
By metal-powder and/or metal-oxide powder blended, carry out shaping after forming the powder that mixes, carry out high temperature reduction under reducing atmosphere, form three-dimensional porous metal base;
Adopt chemical Vapor deposition process growing graphene in described three-dimensional porous metal base, obtain Graphene/porous metal composite material;
Under organic protection, Graphene/porous metal composite material is put into etching liquid and removes porous metal substrate, obtain three-dimensional porous Graphene.
In a preferred embodiment, the preparation method of described porous graphene also comprises: metal-powder and oxide powder thereof are carried out ground and mixed.
In a preferred embodiment, the preparation method of described porous graphene also comprises: in the powder mixed, add binding agent, obtain perforated substrate by forming method.
In embodiments of the present invention, described metal-powder is selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and their combinations thereof.The oxide compound of described metal-powder is selected from the oxide compound of above-mentioned metal-powder.
In embodiments of the present invention, described forming method comprises: Mechanical pressing method, spread coating, spin-coating method and their combination.
In embodiments of the present invention, described high temperature reduction carries out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 DEG C, and the reduction reaction time is between 0.1 hour-20 hours.
In embodiments of the present invention, the carbon source that described chemical Vapor deposition process adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas adopted is hydrogen.
In a preferred embodiment, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate, at 0.5-20 DEG C/min, is heated to temperature of reaction 700-1500 DEG C, constant temperature 1-240 minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
Controlling rate of temperature fall is after completion of the reaction 10-50 DEG C/min, is cooled to room temperature.
Again on the one hand, the invention provides the porous graphene that above-mentioned preparation method obtains.
In addition, the invention still further relates to above-mentioned Graphene/porous metal composite material or the application of porous graphene in energy storage material, photovoltaic material and heat sink material.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the Graphene/porous metal composite material in one embodiment of the present invention.
Fig. 2 is Raman (Raman) collection of illustrative plates of the Graphene/porous metal composite material in one embodiment of the present invention.
Fig. 3 is the stereoscan photograph of the porous graphene in one embodiment of the present invention.
Embodiment
In the present invention, contriver is with metal-powder, and metal oxide or its mixture powder, as base material, obtain the adjustable perforated substrate in aperture by the method for blade coating film forming etc., obtain the metallic film of shaping porous through high temperature reduction.Utilize chemical vapour deposition (CVD) method, by the method for direct macroscopic preparation of graphene on the metallic substrate, obtain a kind of Graphene/porous metal composite material.By etching skeleton, porous graphene can be obtained.
In the present invention, the preparation method of described Graphene/porous metal composite material obtains matrix material by being deposited in porous metal substrate by Graphene.Described method specifically comprises:
(1) using the powder of the materials such as metal-powder lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and/or its metal oxide as base material, pass through Mechanical pressing, blade coating, the methods such as spin coating obtain perforated substrate.The preferred spread coating of this programme.Preferably, by adding appropriate binding agent in powder, make uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on insulating substrate of blade coating, put into vacuum drying oven reasonable time at a certain temperature.
(2) sample after oven dry is put into chemical vapor deposition reaction chamber, seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 400-1500 DEG C, after constant temperature 1-180 minute, import hydrogen and rare gas element, gas flow is 1-500sccm (mark condition milliliter per minute), reaction times 1-180 minute.After completion of the reaction, control temperature rise rate is 10-50 DEG C/min, is warming up to 700 DEG C-1500 DEG C, insulation 1-60 minute; Pass into carbon source, and the flow adjusting hydrogen and rare gas element is respectively 1-400sccm and 1-1000sccm, reaction 1-120 minute.After having reacted, stop pass into carbon source, control cooling temperature be 10-50 DEG C/min to room temperature.
In the present invention, in order to obtain three-dimensional porous Graphene, Graphene/porous metal composite material that above-mentioned preparation method obtains is further processed:
(3) etch processes is carried out in Graphene/porous metal composite material organism protection.Etching liquid is by sulfuric acid, and hydrochloric acid, nitric acid, hydrofluoric acid, one or more in the acid solutions such as ammonium persulphate are obtained by mixing according to a certain percentage.Control the concentration of etching liquid at 0.1-5mol/L.After porous material being put into etching liquid certain hour removal skeleton (i.e. porous metal substrate), sample is put in acetone soln and removes organic protection layer, namely obtain three-dimensional porous Graphene.
In described (1), the metallic substance that the preparation of perforated substrate needs is lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh etc. and their combination thereof, and described metal oxide is the oxide compound of above-mentioned metallic substance.
In described (1), one or more metals and/or one or more oxide compounds are mixed with certain proportion, within 0.5 hour-20 hours, obtain the powder mixed through ball milling.
In described (1), the shaping of porous metal substrate is divided into: Mechanical pressing method, spread coating, spin-coating method etc.The preferred spread coating of the present invention.Concrete grammar is: select silica glass, silicon, silicon carbide etc. to carry out blade coating as insulating substrate shaping.By the slurry blade coating film forming mixed, by controlling the thickness of the number of plies controlling diaphragm of adhesive tape.Then sample is put into vacuum drying oven 50-100 DEG C of dry 0.1-4 hour.
In described (1), the binding agent added in powder is propylene glycol, polyvinylidene difluoride (PVDF) (PVDF), PVP (polyvinylpyrrolidone), PEG (polyoxyethylene glycol), PVA (polyvinyl alcohol), PMMA (polymethylmethacrylate) etc. and their mixed solvent.Its ratio accounts for the 0.1%-99% of powder quality, fully the obtained slurry mixed after grinding.Wherein preferably PMMA dissolves in methyl-phenoxide solution that to be configured to massfraction be 3%PMMA binding agent.
In described (2), high temperature reduction reaction need be heated to temperature of reaction 400-1500 DEG C, and after constant temperature 10-30 minute, import hydrogen and rare gas element, gas flow is respectively 1-300sccm and 1-500sccm, reaction times 1-180 minute.
In described (2), the carbon source that chemical Vapor deposition process adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture.The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gas mixture.The reducing gas (division gas) adopted is hydrogen.
In described (2), temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Then carry out being heated to temperature of reaction 800-1500 DEG C, after constant temperature 1-240 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction times 1-480 minute reacts complete, and control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
In described (3), use the methyl-phenoxide solution of 3%PMMA as protective material.Etching liquid selects the sulfuric acid of concentration 0.1-5mol/L, hydrochloric acid, nitric acid, hydrofluoric acid, the acid solutions such as ammonium persulphate or its mixing solutions.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.But, should be understood that these embodiments only do not form limitation of the scope of the invention for illustration of the present invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all per-cent and number are by weight.
Embodiment 1
Commercially available high pure metal powder Co and CoO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material, the stereoscan photograph of sample and Raman spectrum are as depicted in figs. 1 and 2.Stereoscan photograph can see the fold of Graphene, shows that graphene growth is on stephanoporate framework.Fig. 2 is the Raman collection of illustrative plates of Graphene under different growth time, proves that controlling different experiment conditions can obtain the controlled Graphene of the number of plies.
By the PMMA protection of 3% of Graphene/porous metal composite material, put in the HF solution of 1mol/L and etch away skeleton; Then put into acetone soln to dissolve PMMA and obtain three-dimensional porous Graphene.The scanning electron microscope of three-dimensional porous Graphene sample as shown in Figure 3.Can find out from electromicroscopic photograph, after removing skeleton, Graphene still remains three-dimensional porous structure.
Embodiment 2
Metal-powder Cu and CuO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
By the PMMA protection of 3% of Graphene/porous metal composite material, put in the HF solution of 1mol/L and etch away skeleton; Then put into acetone soln to dissolve PMMA and obtain three-dimensional porous Graphene.In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph and Raman spectrum are shown in Fig. 1, Fig. 2 and Fig. 3) close, confirm the Graphene/porous metal composite material needed for obtaining or porous graphene.
Embodiment 3
Commercially available high pure metal powder Ni and NiO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
By the PMMA protection of 3% of Graphene/porous metal composite material, put in the HF solution of 1mol/L and etch away skeleton; Then put into acetone soln to dissolve PMMA and obtain three-dimensional porous Graphene.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1, Fig. 2 and Fig. 3), confirms the Graphene/porous metal composite material needed for obtaining or porous graphene.
Embodiment 4
By commercially available high pure metal powder Fe and Fe
2o
3powder body material mixes and ball milling 0.5 hour with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1, obtains the powder mixed, and by adding the binding agent of massfraction 45%, makes uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 5
Commercially available high pure metal powder Cu and NiO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 6
Commercially available high pure metal powder Cu and CoO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 7
Mixing commercially available high pure metal powder Fe and CuO powder body material with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 8
By commercially available high pure metal powder Ni and Fe
2o
3powder body material mixes and ball milling 0.5 hour with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1, obtains the powder mixed, and by adding the binding agent of massfraction 45%, makes uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 9
Commercially available high pure metal powder Fe and oO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
Embodiment 10
Commercially available high pure metal powder W and CuO powder body material are mixed with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, obtaining the powder mixed, by adding the binding agent of massfraction 45%, making uniform slurry through grinding.By the slurry for preparing by method blade coating film forming on quartzy end liner of blade coating, at 70 DEG C, put into vacuum drying oven 2 hours.
Sample after drying is put into chemical vapor deposition reaction chamber, and seal and check pyroreaction chamber air-tightness, discharging residual gas in pyroreaction room under protective atmosphere, then carry out temperature programming, temperature rise rate is at 0.5-20 DEG C/min.Be heated to temperature of reaction 500 DEG C, 600 DEG C, 700 DEG C, constant temperature is after 10 minutes, regulate hydrogen and inert gas flow, gas flow is respectively 50sccm, 70sccm, 90sccm and 150sccm, 200sccm, 250sccm, 50 minutes reaction times, 60 minutes, 70 minutes.After completion of the reaction, controlling temperature rise rate is 10 DEG C/min, is warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, is incubated 10 minutes, 30 minutes, 60 minutes; Pass into 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity to 10sccm, 20sccm50sccm, calm the anger flow 300sccm, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times.Reaction terminates rear stopping and passing into methane, keeps the flow of hydrogen and argon gas constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature.Obtain Graphene/porous metal composite material.
In the stereoscan photograph of this embodiment gained sample and Raman spectrum and embodiment 1, sample gained stereoscan photograph is close with Raman spectrum (see Fig. 1 and Fig. 2), confirms the Graphene/porous metal composite material needed for obtaining.
After having read above-mentioned teachings of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Claims (13)
1. a preparation method for Graphene/porous metal composite material, described method comprises:
By metal-powder and metal-oxide powder blended, carry out shaping after forming the powder that mixes, carry out high temperature reduction under reducing atmosphere, form three-dimensional porous metal base;
Adopt chemical Vapor deposition process growing graphene in described three-dimensional porous metal base, obtain Graphene/porous metal composite material;
Wherein, described metal-powder is selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and they combine one or more;
Described high temperature reduction carries out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 DEG C, and the reduction reaction time is between 0.1 hour-20 hours; And
Described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate, at 0.5-20 DEG C/min, is heated to temperature of reaction 700-1500 DEG C, constant temperature 1-240 minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
Controlling rate of temperature fall is after completion of the reaction 10-50 DEG C/min, is cooled to room temperature.
2. the preparation method of Graphene/porous metal composite material as claimed in claim 1, it is characterized in that, described method also comprises:
Metal-powder and oxide powder thereof are carried out ground and mixed.
3. the preparation method of Graphene/porous metal composite material as claimed in claim 1, it is characterized in that, described method also comprises:
In the powder mixed, add binding agent, obtain perforated substrate by forming method.
4. the preparation method of Graphene/porous metal composite material as claimed in claim 2, it is characterized in that, described forming method comprises: Mechanical pressing method, spread coating, spin-coating method and their combination.
5. the preparation method of Graphene/porous metal composite material according to claim 1, is characterized in that, the carbon source that described chemical Vapor deposition process adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas adopted is hydrogen.
6. according to Graphene/porous metal composite material that preparation method described in any one of claim 1-5 obtains.
7. a preparation method for porous graphene, described method comprises:
By metal-powder and metal-oxide powder blended, carry out shaping after forming the powder that mixes, carry out high temperature reduction under reducing atmosphere, form three-dimensional porous metal base;
Adopt chemical Vapor deposition process growing graphene in described three-dimensional porous metal base, obtain Graphene/porous metal composite material;
Under organic protection, Graphene/porous metal composite material is put into etching liquid and removes porous metal substrate, obtain three-dimensional porous Graphene;
Wherein, described metal-powder is selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and they combine one or more;
Described high temperature reduction carries out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 DEG C, and the reduction reaction time is between 0.1 hour-20 hours; And
Described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate, at 0.5-20 DEG C/min, is heated to temperature of reaction 700-1500 DEG C, constant temperature 1-240 minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
Controlling rate of temperature fall is after completion of the reaction 10-50 DEG C/min, is cooled to room temperature.
8. the preparation method of porous graphene as claimed in claim 7, it is characterized in that, described method also comprises:
Metal-powder and oxide powder thereof are carried out ground and mixed.
9. the preparation method of porous graphene as claimed in claim 7, it is characterized in that, described method also comprises:
In the powder mixed, add binding agent, obtain perforated substrate by forming method.
10. the preparation method of porous graphene as claimed in claim 8, it is characterized in that, described forming method comprises: Mechanical pressing method, spread coating, spin-coating method and their combination.
The preparation method of 11. porous graphenes according to claim 7, it is characterized in that, the carbon source that described chemical Vapor deposition process adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas adopted is hydrogen.
12. porous graphenes obtained according to preparation method described in any one of claim 7-11.
The application of porous graphene in energy storage material, photovoltaic material and heat sink material described in Graphene/porous metal composite material described in 13. claims 6 or claim 12.
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