CN103215469A - Porous graphene, graphene/porous metal composite material, and preparation methods of porous graphene and composite material - Google Patents
Porous graphene, graphene/porous metal composite material, and preparation methods of porous graphene and composite material Download PDFInfo
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Abstract
The invention relates to a novel porous graphene or a graphene/porous metal composite material, and preparation methods of the porous graphene and the composite material. The preparation method of the composite material comprises the following steps: blending metal powder and/or metal oxide powder, blade-coating to form a film, and carrying out high temperature reduction in a reducing atmosphere to form a three-dimensional porous metal substrate; and growing graphene through adopting a chemical vapor deposition process to obtain the graphene/porous metal composite material. The material is a graphene composite material and has a wide application prospect. The preparation of the porous graphene or the graphene/porous metal composite material has an original creativity and is of positive scientific significance.
Description
Technical field
The invention belongs to the graphene composite material technical field, be specifically related to a kind of porous graphite alkene, Graphene/porous metal composite material and their preparation method.
In the present invention, the method by a kind of novelty prepares three-dimensional porous metallic membrane, and with it as substrate, the method by vapour deposition obtains high-quality, Graphene/porous metal composite material that the number of plies is adjustable.The invention still further relates to the porous metal film of the different multi-element metal substrate preparation of molten carbon amount, the utilization principle of dynamics selects suitable reaction temperature and time to obtain the adjustable Graphene/porous metal composite material of the number of plies.
Technical background
Graphene is just caused the extensive interest of scientific circles from successfully separating because of its excellent physical characteristics.As electroconductibility best material in the world, the electronic movement velocity in the Graphene has reached 1/300 of the light velocity, considerably beyond the conduction of velocity of electronics in general conductor.According to its excellent electroconductibility, make it also have huge application potential at microelectronic.Grapheme material still is a kind of good properties-correcting agent in addition, and is compound as electro-conductive material and various material Graphene, is applied to new energy field such as photovoltaic, and energy storage field such as lithium ion battery and ultracapacitor are in the fields such as heat radiation, conduction.Because its highly conc, high-specific surface area, applicable to as the electrode materials auxiliary agent.At present, the research of Graphene and preparation concentrate on low-dimensional Graphene, especially two-dimensional film graphene film aspect mostly, need further exploration in the research to three-dimensional Graphene.And the preparation of three-dimensional porous Graphene and matrix material thereof is especially owing to be limited by the restriction of porous substrate, and the aperture can't be adjusted, complicated process of preparation, and porosity is low.It is adjustable how to prepare the aperture, and simple high-quality three-dimensional porous Graphene of technology and three-dimensional graphene composite material become the problem that urgent need will solve.The product that the present invention obtains can be applied to energy storage, photovoltaic, and numerous areas such as heat radiation have 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:
With metal-powder and/or metal-oxide powder blend, carry out moulding behind the powder that formation mixes, under reducing atmosphere, carry out high temperature reduction, form three-dimensional porous metal base;
Adopt the chemical Vapor deposition process Graphene of on described three-dimensional porous metal base, growing, 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: add binding agent in the powder that mixes, obtain the porous substrate by forming method.
In embodiments of the present invention, described metal-powder is to be 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 pressed disc method, spread coating, spin-coating method and their combination.
In embodiments of the present invention, described high temperature reduction is to carry out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 ℃, 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 adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas that adopts is a hydrogen.
In preferred embodiment, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate are heated to temperature of reaction 700-1500 ℃, constant temperature 1-240 minute at 0.5-20 ℃/minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
The control rate of temperature fall was 10-50 ℃/minute after reaction finished, and was cooled to room temperature.
On the other hand, the invention provides Graphene/porous metal composite material that above-mentioned preparation method makes.
Another aspect the invention provides a kind of preparation method of porous graphite alkene, and described method comprises:
With metal-powder and/or metal-oxide powder blend, carry out moulding behind the powder that formation mixes, under reducing atmosphere, carry out high temperature reduction, form three-dimensional porous metal base;
Adopt the chemical Vapor deposition process Graphene of on described three-dimensional porous metal base, growing, obtain Graphene/porous metal composite material;
Under organic protection, Graphene/porous metal composite material is put into etching liquid remove the porous metal substrate, obtain three-dimensional porous Graphene.
In a preferred embodiment, the preparation method of described porous graphite alkene also comprises: metal-powder and oxide powder thereof are carried out ground and mixed.
In a preferred embodiment, the preparation method of described porous graphite alkene also comprises: add binding agent in the powder that mixes, obtain the porous substrate by forming method.
In embodiments of the present invention, described metal-powder is to be 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 pressed disc method, spread coating, spin-coating method and their combination.
In embodiments of the present invention, described high temperature reduction is to carry out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 ℃, 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 adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas that adopts is a hydrogen.
In preferred embodiment, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate are heated to temperature of reaction 700-1500 ℃, constant temperature 1-240 minute at 0.5-20 ℃/minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
The control rate of temperature fall was 10-50 ℃/minute after reaction finished, and was cooled to room temperature.
On the one hand, the invention provides the porous graphite alkene that above-mentioned preparation method makes again.
In addition, the invention still further relates to above-mentioned Graphene/porous metal composite material or the application of porous graphite alkene in energy storage material, photovoltaic material and heat sink material.
Description of drawings
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 graphite alkene in one embodiment of the present invention.
Embodiment
In the present invention, the contriver is with metal-powder, and metal oxide or its mixture powder be as base material, and the method by blade coating film forming etc. obtains the adjustable porous substrate in aperture, obtains moulding porous metallic film through high temperature reduction.Utilize the chemical vapor deposition (CVD) method, by on metal base directly magnanimity prepare the method for Graphene, obtain a kind of Graphene/porous metal composite material.By the etching skeleton, can obtain porous graphite alkene.
In the present invention, the preparation method of described Graphene/porous metal composite material obtains matrix material by Graphene is deposited in the porous metal substrate.Described method specifically comprises:
(1) with the powder of 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, by mechanical compressing tablet, blade coating, methods such as spin coating obtain the porous substrate.The preferred spread coating of this programme.Preferably, by in powder, adding an amount of binding agent, make uniform slurry through grinding.The slurry for preparing is passed through method blade coating film forming on the insulation end liner of blade coating, put into the vacuum drying oven reasonable time at a certain temperature.
(2) sample after will drying is put into chemical vapor deposition reaction chamber, and the pyroreaction chamber air-tightness is also checked in sealing, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to temperature of reaction 400-1500 ℃, after constant temperature 1-180 minute, import hydrogen and rare gas element, gas flow is 1-500sccm (a mark condition milliliter per minute), reaction times 1-180 minute.After reaction finished, the control temperature rise rate was 10-50 ℃/minute, is warming up to 700 ℃-1500 ℃, is incubated 1-60 minute; Feed carbon source, and the flow of adjusting hydrogen and rare gas element is respectively 1-400sccm and 1-1000sccm, reacted 1-120 minute.After reaction is finished, stop to feed carbon source, control cooling temperature be 10-50 ℃/minute 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) Graphene/porous metal composite material is carried out etch processes with the organism protection.Etching liquid is by sulfuric acid, hydrochloric acid, and nitric acid, hydrofluoric acid, one or more in the acid solutions such as ammonium persulphate mix according to a certain percentage and get.The concentration of control etching liquid is at 0.1-5mol/L.After porous material put into the etching liquid certain hour and remove skeleton (being the porous metal substrates), sample put into remove organic protection layer in the acetone soln, promptly obtain three-dimensional porous Graphene.
In described (1), the metallic substance that the preparation of porous 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 the powder that the process ball milling obtained mixing in 0.5 hour-20 hours with certain proportion.
In described (1), the moulding of porous metal substrate is divided into: mechanical pressed disc method, spread coating, spin-coating method or the like.The preferred spread coating of the present invention.Concrete grammar is: select for use silica glass, silicon, silicon carbide etc. to carry out the blade coating moulding as insulating substrate.With the slurry blade coating film forming that mixes, by the thickness of number of plies controlling diaphragm of control adhesive tape.Then sample is put into vacuum drying oven 50-100 ℃ dry 0.1-4 hour.
In described (1), the binding agent that adds 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, makes the slurry that mixes after fully grinding.Wherein preferred PMMA dissolves in that to be configured to massfraction in the methyl-phenoxide solution be the 3%PMMA binding agent.
In described (2), the high temperature reduction reaction need be heated to temperature of reaction 400-1500 ℃, after constant temperature 10-30 minute, imports hydrogen and rare gas element, and 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 adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture.The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gas mixture.The reducing gas (division gas) that adopts is a hydrogen.
In described (2), temperature programming, temperature rise rate is at 0.5-20 ℃/minute.Be heated to temperature of reaction 800-1500 ℃ then, after constant temperature 1-240 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction times 1-480 minute, reaction finished, and the control rate of temperature fall is 10-50 ℃/minute, is cooled to room temperature.
In described (3), the methyl-phenoxide solution that uses 3%PMMA is as protective material.Etching liquid is selected the sulfuric acid of concentration 0.1-5mol/L, hydrochloric acid, nitric acid, hydrofluoric acid, acid solution or its mixing solutionss such as ammonium persulphate for use.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.But, should be understood that these embodiment only are used to the present invention is described and do not constitute limitation of the scope of the invention.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all per-cent and umber are by weight.
Embodiment 1
Commercially available high pure metal powder Co and CoO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.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 be seen the fold of Graphene, shows that Graphene is grown on stephanoporate framework.Fig. 2 is the Raman collection of illustrative plates of Graphene under the different growth time, proves that the different experiment condition of control can obtain the controlled Graphene of the number of plies.
Graphene/porous metal composite material with 3% PMMA protection, is put in the HF solution of 1mol/L and etched away skeleton; Put into the molten PMMA of going of acetone soln then and obtain three-dimensional porous Graphene.The scanning electron microscope of three-dimensional porous Graphene sample as shown in Figure 3.Can find out that from electromicroscopic photograph Graphene is still keeping three-dimensional porous structure behind the removal skeleton.
Embodiment 2
Metal-powder Cu and CuO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Graphene/porous metal composite material with 3% PMMA protection, is put in the HF solution of 1mol/L and etched away skeleton; Put into the molten PMMA of going of acetone soln then and obtain three-dimensional porous Graphene.Sample gained stereoscan photograph and Raman spectrum are seen Fig. 1, Fig. 2 and Fig. 3 among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1) close, confirm to obtain required Graphene/porous metal composite material or porous graphite alkene.
Embodiment 3
Commercially available high pure metal powder Ni and NiO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Graphene/porous metal composite material with 3% PMMA protection, is put in the HF solution of 1mol/L and etched away skeleton; Put into the molten PMMA of going of acetone soln then and obtain three-dimensional porous Graphene.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1, Fig. 2 and Fig. 3) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material or porous graphite alkene.
Embodiment 4
With commercially available high pure metal powder Fe and Fe
2O
3Powder body material mixes with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, and the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 5
Commercially available high pure metal powder Cu and NiO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 6
Commercially available high pure metal powder Cu and CoO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 7
With mixing and ball milling 0.5 hour with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 of commercially available high pure metal powder Fe and CuO powder body material, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 8
With commercially available high pure metal powder Ni and Fe
2O
3Powder body material mixes with mass ratio 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, and the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 9
Commercially available high pure metal powder Fe and oO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
Embodiment 10
Commercially available high pure metal powder W and CuO powder body material mixed with mass ratio in 1: 1,2: 1,3: 1,4: 1,5: 1 and ball milling 0.5 hour, the powder that obtains mixing by adding the binding agent of massfraction 45%, is made uniform slurry through grinding.With the slurry for preparation method blade coating film forming on quartzy end liner, under 70 ℃, put into vacuum drying oven 2 hours by blade coating.
Sample after the oven dry is put into chemical vapor deposition reaction chamber, and sealing is also checked the pyroreaction chamber air-tightness, discharges residual gas in the pyroreaction chamber under protective atmosphere, carries out temperature programming then, and temperature rise rate is at 0.5-20 ℃/minute.Be heated to 500 ℃ of temperature of reaction, 600 ℃, 700 ℃, behind the constant temperature 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 reaction finished, the control temperature rise rate was 10 ℃/minute, is warming up to 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, is incubated 10 minutes, 30 minutes, 60 minutes; Feed 1sccm, 5sccm, 10sccm, 20sccm methane afterwards, regulate hydrogen flowing quantity, the flow 300sccm that calms the anger, 10 minutes, 20 minutes, 30 minutes, 60 minutes respectively reaction times to 10sccm, 20sccm50sccm.Reaction stops to feed methane after finishing, and keeps the flow of hydrogen and argon gas constant, and the control rate of temperature fall is 10 ℃/minute and drops to 400 ℃, naturally cools to room temperature then.Obtain Graphene/porous metal composite material.
Sample gained stereoscan photograph and Raman spectrum (seeing Fig. 1 and Fig. 2) are close among the stereoscan photograph of this embodiment gained sample and Raman spectrum and the embodiment 1, confirm to obtain required Graphene/porous metal composite material.
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 institute restricted portion equally.
Claims (19)
1. the preparation method of a Graphene/porous metal composite material, described method comprises:
With metal-powder and/or metal-oxide powder blend, carry out moulding behind the powder that formation mixes, under reducing atmosphere, carry out high temperature reduction, form three-dimensional porous metal base;
Adopt the chemical Vapor deposition process Graphene of on described three-dimensional porous metal base, growing, obtain Graphene/porous metal composite material.
2. the preparation method of Graphene/porous metal composite material as claimed in claim 1 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 is characterized in that, described method also comprises:
In the powder that mixes, add binding agent, obtain the porous substrate by forming method.
4. the preparation method of Graphene/porous metal composite material as claimed in claim 1, it is characterized in that described metal-powder is to be selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and they make up one or more.
5. the preparation method of Graphene/porous metal composite material as claimed in claim 2 is characterized in that, described forming method comprises: mechanical pressed disc method, spread coating, spin-coating method and their combination.
6. the preparation method of Graphene/porous metal composite material according to claim 1 is characterized in that, described high temperature reduction is to carry out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 ℃, and the reduction reaction time is between 0.1 hour-20 hours.
7. 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 adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas that adopts is a hydrogen.
8. the preparation method of Graphene/porous metal composite material according to claim 1 is characterized in that, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate are heated to temperature of reaction 700-1500 ℃, constant temperature 1-240 minute at 0.5-20 ℃/minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
The control rate of temperature fall was 10-50 ℃/minute after reaction finished, and was cooled to room temperature.
9. Graphene/the porous metal composite material that makes according to each described preparation method of claim 1-8.
10. the preparation method of a porous graphite alkene, described method comprises:
With metal-powder and/or metal-oxide powder blend, carry out moulding behind the powder that formation mixes, under reducing atmosphere, carry out high temperature reduction, form three-dimensional porous metal base;
Adopt the chemical Vapor deposition process Graphene of on described three-dimensional porous metal base, growing, obtain Graphene/porous metal composite material;
Under organic protection, Graphene/porous metal composite material is put into etching liquid remove the porous metal substrate, obtain three-dimensional porous Graphene.
11. the preparation method as porous graphite alkene as described in the claim 10 is characterized in that described method also comprises:
Metal-powder and oxide powder thereof are carried out ground and mixed.
12. the preparation method as porous graphite alkene as described in the claim 10 is characterized in that described method also comprises:
In the powder that mixes, add binding agent, obtain the porous substrate by forming method.
13. the preparation method as porous graphite alkene as described in the claim 10 is characterized in that, described metal-powder is to be selected from lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, Cu, V, Rh and their combinations thereof.
14. the preparation method as porous graphite alkene as described in the claim 11 is characterized in that described forming method comprises: mechanical pressed disc method, spread coating, spin-coating method and their combination.
15. the preparation method according to the described porous graphite alkene of claim 10 is characterized in that, described high temperature reduction is to carry out in High Temperature Furnaces Heating Apparatus, and the temperature of High Temperature Furnaces Heating Apparatus is between 400-1500 ℃, and the reduction reaction time is between 0.1 hour-20 hours.
16. the preparation method according to the described porous graphite alkene of claim 10 is characterized in that, the carbon source that described chemical Vapor deposition process adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gas mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gas mixture; And the reducing gas that adopts is a hydrogen.
17. the preparation method according to the described porous graphite alkene of claim 10 is characterized in that, described chemical Vapor deposition process comprises:
Temperature programming, temperature rise rate are heated to temperature of reaction 700-1500 ℃, constant temperature 1-240 minute at 0.5-20 ℃/minute;
Import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction times 1-480 minute;
The control rate of temperature fall was 10-50 ℃/minute after reaction finished, and was cooled to room temperature.
18. the porous graphite alkene that makes according to each described preparation method of claim 10-17.
19. the application of the described porous graphite alkene of described Graphene/porous metal composite material of claim 9 or claim 18 in energy storage material, photovoltaic material and heat sink material.
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