CN103219089A - Porous graphite or graphene/porous composite ceramic conductive material and preparation method thereof - Google Patents
Porous graphite or graphene/porous composite ceramic conductive material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to porous graphite or graphene/porous composite ceramic conductive material and a preparation method of the porous graphite or graphene/porous composite ceramic conductive material. The preparation method includes the following steps: mixing metal powders and ceramic powder materials evenly to form a porous substrate in a certain mode, and growing the graphene by using a chemical vapor deposition method to obtain the porous graphite or graphene/porous composite ceramic conductive material. The porous graphite or graphene/porous composite ceramic conductive material has good electrical conduction performance. The ceramic material is composed of silicon dioxide, aluminum oxide, aluminum nitride, silicon carbide, zirconium oxide, boron carbide and other materials, and metals which are used are Cu, Lr, Pt, Mo, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh or other combinations. The porous graphite or graphene/porous composite ceramic conductive material does not exist in the prior art, has good technical effects and application, and can be used in a plurality of fields of photovoltaics, electric conduction, heat dissipation and the like.
Description
Technical field
The invention belongs to the graphene composite material field, specifically relate to a kind of porous graphite alkene or Graphene/porous composite ceramics electric conducting material and preparation method thereof, described porous graphite alkene or Graphene/porous composite ceramics electric conducting material is mainly used in fields such as photovoltaic, electric conducting material, heat radiation.
Technical background
Graphene is just caused the extensive interest of scientific circles from successfully separating because of its excellent physical characteristics.As conductivity 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 conductivity, make it also have huge application potential at microelectronic.Grapheme material still is a kind of good modifier in addition, and is compound as electric conducting 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 high conductance, high-specific surface area, applicable to as the electrode material 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 composite 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
For the electric conductivity of conducting ceramic material, a kind of Graphene of the proposition of originality of the present invention/porous composite ceramics electric conducting material and preparation method thereof, wherein, described electric conducting material is made up of Graphene and porous composite ceramics.
In one embodiment of the present invention, the invention provides the preparation method of Graphene/porous composite ceramics electric conducting material, described method comprises:
(a) with one or more ceramic powders and the grinding becoming of one or more metal-powders uneven ceramic powder of particle diameter and metal-powder;
(b) one or more ceramic powders and one or more metal-powders are mixed;
(c) add binding agent in the powder that mixes, ground and mixed is also oven dry evenly, forms the sample after drying;
(d), obtain the substrate of porous with the mechanical compressing tablet in mould of the sample after the described oven dry;
(e), obtain the ceramic bases of porous with the substrate high annealing moulding of described porous;
(f), obtain Graphene/porous composite ceramics electric conducting material by chemical gaseous phase depositing process direct growth Graphene on the ceramic bases of described porous.
In embodiment of the present invention, described ceramic powders is the powder that is selected from silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia, boron carbide and its combination; Described metal-powder is to be selected among Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and the Rh one or more.
In embodiment of the present invention, described binding agent is propylene glycol, Kynoar (PVDF), PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol) and their mixed solvent.Wherein, described binding agent accounts for the 0.1%-99% of powder quality.
In embodiment of the present invention, the internal diameter of described mould is between 7mm-250mm; Described mechanical compressing tablet carried out under the pressure range of 1MPa-100MPa 1 minute-60 minutes.
In a preferred embodiment of this invention, described method also comprises the projection removing with the porous substrates edge behind the mechanical compressing tablet.
In embodiments of the present invention, the temperature of described high annealing is between 800-1600 ℃, and temperature retention time is between 0.5 hour-20 hours.
In embodiments of the present invention, the carbon source that described chemical vapour deposition technique adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas that adopts is a hydrogen.
In preferred embodiment, described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 ℃/minute; Be heated to reaction temperature 600-1400 ℃, constant temperature 1-240 minute;
(b) import carbon source, hydrogen and protection gas then, gas flow is 1-800sccm (a mark condition milliliter per minute), reaction time 1-480 minute;
(c) after reaction finished, the control rate of temperature fall was 10-50 ℃/minute, is cooled to room temperature.
In another execution mode of the present invention, the invention provides a kind of preparation method of three-dimensional porous grapheme material, described method comprises:
(a) one or more ceramic powders and one or more metal-powders are ground ceramic powder and the metal-powder that becomes the particle size inequality;
(b) one or more ceramic powders and one or more metal-powders are mixed;
(c) add binding agent in the powder that mixes, ground and mixed is also oven dry evenly, forms the sample after drying;
(d) sample after the described oven dry is carried out moulding, obtaining the substrate of porous;
(e), obtain the ceramic bases of porous with the substrate high annealing moulding of described porous;
(f), obtain Graphene/porous composite ceramics electric conducting material by chemical gaseous phase depositing process direct growth Graphene on the ceramic bases of described porous; With
(g) by the method for skeleton etching, remove ceramic bases, obtain three-dimensional porous Graphene as the porous of skeleton.
In embodiment of the present invention, described ceramic powders is the powder that is selected from silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia, boron carbide and its combination; Described metal-powder is to be selected among Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and the Rh one or more.
In embodiment of the present invention, described binding agent is propylene glycol, Kynoar (PVDF), PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol) and their mixed solvent.In embodiment of the present invention, described binding agent accounts for the 0.1%-99% of powder quality.
In embodiment of the present invention, described moulding is undertaken by mechanical pressed disc method, spin-coating method, knife coating; The preferred mechanical pressed disc method, wherein, the internal diameter of used mould is between 7mm-250mm; Described mechanical compressing tablet carried out under the pressure range of 1MPa-100MPa 1 minute-60 minutes.
In embodiment of the present invention, described method also comprises removes the projection at the porous substrates edge behind the mechanical compressing tablet.
In embodiment of the present invention, the temperature of high annealing is between 800-1600 ℃, and temperature retention time is between 0.5 hour-20 hours.
In embodiment of the present invention, the carbon source that chemical vapour deposition technique adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas that adopts is a hydrogen.
In embodiment of the present invention, described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 ℃/minute; Be heated to reaction temperature 600-1400 ℃, constant temperature 1-240 minute;
(b) import carbon source, hydrogen and protection gas then, gas flow is 1-800sccm, reaction time 1-480 minute;
(c) after reaction finished, the control rate of temperature fall was 10-50 ℃/minute, is cooled to room temperature.
In embodiment of the present invention, described Graphene/porous composite ceramics electric conducting material is put into the ceramic bases of etching liquid removal as the porous of skeleton under the organic substance protection, obtain three-dimensional porous Graphene.In preferred embodiment, with Graphene/porous composite ceramics electric conducting material earlier down, put into the HCl solution of 1mol/L and remove the composite ceramics skeleton with the PMMA protection; The molten PMMA that goes in acetone soln obtains porous graphite alkene then.
On the other hand, the present invention also provides the porous graphite alkene or the Graphene/porous composite ceramics electric conducting material of above-mentioned preparation method's system, and wherein said porous graphite alkene or Graphene/porous composite ceramics electric conducting material is made up of Graphene or Graphene and porous composite ceramics.
On the one hand, the invention provides above-mentioned porous graphite alkene or the Graphene/application of porous composite ceramics electric conducting material in photovoltaic, electric conducting material, radiating element again.
Preparation method's technology of porous graphite alkene that the invention discloses or Graphene/porous composite ceramics electric conducting material is simple, process is easy to control, and the electric conductivity excellence need not implemented the deposition of back contact under vacuum condition, equipment investment is few, can large-scale production.In addition, porous graphite alkene or Graphene/porous composite ceramics electric conducting material has obtained the superior electrical conductivity energy that square resistance is lower than 0.2 Ω/sq (ohm-sq) as conductive substrates.
Description of drawings
Fig. 1: the stereoscan photograph of the Graphene in one embodiment of the present invention/porous composite ceramics electric conducting material.
Fig. 2: the Raman of Graphene (Raman) spectrum in one embodiment of the present invention.
Embodiment
In the present invention, the preparation method of described porous graphite alkene or Graphene/porous composite ceramics electric conducting material with the powder of materials such as high-purity silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia and boron carbide as base material; From metal-powder Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh etc., select one or more, fully mix with one or more ceramic powders in certain proportion, method by mechanical compressing tablet obtains the porous substrate, obtains the ceramic material of porous through high annealing.Utilize chemical vapor deposition (CVD) method magnanimity to prepare the method for Graphene, obtain a kind of Graphene/porous composite ceramics electric conducting material.The preparation technology of this composite conducting material is simple, the electric conductivity excellence, and environmental friendliness is drawn materials extensively.The preparation of this Graphene/porous composite ceramics electric conducting material has original and positive scientific meaning, and can be applied to numerous areas such as photovoltaic, conduction, heat radiation.
Graphene of the present invention/porous composite ceramics electric conducting material is to be deposited on the composite material that obtains in the substrate of porous composite ceramics by Graphene, and its preparation method is specific as follows:
(1) with the ceramic powder of commercially available high-purity materials such as silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia and boron carbide as base material, from metal-powder Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh etc., select one or more, fully mix with one or more ceramic powders in certain proportion; By adding an amount of binding agent, after grinding, drying, obtain the compressing tablet material.The powder body material that weighing is an amount of is put into grinding tool, in suitable pressure lower sheeting and an amount of time of pressurize.Substrate after the compression moulding takes out from mould, obtains smooth disk shape substrate by the cleaning edge protuberance.Substrate is annealed into porous ceramic in high temperature furnace.
(2) pottery after will annealing 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 heating rate is at 0.5-20 ℃/minute.Be heated to reaction temperature 600-1300 ℃, after constant temperature 1-180 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction time 1-180 minute, reaction finished, and the control rate of temperature fall is 10-50 ℃/minute, is cooled to room temperature.
In order to make three-dimensional grapheme material, carry out following steps again:
Put into the HF solution of 0.5mol/L remove composite ceramics skeleton (3) earlier down, with the PMMA protection with Graphene/porous composite ceramics electric conducting material; The molten PMMA that goes in acetone soln obtains porous graphite alkene after 50 ℃ of oven dry then.
In the described step (1), the material that the preparation of porous composite ceramics needs is materials such as silicon dioxide, alundum (Al, carborundum, zirconia and boron carbide, obtains evengranular powder through the ball milling reasonable time.
In the described step (1), needed metal-powder is Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh etc.Therefrom select one or more, mix with one or more ceramic powders with the certain quality ratio, the quality of metal-powder accounts for the proportional control of powder mixing between 1%-20%, through the ball milling regular hour it is fully mixed.
In the described step (1), adding binding agent in powder is propylene glycol, Kynoar (PVDF), PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol) etc. or their mixed solvent.Its ratio accounts for the 0.1%-99% of powder quality.Fully grind the dry certain hour of final vacuum.The preferred PVA solvent of described binding agent.
In the described step (1), the powder body material that is mixed with binding agent that weighing is an amount of joins in the compression mold (internal diameter of mould is between 7mm-250mm) compressing tablet in tablet press machine.Regulate the pressure of appropriateness, pressure range is between 1MPa-100MPa; The pressurize regular hour, time range is between 1 minute-60 minutes.The substrate that presses is removed the projection back at edge and waited for subsequent reactions.
In the described step (1), the temperature of carrying out high annealing in high temperature furnace is between 1000-1600 ℃, and holding temperature is between 0.1-10 hour.Preferred temperature is 1250 ℃, 1300 ℃ or 1350 ℃.
In the described step (2), the carbon source that chemical vapour deposition technique adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture.The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gaseous mixture.The reducing gas (division gas) that adopts is a hydrogen.
In the described step (2), temperature programming, heating rate is at 0.5-20 ℃/minute.Be heated to reaction temperature 600-1400 ℃ then, after constant temperature 1-240 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction time 1-480 minute, reaction finished, and the control rate of temperature fall is 10-50 ℃/minute, is cooled to room temperature.
In the described step (3), organic protective agent is the methyl phenyl ethers anisole solution of 3% PMMA; Etching liquid is the HF solution of 0.5mol/L.
Prepared graphene/porous composite ceramics electric conducting material can be applicable to fields such as photovoltaic, electric conducting material, radiating element.
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 percentage and umber are by weight.
Embodiment 1
With Al
2O
3Add mass fraction and be 10% nickel powder and carried out ball milling 1 hour, and mix.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.3g, 0.45g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic chemical vapor deposition (CVD) reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.The stereoscan photograph of sample and Raman spectrum are as depicted in figs. 1 and 2.Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is minimum to be 0.1572 Ω/sq (ohm-sq).
The sample that obtains is protected with PMMA earlier, put into the HF solution of 0.5mol/L and remove the composite ceramics skeleton; The molten PMMA that goes in acetone soln obtains porous graphite alkene after 50 ℃ of oven dry then.
Table 1: the electric property of porous graphite alkene or Graphene/porous composite ceramics electric conducting material.
Embodiment 2
With SiO
2Add mass fraction and be 10% cobalt powder and carried out ball milling 1 hour, and mix.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1200 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2854 Ω/sq (ohm-sq).
Embodiment 3
With ZrO
2Add mass fraction and be 10% nickel powder and carried out ball milling 1 hour, and mix.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.15g, 0.3g, 0.5g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is minimum to be 0.3124 Ω/sq (ohm-sq).
Embodiment 4
It is that 10% nickel powder carried out ball milling 1 hour that SiC is added mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2762 Ω/sq (ohm-sq).
Embodiment 5
It is that 10% iron powder carried out ball milling 1 hour that SiC is added mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.3025 Ω/sq (ohm-sq).
Embodiment 6
With B
4It is that 10% iron powder carried out ball milling 1 hour that C adds mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2954 Ω/sq (ohm-sq).
Embodiment 7
It is that 5% nickel powder and 5% iron powder carried out ball milling 1 hour that B4C is added mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2963 Ω/sq (ohm-sq).
Embodiment 8
With B
4It is that 5% nickel powder and 5% cobalt powder carried out ball milling 1 hour that C adds mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1250 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2462 Ω/sq (ohm-sq).
Embodiment 9
With B
4It is that 5% nickel powder and 5% niobium powder carried out ball milling 1 hour that C adds mass fraction, and mixes.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1250 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2618 Ω/sq (ohm-sq).
Embodiment 10
With Al
2O
3The niobium powder that adds mass fraction and be 5% nickel powder and 5% carries out ball milling and mixed in 1 hour.The binding agent of adding 5% by abundant grinding vacuumize, obtains dry back sample; Take by weighing dry back sample 0.2g, 0.4g, 0.6g and put into the mould of internal diameter 10mm, pressurize is 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.The substrate that taking-up suppresses is disposed the projection of substrate edge.Substrate is put in the high temperature furnace, be warming up to 1300 ℃, be incubated after 1 hour, naturally cool to room temperature with 10 ℃/minute speed.
With the porous ceramic CVD reacting furnace of packing into, feed 100sccm hydrogen and 300sccm argon gas, be heated to 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ with 10 ℃/minute programming rates, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, feed 10sccm, 20sccm, 30sccm, 40sccm methane afterwards, regulate hydrogen flowing quantity to 50sccm, 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes respectively reaction time, 300 minutes.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.
Sample by the test of Hall instrument, is found that sample has excellent electric conductivity, and square resistance is low to moderate 0.2536 Ω/sq (ohm-sq).
After having read above-mentioned instruction content 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 (22)
1. the preparation method of Graphene/porous composite ceramics electric conducting material, described electric conducting material is made up of Graphene and porous composite ceramics, and described method comprises:
(a) one or more ceramic powders and one or more metal-powders are ground ceramic powder and the metal-powder that becomes the particle size inequality;
(b) one or more ceramic powders and one or more metal-powders are mixed;
(c) add binding agent in the powder that mixes, ground and mixed is also oven dry evenly, forms the sample after drying;
(d) sample after the described oven dry is carried out moulding, obtaining the substrate of porous;
(e), obtain the ceramic bases of porous with the substrate high annealing moulding of described porous; With
(f), obtain Graphene/porous composite ceramics electric conducting material by chemical gaseous phase depositing process direct growth Graphene on the ceramic bases of described porous.
2. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material is characterized in that: described ceramic powders is the powder that is selected from silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia, boron carbide and its combination; Described metal-powder is to be selected among Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and the Rh one or more.
3. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material is characterized in that: described binding agent is propylene glycol, Kynoar, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and their mixed solvent.
4. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, it is characterized in that: described binding agent accounts for the 0.1%-99% of powder quality.
5. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material is characterized in that: described moulding is undertaken by mechanical pressed disc method, spin-coating method, knife coating; The preferred mechanical pressed disc method, wherein, the internal diameter of the mould that mechanical pressed disc method is used is between 7mm-250mm; Described mechanical compressing tablet carried out under the pressure range of 1MPa-100MPa 1 minute-60 minutes.
6. the preparation method of Graphene according to claim 5/porous composite ceramics electric conducting material is characterized in that: described method also comprises removes the projection at the porous substrates edge behind the mechanical compressing tablet.
7. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material is characterized in that: the temperature of high annealing is between 800-1600 ℃, and temperature retention time is between 0.5 hour-20 hours.
8. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, it is characterized in that: the carbon source that chemical vapour deposition technique adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas that adopts is a hydrogen.
9. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, it is characterized in that: described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 ℃/minute; Be heated to reaction temperature 600-1400 ℃, constant temperature 1-240 minute;
(b) import carbon source, hydrogen and protection gas then, gas flow is 1-800sccm, reaction time 1-480 minute;
(c) after reaction finished, the control rate of temperature fall was 10-50 ℃/minute, is cooled to room temperature.
10. the preparation method of a three-dimensional porous grapheme material, described method comprises:
(a) one or more ceramic powders and one or more metal-powders are ground ceramic powder and the metal-powder that becomes the particle size inequality;
(b) one or more ceramic powders and one or more metal-powders are mixed;
(c) add binding agent in the powder that mixes, ground and mixed is also oven dry evenly, forms the sample after drying;
(d) sample after the described oven dry is carried out moulding, obtaining the substrate of porous;
(e), obtain the ceramic bases of porous with the substrate high annealing moulding of described porous;
(f), obtain Graphene/porous composite ceramics electric conducting material by chemical gaseous phase depositing process direct growth Graphene on the ceramic bases of described porous; With
(g) by the method for skeleton etching, remove ceramic bases, obtain three-dimensional porous Graphene as the porous of skeleton.
11. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: described ceramic powders is the powder that is selected from silicon dioxide, alundum (Al, aluminium nitride, carborundum, zirconia, boron carbide and its combination; Described metal-powder is to be selected among Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and the Rh one or more.
12. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: described binding agent is propylene glycol, Kynoar, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and their mixed solvent.
13. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: described binding agent accounts for the 0.1%-99% of powder quality.
14. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: described moulding is undertaken by mechanical pressed disc method, spin-coating method, knife coating; The preferred mechanical pressed disc method, wherein, the internal diameter of used mould is between 7mm-250mm; Described mechanical compressing tablet carried out under the pressure range of 1MPa-100MPa 1 minute-60 minutes.
15. the preparation method of three-dimensional porous grapheme material according to claim 14 is characterized in that: described method also comprises removes the projection at the porous substrates edge behind the mechanical compressing tablet.
16. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: the temperature of high annealing is between 800-1600 ℃, and temperature retention time is between 0.5 hour-20 hours.
17. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: the carbon source that chemical vapour deposition technique adopted comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag that adopts is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas that adopts is a hydrogen.
18. the preparation method of three-dimensional porous grapheme material according to claim 10 is characterized in that: described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 ℃/minute; Be heated to reaction temperature 600-1400 ℃, constant temperature 1-240 minute;
(b) import carbon source, hydrogen and protection gas then, gas flow is 1-800sccm, reaction time 1-480 minute;
(c) after reaction finished, the control rate of temperature fall was 10-50 ℃/minute, is cooled to room temperature.
19. the preparation method of three-dimensional porous grapheme material according to claim 10; it is characterized in that: described Graphene/porous composite ceramics electric conducting material is put into the ceramic bases of etching liquid removal as the porous of skeleton under the organic substance protection, obtain three-dimensional porous Graphene.
20. according to the Graphene/porous composite ceramics electric conducting material of each described preparation method's system of claim 1-9, wherein said Graphene/porous composite ceramics electric conducting material is made up of Graphene and porous composite ceramics.
21. three-dimensional porous grapheme material according to each described preparation method's system of claim 10-19.
22. the described Graphene of claim 20/porous composite ceramics electric conducting material or the application of the described three-dimensional porous grapheme material of claim 21 in photovoltaic, electric conducting material, radiating element.
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