CN103219089B - Porous graphene or Graphene/porous composite ceramics electric conducting material and preparation method thereof - Google Patents
Porous graphene or Graphene/porous composite ceramics electric conducting material and preparation method thereof Download PDFInfo
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- CN103219089B CN103219089B CN201210015932.4A CN201210015932A CN103219089B CN 103219089 B CN103219089 B CN 103219089B CN 201210015932 A CN201210015932 A CN 201210015932A CN 103219089 B CN103219089 B CN 103219089B
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Abstract
The present invention relates to a kind of novel porous graphene or Graphene/porous composite ceramics electric conducting material and preparation method, it is characterized in that the method comprises: shaping in a certain way after being mixed with ceramic powder material by metal-powder, form perforated substrate; Adopt chemical gaseous phase depositing process growing graphene, obtain porous graphene or Graphene/porous composite ceramics electric conducting material.Material of the present invention has excellent electric conductivity.The present invention's ceramic material used is the materials such as silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia and boron carbide; Metal used is Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh or its combination.This Graphene/porous composite ceramics electric conducting material does not occur in the prior art, and, there is positive technique effect and application, comprise numerous areas such as can being applied to photovoltaic, conduction, heat radiation.
Description
Technical field
The invention belongs to graphene composite material field, specifically relate to a kind of porous graphene or Graphene/porous composite ceramics electric conducting material and preparation method thereof, described porous graphene or Graphene/porous composite ceramics electric conducting material are mainly used in the fields such as photovoltaic, electric conducting material, heat radiation.
Technical background
Graphene from being successfully separated, just because the physical characteristic of its excellence causes the broad interest of scientific circles.As conductivity 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 conductivity of its excellence, it is made also to have huge application potential at microelectronic.Grapheme material or a kind of excellent modifier in addition, using Graphene as electric conducting 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 high conductance, high-specific surface area, be applicable to as electrode material 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 composite 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
In order to the electric conductivity of conducting ceramic material, a kind of Graphene/porous composite ceramics electric conducting material of proposition of originality of the present invention 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 one or more ceramic powders and the grinding of one or more metal-powders are become the uneven ceramic powder of particle diameter and metal-powder by ();
B one or more ceramic powders mix with one or more metal-powders by ();
C () adds binding agent in the powder mixed, ground and mixed evenly and dry, forms the sample after drying;
D (), by the Mechanical pressing in a mold of the sample after described oven dry, obtains the substrate of porous;
E (), by shaping for the substrate high annealing of described porous, obtains the ceramic bases of porous;
F (), by chemical gaseous phase depositing process direct growth Graphene in the ceramic bases of described porous, obtains Graphene/porous composite ceramics electric conducting material.
In embodiments of the present invention, described ceramic powders is be selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia, boron carbide and its powder combined; Described metal-powder be selected from Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and Rh one or more.
In embodiments 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 embodiments of the present invention, the internal diameter of described mould is between 7mm-250mm; Described Mechanical pressing carries out 1 minute-60 minutes under the pressure range of 1MPa-100MPa.
In a preferred embodiment of this invention, described method also comprises the projection removing at the porous substrates edge after by Mechanical pressing.
In embodiments of the present invention, the temperature of described high annealing is between 800-1600 DEG C, 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 adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas adopted is hydrogen.
In a preferred embodiment, described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 DEG C/min; Be heated to reaction temperature 600-1400 DEG C, constant temperature 1-240 minute;
B () then imports carbon source, hydrogen and protection gas, gas flow is 1-800sccm (mark condition milliliter is per minute), reaction time 1-480 minute;
C () after completion of the reaction, control rate of temperature fall is 10-50 DEG C/min, 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 the grinding of one or more metal-powders are become ceramic powder and the metal-powder of particle size inequality by ();
B one or more ceramic powders mix with one or more metal-powders by ();
C () adds binding agent in the powder mixed, ground and mixed evenly and dry, forms the sample after drying;
D sample after described oven dry is carrying out shaping by (), obtain the substrate of porous;
E (), by shaping for the substrate high annealing of described porous, obtains the ceramic bases of porous;
F (), by chemical gaseous phase depositing process direct growth Graphene in the ceramic bases of described porous, obtains Graphene/porous composite ceramics electric conducting material; With
G method that () is etched by skeleton, removes the ceramic bases of the porous as skeleton, obtains three-dimensional porous Graphene.
In embodiments of the present invention, described ceramic powders is be selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia, boron carbide and its powder combined; Described metal-powder be selected from Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and Rh one or more.
In embodiments 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 embodiments of the present invention, described binding agent accounts for the 0.1%-99% of powder quality.
In embodiments of the present invention, describedly shapingly to be undertaken by Mechanical pressing method, spin-coating method, knife coating; Preferred mechanical pressed disc method, wherein, the internal diameter of mould used is between 7mm-250mm; Described Mechanical pressing carries out 1 minute-60 minutes under the pressure range of 1MPa-100MPa.
In embodiments of the present invention, described method also comprises the projection removing at the porous substrates edge after by Mechanical pressing.
In embodiments of the present invention, the temperature of high annealing is between 800-1600 DEG C, and temperature retention time is between 0.5 hour-20 hours.
In embodiments of the present invention, the carbon source that chemical vapour deposition technique adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas adopted is hydrogen.
In embodiments of the present invention, described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 DEG C/min; Be heated to reaction temperature 600-1400 DEG C, constant temperature 1-240 minute;
B () then imports carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction time 1-480 minute;
C () after completion of the reaction, control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
In embodiments of the present invention, described Graphene/porous composite ceramics electric conducting material is entered in etching liquid the ceramic bases of the porous removed as skeleton at organic substance protection down, obtain three-dimensional porous Graphene.In a preferred embodiment, by Graphene/porous composite ceramics electric conducting material first with under PMMA protection, the HCl solution putting into 1mol/L removes composite ceramics skeleton; Then in acetone soln, dissolve PMMA, obtain porous graphene.
On the other hand, the present invention also provides porous graphene or the Graphene/porous composite ceramics electric conducting material of above-mentioned preparation method, and wherein said porous graphene or Graphene/porous composite ceramics electric conducting material are made up of Graphene or Graphene and porous composite ceramics.
Again on the one hand, the invention provides above-mentioned porous graphene or the Graphene/application of porous composite ceramics electric conducting material in photovoltaic, electric conducting material, radiating element.
Preparation method's technique of the porous graphene that the invention discloses or Graphene/porous composite ceramics electric conducting material is simple, process is easy to control, and electric conductivity is excellent, does not need the deposition implementing back contact under vacuum, equipment investment is few, can large-scale production.In addition, porous graphene or Graphene/porous composite ceramics electric conducting material are used as conductive substrates and obtain the superior electrical conductivity energy of square resistance lower than 0.2 Ω/sq (ohm-sq).
Accompanying drawing explanation
Fig. 1: the stereoscan photograph of the Graphene in one embodiment of the present invention/porous composite ceramics electric conducting material.
Fig. 2: Raman (Raman) spectrum of Graphene in one embodiment of the present invention.
Embodiment
In the present invention, the preparation method of described porous graphene or Graphene/porous composite ceramics electric conducting material is using the powder of the materials such as high-purity silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia and boron carbide as base material; One or more are selected from metal-powder Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V, Rh etc., fully mix with one or more ceramic powders in certain proportion, obtain perforated substrate by the method for Mechanical pressing, obtain the ceramic material of porous through high annealing.Utilize the method for chemical vapour deposition (CVD) (CVD) method macroscopic preparation of graphene, obtain a kind of Graphene/porous composite ceramics electric conducting material.The preparation technology of this composite conducting material is simple, and electric conductivity is excellent, environmental friendliness, draws materials extensively.The preparation of this Graphene/porous composite ceramics electric conducting material has original and positive scientific meaning, and can be applied to the numerous areas such as photovoltaic, conduction, heat radiation.
Graphene of the present invention/porous composite ceramics electric conducting material is deposited on by Graphene the composite material that the substrate of porous composite ceramics obtains, and its preparation method is specific as follows:
(1) using the ceramic powder of the materials such as commercially available high-purity silicon dioxide, alundum (Al2O3), 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 appropriate binding agent, after grinding, oven dry, obtain compressing tablet material.Weigh appropriate powder body material, put into grinding tool, at suitable pressure lower sheeting and pressurize appropriate time.Substrate after compressing takes out from mould, obtains smooth disc-shaped substrate by cleaning edge protuberance.Substrate is annealed into porous ceramic in high temperature furnace.
(2) pottery after annealing 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, heating rate is at 0.5-20 DEG C/min.Be heated to reaction temperature 600-1300 DEG C, after constant temperature 1-180 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction time 1-180 minute reacts complete, and control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
In order to obtained three-dimensional grapheme material, then carry out following steps:
(3), under first being protected with PMMA by Graphene/porous composite ceramics electric conducting material, the HF solution putting into 0.5mol/L removes composite ceramics skeleton; Then in acetone soln, dissolve PMMA, after 50 DEG C of oven dry, obtain porous graphene.
In described step (1), the material that the preparation of porous composite ceramics needs is the materials such as silicon dioxide, alundum (Al2O3), carborundum, zirconia and boron carbide, obtains evengranular powder through ball milling reasonable time.
In described step (1), required 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 certain mass ratio with one or more ceramic powders, the quality of metal-powder accounts for the proportional control of powder mixing between 1%-20%, it is fully mixed through the ball milling regular hour.
In described step (1), in powder, add binding agent 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.The dry certain hour of abundant grinding final vacuum.The preferred PVA solvent of described binding agent.
In described step (1), weigh the appropriate powder body material being mixed with binding agent, join in 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.Subsequent reactions is waited for after the substrate pressed being removed the projection at edge.
In described step (1), in high temperature furnace, carry out the temperature of high annealing between 1000-1600 DEG C, holding temperature is between 0.1-10 hour.Preferable temperature is 1250 DEG C, 1300 DEG C or 1350 DEG C.
In described step (2), the carbon source that chemical vapour deposition technique adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture.The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gaseous mixture.The reducing gas (division gas) adopted is hydrogen.
In described step (2), temperature programming, heating rate is at 0.5-20 DEG C/min.Then carry out being heated to reaction temperature 600-1400 DEG C, after constant temperature 1-240 minute, import carbon source, hydrogen and protection gas, gas flow is 1-800sccm, and reaction time 1-480 minute reacts complete, and control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
In described step (3), organic protective agent is the methyl phenyl ethers anisole solution of the PMMA of 3%; Etching liquid is the HF solution of 0.5mol/L.
Prepared Graphene/porous composite ceramics electric conducting material can be applicable to the fields such as photovoltaic, electric conducting material, radiating element.
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 percentage and number are by weight.
embodiment 1
By Al
2o
3add mass fraction be 10% nickel powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.3g, 0.45g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded chemical vapour deposition (CVD) (CVD) reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.The stereoscan photograph of sample and Raman spectrum are as depicted in figs. 1 and 2.Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is minimum is 0.1572 Ω/sq (ohm-sq).
First protected with PMMA by the sample obtained, the HF solution putting into 0.5mol/L removes composite ceramics skeleton; Then in acetone soln, dissolve PMMA, after 50 DEG C of oven dry, obtain porous graphene.
Table 1: the electric property of porous graphene or Graphene/porous composite ceramics electric conducting material.
Embodiment 2
By SiO
2add mass fraction be 10% cobalt powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1200 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2854 Ω/sq (ohm-sq).
Embodiment 3
By ZrO
2add mass fraction be 10% nickel powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.15g, 0.3g, 0.5g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is minimum is 0.3124 Ω/sq (ohm-sq).
Embodiment 4
SiC is added mass fraction be 10% nickel powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2762 Ω/sq (ohm-sq).
Embodiment 5
SiC is added mass fraction be 10% iron powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.3025 Ω/sq (ohm-sq).
Embodiment 6
By B
4c add mass fraction be 10% iron powder carry out ball milling 1 hour, and to mix.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2954 Ω/sq (ohm-sq).
Embodiment 7
B4C being added mass fraction is that the nickel powder of 5% and the iron powder of 5% carry out ball milling 1 hour, and mixes.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2963 Ω/sq (ohm-sq).
Embodiment 8
By B
4it is that the nickel powder of 5% and the cobalt powder of 5% carry out ball milling 1 hour that C adds mass fraction, and mixes.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1250 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2462 Ω/sq (ohm-sq).
Embodiment 9
By B
4it is that the nickel powder of 5% and the niobium powder of 5% carry out ball milling 1 hour that C adds mass fraction, and mixes.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1250 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, square resistance is low to moderate 0.2618 Ω/sq (ohm-sq).
Embodiment 10
By Al
2o
3adding mass fraction is that the nickel powder of 5% and the niobium powder of 5% carry out ball milling and mix for 1 hour.Adding the binding agent of 5%, by fully grinding vacuumize, obtaining dry rear sample; Take the mould that dry rear sample 0.2g, 0.4g, 0.6g put into internal diameter 10mm, pressurize 10 minutes, 20 minutes, 30 minutes under the pressure of 5MPa, 10MPa, 15MPa, 20MPa.Take out the substrate suppressed, dispose the projection of substrate edge.Substrate is put in high temperature furnace, be warming up to 1300 DEG C with the speed of 10 DEG C/min, be incubated after 1 hour, naturally cool to room temperature.
Porous ceramic is loaded CVD reacting furnace, pass into 100sccm hydrogen and 300sccm argon gas, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, pass into 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 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.
Tested by Hall instrument by sample, find that sample has excellent electric conductivity, 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 limited range equally.
Claims (21)
1. a preparation method for 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 the grinding of one or more metal-powders are become ceramic powder and the metal-powder of particle size inequality by ();
B one or more ceramic powders mix with one or more metal-powders by ();
C () adds binding agent in the powder mixed, ground and mixed evenly and dry, forms the sample after drying;
D sample after described oven dry carries out shaping by () again, obtain the substrate of porous;
E (), by shaping for the substrate high annealing of described porous, obtains the ceramic bases of porous; With
F (), by chemical gaseous phase depositing process direct growth Graphene in the ceramic bases of described porous, obtains Graphene/porous composite ceramics electric conducting material.
2. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, is characterized in that: described ceramic powders is be selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia, boron carbide and its powder combined; Described metal-powder be selected from Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and 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 hybrid adhesive.
4. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, 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: describedly shapingly to be undertaken by Mechanical pressing method, spin-coating method, knife coating.
6. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, is characterized in that: describedly shapingly to be undertaken by Mechanical pressing method, and wherein, the internal diameter of the mould that Mechanical pressing method is used is between 7mm-250mm; Described Mechanical pressing carries out 1 minute-60 minutes under the pressure range of 1MPa-100MPa.
7. the preparation method of the Graphene according to claim 5 or 6/porous composite ceramics electric conducting material, is characterized in that: the projection that described method also comprises the porous substrates edge after by Mechanical pressing is removed.
8. 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 DEG C, and temperature retention time is between 0.5 hour-20 hours.
9. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, is characterized in that: the carbon source that chemical vapour deposition technique adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas adopted is hydrogen.
10. the preparation method of Graphene according to claim 1/porous composite ceramics electric conducting material, is characterized in that: described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 DEG C/min; Be heated to reaction temperature 600-1400 DEG C, constant temperature 1-240 minute;
B () then imports carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction time 1-480 minute;
C () after completion of the reaction, control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
The preparation method of 11. 1 kinds of three-dimensional porous grapheme materials, described method comprises:
A one or more ceramic powders and the grinding of one or more metal-powders are become ceramic powder and the metal-powder of particle size inequality by ();
B one or more ceramic powders mix with one or more metal-powders by ();
C () adds binding agent in the powder mixed, ground and mixed evenly and dry, forms the sample after drying;
D sample after described oven dry carries out shaping by () again, obtain the substrate of porous;
E (), by shaping for the substrate high annealing of described porous, obtains the ceramic bases of porous;
F (), by chemical gaseous phase depositing process direct growth Graphene in the ceramic bases of described porous, obtains Graphene/porous composite ceramics electric conducting material; With
G method that () is etched by skeleton, removes the ceramic bases of the porous as skeleton, obtains three-dimensional porous Graphene.
The preparation method of 12. three-dimensional porous grapheme materials according to claim 11, is characterized in that: described ceramic powders is be selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia, boron carbide and its powder combined; Described metal-powder be selected from Cu, lr, Pt, Mo, W, Zn, Nb, Ta, Ru, Ti, Zr, Pd, Fe, Co, Ni, V and Rh one or more.
The preparation method of 13. three-dimensional porous grapheme materials according to claim 11, is characterized in that: described binding agent is propylene glycol, Kynoar, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and their hybrid adhesive.
The preparation method of 14. three-dimensional porous grapheme materials according to claim 11, is characterized in that: described binding agent accounts for the 0.1%-99% of powder quality.
The preparation method of 15. three-dimensional porous grapheme materials according to claim 11, is characterized in that: describedly shapingly to be undertaken by Mechanical pressing method, spin-coating method, knife coating.
The preparation method of 16. three-dimensional porous grapheme materials according to claim 11, is characterized in that: describedly shapingly to be undertaken by Mechanical pressing method, and wherein, the internal diameter of mould used is between 7mm-250mm; Described Mechanical pressing carries out 1 minute-60 minutes under the pressure range of 1MPa-100MPa.
The preparation method of 17. three-dimensional porous grapheme materials according to claim 15 or 16, is characterized in that: the projection that described method also comprises the porous substrates edge after by Mechanical pressing is removed.
The preparation method of 18. three-dimensional porous grapheme materials according to claim 11, is characterized in that: the temperature of high annealing is between 800-1600 DEG C, and temperature retention time is between 0.5 hour-20 hours.
The preparation method of 19. three-dimensional porous grapheme materials according to claim 11, is characterized in that: the carbon source that chemical vapour deposition technique adopts comprises: methane, ethene, acetylene, ethanol, ethane, propane and their gaseous mixture; The protection gas bag adopted is drawn together: nitrogen, argon gas, helium and their gaseous mixture; And the reducing gas adopted is hydrogen.
The preparation method of 20. three-dimensional porous grapheme materials according to claim 11, is characterized in that: described chemical vapour deposition technique comprises:
(a) temperature programming, heating rate is at 0.5-20 DEG C/min; Be heated to reaction temperature 600-1400 DEG C, constant temperature 1-240 minute;
B () then imports carbon source, hydrogen and protection gas, gas flow is 1-800sccm, reaction time 1-480 minute;
C () after completion of the reaction, control rate of temperature fall is 10-50 DEG C/min, is cooled to room temperature.
The preparation method of 21. three-dimensional porous grapheme materials according to claim 11; it is characterized in that: the ceramic bases described Graphene/porous composite ceramics electric conducting material being entered in etching liquid the porous removed as skeleton at organic substance protection down, obtains three-dimensional porous Graphene.
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