CN103219061B - Graphene/porous ceramic composite conducting material and preparation method thereof - Google Patents
Graphene/porous ceramic composite conducting material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of novel Graphene/porous ceramic composite conducting material and preparation method.Described method comprises: by powder body material through compression molding, forms perforated substrate; And adopting the method for direct growth Graphene on insulating substrate to obtain Graphene/porous ceramic composite conducting material, this material 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, obtains porous material by forming method; Utilize the method for chemical vapour deposition (CVD), use the technique macroscopic preparation of graphene/porous ceramic composite conducting material of directly growing graphene on insulating substrate.The preparation of this Graphene/porous ceramic composite conducting material has original and positive scientific meaning, and can be applied to the numerous areas such as photovoltaic, conduction, heat radiation.
Description
Technical field
The invention belongs to graphene composite material field, be specifically related to a kind of Graphene/porous ceramic composite conducting material and preparation method thereof.Described Graphene/porous ceramic composite conducting material is 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.In conductivity ceramics exploitation, mostly current conductivity ceramics is the composite conductive ceramic obtained through the method such as compound, doping high annealing by the compound of complexity.But their raw materials for production cost is high, complicated process of preparation, compositely proportional requires strict, and its application is subject to the restriction of each side.Therefore, how to break through this bottleneck, develop low cost, electric property conductivity ceramics that is excellent, that can be mass-produced is the key improving composite conducting material electric conductivity, reduce costs.By such as silicon dioxide, the sintering such as alundum (Al2O3) forms porous ceramic itself and does not have electric conductivity.And the electric conductivity utilizing Graphene excellent, by it and porous ceramic compound, not only make the conductivity that porous ceramic possesses, and function admirable.This preparation being conductivity ceramics provides new method and new thinking.
Summary of the invention
In order to promote the electric conductivity of conducting ceramic material, a kind of Graphene/porous ceramic composite conducting material of proposition of originality of the present invention and preparation method thereof, wherein, described Graphene/porous ceramic composite conducting material is the composite material formed by Graphene, porous ceramic.
In one embodiment of the present invention, the invention provides the preparation method of described Graphene/porous ceramic composite conducting material, described method comprises:
(a) grinding of one or more ceramic powders is become mix, ceramic powder that particle size differs;
B () is by described ceramic powder and binding agent is blended and grinding, mixes post-drying, obtains the sample after drying;
C sample after oven dry carries out shaping by (), obtain the substrate of porous;
D (), by shaping for the substrate high annealing of porous, obtains the ceramic bases of porous;
E (), by chemical gaseous phase depositing process direct growth Graphene in the ceramic bases of this porous, obtains Graphene/porous ceramic composite conducting material.
In embodiments of the present invention, one or more ceramic powders described are the ceramic powder being selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia and boron carbide.
In embodiments of the present invention, described binding agent is propylene glycol, PVDF (Kynoar), PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol) and their mixed solvent.In a preferred embodiment, 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 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.
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, in the temperature of high annealing between 1000-1600 DEG C, temperature retention time is between 0.5 hour-10 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 0-240 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.
On the other hand, the Graphene that the present invention also provides above-mentioned preparation method to obtain/porous ceramic composite conducting material, wherein, described Graphene/porous ceramic composite conducting material is the composite material formed by Graphene, porous ceramic.
Again on the one hand, the invention provides the above-mentioned Graphene/application of porous ceramic composite conducting material in photovoltaic, electric conducting material, radiating element.
The preparation method's technique that the invention discloses a kind of novel Graphene/porous ceramic composite conducting material is simple, and process is easy to control, and electric conductivity is excellent, and do not need the deposition implementing back contact under vacuum, equipment investment is few, can large-scale production.In addition, Graphene/porous ceramic composite conducting material is used as conductive substrates and obtains the superior electrical conductivity energy of square resistance lower than 0.3 Ω/sq (ohm-sq).
Accompanying drawing explanation
Fig. 1: the stereoscan photograph of the Graphene/porous ceramic composite in one embodiment of the present invention.
Fig. 2: Raman (Raman) spectrum of Graphene in one embodiment of the present invention.
Embodiment
In the present invention, the preparation method of described Graphene/porous ceramic composite is using the powder of the materials such as commercially available high-purity silicon dioxide, alundum (Al2O3), carborundum, zirconia and boron carbide as base material, obtain perforated substrate by the method for Mechanical pressing, obtain the ceramic material of porous through high annealing.Utilize chemical vapour deposition (CVD) (CVD) method, by the method for direct macroscopic preparation of graphene on an insulating substrate, obtain a kind of Graphene/porous ceramic composite 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 ceramic composite conducting material has original and positive scientific meaning, and can be applied to the numerous areas such as photovoltaic, conduction, heat radiation.
A kind of Graphene/porous ceramic composite conducting material of the present invention is deposited on by Graphene the composite material that porous ceramic substrate 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), carborundum, zirconia and boron carbide as base material, by adding appropriate binding agent, after grinding, oven dry, compressing tablet material is obtained.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 described step (1), the material that the preparation of porous ceramic needs is the materials such as silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia and boron carbide, obtains evengranular powder through ball milling reasonable time.
In described step (1), in powder, add binding agent is propylene glycol, Kynoar (PVDF), PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol) etc. and their mixed solvent.Its ratio accounts for the 0.1%-99% of powder quality.The dry certain hour of abundant grinding final vacuum.
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 hour-10 hours.
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 0-240 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.
Prepared Graphene/porous ceramic composite 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
3ball milling 1 hour.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 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 0.1879 Ω/sq (ohm-sq).
Table 1: the square resistance test of Graphene/porous ceramic composite.
Embodiment 2
By SiO2 ball milling 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 minimum is 0.311 Ω/sq (ohm-sq).
Embodiment 3
By ZrO
2ball milling 1 hour.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 0.366 Ω/sq (ohm-sq).
Embodiment 4
By SiC ball milling 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 minimum is 0.3043 Ω/sq (ohm-sq).
Embodiment 5
By B4C ball milling 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 minimum is 0.3261 Ω/sq (ohm-sq).
Embodiment 6
By B
4c and Al
2o
3ball milling 1 hour after mixing with the ratio of mass ratio 1: 1.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 minimum is 0.3351 Ω/sq (ohm-sq).
Embodiment 7
By Al
2o
3with SiO
2ball milling 1 hour after mixing with the ratio of mass ratio 1: 1.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 minimum is 0.1951 Ω/sq (ohm-sq).
Embodiment 8
By Al
2o
3with ZrO
2ball milling 1 hour after mixing with the ratio of mass ratio 1: 1.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 minimum is 0.1862 Ω/sq (ohm-sq).
Embodiment 9
By SiO
2with ZrO
2ball milling 1 hour after mixing with the ratio of mass ratio 1: 1.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 minimum is 0.2256 Ω/sq (ohm-sq).
Embodiment 10
By SiO
2ball milling 1 hour after mixing with the ratio of mass ratio 1: 1 with SiC.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 0.1758 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 (12)
1. a preparation method for Graphene/porous ceramic composite conducting material, wherein, described Graphene/porous ceramic composite conducting material is the composite material formed by Graphene, porous ceramic; Described method comprises:
A the grinding of one or more ceramic powders is become the powder that particle size differs by ();
B () is by described powder and binding agent is blended and grinding, mixes post-drying, obtains the sample after drying;
C mixture after oven dry carries out shaping by (), obtain the substrate of porous;
D (), by shaping for the substrate high annealing of porous, obtains the ceramic bases of porous;
E (), by chemical gaseous phase depositing process, direct growth Graphene in the ceramic bases of this porous, obtains Graphene/porous ceramic composite conducting material.
2. the preparation method of Graphene according to claim 1/porous ceramic composite conducting material, it is characterized in that, one or more ceramic powders described are the ceramic powder being selected from silicon dioxide, alundum (Al2O3), aluminium nitride, carborundum, zirconia and boron carbide.
3. the preparation method of Graphene according to claim 1/porous ceramic composite conducting material, is characterized in that, described binding agent is selected from propylene glycol, Kynoar, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol or their mixed solvent.
4. the preparation method of Graphene according to claim 1/porous ceramic composite 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 ceramic composite 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 ceramic composite 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 ceramic composite conducting material, is characterized in that, the projection that described method also comprises the basal edge of the porous after by Mechanical pressing is removed.
8. the preparation method of Graphene according to claim 1/porous ceramic composite conducting material, is characterized in that, the temperature of high annealing is between 1000-1600 DEG C, and temperature retention time is between 0.5 hour-10 hours.
9. the preparation method of Graphene according to claim 1/porous ceramic composite conducting material, is characterized in that, the carbon source that chemical vapour deposition technique adopts is selected from methane, ethene, acetylene, ethanol, ethane, propane or their gaseous mixture; The protection gas adopted is selected from nitrogen, argon gas, helium or their gaseous mixture; And the reducing gas adopted is hydrogen.
10. the preparation method of Graphene according to claim 1/porous ceramic composite 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 0-240 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.
11. Graphene that preparation method obtains according to any one of claim 1-10/porous ceramic composite conducting materials, wherein, described Graphene/porous ceramic composite conducting material is the composite material formed by Graphene, porous ceramic.
Graphene described in the 12. claims 11/application of porous ceramic composite conducting material in photovoltaic, electric conducting material, radiating element.
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