CN108069420B - A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material - Google Patents
A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material Download PDFInfo
- Publication number
- CN108069420B CN108069420B CN201711191049.XA CN201711191049A CN108069420B CN 108069420 B CN108069420 B CN 108069420B CN 201711191049 A CN201711191049 A CN 201711191049A CN 108069420 B CN108069420 B CN 108069420B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- nano tube
- compound material
- carbon nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of graphene/graphene oxide-carbon nano tube compound material, first by the way that graphene or graphene oxide to be dispersed in the mixed liquor of second alcohol and water using ultrasound, it is configured to the dispersion liquid of graphene or graphene oxide, then iron content class nanocatalyst and sulphur-containing substance are loaded to by graphene or surface of graphene oxide by hydro-thermal method, again by chemical vapour deposition technique deposition of carbon nanotubes on the graphene or graphene oxide of catalyst supported on surface, the mechanical and excellent isotropic composite material of electric property is obtained.
Description
Technical field
The present invention relates to graphene composite material field more particularly to a kind of graphene/graphene oxide-carbon nanotube are multiple
The preparation method of condensation material.
Background technique
As presently found most thin, maximum intensity, a kind of strongest novel nano-material of electrical and thermal conductivity performance, graphene
Referred to as " dark fund " is " king of new material ", and graphene (Graphene) is that one kind is formed by carbon atom with sp2 hybrid form
Honeycomb flat film, be a kind of quasi- two-dimensional material of only one atomic layer level thickness.And carbon nanotube can regard stone as
Black alkene lamella curling forms seamless hollow tube body, is typical monodimension nanometer material.Both there is very excellent intensity, soft
The physical characteristics such as tough, conductive, thermally conductive, optics have huge scientific value and wide application prospect.
Although graphene and carbon nanotube are had excellent performance, have a wide range of applications, two kinds of materials are due to Van der Waals force
Effect is all easy to reunite during the preparation process, it is suppressed that the release of skin effect affects its electrochemistry and heat, mechanical property.
There are many similarities in chemical structure for carbon nanotube and graphene, and the two is in the direction thermal conductivity for being parallel to its graphite lattice
It can be very prominent.In terms of mechanics carbon nanotube weaker perpendicular to axial direction intensity, graphene is in perpendicular lattice direction
The presently found highest material of intensity.Therefore it is multiple that the characteristics of people both start with synthesizes a kind of graphene-carbon nano tube
Condensation material obtains more preferably electrochemistry and heat, mechanical property by synergistic effect between the two.For example preferably items are gone together
Conduction, heating conduction and higher mechanical strength.
Currently, graphene-carbon nano tube composite material preparation method includes electrophoretic deposition, vacuum filtration method, painting is made
Embrane method, in-situ chemical reducing process.But these methods limit the area of film, and obtained film thickness is difficult to control unevenness
It is even.Chemical vapour deposition technique can prepare large area film in homogeneous thickness, be that prepare carbon nanomaterial at present most commonly used
Method, but general synthetic method is all that another layer of carbon nanotube is synthesized on one layer of graphene-based bottom either in one layer of carbon nanometer
Another layer of graphene is synthesized in pipe substrate, the two is difficult to really carry out In-situ reaction.
Summary of the invention
The present invention is directed to graphene and carbon nanotube These characteristics, it is desirable to provide one kind have good isotropism it is conductive,
Graphene/graphene oxide-carbon nano tube compound material preparation method of heating conduction and more high strength.
Technical scheme is as follows:
A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material, comprising the following steps:
Step 1, graphene or graphene oxide are dispersed in the mixed liquor of second alcohol and water using ultrasound, are configured to
The dispersion liquid that graphene or graphene oxide content are 0.1-5mg/mL；
Step 2, iron content class nanocatalyst and sulphur-containing substance are added in dispersion liquid, are ultrasonically formed each component and uniformly divide
Scattered mixed dispersion liquid；
Step 3, mixed dispersion liquid is subjected to hydro-thermal reaction under agitation, then cooled to room temperature, product from
Washing, drying, obtain reaction product after heart separation；
Step 4, reaction product is deposited by chemical vapour deposition technique, deposition is divided into three humidity provinces, respectively
Gasification zone, the first flat-temperature zone and the second flat-temperature zone, deposition process are that gasification zone is first warming up to 150-600 under vacuum conditions
DEG C, the first flat-temperature zone and the second flat-temperature zone are warming up to 1100-1400 DEG C, argon gas and hydrogen are then passed to, so that argon gas and hydrogen
Full of entire reaction compartment, then it is passed through carbon source, makes carbon source successively by gasification zone, the first flat-temperature zone and the second flat-temperature zone, anti-
It answers surface to grow nano-sized carbon, obtains graphene/graphene oxide-carbon nano tube compound material.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, iron content in step 2
Class nanocatalyst is one or more of in ferrocene, ferroso-ferric oxide, green vitriol.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, sulfur-bearing in step 2
Substance is thiophene or simple substance sulphur powder.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, iron content in step 2
The mass ratio of class nanocatalyst and graphene is 10:1-1:10.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, sulfur-bearing in step 2
The mass ratio of substance and graphene is 2:1-1:10.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, described in step 1
Graphene film diameter is 1-5 μm, and with a thickness of 1-2nm, carbon content 99.5%, graphene oxide microplate specification is 0.5-5 μm of piece diameter,
With a thickness of 0.8-1.2nm, carbon content 99.5%.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, hydro-thermal in step 3
Reaction temperature is 80-250 DEG C, reaction time 10-12h.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, three in step 4
The head of district of humidity province is 350mm or more.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, argon gas in step 4
The speed that is passed through with hydrogen is 1-3L/min, and the volume ratio that is passed through of argon gas and hydrogen is 1:1-4.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, anti-in step 4
After answering surface to grow nano-sized carbon, first stop being passed through hydrogen, band temperature of reaction system stops being passed through argon again after being reduced to room temperature
Gas obtains graphene/graphene oxide-carbon nano tube compound material.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method, described in step 4
Carbon source is any one in dehydrated alcohol, benzene, methane or ethylene.
Further, graphene/graphene oxide-carbon nano tube compound material preparation method is passed through in step 4
Carbon source is carried out using syringe pump, and charge velocity is 5-20 mL/min, deposition reaction time 60-120min.
The present invention passes through in hydro-thermal method load first with graphene or the biggish specific surface area of graphene oxide on its surface
Nanometer iron-containing catalyst and sulphur-containing substance, then carbon nanometer is grown in graphene or graphene oxide table with chemical vapour deposition technique
Pipe, while realizing that graphene or graphene oxide and carbon pipe carry out In-situ reaction and obtain graphene/graphene oxide-carbon nanotube
Composite material.In addition graphene oxide heat-treats removal surface group under high temperature anaerobic environment and forms redox graphene tool
There are physicochemical properties similar with graphene.
In the preparation method of graphene/graphene oxide-carbon nano tube compound material provided by the invention, reaction is produced
Object is by chemical vapor deposition carbon nanotubes, and present invention employs three sections of temperature regions, respectively gasification zone, the first perseverance
Warm area and the second flat-temperature zone, compared to conventional chemical vapour deposition technique, flat-temperature zone of the invention is provided with two, this is because
In the present invention, first by loading nanometer iron-containing catalyst and sulphur-containing substance in graphene or surface of graphene oxide, then
Carbon nanotube is grown in graphene or surface of graphene oxide by chemical vapour deposition technique again, in the growth course of carbon nanotube
In, time longer than Common deposition and distance are needed, carbon source and graphene or graphene oxide after gasification can be triggered
The abundant reaction of the nanometer iron-containing catalyst and sulphur-containing substance of area load, forms the carbon nanotube of In-situ reaction, this is this hair
Otherwise the bright key point for being different from conventional deposition method can not form good In-situ reaction effect.
The present invention mixes film build method compared to other graphenes (graphene oxide)-carbon nanotube, using chemical gaseous phase
Graphene (graphene oxide) and carbon nanotube are carried out In-situ reaction by sedimentation, and without introducing other surfaces activating agent and dividing
Powder etc., the material finally obtained have superior performance.It is compared with conventional chemical vapor method, the present invention first bears catalyst
It is loaded on graphene (graphene oxide) lamella for use, waits and put the graphene (graphene oxide) for having loaded catalyst when reactions
Enter reaction chamber, can both make catalyst and graphene (graphene oxide) enter vapor deposition in the form of integrated anti-
Region is answered, solves the problems, such as that catalyst enters reaction chamber, and catalyst distribution can be made more evenly, obtains each uniform to performance
Carbon nanotube sedimentary.In addition it is compared with conventional chemical vapor sedimentation, reaction divides into three sections, and reaction zone constant temperature zone is more
Long, catalyst and vapor deposition reaction separate, and catalyst can prepare in advance, can preferably save the time, increase anti-every time
The yield of material should be prepared.
Specific embodiment:
Below by specific embodiment, the invention will be further described, but should not be construed the above-mentioned theme model of the present invention
It encloses and is only limitted to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge
And customary means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1
It 1) is 1-3 μm by piece diameter, with a thickness of 1-2nm, the graphene microchip that carbon content is 99.5% is uniform under ultrasonication
It is dispersed in dehydrated alcohol and water mixed solution, is configured to the dispersion liquid that graphene content is 0.1mg/mL；
2) ferrocene and thiophene are added in the scattered dispersion liquid of step 1), ultrasound 15 minutes evenly dispersed.Two cyclopentadienyls
Iron and graphene mass ratio are 10:1, and thiophene and graphene mass ratio are 2:1.
3) dispersion liquid prepared in step 2 is put into the stainless steel water thermal response of polytetrafluoroethyllining lining under stiring
In kettle.12h, after reaction, cooled to room temperature are reacted at 200 DEG C.Reaction product separating, washing, drying, for use.
4) reaction product dried in step 3) is added in corundum crucible, is deposited by chemical vapour deposition technique
Carbon source, deposition reaction area include three humidity provinces, respectively gasification zone, the first flat-temperature zone and the second flat-temperature zone, deposition reaction area
Vacuumize, gasification zone temperature then risen to 600 DEG C, the first flat-temperature zone and the second flat-temperature zone temperature rise to 1400 DEG C, then to
Deposition reaction area is passed through the argon gas and hydrogen of 1L/mim, and it is 1:1 that argon gas and hydrogen, which are passed through volume ratio,.It is being passed through argon gas and hydrogen
It is full of entire reaction compartment after 4min, dehydrated alcohol is then passed through to reaction zone by syringe pump, charge velocity 20mL/min,
React 60min.After the reaction was completed, stop heating, close hydrogen, when the temperature in the furnace chamber all drops to room temperature, close
Argon gas.It opens furnace chamber and takes out reaction product.Obtain graphene-carbon nano tube composite material.
Embodiment 2
It 1) is 1-3 μm by piece diameter, with a thickness of 1-2nm, the graphene microchip that carbon content is 99.5% is uniform under ultrasonication
It is dispersed in dehydrated alcohol and water mixed solution, is configured to the dispersion liquid that graphene content is 0.1mg/mL；
2) ferrocene and thiophene are added in the scattered dispersion liquid of step 1), ultrasound 15 minutes evenly dispersed.Two cyclopentadienyls
Iron and graphene mass ratio are 1:10, and thiophene and graphene mass ratio are 1:10.
3) dispersion liquid prepared in step 2 is put into the stainless steel water thermal response of polytetrafluoroethyllining lining under stiring
In kettle.12h, after reaction, cooled to room temperature are reacted at 200 DEG C.Reaction product separating, washing, drying, for use.
4) reaction product dried in step 3) is added in corundum crucible, is deposited by chemical vapour deposition technique
Carbon source, deposition reaction area include that three humidity provinces as described in example 1 above first vacuumize deposition reaction area, then will gasification
Area's temperature rises to 150 DEG C, and the first flat-temperature zone and the second flat-temperature zone temperature rise to 1100 DEG C, is then passed through 2L/ to deposition reaction area
It is 1:2 that the argon gas and hydrogen of mim, argon gas and hydrogen, which are passed through volume ratio,.Full of entire reaction after being passed through argon gas and hydrogen 3min
Then space is passed through benzene to reaction zone by syringe pump, charge velocity 5mL/min reacts 120min.After the reaction was completed, stop
It only heats, closes hydrogen, when the temperature in the furnace chamber all drops to room temperature, close argon gas.It opens furnace chamber and takes out reaction production
Object.Obtain graphene-carbon nano tube composite material.
Embodiment 3
It 1) is 0.5-5 μm of piece diameter by specification, with a thickness of 0.8-1.2nm, the graphene oxide microplate that carbon content is 99.5% exists
It is dispersed in dehydrated alcohol and water mixed solution under ultrasonication, is configured to the dispersion that graphene oxide content is 5mg/mL
Liquid；
2) ferrocene and thiophene are added in the scattered dispersion liquid of step 1), ultrasound 15 minutes evenly dispersed.Two cyclopentadienyls
Iron and graphene oxide mass ratio are 10:1, and thiophene and graphene oxide mass ratio are 2:1.
3) dispersion liquid prepared in step 2 is put into the stainless steel water thermal response of polytetrafluoroethyllining lining under stiring
In kettle.12h, after reaction, cooled to room temperature are reacted at 200 DEG C.Reaction product separating, washing, drying, for use.
4) reaction product dried in step 3) is added in corundum crucible, is deposited by chemical vapour deposition technique
Carbon source, deposition reaction area include that three humidity provinces as described in example 1 above first vacuumize deposition reaction area, then will gasification
Area's temperature rises to 500 DEG C, and the first flat-temperature zone and the second flat-temperature zone temperature rise to 1300 DEG C, is then passed through 3L/ to deposition reaction area
It is 1:3 that the argon gas and hydrogen of mim, argon gas and hydrogen, which are passed through volume ratio,.Full of entire reaction after being passed through argon gas and hydrogen 3min
Then space is passed through methane to reaction zone by syringe pump, charge velocity 10mL/min reacts 100min.After the reaction was completed,
Stop heating, close hydrogen, when the temperature in the furnace chamber all drops to room temperature, closes argon gas.It opens furnace chamber and takes out reaction
Product.Obtain graphene-carbon nano tube composite material.
Embodiment 4
It 1) is 0.5-5 μm of piece diameter by specification, with a thickness of 0.8-1.2nm, the graphene oxide microplate that carbon content is 99.5% exists
It is dispersed in dehydrated alcohol and water mixed solution under ultrasonication, is configured to the dispersion that graphene oxide content is 5mg/mL
Liquid；
2) ferroso-ferric oxide and simple substance sulphur powder are added in the scattered dispersion liquid of step 1), are uniformly divided within ultrasound 15 minutes
It dissipates.Ferroso-ferric oxide and graphene oxide mass ratio are 10:1, and simple substance sulphur powder and graphene oxide mass ratio are 2:1.
3) dispersion liquid prepared in step 2 is put into the stainless steel water thermal response of polytetrafluoroethyllining lining under stiring
In kettle.11h, after reaction, cooled to room temperature are reacted at 200 DEG C.Reaction product separating, washing, drying, for use.
4) reaction product dried in step 3) is added in corundum crucible, is deposited by chemical vapour deposition technique
Carbon source, deposition reaction area include that three humidity provinces as described in example 1 above first vacuumize deposition reaction area, then will gasification
Area's temperature rises to 600 DEG C, and the first flat-temperature zone and the second flat-temperature zone temperature rise to 1300 DEG C, is then passed through 3L/ to deposition reaction area
It is 1:4 that the argon gas and hydrogen of mim, argon gas and hydrogen, which are passed through volume ratio,.Full of entire reaction after being passed through argon gas and hydrogen 3min
Then space is passed through ethylene to reaction zone by syringe pump, charge velocity 15mL/min reacts 60min.After the reaction was completed,
Stop heating, close hydrogen, when the temperature in the furnace chamber all drops to room temperature, closes argon gas.It opens furnace chamber and takes out reaction
Product.Obtain graphene-carbon nano tube composite material.
Embodiment 5
It 1) is 3-5 μm of piece diameter by specification, with a thickness of 0.8-1.2nm, the graphene oxide microplate that carbon content is 99.5% is super
It is dispersed in dehydrated alcohol and water mixed solution under sound effect, is configured to the dispersion that graphene oxide content is 5mg/mL
Liquid；
2) green vitriol and simple substance sulphur powder are added in the scattered dispersion liquid of step 1), ultrasound 15 minutes equal
Even dispersion.Green vitriol and graphene oxide mass ratio are 10:1, and simple substance sulphur powder and graphene oxide mass ratio are 2:
1。
3) dispersion liquid prepared in step 2 is transferred in three-necked flask, is stirred to react 50min under argon filling gas shielded,
Then 10h is dried under 80 DEG C of vacuum conditions, it is stand-by after reaction product drying.
4) reaction product dried in step 3) is added in corundum crucible, is deposited by chemical vapour deposition technique
Carbon source, deposition reaction area include that three humidity provinces as described in example 1 above first vacuumize deposition reaction area, then will gasification
Area's temperature rises to 600 DEG C, and the first flat-temperature zone and the second flat-temperature zone temperature rise to 1300 DEG C, is then passed through 3L/ to deposition reaction area
It is 1:4 that the argon gas and hydrogen of mim, argon gas and hydrogen, which are passed through volume ratio,.Full of entire reaction after being passed through argon gas and hydrogen 3min
Then space is passed through ethylene to reaction zone by syringe pump, charge velocity 15mL/min reacts 60min.After the reaction was completed,
Stop heating, close hydrogen, when the temperature in the furnace chamber all drops to room temperature, closes argon gas.It opens furnace chamber and takes out reaction
Product.Obtain graphene-carbon nano tube composite material.
In above embodiments 1-5, three humidity provinces in step 4) in chemical vapor deposition, the length in each area is
350mm or more.
It is tested for the property after the composite material film that the present invention obtains, as a result as follows:
| Sheet resistance (Ω/) | Conductivity (S/m) | Intensity (Mpa) | Thermally conductive (W/m*k) |
| 1-2 | 1-5×105 | 80-200 | 400-600 |
The composite material that method provided by the invention is prepared, wherein conductivity 1-5 × 105S/m is respectively higher than more
Wall carbon nano tube and the respective conductivity of multi-layer graphene, can reach the level of volume production single-walled carbon nanotube, thermal coefficient
400-600 W/m*k is higher than the thermally conductive preferable metals such as copper, silver.Intensity 80-200Mpa will be apparently higher than suction filtration, the methods of spin coating
Obtained composite material.And it finds during the test, the conductivity and thermal coefficient of material are very uniform, and different directions are measured
Conductivity and thermal coefficient very close to isotropism is good.
The preparation method that the present invention improves first passes through hydro-thermal method and loads to catalyst on graphene or graphene oxide,
Then by chemical vapor deposition carbon nanotube, during the deposition process, due in order to reach expected deposition effect, this
Flat-temperature zone is provided with two regions by invention, and the length in each region is all larger than 350mm, the study found that improved in the present invention
When depositing under the conditions of the head of district, deposition reaction can be triggered well, and then deposited and obtained uniform carbon nanotube deposition
Layer, reaches good In-situ reaction effect.
Claims (12)
1. a kind of preparation method of graphene/graphene oxide-carbon nano tube compound material, which is characterized in that including following step
It is rapid:
Step 1, graphene or graphene oxide are dispersed in the mixed liquor of second alcohol and water using ultrasound, are configured to graphite
The dispersion liquid that alkene or graphene oxide content are 0.1-5mg/mL；
Step 2, iron content class nanocatalyst and sulphur-containing substance are added in dispersion liquid, it is evenly dispersed is ultrasonically formed each component
Mixed dispersion liquid；
Step 3, mixed dispersion liquid is subjected to hydro-thermal reaction under agitation, then cooled to room temperature, product centrifugation point
From rear washing, drying, reaction product is obtained；
Step 4, reaction product is subjected to deposition carbon source by chemical vapour deposition technique, deposition is divided into three humidity provinces, respectively
Gasification zone, the first flat-temperature zone and the second flat-temperature zone, deposition process are that gasification zone is first warming up to 150-600 under vacuum conditions
DEG C, the first flat-temperature zone and the second flat-temperature zone are warming up to 1100-1400 DEG C, argon gas and hydrogen are then passed to, so that argon gas and hydrogen
Full of entire reaction compartment, then it is passed through carbon source, makes carbon source successively by gasification zone, the first flat-temperature zone and the second flat-temperature zone, anti-
It answers surface to grow nano-sized carbon, obtains graphene/graphene oxide-carbon nano tube compound material.
2. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, iron content class nanocatalyst is one or more of in ferrocene, ferroso-ferric oxide, green vitriol in step 2.
3. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, sulphur-containing substance is thiophene or simple substance sulphur powder in step 2.
4. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, the mass ratio of iron content class nanocatalyst and graphene is 10:1-1:10 in step 2.
5. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, the mass ratio of sulphur-containing substance and graphene is 2:1-1:10 in step 2.
6. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, graphene film diameter described in step 1 is 1-5 μm, with a thickness of 1-2nm, carbon content 99.5%, graphene oxide microplate rule
Lattice are 0.5-5 μm of piece diameter, with a thickness of 0.8-1.2nm, carbon content 99.5%.
7. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, hydrothermal temperature is 80-250 DEG C in step 3, reaction time 10-12h.
8. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, the head of district of three humidity provinces is 350mm or more in step 4.
9. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, the speed that is passed through of argon gas and hydrogen is 1-3L/min in step 4, and the volume ratio that is passed through of argon gas and hydrogen is 1:1-4.
10. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, in step 4 after reaction product surface has grown nano-sized carbon, first stops being passed through hydrogen, be reduced to room to temperature of reaction system
Wen Houzai stopping is passed through argon gas, obtains graphene/graphene oxide-carbon nano tube compound material.
11. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, carbon source described in step 4 is any one in dehydrated alcohol, benzene, methane or ethylene.
12. the preparation method of graphene/graphene oxide-carbon nano tube compound material according to claim 1, feature
It is, carbon source is passed through in step 4 and is carried out using syringe pump, and charge velocity is 5-20 mL/min, deposition reaction time 60-
120min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711191049.XA CN108069420B (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711191049.XA CN108069420B (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108069420A CN108069420A (en) | 2018-05-25 |
| CN108069420B true CN108069420B (en) | 2019-02-19 |
Family
ID=62157448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711191049.XA Active CN108069420B (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108069420B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109862637A (en) * | 2019-01-18 | 2019-06-07 | 南京航空航天大学 | A kind of anti-deicing electric heating device and preparation method with graphene-carbon nano tube composite material |
| CN111138627B (en) * | 2020-01-09 | 2022-04-22 | 新疆亿元达光电科技有限公司 | Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof |
| CN111154279A (en) * | 2020-01-09 | 2020-05-15 | 新疆宏宇志祥工程咨询有限公司 | Graphene/carbon nanotube modified epoxy resin asphalt material and preparation method thereof |
| CN111138150A (en) * | 2020-01-09 | 2020-05-12 | 新疆宏宇志祥工程咨询有限公司 | Preparation method of graphene oxide/carbon nanotube high-strength building concrete |
| CN111952577B (en) * | 2020-08-25 | 2022-05-06 | 浙江理工大学 | C/Si/CNTs composite carbon nanofiber membrane, preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811690B (en) * | 2009-02-24 | 2012-02-29 | 国家纳米科学中心 | Method for forming carbon composite structure by using carbon nano tube and graphene |
| CN102530931B (en) * | 2011-12-14 | 2014-04-02 | 天津大学 | Graphene-based nano composite material and preparation method thereof |
| CN103303901B (en) * | 2013-06-05 | 2016-02-17 | 山西大同大学 | A kind of method at graphenic surface carbon nano-tube |
| CN105000542B (en) * | 2015-04-27 | 2017-07-07 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method of graphene carbon nanotube three-dimensional structure composite |
-
2017
- 2017-11-24 CN CN201711191049.XA patent/CN108069420B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108069420A (en) | 2018-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108069420B (en) | A kind of preparation method of graphene/graphene oxide-carbon nano tube compound material | |
| Wu et al. | Biomass-derived 3D magnetic porous carbon fibers with a helical/chiral structure toward superior microwave absorption | |
| Wang et al. | Controllable seeding of nitrogen-doped carbon nanotubes on three-dimensional Co/C foam for enhanced dielectric loss and microwave absorption characteristics | |
| Dong et al. | Biomass-derived carbon and polypyrrole addition on SiC whiskers for enhancement of electromagnetic wave absorption | |
| Ji et al. | Electromagnetic shielding behavior of heat-treated Ti3C2TX MXene accompanied by structural and phase changes | |
| Ganesan et al. | Activated graphene-derived porous carbon with exceptional gas adsorption properties | |
| CN105368045B (en) | Graphene polypyrrole composite aerogel and preparation method and application | |
| Mikhalchan et al. | Continuous and scalable fabrication and multifunctional properties of carbon nanotube aerogels from the floating catalyst method | |
| Wu et al. | Biomass-derived sponge-like carbonaceous hydrogels and aerogels for supercapacitors | |
| Nieto-Márquez et al. | Carbon nanospheres: synthesis, physicochemical properties and applications | |
| Reyhani et al. | H2 adsorption mechanism in Mg modified multi-walled carbon nanotubes for hydrogen storage | |
| Lei et al. | Porous graphitic carbon materials prepared from cornstarch with the assistance of microwave irradiation | |
| Gherghel et al. | Pyrolysis in the mesophase: a chemist's approach toward preparing carbon nano-and microparticles | |
| Li et al. | Synthesis of carbon nanofiber/graphite-felt composite as a catalyst | |
| CN106517171B (en) | A kind of preparation method of graphene aerogel | |
| Dassios et al. | Polymer–nanotube interaction in MWCNT/poly (vinyl alcohol) composite mats | |
| Qi et al. | Simultaneous synthesis of carbon nanobelts and carbon/Fe–Cu hybrids for microwave absorption | |
| CN105000542A (en) | Preparation method for graphene-carbon nano tube three-dimensional structure composite material | |
| CN106024424A (en) | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof | |
| CN106629690A (en) | Method for reinforcing three-dimensional graphene porous material structure | |
| Castillejos et al. | Structural and surface modifications of carbon nanotubes when submitted to high temperature annealing treatments | |
| Zhang et al. | Construction of chiral-magnetic-dielectric trinity composites for efficient microwave absorption with low filling ratio and thin thickness | |
| He et al. | Construction of heterointerfaces and honeycomb-like structure for ultrabroad microwave absorption | |
| Qian et al. | Synthesis and tunable electromagnetic shielding and absorption performance of the three-dimensional SiC nanowires/carbon fiber composites | |
| Zhao et al. | Biomass-derived ultralight superior microwave absorber Towards X and Ku bands |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 211805 No. 29 Buyue Road, Pukou Economic Development Zone, Qiaolin Street, Pukou District, Nanjing City, Jiangsu Province Patentee after: Jiangsu Xianfeng nano Mstar Technology Ltd Address before: 211805 No. 29, bu Yue Road, Qiaolin street, Pukou District, Nanjing, Jiangsu. Patentee before: Jiangsu Xianfeng nano Mstar Technology Ltd |