CN108439389A - A kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance - Google Patents
A kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance Download PDFInfo
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- CN108439389A CN108439389A CN201810318432.5A CN201810318432A CN108439389A CN 108439389 A CN108439389 A CN 108439389A CN 201810318432 A CN201810318432 A CN 201810318432A CN 108439389 A CN108439389 A CN 108439389A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The present invention relates to a kind of preparation methods of the carbon nano tube/graphene foam with Meta Materials performance, it is related to a kind of preparation method of carbon nano tube/graphene foam.Meta Materials are the new academic vocabulary that this century physics field occurs, and are a kind of artificial composite structures or Composite Media with the extraordinary physical property not available for natural medium, have negative dielectric constant and negative magnetic conductivity.Meta Materials all concentrate on the design of complicated geometry so far.The dielectric constant of carbon nano tube/graphene foam prepared by the present invention is complete negative within the scope of 1MHz 1GHz, and magnetic conductivity is in 5.3x108 Hz–109Occurs negative value within the scope of Hz.The present invention prepares Meta Materials by the method for materials synthesis, helps to expand application of the Meta Materials in the fields such as stealthy, miniature antenna and electronic component.The present invention can be used for preparing nano combined electromagnetism Meta Materials.
Description
Technical field
The present invention relates to a kind of preparation methods of the carbon nano tube/graphene foam with Meta Materials performance.
Background technology
Graphene is by sp2The carbon atom of hydridization be interconnected to constitute only there are one the two-dimentional crystalline state of atomic layer level thickness is super
Thin material, it is cellular in hexagonal annular between carbon atom, it is connected with each other with covalent bond, is proper two dimensional surface material
Material, grapheme foam is that graphene sheet layer stacked in multi-layers is formed, and has three-dimensional net structure, the three-dimensional network of grapheme foam is led
Electric structure has important influence for the negative permittivity of Meta Materials and the performance of negative magnetoconductivity.The method aoxidized by strong acid
Carbon nanotube is carried out surface to be modified being a kind of common chemical modification method, carbon nanotube is carried out at reflux using all kinds of acid
Reason, can obtain length more uniformly, the carbon nanotube of both ends open, and introduce a large amount of carboxyls and hydroxyl in port and side wall
Equal functional groups.Water-heat process addition carbon pipe modified graphene foam can improve the electromagnetic performance of grapheme foam.But at present
Still no carbon nano tube/graphene foam has the research of Meta Materials performance.Some researches show that normal by positive dielectric appropriate
Meta Materials may be implemented in stealthy, miniature antenna and electronic component in number, negative permittivity, positive magnetic conductivity and negative magnetoconductivity combination
The application in equal fields.
Therefore the negative permittivity using control carbon nanotube additive amount control carbon nano tube/graphene foam and negative magnetic conductance
Rate is of great significance for its application in Meta Materials field.
Invention content
The carbon nano tube/graphene with negative permittivity and negative magnetoconductivity can not be synthesized the invention solves existing method
The problem of foam, and a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance provided.
A kind of preparation method of carbon nano tube/graphene foam with Meta Materials performance proposed by the present invention is specific to walk
It is rapid as follows：
（1）Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, is measured 120ml mixed acid solutions and is added
Into single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, and then single-necked flask is placed on magnetic stirring apparatus,
40-60 °C of oil bath is heated at reflux, and reacts 3-8h；Then it is washed until filter with 0.45 μm of PP filtering with microporous membrane, deionized water
Until liquid is in neutrality, vacuum drying is for 24 hours to get acidification carbon nanotube at 80 DEG C（CNTs-COOH4h）；
（2）Prepare graphene oxide：Under 0 °C of ice-water bath, by 5g natural flake graphites be added slowly with stirring equipped with
In the three-necked flask of the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, continues to tie up under stiring
0 °C of stirring half an hour is held, is then stirred 2 hours under the conditions of temperature is not above 20 °C, then 35 °C of conditions are not higher than in temperature
Lower stirring 2 hours；Then it is keeping under room temperature, deionized water being added until there is no sputtering phenomenon in three-necked flask, after
Continuous stirring half an hour；30% hydrogen peroxide is added, until mixture becomes glassy yellow and there is no bubble generations from dark brown；It will mix
Object sedimentation separation is closed, the acid waste liquid dissolved with small amounts graphene is removed, 5-10% hydrochloric acid solutions are added and fully wash mixture,
Until there is no S042—It generates；Ammonium hydroxide is added into the mixture graphite oxide after salt acid elution to pH value close to neutrality, then
It is washed repeatedly with deionized water, until using AgN03Solution is examined to be occurred without precipitation；Neutral product sedimentation separation or logical will be washed till
Centrifuge separation of solid and liquid is crossed, finally obtained graphite oxide is tacky, brown colloidal；It is cold that gained graphite oxide is put into vacuum
Freeze in drying equipment and processing is dried, obtains graphite oxide fluffy solid.The cotton-shaped powder of dried graphite oxide is taken, is dissolved in
It in deionized water, is sufficiently stirred, then so that oxidized graphite flake layer is removed to be ultrasonically treated in ultrasonic cleaner, obtain light
The graphite oxide suspension of yellow；
（3）Prepare carbon nano tube/graphene foam：By step（2）The graphene oxide suspension 30ml of obtained 10mg/ml and
Step（1）Solution is placed in hydro-thermal by obtained acidification carbon nanotube mixing, stirring 2h in being ultrasonically treated 2h in supersonic cleaning machine
In reaction kettle, 150-210 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon
Nanotube composite graphite alkene hydrogel；By carbon nanotube composite graphite alkene hydrogel in the pre- lower freezing of -50 DEG C of conditions of low temperature refrigerator
2h is placed in freeze drier, is freeze-dried 3 days, is obtained carbon nanotube composite graphite alkene aeroge；Wherein：Graphene oxide
Suspension is 1 with acidification carbon nanotube mass ratio:1 - 1:5；
（4）Foam post-processes：By step（3）Obtained carbon nanotube composite graphite alkene aeroge is in 900-1100 DEG C in tube furnace
At a temperature of be heat-treated, remove extra oxygen-containing functional group, obtain carbon nano tube/graphene foam.
In the present invention, step（1）Described in mixed acid solution by dense HNO3With dense H2SO4Solution composition, dense HNO3：It is dense
H2SO4Mass ratio is 1:1 to 1:3.
The beneficial effects of the present invention are：One, the present invention changes carbon nanotube progress surface by the method that strong acid aoxidizes
Property, reflow treatment is carried out to carbon nanotube using nitration mixture, can obtain length more uniformly, the carbon nanotube of both ends open, and
And the functional groups such as a large amount of carboxyls and hydroxyl are introduced in port and side wall, addition acidification carbon pipe, improves graphite in water-heat process
The electromagnetic performance of alkene foam.Two, the dielectric constant of carbon nano tube/graphene foam prepared by the present invention is in 1MHz-1GHz ranges
Interior to be born to be complete, magnetic conductivity is in 5.3x108 Hz– 109Occurs negative value within the scope of Hz.Compared with the conventional method, the spy with negative value
Property.Three, carbon nano tube/graphene foam prepared by the present invention can be applicable to Meta Materials in stealthy, miniature antenna and electronics member device
The fields such as part.
Description of the drawings
Fig. 1 is the carbon nano tube/graphene foam tested in one（GA-CNT-1:3）Scanning electron microscope (SEM) photograph.
Specific implementation mode
The following examples are the further explanations to the present invention, rather than are limited the scope of the invention.
Embodiment 1：The present embodiment is a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance,
It carries out according to the following steps.
（1）Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, measures 120ml mixed acid solutions
（Dense HNO3：Dense H2SO4Mass ratio is 1:1）It is added in single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, so
Reaction unit is placed on magnetic stirring apparatus afterwards, 50 °C of oil baths are heated at reflux, and react 4h；Then with 0.45 μm of PP miillpore filters
Until filtrate is in neutrality, vacuum drying is for 24 hours up to acidification carbon nanotube at 80 DEG C for filtering, deionized water washing（CNTs-
COOH4h）.
（2）Prepare graphene oxide：Under 0 DEG C of ice-water bath, 5g natural flake graphites are added slowly with stirring dress
In the three-necked flask for having the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, is continued under stiring
It maintains 0 DEG C of stirring half an hour, control temperature to be stirred 2 hours not above 20 DEG C, is stirred 2 hours not higher than 35 DEG C；Keeping room
Under the conditions of temperature, appropriate amount of deionized water is added until there is no sputtering phenomenon in reaction bulb, continues to stir half an hour；It is added appropriate
30% hydrogen peroxide, until mixture becomes glassy yellow and there is no bubble generations from dark brown.By mixture sedimentation separation, remove
Dissolved with the acid waste liquid of small amounts graphene, 5-10% hydrochloric acid solutions are added and fully wash mixture, until there is no S042—；To
Appropriate ammonium hydroxide is added in graphite oxide after salt acid elution to pH value close to neutrality, is then washed repeatedly with deionized water, until using
AgN03Solution is examined to be occurred without precipitation；Neutral product sedimentation separation will be washed till or is separated by solid-liquid separation by centrifuge, final
The graphite oxide that arrives is tacky, brown colloidal；Gained graphite oxide is put into vacuum freeze, place is dried
Reason, obtains graphite oxide fluffy solid.
（3）Prepare carbon nano tube/graphene foam：The graphene oxide solution 30ml for configuring 10mg/ml, respectively according to oxygen
Graphite olefinic carbon Nanotube quality ratio is 1:3, solution is stirred into 2h, in being ultrasonically treated 2h in supersonic cleaning machine, solution is placed in
In hydrothermal reaction kettle, 200 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon
Nanotube composite graphite alkene hydrogel.By carbon nanotube composite graphite alkene hydrogel in -50 DEG C of condition precooling 2h of low temperature refrigerator
It is placed in freeze drier, is freeze-dried 3 days, obtains carbon nanotube composite graphite alkene aeroge.
（4）Foam post-processes：By carbon nanotube composite graphite alkene aeroge in 900 DEG C of heat treatment in tube furnace, removal is more
Remaining oxygen-containing functional group.
Advantages of the present invention：One, the present invention carries out surface modification by the method that strong acid aoxidizes to carbon nanotube, using mixed
Acid carries out reflow treatment to carbon nanotube, can obtain length more uniformly, the carbon nanotube of both ends open, and in port and
Side wall introduces the functional groups such as a large amount of carboxyls and hydroxyl；Two, high-speed stirred is used during the reaction, ensure that the equal of reaction system
The dispersibility of one property and multi-walled carbon nanotube；Just multi-walled carbon nanotube is added when three, configuring dispersion liquid, and by its ultrasound anti-
It answers in liquid, ensure that its dispersibility in synthetic system.Four, water-heat process adds carbon pipe, improves the electricity of grapheme foam
Magnetic characteristic.
The dielectric constant of carbon nano tube/graphene foam prepared by the present invention is complete negative, magnetic conductance within the scope of 1MHz-1GHz
Rate is in 5.3x108 Hz– 109Occur negative value within the scope of Hz, compared with the conventional method, the characteristic with negative value.
Carbon nano tube/graphene foam prepared by the present invention can be applicable to the necks such as stealthy, miniature antenna and electronic component
Domain.
Embodiment 2：The present embodiment is a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance,
It carries out according to the following steps.
（1）Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, measures 120ml mixed acid solutions
（Dense HNO3：Dense H2SO4Mass ratio is 1:2）It is added in single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, so
Reaction unit is placed on magnetic stirring apparatus afterwards, 60 °C of oil baths are heated at reflux, and react 5h；Then it is filtered with 0.45 μm of PP micropores
Until filtrate is in neutrality, vacuum drying is for 24 hours up to acidification carbon nanotube at 80 DEG C for membrane filtration, deionized water washing
（CNTs-COOH4h）.
（2）Prepare graphene oxide：Under 0 DEG C of ice-water bath, 5g natural flake graphites are added slowly with stirring dress
In the three-necked flask for having the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, is continued under stiring
It maintains 0 DEG C of stirring half an hour, control temperature to be stirred 2 hours not above 20 DEG C, is stirred 2 hours not higher than 35 DEG C；Keeping room
Under the conditions of temperature, appropriate amount of deionized water is added until there is no sputtering phenomenon in reaction bulb, continues to stir half an hour；It is added appropriate
30% hydrogen peroxide, until mixture becomes glassy yellow and there is no bubble generations from dark brown.By mixture sedimentation separation, remove
Dissolved with the acid waste liquid of small amounts graphene, 5-10% hydrochloric acid solutions are added and fully wash mixture, until there is no S042—；To
Appropriate ammonium hydroxide is added in graphite oxide after salt acid elution to pH value close to neutrality, is then washed repeatedly with deionized water, until using
AgN03Solution is examined to be occurred without precipitation；Neutral product sedimentation separation will be washed till or is separated by solid-liquid separation by centrifuge, final
The graphite oxide that arrives is tacky, brown colloidal；Gained graphite oxide is put into vacuum freeze, place is dried
Reason, obtains graphite oxide fluffy solid.
（3）Prepare carbon nano tube/graphene foam：The graphene oxide solution 30ml for configuring 10mg/ml, respectively according to oxygen
Graphite olefinic carbon Nanotube quality ratio is 1:4, solution is stirred into 2h, in being ultrasonically treated 2h in supersonic cleaning machine, solution is placed in
In hydrothermal reaction kettle, 210 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon
Nanotube composite graphite alkene hydrogel.By carbon nanotube composite graphite alkene hydrogel in -50 DEG C of condition precooling 2h of low temperature refrigerator
It is placed in freeze drier, is freeze-dried 3 days, obtains carbon nanotube composite graphite alkene aeroge.
（4）Foam post-processes：By carbon nanotube composite graphite alkene aeroge in 1100 DEG C of heat treatment in tube furnace, removal is more
Remaining oxygen-containing functional group.
Advantages of the present invention：One, the present invention carries out surface modification by the method that strong acid aoxidizes to carbon nanotube, using mixed
Acid carries out reflow treatment to carbon nanotube, can obtain length more uniformly, the carbon nanotube of both ends open, and in port and
Side wall introduces the functional groups such as a large amount of carboxyls and hydroxyl；Two, high-speed stirred is used during the reaction, ensure that the equal of reaction system
The dispersibility of one property and multi-walled carbon nanotube；Just multi-walled carbon nanotube is added when three, configuring dispersion liquid, and by its ultrasound anti-
It answers in liquid, ensure that its dispersibility in synthetic system.Four, water-heat process adds carbon pipe, improves the electricity of grapheme foam
Magnetic characteristic.
The dielectric constant of carbon nano tube/graphene foam prepared by the present invention is complete negative, magnetic conductance within the scope of 1MHz-1GHz
Rate is in 5.3x108 Hz– 109Occur negative value within the scope of Hz, compared with the conventional method, the characteristic with negative value.
Carbon nano tube/graphene foam prepared by the present invention can be applicable to the necks such as stealthy, miniature antenna and electronic component
Domain.
Embodiment 3：The present embodiment is a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance,
It carries out according to the following steps.
（1）Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, measures 120ml mixed acid solutions
（Dense HNO3：Dense H2SO4Mass ratio is 1:3）It is added in single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, so
Reaction unit is placed on magnetic stirring apparatus afterwards, 40 °C of oil baths are heated at reflux, and react 6h；Then it is filtered with 0.45 μm of PP micropores
Until filtrate is in neutrality, vacuum drying is for 24 hours up to acidification carbon nanotube at 80 DEG C for membrane filtration, deionized water washing
（CNTs-COOH4h）.
（2）Prepare graphene oxide：Under 0 DEG C of ice-water bath, 5g natural flake graphites are added slowly with stirring dress
In the three-necked flask for having the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, is continued under stiring
It maintains 0 DEG C of stirring half an hour, control temperature to be stirred 2 hours not above 20 DEG C, is stirred 2 hours not higher than 35 DEG C；Keeping room
Under the conditions of temperature, appropriate amount of deionized water is added until there is no sputtering phenomenon in reaction bulb, continues to stir half an hour；It is added appropriate
30% hydrogen peroxide, until mixture becomes glassy yellow and there is no bubble generations from dark brown.By mixture sedimentation separation, remove
Dissolved with the acid waste liquid of small amounts graphene, 5-10% hydrochloric acid solutions are added and fully wash mixture, until there is no S042—；To
Appropriate ammonium hydroxide is added in graphite oxide after salt acid elution to pH value close to neutrality, is then washed repeatedly with deionized water, until using
AgN03Solution is examined to be occurred without precipitation；Neutral product sedimentation separation will be washed till or is separated by solid-liquid separation by centrifuge, final
The graphite oxide that arrives is tacky, brown colloidal；Gained graphite oxide is put into vacuum freeze, place is dried
Reason, obtains graphite oxide fluffy solid.
（3）Prepare carbon nano tube/graphene foam：The graphene oxide solution 30ml for configuring 10mg/ml, respectively according to oxygen
Graphite olefinic carbon Nanotube quality ratio is 1:4, solution is stirred into 2h, in being ultrasonically treated 2h in supersonic cleaning machine, solution is placed in
In hydrothermal reaction kettle, 1800 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains
Carbon nanotube composite graphite alkene hydrogel.By carbon nanotube composite graphite alkene hydrogel in -50 DEG C of condition precoolings of low temperature refrigerator
2h is placed in freeze drier, is freeze-dried 3 days, is obtained carbon nanotube composite graphite alkene aeroge.
（4）Foam post-processes：By carbon nanotube composite graphite alkene aeroge in 950 DEG C of heat treatment in tube furnace, removal is more
Remaining oxygen-containing functional group.
Advantages of the present invention：One, the present invention carries out surface modification by the method that strong acid aoxidizes to carbon nanotube, using mixed
Acid carries out reflow treatment to carbon nanotube, can obtain length more uniformly, the carbon nanotube of both ends open, and in port and
Side wall introduces the functional groups such as a large amount of carboxyls and hydroxyl；Two, high-speed stirred is used during the reaction, ensure that the equal of reaction system
The dispersibility of one property and multi-walled carbon nanotube；Just multi-walled carbon nanotube is added when three, configuring dispersion liquid, and by its ultrasound anti-
It answers in liquid, ensure that its dispersibility in synthetic system.Four, water-heat process adds carbon pipe, improves the electricity of grapheme foam
Magnetic characteristic.
The dielectric constant of carbon nano tube/graphene foam prepared by the present invention is complete negative, magnetic conductance within the scope of 1MHz-1GHz
Rate is in 5.3x108 Hz– 109Occur negative value within the scope of Hz, compared with the conventional method, the characteristic with negative value.
Carbon nano tube/graphene foam prepared by the present invention can be applicable to the necks such as stealthy, miniature antenna and electronic component
Domain.
Embodiment 4：The present embodiment is a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance,
The present embodiment is as different from Example 3：Step（3）In using use carbon pipe graphene oxide mass ratio for 1:2, other
Step is identical.
Embodiment 5：The present embodiment is a kind of preparation side of the carbon nano-tube/poly aniline nano particle of Meta Materials performance parameters
Method, the present embodiment is as different from Example 2：Step（1）In using the nitration mixture mass ratio used for 1:3, other steps
It is identical.
Using the effect of following experimental verifications present invention：
Experiment one：
Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, measures 120ml mixed acid solutions（It is dense
HNO3：Dense H2SO4Mass ratio is 1:1）It is added in single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, then will
Reaction unit is placed on magnetic stirring apparatus, and 50 °C of oil baths are heated at reflux, and reacts 4h；Then with 0.45 μm of PP miillpore filter mistakes
Until filtrate is in neutrality, vacuum drying is for 24 hours up to acidification carbon nanotube at 80 DEG C for filter, deionized water washing（CNTs-
COOH4h）.
Prepare graphene oxide：Under 0 DEG C of ice-water bath, by 5g natural flake graphites be added slowly with stirring equipped with
In the three-necked flask of the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, continues to tie up under stiring
0 DEG C of stirring half an hour is held, control temperature stirs 2 hours not above 20 DEG C, is stirred 2 hours not higher than 35 DEG C；Keeping room temperature
Under the conditions of, appropriate amount of deionized water is added until there is no sputtering phenomenon in reaction bulb, continues to stir half an hour；It is added appropriate 30%
Hydrogen peroxide, until mixture becomes glassy yellow and there is no bubble generations from dark brown.By mixture sedimentation separation, remove dissolved with
The acid waste liquid of small amounts graphene is added 5-10% hydrochloric acid solutions and fully washs mixture, until there is no S042—；To hydrochloric acid
Appropriate ammonium hydroxide is added in graphite oxide after washing to pH value close to neutrality, is then washed repeatedly with deionized water, until using AgN03
Solution is examined to be occurred without precipitation；Neutral product sedimentation separation will be washed till or is separated by solid-liquid separation by centrifuge, it is finally obtained
Graphite oxide is tacky, brown colloidal；Gained graphite oxide is put into vacuum freeze, processing is dried, obtained
To graphite oxide fluffy solid.The a certain amount of cotton-shaped powder of dried graphite oxide is taken, is dissolved in deionized water by a certain concentration,
Be sufficiently stirred, then in ultrasonic cleaner with certain power ultrasonic for a period of time, so that oxidized graphite flake layer is removed, obtain it is light
The graphite oxide suspension of yellow.
Prepare carbon nano tube/graphene foam：The graphene oxide solution 30ml for configuring 10mg/ml, respectively according to oxidation
Graphene carbon Nanotube quality ratio is 1:3, solution is stirred into 2h, in being ultrasonically treated 2h in supersonic cleaning machine, solution is placed in water
In thermal response kettle, 200 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon and receive
Mitron composite graphite alkene hydrogel.By carbon nanotube composite graphite alkene hydrogel after -50 DEG C of condition precooling 2h of low temperature refrigerator
It is placed in freeze drier, is freeze-dried 3 days, obtains carbon nanotube composite graphite alkene aeroge.
Foam post-processes：By carbon nanotube composite graphite alkene aeroge in 900 DEG C of heat treatment in tube furnace, it is extra to remove
Oxygen-containing functional group.
A kind of carbon nano tube/graphene foam with Meta Materials performance prepared by this experiment is named as GA-CNT-1:3.
The carbon nano tube/graphene foam of the Meta Materials performance parameters of this experiment preparation is observed using scanning electron microscope
（GA-CNT-1:3）, the results are shown in Figure 1 for observation, and Fig. 1 is carbon nanotube/graphite with Meta Materials performance prepared by this experiment
Alkene foam, as shown in Figure 1 graphene sheet layer mutually overlap, carbon nanotube is attached on graphene sheet layer.These mutually overlap shape
At vesicular texture, be the reason of it is with negative magnetoconductivity.
The carbon nano tube/graphene foam with Meta Materials performance of this experiment preparation is tested using Agilent E4991A
（GA-CNT-1:3）Dielectric properties, this experiment prepare the carbon nano tube/graphene foam with Meta Materials performance（GA-
CNT-1:3）The performance map of dielectric constant and magnetic conductivity within the scope of 1MHz-1GHz has negative simultaneously within the scope of 1MHz-1GHz
Dielectric constant and negative magnetoconductivity realize Meta Materials performance.
Experiment two：
Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, measures 120ml mixed acid solutions（It is dense
HNO3：Dense H2SO4Mass ratio is 1:2）It is added in single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, then will
Reaction unit is placed on magnetic stirring apparatus, and 60 °C of oil baths are heated at reflux, and reacts 5h；Then with 0.45 μm of PP miillpore filter mistakes
Until filtrate is in neutrality, vacuum drying is for 24 hours up to acidification carbon nanotube at 80 DEG C for filter, deionized water washing（CNTs-
COOH4h）.
Prepare graphene oxide：Under 0 °C of ice-water bath, by 5g natural flake graphites be added slowly with stirring equipped with
In the three-necked flask of the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, continues to tie up under stiring
0 °C of stirring half an hour is held, control temperature stirs 2 hours not above 20 °C, is stirred 2 hours not higher than 35 °C；Keeping room temperature
Under the conditions of, appropriate amount of deionized water is added until there is no sputtering phenomenon in reaction bulb, continues to stir half an hour；It is added appropriate 30%
Hydrogen peroxide, until mixture becomes glassy yellow and there is no bubble generations from dark brown.By mixture sedimentation separation, remove dissolved with
The acid waste liquid of small amounts graphene is added 5-10% hydrochloric acid solutions and fully washs mixture, until there is no S042—；To hydrochloric acid
Appropriate ammonium hydroxide is added in graphite oxide after washing to pH value close to neutrality, is then washed repeatedly with deionized water, until using AgN03
Solution is examined to be occurred without precipitation；Neutral product sedimentation separation will be washed till or is separated by solid-liquid separation by centrifuge, it is finally obtained
Graphite oxide is tacky, brown colloidal；Gained graphite oxide is put into vacuum freeze, processing is dried, obtained
To graphite oxide fluffy solid.The a certain amount of cotton-shaped powder of dried graphite oxide is taken, is dissolved in deionized water by a certain concentration,
Be sufficiently stirred, then in ultrasonic cleaner with certain power ultrasonic for a period of time, so that oxidized graphite flake layer is removed, obtain it is light
The graphite oxide suspension of yellow.
Prepare carbon nano tube/graphene foam：The graphene oxide solution 30ml for configuring 10mg/ml, respectively according to oxidation
Graphene carbon Nanotube quality ratio is 1:4, solution is stirred into 2h, in being ultrasonically treated 2h in supersonic cleaning machine, solution is placed in water
In thermal response kettle, 210 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon and receive
Mitron composite graphite alkene hydrogel.By carbon nanotube composite graphite alkene hydrogel after -50 DEG C of condition precooling 2h of low temperature refrigerator
It is placed in freeze drier, is freeze-dried 3 days, obtains carbon nanotube composite graphite alkene aeroge.
Foam post-processes：By carbon nanotube composite graphite alkene aeroge in 1100 DEG C of heat treatment in tube furnace, removal is extra
Oxygen-containing functional group.
A kind of carbon nano tube/graphene foam with Meta Materials performance prepared by this experiment is named as GA-CNT-1:4.
The carbon nano tube/graphene foam of the Meta Materials performance parameters of this experiment preparation is observed using scanning electron microscope
（GA-CNT-1:4）, the carbon nano tube/graphene foam with Meta Materials performance prepared by this experiment, graphene sheet layer phase interconnection
It connects, carbon nanotube is attached on graphene sheet layer.These mutually overlap the vesicular texture of formation, are them with negative magnetoconductivity
Reason.
The carbon nano tube/graphene foam with Meta Materials performance of this experiment preparation is tested using Agilent E4991A
（GA-CNT-1:4）Dielectric properties, this experiment prepare the carbon nano tube/graphene foam with Meta Materials performance（GA-
CNT-1:4）The performance map of dielectric constant and magnetic conductivity within the scope of 1MHz-1GHz has negative simultaneously within the scope of 1MHz-1GHz
Dielectric constant and negative magnetoconductivity realize Meta Materials performance.
The above-mentioned description to embodiment is understood and applied the invention for the ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to embodiment here,
Those skilled in the art's announcement according to the present invention, the improvement and modification made to the present invention all should be in the protection models of the present invention
Within enclosing.
Claims (2)
1. a kind of preparation method of the carbon nano tube/graphene foam with Meta Materials performance, it is characterised in that specific steps are such as
Under：
（1）Prepare acidification carbon pipe：The p-CNTs for weighing 1g is put into the single-necked flask of 250ml, is measured 120ml mixed acid solutions and is added
Into single-necked flask；The ultrasonic wave for being 60KHz with frequency disperses 15min, and then single-necked flask is placed on magnetic stirring apparatus,
40-60 °C of oil bath is heated at reflux, and reacts 3-8h；Then it is washed until filter with 0.45 μm of PP filtering with microporous membrane, deionized water
Until liquid is in neutrality, vacuum drying is for 24 hours to get acidification carbon nanotube at 80 DEG C（CNTs-COOH4h）；
（2）Prepare graphene oxide：Under 0 °C of ice-water bath, by 5g natural flake graphites be added slowly with stirring equipped with
In the three-necked flask of the 120ml concentrated sulfuric acids；After persistently stirring half an hour, it is slowly added to potassium permanganate 18g, continues to tie up under stiring
0 °C of stirring half an hour is held, is then stirred 2 hours under the conditions of temperature is not above 20 °C, then 35 °C of conditions are not higher than in temperature
Lower stirring 2 hours；Then it is keeping under room temperature, deionized water being added until there is no sputtering phenomenon in three-necked flask, after
Continuous stirring half an hour；30% hydrogen peroxide is added, until mixture becomes glassy yellow and there is no bubble generations from dark brown；It will mix
Object sedimentation separation is closed, the acid waste liquid dissolved with small amounts graphene is removed, 5-10% hydrochloric acid solutions are added and fully wash mixture,
Until there is no S042—It generates；Ammonium hydroxide is added into the mixture graphite oxide after salt acid elution to pH value close to neutrality, then
It is washed repeatedly with deionized water, until using AgN03Solution is examined to be occurred without precipitation；Neutral product sedimentation separation or logical will be washed till
Centrifuge separation of solid and liquid is crossed, finally obtained graphite oxide is tacky, brown colloidal；It is cold that gained graphite oxide is put into vacuum
Freeze in drying equipment and processing is dried, obtains graphite oxide fluffy solid；The cotton-shaped powder of dried graphite oxide is taken, is dissolved in
It in deionized water, is sufficiently stirred, then so that oxidized graphite flake layer is removed to be ultrasonically treated in ultrasonic cleaner, obtain light
The graphite oxide suspension of yellow；
（3）Prepare carbon nano tube/graphene foam：By step（2）The graphene oxide suspension 30ml of obtained 10mg/ml and
Step（1）Solution is placed in hydro-thermal by obtained acidification carbon nanotube mixing, stirring 2h in being ultrasonically treated 2h in supersonic cleaning machine
In reaction kettle, 150-210 DEG C of temperature is set, waits for that hydrothermal reaction kettle is cooled to room temperature taking-up after reaction time 12h, 12h, obtains carbon
Nanotube composite graphite alkene hydrogel；By carbon nanotube composite graphite alkene hydrogel in the pre- lower freezing of -50 DEG C of conditions of low temperature refrigerator
2h is placed in freeze drier, is freeze-dried 3 days, is obtained carbon nanotube composite graphite alkene aeroge；Wherein：Graphene oxide
Suspension is 1 with acidification carbon nanotube mass ratio:1 - 1:5；
（4）Foam post-processes：By step（3）Obtained carbon nanotube composite graphite alkene aeroge is in 900-1100 DEG C in tube furnace
At a temperature of be heat-treated, remove extra oxygen-containing functional group, obtain carbon nano tube/graphene foam.
2. a kind of preparation method of carbon nano tube/graphene foam with Meta Materials performance according to claim 1,
It is characterized in that step（1）Described in mixed acid solution by dense HNO3With dense H2SO4Solution composition, dense HNO3：Dense H2SO4Mass ratio is
1:1 to 1:3.
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