CN110255541A - Carbon nanotube enhances graphene and preparation method thereof - Google Patents
Carbon nanotube enhances graphene and preparation method thereof Download PDFInfo
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- CN110255541A CN110255541A CN201910567859.3A CN201910567859A CN110255541A CN 110255541 A CN110255541 A CN 110255541A CN 201910567859 A CN201910567859 A CN 201910567859A CN 110255541 A CN110255541 A CN 110255541A
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- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a kind of preparation method of carbon nanotube enhancing graphene, include the following steps: that (1) prepares the mixed solution containing graphene oxide, carbon nanotube, reducing agent and foaming agent；(2) mixed solution is foamed, obtains carbon nanotube enhancing graphene hydrogel；(3) the graphene hydrogel by carbon nanotube enhancing freezes, and then by annealing, obtains carbon nanotube enhancing graphene.The carbon nanotube enhancing graphene that this method is prepared has good compressive property and lower density.
Description
Technical field
The present invention relates to a kind of carbon nanotube enhancing graphenes and preparation method thereof.
Background technique
Aeroge is a kind of solid matter form, is the smallest solid of world's upper density.The type of aeroge has very much, has
Silicon systems, carbon system, sulphur system, metal oxide system etc..Graphene aerogel is a kind of high-intensitive oxidation aeroge, have high resiliency,
It the characteristics of strong absorption, has a extensive future.
CN104998589A discloses a kind of preparation method of efficient oil suction carbon aerogels material: (1) by the carbon of 1 parts by weight
The surfactant-dispersed of nanotube and 0.01 parts by weight forms carbon nano tube dispersion liquid in the ethyl alcohol of 4~10 parts by weight；(2)
Carbon nano tube dispersion liquid is slowly added to the graphene oxide dispersion in stirring, forms graphene oxide-carbon nanotube dispersion
Liquid；(3) graphene oxide-carbon nano tube dispersion liquid is restored using chemical water thermal reduction, obtains graphene-carbon nano tube water
Gel；(4) washing of graphene-carbon nano tube hydrogel with water, displacement and freeze-drying are obtained porous graphene-carbon and received
Mitron aerogel composite；(5) obtained aerogel material is made annealing treatment, obtains carbon aerogels material.This method
The carbon aerogels material being prepared, density is larger, and compression strength is not high.
CN107686107A discloses a kind of preparation method of elastic hydrophobic carbon nanotube-graphene alkene composite aerogel: (1)
Prepare the homogeneous phase aqueous solution of graphene oxide, carboxyl carbon nanotube, reducing agent and crosslinking agent；(2) it is prepared through a step hydrothermal reduction
Carbon nanotube-graphene hydrogel；(3) dialysis, immersion treatment obtain carbon nanotube-graphene aerogel after dry.This method
The carbon nanotube being prepared-graphene aerogel density is larger, and compression strength is not high.
CN108745290A discloses a kind of system of graphene/carbon nano-tube composite aerogel with efficient oil absorbency
Preparation Method: (1) by graphene oxide ultrasonic disperse in deionized water, graphene oxide dispersion is obtained；(2) by carbon nanotube
It is added in graphene oxide dispersion, ultrasonic disperse, obtains graphene oxide/carbon nanotube mixed dispersion liquid；(3) to oxidation
Polyvinylpyrrolidone, polyvinyl alcohol, ethylenediamine are added in graphene/carbon nano-tube mixed dispersion liquid, stirs evenly and is placed on
120 DEG C of reaction 12h, obtain graphene/carbon nano-tube product in water heating kettle；(4) by graphene/carbon nano-tube product be placed in from
It is soaked in 8h in ethanol solution after sub- water dialysis, 48h is freeze-dried after taking-up, obtains graphene/carbon nano-tube aeroge.Using
The graphene/carbon nano-tube aeroge density that this method is prepared is larger, and compressive property is bad.
Summary of the invention
In view of this, it is an object of the present invention to provide a kind of preparation method of carbon nanotube enhancing graphene, by
The carbon nanotube enhancing graphene that this method is prepared has good compressive property and lower density.
It is another object of the present invention to provide a kind of carbon nanotubes to enhance graphene, which enhances graphite
Alkene has good compressive property and lower density.
On the one hand, the present invention provides a kind of preparation method of carbon nanotube enhancing graphene, includes the following steps:
(1) mixed solution containing graphene oxide, carbon nanotube, reducing agent and foaming agent is prepared；
(2) mixed solution is foamed, obtains carbon nanotube enhancing graphene hydrogel；
(3) the graphene hydrogel by carbon nanotube enhancing freezes, and then by annealing, obtains carbon nanotube enhancing
Graphene.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and reducing agent is 1 in mixed solution:
0.5~5.
Preparation method according to the present invention, it is preferable that reducing agent is selected from alkaline reducer, acidic reduction agent or activated sludge
One of or it is a variety of.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and foaming agent is 1:0.3~3.
Preparation method according to the present invention, it is preferable that foaming agent be selected from cationic foaming agent, anion foaming agent, it is non-from
One of subtype foaming agent or protein-based foaming agent are a variety of.
Preparation method according to the present invention, it is preferable that graphene oxide and the mass ratio of carbon nanotube be 1:0.05~
0.5。
Preparation method according to the present invention, it is preferable that carbon nano pipe purity > 93%, draw ratio are 500~8000, compare table
Area > 150m2/g。
Preparation method according to the present invention, it is preferable that the purity of graphene oxide is 95% or more, piece diameter≤50 μm, piece
Thickness degree≤30nm, oxygen carbon molar ratio are 0.15~0.65.
Preparation method according to the present invention, it is preferable that in step (2), make mixed solution foam by way of stirring, turn
Speed is 5000~20000rpm, and mixing time is 10~60min.
On the other hand, the present invention provides a kind of carbon nanotubes to enhance graphene, which enhances graphene by upper
The method of stating is prepared.
The present invention will foam containing the mixed solution of graphene oxide, carbon nanotube, reducing agent and foaming agent, obtains carbon and receives
Mitron enhances graphene hydrogel, and obtained hydrogel is freezed into crossing, then makes annealing treatment, it is low and have that density is prepared
The carbon nanotube of good compressive property enhances graphene.Mixed solution can make the carbon nanotube being prepared by foaming step
Enhance graphene porosity to increase, aperture is regular, uniform, and enhancing carbon nanotube enhances the compression strength of graphene and reduces close
Degree.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
Production method of the invention includes the following steps: that (1) prepares mixed solution；(2) preparation carbon nanotube enhances graphite
Alkene hydrogel；(3) preparation carbon nanotube enhances graphene.It is further explained below.
<preparing mixed solution>
Prepare the mixed solution containing graphene oxide, carbon nanotube, reducing agent and foaming agent.It can be by graphite oxide
Alkene, carbon nanotube, reducing agent and foaming agent co-dissolve Yu Shuizhong form mixed solution.It can also first prepare to obtain oxidation stone
Black aqueous solution, then by reducing agent, carbon nanotube and foaming agent or will be mixed containing reducing agent, carbon nanotube and foaming agent
It closes solution to mix with graphene oxide water solution, forms mixed solution.
In the present invention, the concentration of graphene oxide can be 0.5~20mg/ml in graphene oxide water solution.It is preferred that
Ground, the concentration of graphene oxide are 1~15mg/ml.It is highly preferred that the concentration of graphene oxide is 2~7mg/ml.
In the present invention, reducing agent, carbon nanotube and foaming agent and water can be mixed to get containing reducing agent, carbon nanometer
Pipe and foaming agent mixed solution；First foaming agent can also be mixed with water, then by the water of carbon nanotube and reducing agent and foaming agent
Solution mixing, obtains containing reducing agent, carbon nanotube and foaming agent mixed solution.
Graphene oxide in the present invention can be obtained using conventional method.Including but not limited to pass through Hummers method, change
Into Hummers method, liquid phase method, Mechanical Method, the methods of electrochemical oxidation process be prepared.One according to the present invention specific
Embodiment, graphene oxide are prepared by improved Hummers method.
In the present invention, the purity of graphene oxide is 95% or more, piece diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon
Molar ratio is 0.15~0.65.Preferably, the purity of graphene oxide is 96% or more.It is highly preferred that graphene oxide is pure
Degree is 98% or more.For example, can be 99%.Preferably, the piece diameter of graphene oxide is 2~45 μm.It is highly preferred that oxidation ink
The piece diameter of alkene is 20~30 μm.Preferably, the lamellar spacing of graphene oxide is 1~10nm.It is highly preferred that graphene oxide
Lamellar spacing is 5~10nm.Preferably, the oxygen carbon molar ratio of graphene oxide is 0.2~0.5.It is highly preferred that graphene oxide
Oxygen carbon molar ratio be 0.3~0.5.Can make in this way the carbon nanotube being prepared enhancing graphene have lower density and
Higher compression strength.
In the present invention, foaming agent can be selected from cationic foaming agent, anion foaming agent, nonionic foaming agent or egg
One of white class foaming agent is a variety of.Cationic foaming agent can be quaternary ammonium compound.Preferably, cationic foaming agent is selected from
One of cetyl trimethylammonium bromide, benzalkonium chloride or benzalkonium bromide.It is highly preferred that cationic foaming agent is hexadecane
Base trimethylammonium bromide.Anion foaming agent can be hydrosulphate foaming agent or sulphonic acid compound foaming agent.Preferably, sulphation
Object foaming agent is sulfated castor oil or lauryl sodium sulfate.It is highly preferred that hydrosulphate foaming agent is dodecyl sulphate
Sodium.Preferably, sulphonic acid compound foaming agent is selected from dioctyl succinate disulfonate acid, neopelex, sodium glycocholate or poly-
One of sodium styrene sulfonate.It is highly preferred that sulphonic acid compound foaming agent is neopelex or polystyrolsulfon acid
Sodium.A specific embodiment according to the present invention, sulphonic acid compound foaming agent are neopelex.Nonionic lather agent
It can be N vinylamide polymer class foaming agent.Preferably, nonionic lather agent can be polyvinylpyrrolidone.Egg
White class foaming agent can be animal protein or vegetable protein.Preferably, protide foaming agent is vegetable protein.
In the present invention, the mass ratio of graphene oxide and foaming agent is 1:0.3~3.Preferably, graphene oxide and hair
The mass ratio of infusion is 1:0.5~2.It is highly preferred that the mass ratio of graphene oxide and foaming agent is 1:0.8~1.5.In this way may be used
So that the carbon nanotube enhancing graphene being prepared has lower density and higher compression strength.
In the present invention, reducing agent can selected from alkaline reducer, acidic reduction agent or the medium one kind of activated sludge or
It is a variety of.Alkaline reducer can be ethylenediamine, sodium ascorbate, ammonium hydroxide, sodium borohydride, vulcanized sodium, sodium dithionite, boron hydrogen
Change one or more of potassium, sodium tetraborate.Preferably, alkaline reducer is one in ethylenediamine, sodium ascorbate or ammonium hydroxide
Kind is several.It is highly preferred that alkaline reducer is ethylenediamine.Acidic reduction agent can be gallic acid, ferrous sulfate, Vitamin C
One of acid, citric acid, oxalic acid or hydroiodic acid are a variety of.Preferably, acidic reduction agent is gallic acid, ascorbic acid or grass
One of acid is a variety of.It is highly preferred that acidic reduction agent is gallic acid.
In the present invention, the mass ratio of graphene oxide and reducing agent is 1:0.5~5.Preferably, graphene oxide with also
The mass ratio of former agent is 1:0.5~3.It is highly preferred that the mass ratio of graphene oxide and reducing agent is 1:0.8~2.It in this way can be with
Make the carbon nanotube being prepared enhancing graphene that there is lower density and higher compression strength.
Carbon nanotube in the present invention can be prepared using conventional method, including but not limited to arc discharge method,
Laser burn method, chemical vapour deposition technique, solid-phase pyrolysis, electric glow discharge method, gas combustion method and polymerization reaction synthetic method
Deng.
In the present invention, graphene oxide and the mass ratio of carbon nanotube are 1:0.05~0.5.Preferably, graphite oxide
Alkene and the mass ratio of carbon nanotube are 1:0.1~0.4.It is highly preferred that graphene oxide and the mass ratio of carbon nanotube are 1:0.1
~0.3.
In the present invention, carbon nano pipe purity > 93%, draw ratio is 500~8000, specific surface area > 150m2/g.It is preferred that
Ground, carbon nano pipe purity > 95%.It is highly preferred that carbon nano pipe purity > 98%.Preferably, draw ratio is 1000~6500.
It is highly preferred that draw ratio is 2000~4000.Preferably, specific surface area > 250m2/g.It is highly preferred that specific surface area > 350m2/
g.It can make the carbon nanotube being prepared enhancing graphene that there is lower density and higher compression strength in this way.
<preparation carbon nanotube enhances graphene hydrogel>
Mixed solution is foamed, the graphene hydrogel of carbon nanotube enhancing is obtained.Mixed solution can pass through stirring
Mode foams.Revolving speed can be 5000~20000rpm.Preferably, revolving speed is 7000~15000rpm.It is highly preferred that revolving speed is
8000~12000rpm.Mixing time is 10~60min.Preferably, mixing time is 20~50min.It is highly preferred that when stirring
Between be 20~40min.It can make the carbon nanotube being prepared enhancing graphene that there is lower density and higher anti-in this way
Compressive Strength.
Reduction reaction occurs in the presence of a reducing agent for graphene oxide.The temperature of reduction reaction can be 50~120 DEG C.It is excellent
Selection of land, the temperature of reduction reaction are 70~100 DEG C.It is highly preferred that the temperature of reduction reaction is 70~90 DEG C.Reduction reaction when
Between can be 5~20h.Preferably, the reaction time is 7~15h.It is highly preferred that the reaction time is 8~12h.
The step of in the present invention can also including washing carbon nanotube enhancing graphene hydrogel.Wash time can be
10~48h.Preferably, wash time is 15~35h.It is highly preferred that wash time is 20~30h.The washing lotion of washing step can
Think the aqueous solution of water or ethyl alcohol.Preferably, washing lotion is the aqueous solution of ethyl alcohol.It is highly preferred that ethyl alcohol in the aqueous solution of ethyl alcohol
Content is 1~20vol%.
<preparing graphene aerogel>
By the graphene hydrogel freezing of carbon nanotube enhancing, then by annealing, carbon nanotube enhancing stone is obtained
Black alkene.
In the present invention, cooling time is 10~30h.Preferably, cooling time is 15~25h.It is highly preferred that when freezing
Between be 18~22h.
In the present invention, defrosting and dry step can also be included after the step of freezing.Drying can be under normal pressure
It carries out.Drying temperature is 40~90 DEG C.Preferably, drying temperature is 50~80 DEG C.It is highly preferred that drying temperature is 60~75
℃。
In the present invention, the temperature of annealing is 150~600 DEG C.Preferably, the temperature of annealing is 200~500
℃.It is highly preferred that the temperature of annealing is 250~400 DEG C.The time of annealing is 1~6h.Preferably, it makes annealing treatment
Time be 2~5h.It is highly preferred that the time of annealing is 2~4h.The carbon nanotube being prepared can in this way enhanced
Graphene has lower density and higher compression strength.
On the other hand, the present invention provides one kind is prepared carbon nanotube enhancing graphene by the above method.
In the present invention, the density < 5mg/cm of carbon nanotube enhancing graphene3.Preferably, carbon nanotube enhances graphite
The density < 4.7mg/cm of alkene3.It is highly preferred that the density < 4.5mg/cm of carbon nanotube enhancing graphene3.Carbon nanotube enhancing
Compression strength > 1.5kPa of the graphene compressive deformation at 10%.Preferably, carbon nanotube enhancing graphene compressive deformation exists
Compression strength >=1.8kPa when 10%.It is highly preferred that carbon nanotube enhances pressure resistance of the graphene compressive deformation at 10%
Degree >=1.9kPa.
Test method is described below.
Density measurement: signified density is the bulk density of carbon nanotube enhancing graphene sample in this test method.Make
Carbon nanotube enhancing graphene sample is freely fallen by the way that funnel is quantitative, after loose filling, enhances stone with the carbon nanotube fallen
Black alkene sample quality is divided by packing volume to get the freely settled density of carbon nanotube enhancing graphene sample.Each carbon nanometer
Pipe enhancing graphene sample at least measures three times, is averaged.
Intensity test: carbon nanotube enhancing graphene sample is put into universal testing machine testboard, records carbon nanometer
Pipe enhances load of the graphene sample compressive deformation at 10%.The compression strength measured every time is accurate to 0.1kPa, each carbon
Nanotube enhancing graphene sample at least measures three times, is averaged.
Embodiment 1
By 3000mg graphene oxide, (purity 98%, piece diameter are 20 μm, lamellar spacing 5nm, and oxygen carbon molar ratio is
0.3) soluble in water, obtain the graphene oxide water solution that graphene oxide concentration is 3mg/ml.
3000mg neopelex is soluble in water, and preparation obtains sodium dodecyl benzene sulfonate aqueous solution；It will
900mg carbon nanotube (purity 96%, draw ratio 3000, specific surface area > 300m2/ g) and 3000mg ethylenediamine be dissolved in
In sodium dodecyl benzene sulfonate aqueous solution, stand-by solution is obtained.Stand-by solution is mixed with graphene oxide water solution, is mixed
Close solution.
Mixed solution is stirred into 30min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h；It will reaction
Product is washed for 24 hours with the ethanol water of 1vol%, obtains carbon nanotube enhancing graphene hydrogel.
It by carbon nanotube enhancing graphene hydrogel freezing 20h and thaws, carbon nanotube after defrosting is enhanced into graphene water
Gel is dry under the conditions of normal pressure and 65 DEG C, then at 300 DEG C, makes annealing treatment 3h, obtains the graphene of carbon nanotube enhancing
Aeroge.Experimental result is referring to table 1.
Embodiment 2
By 3000mg graphene oxide, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, and oxygen carbon molar ratio is
0.4) soluble in water, obtain the graphene oxide water solution that graphene oxide concentration is 3mg/ml.
3000mg neopelex is soluble in water, and preparation obtains sodium dodecyl benzene sulfonate aqueous solution；It will
600mg carbon nanotube (purity 99%, draw ratio 3500, specific surface area > 400m2/ g) and 3000mg ethylenediamine be dissolved in
In sodium dodecyl benzene sulfonate aqueous solution, stand-by solution is obtained.Stand-by solution is mixed with graphene oxide water solution, is mixed
Close solution.
Mixed solution is stirred into 30min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h；It will reaction
Product is washed for 24 hours with the ethanol water of 1vol%, obtains carbon nanotube enhancing graphene hydrogel.
It by carbon nanotube enhancing graphene hydrogel freezing 20h and thaws, carbon nanotube after defrosting is enhanced into graphene water
Gel is dry under the conditions of normal pressure and 65 DEG C, then at 300 DEG C, makes annealing treatment 3h, obtains the graphene of carbon nanotube enhancing
Aeroge.Experimental result is referring to table 1.
Embodiment 3
By 3000mg graphene oxide, (purity 95%, piece diameter are 40 μm, lamellar spacing 3nm, and oxygen carbon molar ratio is
0.2) soluble in water, obtain the graphene oxide water solution that graphene oxide concentration is 3mg/ml.
3000mg neopelex is soluble in water, and preparation obtains sodium dodecyl benzene sulfonate aqueous solution；It will
300mg carbon nanotube (purity 96%, draw ratio 2500, specific surface area > 300m2/ g) and 3000mg ethylenediamine be dissolved in
In sodium dodecyl benzene sulfonate aqueous solution, stand-by solution is obtained.Stand-by solution is mixed with graphene oxide water solution, is mixed
Close solution.
Mixed solution is stirred into 30min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h；It will reaction
Product is washed for 24 hours with the ethanol water of 1vol%, obtains carbon nanotube enhancing graphene hydrogel.
It by carbon nanotube enhancing graphene hydrogel freezing 20h and thaws, carbon nanotube after defrosting is enhanced into graphene water
Gel is dry under the conditions of normal pressure and 65 DEG C, then at 300 DEG C, makes annealing treatment 3h, obtains the graphene of carbon nanotube enhancing
Aeroge.Experimental result is referring to table 1.
Comparative example 1
By 3000mg graphene oxide, (purity 98%, piece diameter are 20 μm, lamellar spacing 5nm, and oxygen carbon molar ratio is
0.3) soluble in water, obtain the graphene oxide water solution that graphene oxide concentration is 3mg/ml.
3000mg neopelex is soluble in water, and preparation obtains sodium dodecyl benzene sulfonate aqueous solution；By ten
Dialkyl benzene sulfonic acids sodium water solution is mixed with graphene oxide water solution, obtains mixed solution.
Mixed solution is stirred into 30min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h；It will reaction
Product is washed for 24 hours with the ethanol water of 1vol%, obtains carbon nanotube enhancing graphene hydrogel.
It by carbon nanotube enhancing graphene hydrogel freezing 20h and thaws, carbon nanotube after defrosting is enhanced into graphene water
Gel is dry under the conditions of normal pressure and 65 DEG C, then at 300 DEG C, makes annealing treatment 3h, obtains the graphene of carbon nanotube enhancing
Aeroge.Experimental result is referring to table 1.
Table 1
| Test sample | Density (mg/cm3) | Compression strength (10% deformation)/kPa |
| Embodiment 1 | 4.5 | 1.8 |
| Embodiment 2 | 4.2 | 2.0 |
| Embodiment 3 | 4.6 | 1.9 |
| Comparative example 1 | 5.2 | 1.5 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon nanotube enhancing graphene, which comprises the steps of:
(1) mixed solution containing graphene oxide, carbon nanotube, reducing agent and foaming agent is prepared；
(2) mixed solution is foamed, obtains carbon nanotube enhancing graphene hydrogel；
(3) the graphene hydrogel by carbon nanotube enhancing freezes, and then by annealing, obtains carbon nanotube enhancing graphite
Alkene.
2. preparation method according to claim 1, which is characterized in that the matter of graphene oxide and reducing agent in mixed solution
Amount is than being 1:0.5~5.
3. preparation method according to claim 1, which is characterized in that the reducing agent is selected from alkaline reducer, acidity
One of reducing agent or activated sludge are a variety of.
4. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and foaming agent is 1:
0.3~3.
5. preparation method according to claim 1, which is characterized in that the foaming agent is selected from cationic foaming agent, yin
One of ion foaming agent, nonionic foaming agent or protein-based foaming agent are a variety of.
6. preparation method according to claim 1, which is characterized in that graphene oxide and the mass ratio of carbon nanotube are 1:
0.05~0.5.
7. preparation method according to claim 1, which is characterized in that the carbon nano pipe purity > 93%, draw ratio
It is 500~8000, specific surface area > 150m2/g。
8. preparation method according to claims 1 to 7, which is characterized in that the purity of graphene oxide is 95% or more, piece
Diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon molar ratio are 0.15~0.65.
9. preparation method according to claims 1 to 7, which is characterized in that in step (2), make to mix by way of stirring
Solution foaming is closed, revolving speed is 5000~20000rpm, and mixing time is 10~60min.
10. a kind of carbon nanotube enhances graphene, which is characterized in that be prepared by any method of claim 1~9
It arrives.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
| US20120251521A1 (en) * | 2011-04-02 | 2012-10-04 | Bertha Rostro | Technical field and industrial applicability of the invention |
| US20140138587A1 (en) * | 2012-11-08 | 2014-05-22 | William Marsh Rice University | Covalent modification and crosslinking of carbon materials by sulfur addition |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN108975863A (en) * | 2018-07-06 | 2018-12-11 | 中国航发北京航空材料研究院 | Graphene-carbon nano tube composite aerogel based on hydrogen bubble template |
-
2019
- 2019-06-27 CN CN201910567859.3A patent/CN110255541B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120251521A1 (en) * | 2011-04-02 | 2012-10-04 | Bertha Rostro | Technical field and industrial applicability of the invention |
| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
| US20140138587A1 (en) * | 2012-11-08 | 2014-05-22 | William Marsh Rice University | Covalent modification and crosslinking of carbon materials by sulfur addition |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN108975863A (en) * | 2018-07-06 | 2018-12-11 | 中国航发北京航空材料研究院 | Graphene-carbon nano tube composite aerogel based on hydrogen bubble template |
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