CN106927457B - A kind of graphene and preparation method thereof - Google Patents
A kind of graphene and preparation method thereof Download PDFInfo
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- CN106927457B CN106927457B CN201710300748.7A CN201710300748A CN106927457B CN 106927457 B CN106927457 B CN 106927457B CN 201710300748 A CN201710300748 A CN 201710300748A CN 106927457 B CN106927457 B CN 106927457B
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Abstract
The present invention provides a kind of preparation methods of graphene comprising following steps: A) graphite powder is mixed with highly crystalline silk-fibroin nanofiber aqueous solution, then be ultrasonically treated；The crystallinity of highly crystalline silk-fibroin nanofiber is greater than 40% in the highly crystalline silk-fibroin nanofiber aqueous solution, and diameter is 10~30nm, and length is 100nm~3 μm；B) the obtained mixed liquor of step A) is centrifuged, obtains graphene solution.Present invention also provides the graphene of above-mentioned preparation method preparation, for the number of plies within 5 layers, planar dimension is 500nm~5 μm.During the preparation process, the application is finally obtained stable high concentration graphene aqueous solution using highly crystalline silk-fibroin nanofiber as dispersing agent and stabilizer.This kind of preparation method avoids the problem of conformational change in the silk-fibroin ultrasonic procedure of other oroteins stabilizer and other conformations composition, and realize the graphene with application value stablizes preparation.
Description
Technical field
The present invention relates to the preparation technical fields of grapheme material, more particularly to one kind is with highly crystalline silk-fibroin nanofiber
The method and graphene of graphene are prepared as dispersing agent and stabilizer.
Background technique
Graphene due to excellent mechanical property, optical property, electrical and thermal conductivity performance and excellent biocompatibility,
The every field such as battery, electronic device, optical device and bio-medical all have great potential application foreground.How to use
Mild method realizes that the scale preparation of high-quality graphene is to determine that graphene really realizes the core and key of application.
Researcher has developed diversified graphene preparation technology at present, especially in terms of prepare with scale,
Mainly there are the various ways such as the removing of graphite oxide alkylene, electrochemical stripping, ultrasound removing, stabilizer grinding up-stripping.Change
The graphene of removing is learned due to the variation of functional group, causes its comprehensive performance to be remarkably decreased, strongly limits its practical application, and
Although grinding removing the methods of in terms of have advantage, the prepared graphene film number of plies is excessively high, quality by
To very big limitation.Ultrasonic wave added removing, mild condition prepare that the graphene film number of plies is low, and defect is few, and can directly prepare can be into
The solvent dispersion system of one step application, therefore it is constantly subjected to the common concern of people.Although ultrasonic treatment prepares graphene and is producing
There is certain limitation in terms of rate, but by condition optimizing, can satisfy answering for related application, especially bio-medical field substantially
With with great market prospects.
The method of ultrasound removing is varied, in terms of solvent angle, including two kinds of systems of organic solvent and aqueous solution, from point
It then include a variety of types such as surfactant, macromolecule and polysaccharide, protein, polypeptide in powder selection.In view of specific
Using the especially application of field of biomedicine makees solvent using water, and simultaneous selection has the natural material of good biocompatibility
Expect that such as albumen, polysaccharide have more significant advantage as stabilizer and dispersing agent, therefore is rapidly developed in recent years.However,
The natural polymers structural instability such as polysaccharide, albumen, sensitive to ultrasonic treatment reaction, often recurring structure turns in ultrasonic procedure
Become, to reduce the quality and yield of graphene removing.Research has more preferable dispersion with more preferable stability and to graphene
Performance, the new material with biocompatibility, is still the critical issue of field of preparation of graphene.
The special block structure of silk-fibroin makes it have certain hydrophobicity, so as to same graphene stable bond, from
It is expected to be applied to prepare grapheme material theoretically.However common silk protein solution is equally unstable, is easy in ultrasonic mistake
It is transformed into gel in journey, removing is caused to fail.And stable highly crystalline silk-fibroin is then insoluble in water, can not make in aqueous solution
With, therefore removing prepares graphene and has not been reported always in water solution system using silk-fibroin.Therefore, it is based on above-mentioned progress,
It is necessary to provide a kind of suitable silk-fibroin nanofibers as stabilizer and dispersing agent, removes stone in water solution system ultrasound
Ink, prepares the grapheme material of high quality, and by condition optimizing, obtains preparation high concentration, high yield graphene aqueous solution
Method.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of graphene, preparation method provided by the present application
The graphene of a kind of high concentration, high yield and high quality can be prepared.
In view of this, this application provides a kind of preparation methods of graphene, comprising the following steps:
A), graphite powder is mixed with highly crystalline silk-fibroin nanofiber aqueous solution, then is ultrasonically treated；It is described highly crystalline
The crystallinity of highly crystalline silk-fibroin nanofiber is greater than 40% in silk-fibroin nanofiber aqueous solution, and diameter is 10~30nm, long
Degree is 100nm~3 μm；
B), the obtained mixed liquor of step A) is centrifuged, obtains graphene solution.
Preferably, the highly crystalline silk-fibroin nanofiber aqueous solution is prepared by the following method:
Silk protein aqueous solution is concentrated into the first silk protein solution that concentration is 8~12wt%；
First silk protein solution is concentrated into the second silk protein solution that concentration is 18~22wt%；
It is 0.5~2wt% that second silk protein solution, which is diluted with water to concentration, and sealing is cultivated, and obtains highly crystalline silk
Protein nano fiber solution.
Preferably, described to obtain being concentrated in 40~60 DEG C of progress in the first silk protein solution；It is described to obtain second egg
25~35 DEG C of progress are concentrated in white solution, the temperature that the sealing is cultivated is 50~70 DEG C.
Preferably, the concentration of the highly crystalline silk-fibroin nanofiber aqueous solution is 0.1~3wt%；The highly crystalline silk
The mass ratio of highly crystalline silk-fibroin nanofiber and the graphite powder in protein nano fiber aqueous solution is 1:(1~100).
Preferably, step A) in, the power of the ultrasonic treatment is 50~200W, and the time of the ultrasonic treatment is
10min~for 24 hours.
Preferably, step B) in, the rate of the centrifugation is 500~5000rpm, the time of the centrifugation be 5min~
2h。
Preferably, step B) after further include:
C), the graphene solution is centrifuged again, isolated graphene.
Preferably, step C) in, the rate of the centrifugation is 8000~20000rpm, the time of the centrifugation be 5min~
2h。
Present invention also provides graphene prepared by the preparation method described in above scheme, the lamella of the graphene is small
In 5 layers, planar dimension is 500nm~5 μm.
This application provides a kind of preparation methods of graphene, first by graphite powder and highly crystalline silk-fibroin nanofiber
Aqueous solution mixing, then be ultrasonically treated, make graphite remove to form graphene sheet layer；Then mixed liquor ultrasonic treatment obtained
It is centrifuged, to remove unstripped graphite, obtains graphene solution.The application is high during removing prepares graphene
Crystallization silk-fibroin nanofiber aqueous solution both has hydrophobicity, while can disperse in water, therefore it is as dispersing agent and surely
Determine agent, when ultrasound removes graphene, highly crystalline silk-fibroin nanofiber is attached on the graphene of removing, it is inhibited to gather again
Collection and precipitating, finally obtain stable high concentration graphene aqueous solution, the yield of graphene is higher.Graphene prepared by the present invention
Lamella less than 5 layers, planar dimension be 500nm~5 μm.The experimental results showed that the yield of the present embodiment graphene 30% with
On, concentration in water is in 20mg/ml or more.
Detailed description of the invention
Fig. 1 is the photomacrograph of highly crystalline silk-fibroin nanofiber prepared by the embodiment of the present invention 1；
Fig. 2 is the micrograph of highly crystalline silk-fibroin nanofiber prepared by the embodiment of the present invention 1；
Fig. 3 is the infrared spectrogram of highly crystalline silk-fibroin nanofiber prepared by the embodiment of the present invention 1；
Fig. 4 is the photomacrograph of graphene prepared by the embodiment of the present invention 2；
Fig. 5 is the transmission electron microscope photo of graphene prepared by the embodiment of the present invention 2；
Fig. 6 is the Raman spectrogram of graphene prepared by the embodiment of the present invention 2；
Fig. 7 is the photomacrograph of the graphene of comparative example of the present invention and embodiment preparation.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
In the research of applicant, by regulating and controlling the assembling of silk-fibroin, a kind of highly crystalline silk-fibroin nanometer has been prepared
Fiber, surface have more negative electrical charges, to can disperse in water, this silk-fibroin nanofiber avoids tradition
The defect of silk-fibroin is expected to realize the removing and preparation of graphene as stabilizer and dispersing agent.This application discloses one as a result,
The preparation method of kind graphene, comprising the following steps:
A), graphite powder is mixed with highly crystalline silk-fibroin nanofiber aqueous solution, then is ultrasonically treated；It is described highly crystalline
The crystallinity of highly crystalline silk-fibroin nanofiber is greater than 40% in silk-fibroin nanofiber aqueous solution, and diameter is 10~30nm, long
Degree is 100nm~3 μm；
B), the obtained mixed liquor of step A) is centrifuged, obtains graphene solution.
The application is in graphene preparation process, using highly crystalline silk-fibroin nanofiber as dispersing agent and stabilizer, most
The graphene aqueous solution of stable high concentration is obtained eventually, and the quality of graphene is higher.
According to the present invention, during preparing graphene, first by Graphene powder and highly crystalline silk-fibroin nanofiber
Aqueous solution mixing, obtains original mixture, the mixing of this process is a simple mixed process, and any variation does not occur.
Graphite powder is material well known to those skilled in the art, is not particularly limited to this application.The highly crystalline silk-fibroin is received
Rice fiber aqueous solution is a kind of silk-fibroin of special construction, could have preferable effect during removing graphene；Tool
Body, the crystallinity of the highly crystalline silk-fibroin nanofiber in the highly crystalline silk-fibroin nanofiber aqueous solution is greater than 40%,
Diameter is 10~30nm, and length is 100nm~3 μm.The preparation method of the highly crystalline silk-fibroin nanofiber aqueous solution is specific
Are as follows:
Silk protein aqueous solution is concentrated into the first silk protein solution that concentration is 8~12wt%；
First silk protein solution is concentrated into the second silk protein solution that concentration is 18~22wt%；
It is 0.5~2wt% that second silk protein solution, which is diluted with water to concentration, and sealing is cultivated, and obtains highly crystalline silk
Protein nano fiber solution.
It is above-mentioned prepare highly crystalline silk-fibroin nanofiber aqueous solution during, silk protein solution is concentrated into first dense
Degree is 8~12wt%, obtains the first silk protein solution, this process is concentrated at 40~60 DEG C；Then by above-mentioned first
Protein solution continues to be concentrated into 18wt%~22wt% to room temperature, this process intermediate filment is transformed to metastable nanometer
Grain；It is 0.5~2wt% that the second silk protein solution, which is finally diluted with water to concentration, and sealing cultivates, obtains highly crystalline silk-fibroin and receive
Rice fiber solution, the temperature that the sealing is cultivated are 50~70 DEG C.
Highly crystalline silk-fibroin nanofiber used by the application has high crystallinity, specific diameter and length model
It encloses, high crystallinity and charge arrangement make it both have hydrophobicity, while it can disperse in water, this special property
It can be their ability to carry out the key of graphene removing.If the crystal structure and diameter and length of nanofiber change, right
Peeling effect can influence.
In this application, the concentration of the highly crystalline silk-fibroin nanofiber aqueous solution is 0.1~3wt%, specific real
It applies in example, the concentration of the highly crystalline silk-fibroin nanofiber aqueous solution is 0.3~2wt%.The graphite powder and the high knot
The mass ratio of highly crystalline silk-fibroin nanofiber is (1~100) in brilliant silk-fibroin nanofiber aqueous solution: 1.The highly crystalline silk
The excessively high solution viscosity that will lead to of protein nano fiber concentration of aqueous solution is excessive, and energy transmission is obstructed, and graphene is difficult to remove；Concentration
Too low, highly crystalline silk-fibroin nanofiber is reduced with the interaction of graphene, removed graphene stability decline.Dry state is high
The mass ratio for crystallizing silk-fibroin nanofiber and graphite powder is excessive, and prepared graphene amount is too low, lacks actual use value；
Ratio is too low, and the ratio decline for the high-quality graphene prepared in solution, a large amount of low quality Multi-layer graphites exist, yield drop
It is low, therefore the grapheme material of high quality could be only obtained in suitable ratio.
Then above-mentioned initial mixing liquid is ultrasonically treated by the application, graphite is made to remove to form graphene sheet layer.It is described
The time of ultrasonic treatment is 10min~for 24 hours, and power is 50~300W, and in a particular embodiment, the time of the ultrasonic treatment is
1~18h, power are 80~250W.
According to the present invention, then the mixed liquor after ultrasonic treatment is centrifuged, to remove unstripped graphite, obtains silk-fibroin
The stable graphene solution of nanofiber.The revolving speed of the centrifugation is 500~5000rpm, and the time is 5min~2h, specific real
It applies in example, the revolving speed of the centrifugation is 800~3000rpm, and the time is 20min~1.5h.In this step, it has been able to obtain
Graphene, the graphene solution only obtained are highly crystalline silk-fibroin nanofiber at the middle and upper levels, and lower layer is graphene.
For practical application, graphene solution obtained above is centrifuged by the application again, makes graphene with high knot
Brilliant silk-fibroin nanofiber is completely separated, and the grapheme material of lower layer's high-purity is obtained.In above process, the centrifugation
Revolving speed be 8000~20000rpm, the time be 5min~2h；In a particular embodiment, the revolving speed of the centrifugation be 10000~
15000rpm, time are 10~100min.
Present invention also provides the graphene that the above method is prepared, the lamella of the graphene is less than 5 layers, plane meter
Very little is 500nm~5 μm.
The present invention provides a kind of grapheme material and preparation method thereof of highly crystalline silk-fibroin nanofiber up-stripping,
The number of plies of prepared graphene is 5 hereinafter, size is between 500nm~5 μm, and concentration can be in 20mg/ml or more, and yield is 30%
More than, it is significantly better than the graphene aqueous solution for the ultrasonic treatment removing preparation reported at present.In the process for preparing graphene
In, the diameter of the highly crystalline silk-fibroin nanofiber utilized is 10~200nm, and length is 100nm~3 μm, and crystallinity is 40%
More than, this kind of silk-fibroin nanofibrous structures are stablized, and have good hydrophobicity, while can disperse in water, therefore can
Conformational stability is kept in ultrasonic procedure, and is combined with graphene, and reassociating for graphene is inhibited, it is final to realize concentration and yield
Be greatly improved.In addition, silk-fibroin and graphene are combined into physical bond, it can also be by high speed centrifugation, by the same stone of silk-fibroin
Black alkene is completely separated, and obtains the grapheme material of high-purity.Meanwhile this kind of preparation method, simple process, and obtained product without
Organic solvent, good biocompatibility.
Compared with prior art, the application is by the selection of the silk-fibroin of specific conformation and nanostructure, so that silk-fibroin
It can disperse in water, while avoid negative effect of the ultrasound to silk-fibroin conformation, finally realize with silk-fibroin as stabilization
Agent and dispersing agent prepare the high-quality graphene that can disperse in water under the conditions of ultrasonic treatment；By silk-fibroin with addition
The adjustment of graphite ratio, ultrasonic power and time and centrifugation rate realizes graphene high concentration in aqueous solution and height
Yield, maximum concentration can reach 20mg/ml or more, and maximum output is higher than 30%, is all remarkably higher than under existing water solution system
The prepared graphene of ultrasound removing；By the optimization of centrifugation rate, silk-fibroin further can be achieved with the separation of graphene, obtain
High purity graphite alkene is obtained, influence of the certain applications intermediate filment to graphene performance is avoided, is the high effect of grapheme material
With offer more more options and advantage；Graphene number of plies prepared by the final present invention is low, and defect is few, concentration and yield in water
Height, the prospect with prepare with scale and application；Therefore, the preparation method of graphene provided by the present application, takes water as a solvent, work
Skill is simple, obtained product good biocompatibility.
For a further understanding of the present invention, below with reference to embodiment to graphene provided by the invention and preparation method thereof into
Row is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) common silk protein solution is obtained into the silk protein solution that concentration is 10wt% in 40~60 DEG C of slowly concentrations；
(2) silk protein solution that step (1) obtains is transferred to room temperature to continue to be concentrated into 20wt%, in the process silk egg
It is white to be transformed into metastable nano particle；
(3) the silk-fibroin nanoparticles solution that step (2) obtains is diluted with water to 0.5wt%~2wt%, is placed into 60
DEG C sealing cultivate, obtain highly crystalline silk-fibroin nanofiber.
Fig. 1 is the photomacrograph of highly crystalline silk-fibroin nanofiber manufactured in the present embodiment；Fig. 2 is manufactured in the present embodiment
The micrograph of highly crystalline silk-fibroin nanofiber；By Fig. 1 and Fig. 2 it is found that highly crystalline silk-fibroin nanometer manufactured in the present embodiment
Fiber is able to maintain solution state, and fibre diameter is 10~20nm, length be 100nm~μm between；Fig. 3 is the present embodiment preparation
Highly crystalline silk-fibroin nanofiber infrared spectrogram, from the figure 3, it may be seen that highly crystalline silk-fibroin Nanowire manufactured in the present embodiment
The conformation of dimension is mainly beta-sheet crystalline texture.
Embodiment 2
It (1) is that the highly crystalline silk-fibroin nanofiber aqueous solution of 1wt% mixes with 10ml concentration by 100mg graphite powder；
(2) mixture for obtaining step (1) is ultrasonically treated 18h by ultrasonic instrument 80W, and graphite is made to remove to form graphite
Alkene lamella；
(3) by treated, mixed liquor is centrifuged 40min at 800 rpm, removes unstripped graphite, obtains upper layer silk egg
The stable graphene solution of white nanofiber.The yield of graphene is 20%, the concentration 2mg/ml of graphene solution.
Fig. 4 is the photomacrograph of graphene manufactured in the present embodiment, and Fig. 5 is the transmission electricity of graphene manufactured in the present embodiment
Mirror photo；By Fig. 4 and Fig. 5 it is found that graphene number of plies manufactured in the present embodiment at 5 layers hereinafter, planar dimension be 500nm~5 μm；
Fig. 6 is the Raman spectrogram of graphene manufactured in the present embodiment, it will be appreciated from fig. 6 that graphene defect manufactured in the present embodiment is less,
Quality is high.
Embodiment 3
It (1) is that the highly crystalline silk-fibroin nanofiber aqueous solution of 1wt% mixes with 10ml concentration by 100mg graphite powder；
(2) mixture for obtaining step (1) is ultrasonically treated 18h by ultrasonic instrument 80W, and graphite is made to remove to form graphite
Alkene lamella；
(3) by treated, mixed liquor is centrifuged 40min at 800 rpm, removes unstripped graphite, obtains upper layer silk egg
The stable graphene solution of white nanofiber；
(4) graphene solution is continued to be centrifuged 10min in 10000rpm, graphene is separated with silk-fibroin nanofiber,
Obtain the grapheme material of lower layer's high-purity.The yield of graphene is about 16%, and the concentration of graphene solution is about 1.6mg/ml.
Embodiment 4
It (1) is that the highly crystalline silk-fibroin nanofiber aqueous solution of 0.5wt% mixes with 10ml concentration by 1000mg graphite powder；
(2) mixture for obtaining step (1) is ultrasonically treated 1h by ultrasonic instrument 200W, and graphite is removed to form graphite
Alkene lamella；
(3) by treated, mixed liquor is centrifuged 20min at 1500 rpm, removes unstripped graphite, obtains upper layer silk egg
The stable graphene solution of white nanofiber；
(4) graphene solution is continued to be centrifuged 20min in 18000rpm, graphene is separated with silk-fibroin nanofiber,
Obtain the grapheme material of lower layer's high-purity.The yield of graphene is about 20%, the concentration 20mg/ml of graphene solution.
Embodiment 5
It (1) is that the highly crystalline silk-fibroin nanofiber aqueous solution of 2wt% mixes with 20ml concentration by 400mg graphite powder；
(2) mixture for obtaining step (1) is ultrasonically treated 4h by ultrasonic instrument 150W, and graphite is made to remove to form graphite
Alkene lamella；
(3) by treated, mixed liquor is centrifuged 1.5h at 1200rpm, removes unstripped graphite, obtains upper layer silk egg
The stable graphene solution of white nanofiber；
(4) graphene solution is continued to be centrifuged 100min in 10000rpm, graphene is separated with silk-fibroin nanofiber,
Obtain the grapheme material of lower layer's high-purity.The yield of graphene is about 22%, the concentration 4.4mg/ml of graphene solution.
Embodiment 6
It (1) is that the highly crystalline silk-fibroin nanofiber aqueous solution of 0.3wt% mixes with 30ml concentration by 200mg graphite powder；
(2) mixture for obtaining step (1) is ultrasonically treated 8h by ultrasonic instrument 250W, and graphite is made to remove to form graphite
Alkene lamella；
(3) by treated, mixed liquor is centrifuged 20min at 800 rpm, removes unstripped graphite, obtains upper layer silk egg
The stable graphene solution of white nanofiber；
(4) graphene solution is continued to be centrifuged 10min in 12000rpm, graphene is separated with silk-fibroin nanofiber,
Obtain the grapheme material of lower layer's high-purity.The yield 28% of graphene, the concentration 1.87mg/ml of graphene solution.
Comparative example 1
(1) 100mg graphite powder is mixed with 10ml concentration for 1wt% tradition amorphous silk protein aqueous solution；
(2) mixture for obtaining step (1) is ultrasonically treated 18h by ultrasonic instrument 80W, and graphite is made to remove to form graphite
Alkene lamella, but ultrasonic procedure intermediate filment result changes, and solution, which forms gel graphene, can not collect separation, lead to graphite
The preparation failure of alkene solution, as shown in fig. 7, Fig. 7 is macroscopical picture of graphene prepared by comparative example 1 and embodiment 3, in Fig. 7 A and
Picture on the left of B is macroscopical picture of graphene prepared by comparative example 1, and the picture on right side is graphite prepared by embodiment 3
Macroscopical picture of alkene, as seen from the figure, the graphene of this comparative example preparation are gel state, it is difficult to isolated graphene.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (8)
1. a kind of preparation method of graphene, comprising the following steps:
A), graphite powder is mixed with highly crystalline silk-fibroin nanofiber aqueous solution, then is ultrasonically treated；The highly crystalline silk egg
The crystallinity of highly crystalline silk-fibroin nanofiber is greater than 40% in white nanofiber aqueous solution, and diameter is 10~30nm, and length is
100nm~3 μm；The concentration of the highly crystalline silk-fibroin nanofiber aqueous solution is 0.1~3wt%；
B), the obtained mixed liquor of step A) is centrifuged, obtains graphene solution.
2. preparation method according to claim 1, which is characterized in that the highly crystalline silk-fibroin nanofiber aqueous solution is pressed
It is prepared according to following methods:
Silk protein aqueous solution is concentrated into the first silk protein solution that concentration is 8~12wt%；
First silk protein solution is concentrated into the second silk protein solution that concentration is 18~22wt%；
It is 0.5~2wt% that second silk protein solution, which is diluted with water to concentration, and sealing is cultivated, and obtains highly crystalline silk-fibroin
Nanofiber solution.
3. preparation method according to claim 2, which is characterized in that described to obtain being concentrated in the first silk protein solution
40~60 DEG C of progress；Described 25~35 DEG C of progress that are concentrated in obtained in the second silk protein solution, the temperature that the sealing is cultivated
It is 50~70 DEG C.
4. preparation method according to claim 1, which is characterized in that in the highly crystalline silk-fibroin nanofiber aqueous solution
Highly crystalline silk-fibroin nanofiber and the graphite powder mass ratio be 1:(1~100).
5. preparation method according to claim 1, which is characterized in that step A) in, the power of the ultrasonic treatment is 50
~200W, time of the ultrasonic treatment are 10min~for 24 hours.
6. preparation method according to claim 1, which is characterized in that step B) in, the rate of the centrifugation is 500~
5000rpm, the time of the centrifugation are 5min~2h.
7. described in any item preparation methods according to claim 1~6, which is characterized in that step B) after further include:
C), the graphene solution is centrifuged again, isolated graphene.
8. preparation method according to claim 7, which is characterized in that step C) in, the rate of the centrifugation is 8000~
20000rpm, the time of the centrifugation are 5min~2h.
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