CN107416811A - A kind of preparation method of high conductivity graphene - Google Patents
A kind of preparation method of high conductivity graphene Download PDFInfo
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- CN107416811A CN107416811A CN201710476341.XA CN201710476341A CN107416811A CN 107416811 A CN107416811 A CN 107416811A CN 201710476341 A CN201710476341 A CN 201710476341A CN 107416811 A CN107416811 A CN 107416811A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
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Abstract
The invention provides a kind of preparation method of graphene, comprise the following steps, graphite, chromium trioxide and concentrated hydrochloric acid are reacted first, obtain intercalated graphite compounds；Then after intercalated graphite compounds above-mentioned steps obtained are mixed with hydrogen peroxide, expanded graphite is obtained；The expanded graphite that finally above-mentioned steps are obtained is peeled off in aqueous phase, obtains graphene.The present invention is directed to HTHP defect existing for existing conventional graphene liquid phase stripping method, employ the liquid phase stripping method of low-temperature atmosphere-pressure, by to raw material preferably and combination, refine reactions steps, the creative graphene preparation method for realizing the stripping of low temperature intercalation low-temperature expansion aqueous phase, production cost is not only reduced, pollution of the organic solvent for environment is it also avoid, also add the rate of dispersion of graphene.
Description
Technical field
The invention belongs to technical field of graphene, is related to a kind of preparation method of high conductivity graphene, more particularly to one
The low temperature preparation method of kind high conductivity graphene.
Background technology
Graphene (Graphene) is a kind of new material for the individual layer laminated structure being made up of carbon atom.It is one kind by carbon
Atom is with sp2Hybridized orbit composition hexangle type is in the flat film of honeycomb lattice, the two-dimensional material of only one carbon atom thickness.
Since Geim in 2004 etc. prepares graphene using micromechanics stripping method first, graphene just because its have high conductivity,
The excellent performance such as high-specific surface area, high intensity and high electron mobility, causes the extensive concern of people, and then also promotes
The fast development of graphene preparation technology.Just because of with above-mentioned many excellent physical chemical property, its in energy storage material,
Environmental project, it is widely used in terms of sensing sensitive, is referred to as " dark fund " or " king of new material ", and before potentially applying
Scape is vast, turns into global focus and study hotspot at present.
But in actual applications, graphene also there is it is many problem of and restraining factors, the preparation of graphene be exactly
Restrict graphene practical application and a major obstacle of development.Although scientific research personnel has developed numerous graphene systems so far
Preparation Method.Wherein comparing the method for main flow has graphite oxide reducing process, epitaxial growth method and chemical vapour deposition technique etc..Aoxidize stone
Black reducing process is to prepare one of best approach of graphene at present.This method is simple to operate, it is low to prepare cost, can be large-scale
Graphene is prepared, but because it introduces the strong oxidizer concentrated sulfuric acid or potassium permanganate etc. in preparation process, is inevitably destroyed
The lattice structure of graphene, introduces a large amount of defects, so as to cause the serious loss of graphene intrinsic performance.Epitaxial growth method and
Although chemical vapour deposition technique can obtain the high-quality graphene of complete, the few defect of lattice, it prepares costly, yield
Low, preparation technology requires harsh, can not meet the business needs of large-scale production.Thus these above-mentioned preparation methods can't
Meet the requirement of high-quality graphene industrialization in reality.
At present, in research field, liquid phase stripping method can preferably protect graphene perfection of lattice, be a kind of tool
There is the graphene preparation method of good development prospect.One reported on Scientific Reports in 2013《FeCl3Intercalation
Prepare few layer graphene》Pass through FeCl3Intercalated graphite, afterwards with the method for hydrogen peroxide chemistry expansion, it is prepared for lacking for high-quality
Layer graphite, but intercalation needs to carry out at high temperature under high pressure, exists and equipment requirement height, reaction danger and cost height etc. are asked
Topic.
Therefore, in order to preferably realize the business application of graphene, a kind of low cost how is obtained, high yield prepares Gao Pin
The method of matter graphene, it is one of each R ＆ D Enterprises are faced in field key challenges and urgent problem to be solved.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of high conductivity graphene,
Particularly a kind of low temperature preparation method of high conductivity graphene, low temperature liquid phase stripping method provided by the invention, can be had
There is the graphene of more preferable electric conductivity, and preparation method is simple, mild condition, it is often more important that can be carried out in aqueous phase
Peel off, greatly reduce environmental pollution, there is stronger practical application meaning.
The invention provides a kind of preparation method of graphene, comprise the following steps：
A) graphite, chromium trioxide and concentrated hydrochloric acid are reacted, obtain intercalated graphite compounds；
B after) intercalated graphite compounds for obtaining above-mentioned steps are mixed with hydrogen peroxide, expanded graphite is obtained；
C) expanded graphite for obtaining above-mentioned steps is peeled off in aqueous phase, obtains graphene.
Preferably, the temperature of the reaction is 0~30 DEG C；
The time of the reaction is 0.5~48h.
Preferably, the mol ratio of the graphite and the chromium trioxide is 1：(0.5~1)；
The mol ratio of the graphite and the concentrated hydrochloric acid is 1：(0.5~1)；
The graphite includes one kind or more in graphite powder, crystalline flake graphite, Delanium, expansible graphite and expanded graphite
Kind.
Preferably, the granularity of the graphite is 50~10000 mesh；
The carbon content of the graphite is more than or equal to 70%.
Preferably, post-processing step is also included after the reaction；
The post processing includes washing and/or dried.
Preferably, the mode of the washing is washing；
The washing is 6~7.5 to be washed till pH value.
Preferably, the drying is vacuum drying；
The temperature of the drying is 60~100 DEG C；
The time of the drying is 6~24h.
Preferably, the mass ratio of the intercalated graphite compounds and hydrogen peroxide is 1：(100~400)；
The temperature of the mixing is 10~30 DEG C；The time of the mixing is 10~48h.
Preferably, the mode of the stripping includes the one or more in ultrasound, ball milling and shearing.
Preferably, in the stripping process, it is additionally added dispersant；
The dispersant includes tetrabutylammonium, neopelex, dodecyl sodium sulfate, dodecyl
One or more in sodium sulphate, Tween 80, cetyl trimethylammonium bromide, nonyl phenol polyethers, P-123 and Dev2043.
The invention provides a kind of preparation method of graphene, comprise the following steps, first by graphite, chromium trioxide and dense
Hydrochloric acid is reacted, and obtains intercalated graphite compounds；Then the intercalated graphite compounds that above-mentioned steps obtain and hydrogen peroxide are entered
After row mixing, expanded graphite is obtained；The expanded graphite that finally above-mentioned steps are obtained is peeled off in aqueous phase, obtains graphite
Alkene.Compared with prior art, the present invention is directed to HTHP defect existing for existing conventional graphene liquid phase stripping method, adopts
With the liquid phase stripping method of low-temperature atmosphere-pressure, the method that during low temperature liquid phase stripping method organic phase must be used to peel off is directed to again,
By to raw material it is creative preferably and combination, refine reactions steps, creative overcomes existing technology prejudice, success
Realize low temperature intercalation-low-temperature expansion-aqueous phase stripping graphene preparation method, not only reduce production cost, also avoid
Pollution of the organic solvent for environment, also add the rate of dispersion of graphene.
Test result indicates that the graphene yield after the present invention peels off is more than 90%, specific surface area is more than 100m2/ g, electricity
Conductance is more than 30000S/m, can reach 60000S/m.
Brief description of the drawings
Fig. 1 is the graphite that the embodiment of the present invention 1 uses and the XRD diffraction patterns of the intercalated graphite compounds (GIC) prepared；
Fig. 2 is the electron scanning micrograph of quasiflake graphite aggregation (CEWG) prepared by the embodiment of the present invention 1；
Fig. 3 is the metallographic microscope photo of quasiflake graphite aggregation (CEWG) prepared by the embodiment of the present invention 1；
Fig. 4 is the electron scanning micrograph of graphene prepared by the embodiment of the present invention 1.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, its source is not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, its purity is not particularly limited, and present invention preferably employs analyze pure or graphene to prepare
The conventional purity requirement in field.
All raw materials of the present invention, its trade mark and abbreviation belong to this area routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The invention provides a kind of preparation method of graphene, it is characterised in that comprises the following steps：
A) graphite, chromium trioxide and concentrated hydrochloric acid are reacted, obtain intercalated graphite compounds；
B after) intercalated graphite compounds for obtaining above-mentioned steps are mixed with hydrogen peroxide, expanded graphite is obtained；
C) expanded graphite for obtaining above-mentioned steps is peeled off in aqueous phase, obtains graphene.
The present invention is first reacted graphite, chromium trioxide and concentrated hydrochloric acid, obtains intercalated graphite compounds.
Selection of the present invention to the graphite is not particularly limited, and is with graphite material well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The bright graphite preferably includes one kind or more in graphite powder, crystalline flake graphite, Delanium, expansible graphite and expanded graphite
Kind, more preferably graphite powder, crystalline flake graphite, Delanium, expansible graphite or expanded graphite.
The granularity of the graphite powder is not particularly limited the present invention, with the grain of graphite powder well known to those skilled in the art
Footpath, those skilled in the art can be selected and adjusted according to practical condition, product requirement and quality requirement,
The granularity of graphite of the present invention is preferably 50~10000 mesh, more preferably 100~5000 mesh, more preferably 500~3000
Mesh, most preferably 1000~2000 mesh.
The carbon content of the graphite is not particularly limited the present invention, with the carbon of graphite powder well known to those skilled in the art
Content, those skilled in the art can be selected and adjusted according to practical condition, product requirement and quality requirement
Whole, the carbon content of graphite of the present invention is preferably greater than or equal to 70%, more preferably greater than equal to 80%, is most preferably more than or equal to
90%, it is specifically as follows 70%~95%, or 75%~90%, or be 78%~93%.
The dosage of the chromium trioxide is not particularly limited the present invention, and those skilled in the art can be according to actual production
Situation, product requirement and quality requirement are selected and adjusted, and the present invention further realizes to improve the performance of final products
Aqueous phase separation, the mol ratio of the graphite and the chromium trioxide is preferably 1：(0.5~1), more preferably 1：(0.6~0.9),
Most preferably 1：(0.7~0.8).
The dosage of the concentrated hydrochloric acid is not particularly limited the present invention, is with conventional amount used well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The bright performance for raising final products, aqueous phase separation is further realized, the mol ratio of the graphite and the concentrated hydrochloric acid is preferably
1：(0.5~1), more preferably 1：(0.6~0.9), most preferably 1：(0.7~0.8).
The concentration of the concentrated hydrochloric acid is not particularly limited the present invention, with conventional concentrated hydrochloric acid well known to those skilled in the art
Concentration, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the concentration of concentrated hydrochloric acid of the present invention is preferably 10~12mol/L, more preferably 10.5~11.5mol/L, is most preferably
10.8~11.2mol/L.
The temperature of the reaction is not particularly limited the present invention, with liquid phase separation method well known to those skilled in the art
The temperature of conventional intercalation, those skilled in the art can want according to practical condition, product requirement and quality
Ask and selected and adjusted, the present invention further realizes aqueous phase to improve the advantage of the performance of final products and liquid phase separation method
Separation, particularly further reduces reaction temperature, and the temperature of the reaction is preferably 0~30 DEG C, more preferably 5~30 DEG C,
More preferably 10~25 DEG C, more preferably 15~25 DEG C, more preferably 20~25 DEG C.
The time of the reaction is not particularly limited the present invention, with liquid phase separation method well known to those skilled in the art
Conventional intercalation time, those skilled in the art can be according to practical condition, product requirement and quality requirements
Being selected and adjusted, the time of reaction of the present invention is preferably 0.5~48h, more preferably 1~40h, more preferably 5~
30h, most preferably 10~20h.
The present invention carries out intercalation using the combination of concentrated hydrochloric acid and chromium trioxide to graphite, avoids the reaction bar of HTHP
Part, the temperature of intercalation is further lowered, effectively inserting for graphite can be realized under the conditions of lower temperature and common room temperature
Layer, obtains graphite intercalation compound, reduces energy consumption of reaction.
The present invention complete process route, preferably also includes post processing to improve the practicality of preparation method after the reaction
Step.The specific steps of the post processing are not particularly limited the present invention, are walked with post processing well known to those skilled in the art
Rapid, those skilled in the art can be selected and adjusted according to practical condition, product requirement and quality requirement,
Post processing of the present invention is preferably included to wash and/or dried.
The specific steps and condition of the washing are not particularly limited the present invention, are washed with well known to those skilled in the art
The specific steps and condition washed, those skilled in the art can want according to practical condition, product requirement and quality
Ask and selected and adjusted, the mode of washing of the present invention is preferably to wash.The standard of washing of the present invention is preferably to wash
Be 6~7.5 to pH value, that is, the pH value of water is preferably 6~7.5 after washing, and more preferably 6.5~7.
The specific steps and condition of the drying are not particularly limited the present invention, with well known to those skilled in the art dry
Dry specific steps and condition, those skilled in the art can want according to practical condition, product requirement and quality
Ask and selected and adjusted, the mode of drying of the present invention is preferably to be dried in vacuo.The temperature of drying of the present invention is preferred
For 60~100 DEG C, more preferably 70~90 DEG C, more preferably 75~85 DEG C.The time of the drying is preferably 6~24h, more excellent
Elect 10~20h, more preferably 12~18h as.
After the intercalated graphite compounds that the present invention then obtains above-mentioned steps are mixed with hydrogen peroxide, obtain expanding stone
Ink.
The dosage of the hydrogen peroxide is not particularly limited the present invention, is with conventional amount used well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The bright performance for raising final products, further realize the mass ratio of aqueous phase separation, the intercalated graphite compounds and hydrogen peroxide
Preferably 1：(100~400), more preferably 1：(150~350), more preferably 1：(200~300).
The concentration of the hydrogen peroxide is not particularly limited the present invention, with conventional hydrogen peroxide well known to those skilled in the art
Concentration, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the concentration (mass concentration) of hydrogen peroxide of the present invention is preferably 26%~30%, and more preferably 27%~30%, it is optimal
Elect 28%~30% as.
The mode of the mixing is not particularly limited the present invention, is with hybrid mode well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The mode of the bright mixing is preferably to be stirred or soak.
The temperature of the mixing is not particularly limited the present invention, is with mixing temperature well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The temperature of the bright mixing is preferably 10~30 DEG C, more preferably 15~30 DEG C, more preferably 10~25 DEG C, more preferably 20~
25℃.The time of mixing of the present invention is preferably 10~48h, more preferably 15~40h, more preferably 20~35h, most preferably
For 25~30h.
The expanded graphite that the present invention finally obtains above-mentioned steps is peeled off in aqueous phase, obtains graphene.
The mode of the stripping is not particularly limited the present invention, is in a manner of stripping well known to those skilled in the art
Can, those skilled in the art can be selected and adjusted, this hair according to practical condition, product requirement and quality requirement
The bright performance for raising final products, further realizes aqueous phase separation, and the mode of the stripping preferably includes ultrasound, ball milling and cut
The one or more hited, more preferably ultrasound, ball milling or shearing.
The ultrasonic actual conditions is not particularly limited the present invention, with ultrasound condition well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical condition, product requirement and quality requirement, this
Invent to improve the performance of final products, further realize aqueous phase separation, the ultrasonic power is preferably 400~2000W, more
Preferably 800~1600W, more preferably 1000~1200W.The ultrasonic time of the present invention is preferably 1~4h, more preferably
1.5~3.5h, more preferably 2~3h.
The actual conditions of the ball milling is not particularly limited the present invention, with ball milling condition well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical condition, product requirement and quality requirement, this
To invent to improve the performance of final products, further realize aqueous phase separation, the rotating speed of the ball milling is preferably 10~10000rmp,
More preferably 100~5000rmp, more preferably 1000~3000rmp.The time of ball milling of the present invention be preferably 5min~
48h, more preferably 30min~40h, more preferably 1~20h, more preferably 5~10h.
The present invention can also add dispersant in stripping process.The dispersant is not particularly limited the present invention, with
It is well known to those skilled in the art be used for peel off dispersant, those skilled in the art can according to practical condition,
Product requirement and quality requirement are selected and adjusted, and dispersant of the present invention preferably includes tetrabutylammonium, ten
Dialkyl benzene sulfonic acids sodium, dodecyl sodium sulfate, lauryl sodium sulfate, Tween 80, cetyl trimethylammonium bromide, nonyl
One or more in phenol polyethers, P-123 and Dev2043, more preferably tetrabutylammonium, neopelex,
Dodecyl sodium sulfate, lauryl sodium sulfate, Tween 80, cetyl trimethylammonium bromide, nonyl phenol polyethers, P-123 or
Dev2043。
The concentration of the dispersant is not particularly limited the present invention, is used for what is peeled off with well known to those skilled in the art
Dispersant, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the present invention further realize aqueous phase separation, concentration of the dispersant in aqueous phase is excellent to improve the performance of final products
Elect 0.01~0.4mol/L, more preferably 0.05~0.3mol/L, most preferably 0.1~0.2mol/L as.
The present invention further realizes aqueous phase separation, preferably controls graphene in aqueous phase to improve the performance of final products
Concentration is 0.1~20mg/ml, more preferably 1~15mg/ml, more preferably 5~10mg/ml.
Above-mentioned steps of the present invention provide a kind of stripping means of graphene, i.e. low temperature intercalation-low-temperature expansion-aqueous phase is peeled off
Graphene liquid phase stripping method.The present invention using graphite as raw material, first with intercalator to its intercalation to reduce Interaction between layers, adopt
Further increase graphite layers with chemically expansible away from obtained expanded graphite, finally carried out in aqueous phase mechanical stripping prepare it is highly conductive
Property graphene.It is of the invention that intercalation is especially carried out to graphite using the combination of concentrated hydrochloric acid and chromium trioxide, in conjunction with specific ratio,
Intercalation temperature is further reduced, avoids the reaction condition of HTHP, can be in room temperature even zero degree implementation above graphite
Effective intercalation, obtains graphite intercalation compound, reduces energy consumption of reaction.The present invention is by graphite intercalation compound, especially and peroxide
Change hydrogen and chemically expansible occurs at room temperature, in conjunction with specific ratio, and further reduce expansion temperature, caused oxygen increase
Graphite layers are away from having obtained quasiflake graphite aggregation, the problem of overcoming the high energy consumption of traditional thermal expansion, also overcomed biography
The technology prejudice that the liquid phase stripping method of system can not be carried out at lower temperatures.Combination and ratio of the present invention by above-mentioned raw materials
Example, creative first points out that quasiflake graphite aggregation can be peeled off in aqueous phase, equally overcomes traditional liquid phase
The technology prejudice that stripping method can not be carried out in aqueous phase, more avoid pollution of the organic solvent to environment, moreover it is possible to increase graphene
Dispersion concentration, so as to improve peel off after graphene performance.Graphene low temperature strip preparation method provided by the invention, energy
Low temperature intercalation, low-temperature expansion are enough realized, reduces production cost；Aqueous phase is peeled off, and reduces the secondary pollution of organic matter.
Test result indicates that the graphene yield after the present invention peels off is more than 90%, specific surface area is more than 100m2/ g, electricity
Conductance is more than 30000S/m.
In order to further illustrate the present invention, with reference to embodiments to a kind of preparation method of graphene provided by the invention
It is described in detail, but it is to be understood that these embodiments are implemented under premised on technical solution of the present invention, provide
Detailed embodiment and specific operating process, it is simply to further illustrate the features and advantages of the present invention, rather than it is right
The limitation of the claims in the present invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
By 1g expansible graphites (100 mesh, carbon content>70%), 8.5g chromium trioxides are put into 100ml round-bottomed flasks, are added
Enter 7ml concentrated hydrochloric acids (12mol/L), seal, and add device for absorbing tail gas (having chlorine generation, saturation NaOH absorbs), reaction system
The stirring reaction 10h at 25 DEG C, filtering, pure water remove unreacted concentrated hydrochloric acid and chromium trioxide, are dried in vacuo at 60 DEG C
12h, obtain graphite intercalation compound (GIC).
The intercalated graphite compounds prepared to the embodiment of the present invention 1 characterize.
Referring to Fig. 1, Fig. 1 is the graphite that the embodiment of the present invention 1 uses and the XRD of the intercalated graphite compounds (GIC) prepared
Diffraction pattern.
It can be seen from figure 1 that the crystalline structure of graphite illustrates intercalation success there occurs significant change before and after intercalation.
Then 0.2g GIC is put into 40ml hydrogen peroxide, 25 DEG C of submergences stand 48h, filtering, pure water, obtain
Quasiflake graphite aggregation (CEWG), i.e. expanded graphite.
The quasiflake graphite aggregation prepared to the embodiment of the present invention 1 characterizes, and observes pattern.
Referring to Fig. 2, Fig. 2 is the scanning electron microscopy of quasiflake graphite aggregation (CEWG) prepared by the embodiment of the present invention 1
Mirror photo.
Referring to Fig. 3, Fig. 3 is that the metallographic microscope of quasiflake graphite aggregation (CEWG) prepared by the embodiment of the present invention 1 shines
Piece.
From Fig. 2 and Fig. 3, expansion weakens the Van der Waals force of graphite layers, and interlamellar spacing significantly increases, and has vermiform
Structure, be advantageous to graphite and peeling off into graphene.
Finally, obtained 0.1g CEWG is added in the aqueous solution that 50ml contains Dev2043, wherein Dev2043's
Concentration is 0.05mol/L, after 3000W is ultrasonically treated 2h, obtains graphene.It is computed and detects, the yield of graphene is 92%,
Specific surface area is 300m2/ g, electrical conductivity is up to 60000S/m.
The graphene prepared to the embodiment of the present invention 1 characterizes.
Referring to Fig. 4, Fig. 4 is the electron scanning micrograph of graphene prepared by the embodiment of the present invention 1.
As shown in Figure 4, the method prepare graphene sheet layer it is thin and it is regular there is no defect, due to intercalation, expansion and stripping
All carry out at ambient temperature, without heating or high-temperature process, therefore be that a kind of liquid phase that is new, being produced on a large scale is peeled off
Method.
Embodiment 2
By 1g expansible graphites (50 mesh, carbon content>75%), 5g chromium trioxides are put into 100ml round-bottomed flasks, are added
7ml concentrated hydrochloric acids (10mol/L), sealing, and add device for absorbing tail gas (having chlorine generation, saturation NaOH absorbs), reaction system exists
Stirring reaction 5h at 30 DEG C, filtering, pure water remove unreacted concentrated hydrochloric acid and chromium trioxide, 6h are dried in vacuo at 70 DEG C,
Obtain graphite intercalation compound (GIC).
0.2gGIC is put into 20ml hydrogen peroxide, 25 DEG C of submergences stand 24h, filtering, pure water, obtain vermiform
Graphite aggregation (CEWG).
Finally, obtained 0.1gCEWG is added in the aqueous solution that 100ml contains neopelex, wherein ten
The concentration of dialkyl benzene sulfonic acids sodium is 0.2mol/L, and 2000W is ultrasonically treated 2h, obtains graphene.It is computed and detects, graphene
Yield be 95%, specific surface area 200m2/ g, electrical conductivity is up to 45000S/m.
Embodiment 3
By the mixture of 1g graphite powders and crystalline flake graphite (300 mesh, mass ratio 1:1, carbon content>85%), 7g tri- is aoxidized
Chromium is put into 100ml round-bottomed flasks, adds 7ml concentrated hydrochloric acids (12mol/L), sealing, and add device for absorbing tail gas (to have chlorine production
Raw, saturation NaOH absorbs), reaction system stirring reaction 24h at 25 DEG C is filtered, and pure water removes unreacted concentrated hydrochloric acid
And chromium trioxide, 12h is dried in vacuo at 60 DEG C, obtains graphite intercalation compound (GIC).
0.2gGIC is put into 60ml hydrogen peroxide, 25 DEG C of submergences stand 24h, filtering, pure water, obtain vermiform
Graphite aggregation (CEWG).
Finally, obtained 0.1gCEWG is added in the aqueous solution that 100ml contains Tween-80, wherein Tween-80 is dense
Spend and be ultrasonically treated 2h for 0.05mol/L, 1000W, obtain graphene.It is computed and detects, graphene yield is 93%, compares surface
Product is 250m2/ g, electrical conductivity is up to 50000S/m.
A kind of low temperature preparation method of high conductivity graphene provided by the invention is described in detail above, this
Apply specific case in text to be set forth the principle and embodiment of the present invention, the explanation of above example is only intended to
Help to understand method and its core concept of the invention, including best mode, and also cause any person skilled in the art
The present invention can be put into practice, including is manufactured and using any device or system, and implements the method for any combination.It should be pointed out that
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be entered
Some improvement of row and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.Patent of the present invention is protected
The scope of shield is defined by the claims, and may include those skilled in the art it is conceivable that other embodiment.If this
A little other embodiments have the structural element for being not different from claim character express, or if they include wanting with right
Equivalent structural elements of the character express asked without essence difference, then these other embodiments should also be included in the model of claim
In enclosing.
Claims (10)
1. a kind of preparation method of graphene, it is characterised in that comprise the following steps：
A) graphite, chromium trioxide and concentrated hydrochloric acid are reacted, obtain intercalated graphite compounds；
B after) intercalated graphite compounds for obtaining above-mentioned steps are mixed with hydrogen peroxide, expanded graphite is obtained；
C) expanded graphite for obtaining above-mentioned steps is peeled off in aqueous phase, obtains graphene.
2. preparation method according to claim 1, it is characterised in that the temperature of the reaction is 0~30 DEG C；
The time of the reaction is 0.5~48h.
3. preparation method according to claim 1, it is characterised in that the mol ratio of the graphite and the chromium trioxide is
1：(0.5~1)；
The mol ratio of the graphite and the concentrated hydrochloric acid is 1：(0.5~1)；
The graphite includes the one or more in graphite powder, crystalline flake graphite, Delanium, expansible graphite and expanded graphite.
4. preparation method according to claim 3, it is characterised in that the granularity of the graphite is 50~10000 mesh；
The carbon content of the graphite is more than or equal to 70%.
5. preparation method according to claim 1, it is characterised in that also include post-processing step after the reaction；
The post processing includes washing and/or dried.
6. preparation method according to claim 5, it is characterised in that the mode of the washing is washing；
The washing is 6~7.5 to be washed till pH value.
7. preparation method according to claim 5, it is characterised in that the drying is vacuum drying；
The temperature of the drying is 60~100 DEG C；
The time of the drying is 6~24h.
8. preparation method according to claim 1, it is characterised in that the intercalated graphite compounds and the quality of hydrogen peroxide
Than for 1：(100~400)；
The temperature of the mixing is 10~30 DEG C；The time of the mixing is 10~48h.
9. preparation method according to claim 1, it is characterised in that the mode of the stripping includes ultrasound, ball milling and cut
The one or more hited.
10. preparation method according to claim 1, it is characterised in that in the stripping process, be additionally added dispersant；
The dispersant includes tetrabutylammonium, neopelex, dodecyl sodium sulfate, dodecyl sulphate
One or more in sodium, Tween 80, cetyl trimethylammonium bromide, nonyl phenol polyethers, P-123 and Dev2043.
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