CN107973293A - The preparation method and graphene of graphene - Google Patents
The preparation method and graphene of graphene Download PDFInfo
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- CN107973293A CN107973293A CN201711379453.XA CN201711379453A CN107973293A CN 107973293 A CN107973293 A CN 107973293A CN 201711379453 A CN201711379453 A CN 201711379453A CN 107973293 A CN107973293 A CN 107973293A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention belongs to technical field of nano material, it is related to the preparation method and graphene of graphene.The preparation method of graphene provided by the invention, prepares graphene, three rank peels off and is followed successively by single order graphite mechanical stripping and intercalation, second order solution expansion stripping and three ranks ultrasound is peeled off by way of three rank strippings.Single order graphite mechanical stripping and intercalation, graphite and intercalation medium are mixed, mechanically, graphite is carried out a degree of stripping and intercalation, obtains graphene presoma；Second order solution plavini is peeled off, and graphene presoma is added into strong acid solution, graphene is separated, and will obtain Activated Graphite alkene dispersion liquid with further being opened between defective graphene layer；Three ranks ultrasound is peeled off, and by Activated Graphite alkene dispersion liquid, further ultrasound is peeled off, and obtains the graphene dispersing solution that lamellar spacing is small, the number of plies is few.Present invention process is simple, and mild condition, cost is low, and the graphene sheet layer of preparation is thin, defect is few, quality is high.
Description
Technical field
The invention belongs to technical field of nano material, is related to grapheme material, and in particular to the preparation method of graphene and
Graphene.
Background technology
Graphene has excellent performance in electricity, optics, mechanics etc., thus its application field is quite extensive.Perhaps
More researchers have all carried out a series of research work in every field, but in research or actual application, graphite
The performance that alkene has been given play to but is had a greatly reduced quality.Study carefully its cause, the graphene existing defects that one uses are more, its actual performance and theory
Performance difference is larger；Secondly the poor compatibility of graphene and other materials, in product process is made, performance cannot be sent out completely
Wave.
No matter graphene is that defect is more, or poor compatibility, these can all limit the development of graphene, and being unfavorable for downstream should
Exploitation.It is more to solve defect, the problem such as poor compatibility, technological problems can not be ignored.For graphene commercial Application,
Can realize the production technology of industrial applications on a large scale has two kinds.Traditional CVD method, i.e. chemical vapour deposition technique, this method can
With the single-layer graphene film of growing large-area, the product purity height of preparation, quality are good, but expensive, are mainly used in
The field such as thin-film material and semiconductor.Another method is that intercalation peels off graphite method, including chemical method, ball-milling method, liquid phase ultrasound
Stripping method etc..Wherein chemical method includes chemical reduction method and chemical oxidization method, and chemical reduction method is a set of ripe technique, and
The most commonly used technique of macroscopic preparation of graphene；But chemical reduction method is using substantial amounts of strong acid, the material of strong oxidizing property, to environment
There is larger pollution, and there are certain safety problem.Chemical oxidization method has manufactured many defects, thus stone in graphene surface
The performance car following-theory difference of black alkene is larger.It is low that ball milling peels off the graphene cost prepared, can be with scale, but quality of graphene one
As.Graphene defect prepared by ultrasonic stripping method is few, but low yield.
In conclusion existing graphene preparation method has respective strengths and weaknesses, single technique is more difficult to be met at the same time
The requirement of high-quality, low cost, mass production etc..
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of graphene, can be with by the way of three ranks are peeled off
Reach mutual supplement with each other's advantages, maximize favourable factors and minimize unfavourable ones, while product quality is ensured, improve production efficiency, reduce cost, be finally prepared
Low defect, few layer, high-quality graphene.
The second object of the present invention is to provide a kind of graphene, the graphene being prepared by the method for the present invention, tool
There is the characteristics of lamella is thin, defect is few, quality is high.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of graphene, and the method passes through three ranks
Stripping mode prepares graphene, and three rank, which is peeled off, is followed successively by single order graphite mechanical stripping and intercalation, the expansion of second order solution
Peel off and three ranks ultrasound is peeled off.
As further preferred technical solution, the single order graphite mechanical stripping and intercalation include：By graphite powder and intercalation
Agent after mixing, using mechanical lapping mode, obtains mixing presoma.
As further preferred technical solution, the graphite powder includes crystalline flake graphite, expanded graphite, amorphous graphite and artificial
At least one of graphite, the size of graphite powder is 32~10000 mesh；
Preferably, the intercalator is sodium salt, preferably includes sodium carbonate, sodium acid carbonate, sodium sulfite and sodium hydrogensulfite
At least one of；
Preferably, the mass ratio of the graphite powder and intercalator is 1：5~1：100.
As further preferred technical solution, the mechanical lapping mode is using horizontal grinding, planetary grinding or high energy
At least one of ball milling, the time of mechanical lapping is preferably 0.5~100h.
As further preferred technical solution, the second order solution expansion stripping includes：In certain density acid solution
Middle addition neopelex, obtains mixed liquor；
The product of single order graphite mechanical stripping is slowly added into the mixed liquor, after anti-raw reaction, obtains graphene
Dispersion liquid.
As further preferred technical solution, the acid solution is strongly acidic solution, preferably includes hydrochloric acid, sulfuric acid, nitre
At least one of acid and phosphoric acid, the concentration of acid solution is preferably 1~6mol/L；
Preferably, the addition of the neopelex is 0.5~2g.
As further preferred technical solution, the three ranks ultrasound, which is peeled off, to be included：The product peeled off to the expansion of second order solution
Middle addition dispersant, after stirring evenly, ultrasound is peeled off, and is obtained three ranks and is peeled off product；
Preferably, the step that three rank stripping product is washed, separated and is dried to obtain graphene powder is further included
Suddenly.
As further preferred technical solution, the dispersant includes neopelex, polyvinylpyrrolidone
At least one of with polyethylene glycol, the mass concentration of dispersant is preferably 0.1%~20%.
As further preferred technical solution, ultrasonic time is 30~1200min, and ultrasonic power is 50~5000W.
According to another aspect of the present invention, the present invention also provides a kind of graphene, by the preparation side of above-mentioned graphene
Method is made.
Compared with prior art, the beneficial effects of the present invention are：
1st, the method for the invention, by the way of three ranks are peeled off, is followed successively by single order mechanical stripping and intercalation, graphite is shelled
From flakiness, prevent thin slice from stacking, and part intercalation processing is carried out in chip edge and defect；The expansion of second order solution is peeled off, can
To increase the interlamellar spacing at graphite edge and fault location, there is provided it is a large amount of to peel off active notch, reduce Van der Waals force；The ultrasound stripping of three ranks
From can be broken through from active notch, be effectively peeled off out few layer graphene；And then mode is peeled off by three ranks, have complementary advantages, play each
Rank peels off the advantage of mode, greatly improves charge stripping efficiency, and the graphene that lamella is thin, defect is few, quality is high is prepared.
2nd, expand and peel off present invention employs unique solution, overcome interlayer Van der Waals force, increase interlamellar spacing, to graphene
Lossless activity transformation is carried out, final obtained high-quality graphene can be within ten layers.
3rd, the method for the present invention novel and unique, preparation process be simple, mild condition, cost are low, environmental-friendly, suitable for industry
Change large-scale production.
4th, graphene of the invention can be widely applied to the fields such as lithium ion battery, ultracapacitor, functional composite material.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution of the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in describing below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
Put, other attached drawings can also be obtained according to these attached drawings.
Fig. 1 is the three rank stripping process schematic diagrames of the present invention；
Fig. 2 be graphene made from the embodiment of the present invention 1 TEM figure (TransmissionElectronMicroscope,
Transmission electron microscope)；
Fig. 3 is that the XPS of graphene made from the embodiment of the present invention 1 schemes (X-
RayPhotoelectronSpectroscopy, x-ray photoelectron spectroscopy).
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
Enclose.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
Every other embodiment, belongs to the scope of protection of the invention.The person that is not specified actual conditions, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer, is the conventional production that can be obtained by commercially available purchase
Product.
In a first aspect, providing a kind of preparation method of graphene in certain embodiments, the method is peeled off by three ranks
Mode prepares graphene, and three rank, which is peeled off, is followed successively by single order graphite mechanical stripping and intercalation, the expansion stripping of second order solution
Peeled off with three ranks ultrasound.
Graphite mechanical stripping and intercalation can use ball-milling technology, there are stripping and crush two kinds of effects, can be effectively by stone
Ink peels off straticulation graphite, or even graphene.Its feature has：1st, there are shearing and crush two kinds of active forces, the size of graphite and
Thickness can reduce.2nd, the big and thick graphite of the efficient flour of energy, stripping film, but size is small to a certain extent, the number of plies is small to one
Determine degree, its effect is had a greatly reduced quality, thus is more suitable for the stripping and crushing of sheet.3rd, extensive magnanimity can be adapted to prepare, but
It is to have micro destruction to the structure of powder, the fault of construction of a part can be manufactured, this segmental defect can manufactures after overactivation
Active sites notch.4th, there are inverse process, in mechanical milling process, graphite flake crushed or stripping can stack again, cause
Agnail from and flour.5th, can there are intercalation effect, fault location can be ground Filled Dielectrics, phase between piece piece in mechanical milling process
Than chemical graft, which is more suitable for the material of some difficult intercalations, such as soluble-salt, macromolecule.
It is stripping means new in the present invention that solution expansion, which is peeled off, and in the solution, violent chemistry occurs for intercalation chemistry thing
Reaction, produces instantaneous expansion power, so as to be peeled off to graphite.Its feature has：1st, intercalation compound energy and solution reaction, and energy
Expansion power is produced, could be peeled off using this method, conventional chemical graft graphite is not suitable with this method.2nd, intercalation compound
Violent with solution reaction, local expansive force is huge, and local interlamellar spacing increase is obvious.But with the increase of interlamellar spacing, expansive force
Weaken significantly, thus dissection scope is limited, it is difficult to graphite flake layer is completely exfoliated.3rd, during being somebody's turn to do, intercalation thing and solution reaction are thorough
Bottom, entirely expands stripping process, and noresidue impurity, will not damage graphite-structure, and the performance of graphite is not impacted.
Ultrasonic stripping method is that graphene is prepared in ultrasound in the liquid phase by graphite powder, and in ultrasonic procedure, peeling force is come
From under cavitation effect, cavitation effect, bubble breaking, miniature air-flow and vibration wave act on graphite powder surface, produce different answer
Graphite powder can be effectively peeled off by power, positive peeling force.Its feature has：1st, ultrasonic cavitation effect is conducive to the stripping of graphite, but
At the same time defect can be produced, 2, ultrasound peel off the consumption that graphite powder is attributed to a small amount of net energy in stripping process, though peeling effect is good,
It is but less efficient.3rd, graphene concentration, graphite layers away from, the factor such as dispersion liquid volume, solvent surface energy, container dimensional to ultrasound
Stripping has a great impact.
Therefore, above-mentioned three kinds of stripping means, there are respective strengths and weaknesses, and three kinds of stripping means are combined and are peeled off stage by stage,
Mutual supplement with each other's advantages can be reached, play the advantage of various stripping modes, so that while product quality is ensured, improve production effect
Rate, reduces cost.
In a preferred embodiment, the single order graphite mechanical stripping and intercalation include：By graphite powder and intercalation
Agent after mixing, using mechanical lapping mode, obtains mixing presoma.
In a preferred embodiment, the graphite powder includes crystalline flake graphite, expanded graphite, amorphous graphite and artificial
At least one of graphite, the size of graphite powder is 32~10000 mesh；
Preferably, the intercalator is sodium salt, preferably includes sodium carbonate, sodium acid carbonate, sodium sulfite and sodium hydrogensulfite
At least one of；
Preferably, the mass ratio of the graphite powder and intercalator is 1：5~1：100.
Wherein, the size of graphite powder is 32~10000 mesh, is preferably 50~6000 mesh, more preferably 100~5000
Mesh.The typical but non-limiting size of graphite powder is 32 mesh, 40 mesh, 50 mesh, 100 mesh, 150 mesh, 200 mesh, 250 mesh, 300
Mesh, 325 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 600 mesh, 800 mesh, 1000 mesh, 2000 mesh, 3000 mesh, 4000 mesh, 5000
Mesh, 6000 mesh, 8000 mesh or 10000 mesh.
The mass ratio of graphite powder and intercalator is 1：5~1：100, it is preferably 1：10~1：80, more preferably 1：20
~1：50.The typical but non-limiting mass ratio of graphite powder and intercalator is 1：5、1：10、1：15、1：20、1：25、1：30、
1：35、1：40、1：50、1：60、1：70、1：80、1：90 or 1：100.
In a preferred embodiment, the mechanical lapping mode is using horizontal grinding, planetary grinding or high energy
At least one of ball milling, the time of mechanical lapping is preferably 0.5~100h.
Wherein, mechanical polishing time is 0.5~100h, is preferably 2~80h, more preferably 5~50h.Mechanical lapping
Time it is typical but non-limiting for 0.5h, 1h, 2h, 5h, 8h, 10h, 15h, 20h, 30h, 40h, 50h, 60h, 70h, 80h,
90h or 100h.
In this way, under the operating conditions described above, by above-mentioned single order graphite mechanical stripping and intercalation mode, graphite is carried out
A degree of stripping and intercalation, obtain graphene presoma, can prevent thin slice from stacking, and chip edge and defect go out into
Row part intercalation processing.
In a preferred embodiment, the second order solution expansion stripping includes：In certain density acid solution
Middle addition neopelex, obtains mixed liquor；
The product of single order graphite mechanical stripping is slowly added into the mixed liquor, after reacting, obtains graphene
Dispersion liquid.
In a preferred embodiment, the acid solution is strongly acidic solution, preferably includes hydrochloric acid, sulfuric acid, nitre
At least one of acid and phosphoric acid, the concentration of acid solution is preferably 1~6mol/L；
Preferably, the addition of the neopelex is 0.5~2g.
Above-mentioned second order solution expands the specific steps peeled off：Certain density strongly acidic solution is configured, and is added
A certain amount of neopelex, obtains mixed liquor；Above-mentioned mixing presoma is slowly added into the mixed liquor, by force
Acid carries out vigorous reaction with intercalator, discharges a large amount of gases, so that graphite expansion be peeled off, obtains graphene dispersing solution.
Wherein, the concentration of acid solution it is typical but non-limiting for 1mol/L (1M), 2mol/L, 3mol/L, 4mol/L,
5mol/L or 6mol/L.The typical but non-limiting addition of neopelex is 0.5g, 1g, 1.5g or 2g.
In this way, under the operating conditions described above, stripping mode is expanded by above-mentioned second order solution, graphite edge can be increased
With the interlamellar spacing of fault location, there is provided it is a large amount of to peel off active notch, Van der Waals force is reduced, obtains Activated Graphite alkene dispersion liquid.
In a preferred embodiment, the three ranks ultrasound is peeled off and included：The product peeled off to the expansion of second order solution
Middle addition dispersant, after stirring evenly, ultrasound is peeled off, and is obtained three ranks and is peeled off product；
Preferably, the step that three rank stripping product is washed, separated and is dried to obtain graphene powder is further included
Suddenly.
Washing therein can be washing, and separation can be centrifugation.
In a preferred embodiment, the dispersant includes neopelex, polyvinylpyrrolidone
At least one of with polyethylene glycol, the mass concentration of dispersant is preferably 0.1%~20%.The mass concentration typical case of dispersant
But it is nonrestrictive be 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%,
7%th, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
In a preferred embodiment, ultrasonic time is 30~1200min, and ultrasonic power is 50~5000W.Ultrasound
Time it is typical but non-limiting for 30min, 40min, 60min, 60min, 70min, 80min, 90min, 100min,
120min, 150min, 200min, 300min, 400min, 500min, 600min, 800min, 900min, 1000min or
1200min；Ultrasonic power it is typical but non-limiting for 50W, 60W, 80W, 100W, 200W, 300W, 500W, 800W, 1000W,
1500W, 2000W, 2500W, 3000W, 3500W, 4000W, 4500W or 5000W.
In this way, under the operating conditions described above, by three above-mentioned rank ultrasound stripping modes, by Activated Graphite alkene dispersion liquid into
One step ultrasound is peeled off, and can be broken through from active notch, is effectively peeled off out few layer graphene, is obtained the stone that lamellar spacing is small, the number of plies is few
Black alkene dispersion liquid, in addition, after preceding two ranks stripping process, graphite is stripped into thin slice, is greatly improved charge stripping efficiency.
Second aspect, provides a kind of graphene in certain embodiments, is made by the preparation method of above-mentioned graphene.Should
Graphene has the characteristics that lamella is thin, defect is few, quality is high.
Fig. 1 shows the three rank stripping process schematic diagrames of the present invention.As shown in Fig. 1 (a), single order graphite mechanical stripping and insert
Layer, can peel off flakiness by graphite rapidly, prevent thin slice from stacking, and go out to carry out at the intercalation of part in chip edge and defect
Reason；As shown in Fig. 1 (b), the expansion of second order solution is peeled off, and can increase the interlamellar spacing of graphite edge and fault location, there is provided a large amount of strippings
From active notch, Van der Waals force is reduced；As shown in Fig. 1 (c), after two benches stripping, there are a large amount of activity and lack in graphene platelet
Mouthful, three ranks ultrasound is peeled off, and under ultrasonic cavitation effect, can be broken through from active notch, is effectively peeled off out few layer graphene, this
Outside, after preceding two ranks stripping process, graphite is stripped into thin slice, greatly improves charge stripping efficiency.
Compared with prior art, the present invention mainly have the characteristics that：
(1), using a kind of new stripping means --- solution plavini.The method utilizes intercalation compound and solution reaction,
Gas is produced, forms temporal pressure, overcomes interlayer Van der Waals force, increases interlamellar spacing, lossless activity transformation (system is carried out to graphene
Make the active notch of stripping).
(2), the present invention prepares graphene using three rank stripping methods, combines the advantage of three kinds of stripping modes, mechanical milling process
Energy efficiently flour and stripping, and active salt is introduced with interlayer, due to active reactant salt, solution expansion process can increase between interlayer
Away from ultrasonic procedure can realize that the thorough of graphite flake layer peels off in active indentation, there, so as to prepare high-quality graphene.
(3), in addition to a small amount of strong acid, reagent used in the present invention, solvent are nontoxic, environmentally friendly, environmental-friendly；In addition, three
Rank stripping method mild condition, easy to operate, safe and efficient, cost is low, is suitable for extensive magnanimity production.
With reference to specific embodiments and the drawings, the invention will be further described.
Embodiment 1
A kind of preparation method of graphene, comprises the following steps：
(a) 100 mesh crystalline flake graphite 50g are weighed, sodium hydrogensulfite 1000g, after mixing, is put into ball grinder, uses
Planetary type ball-milling, ball milling 20h, ball milling finish, and obtain mixing presoma；
(b) the hydrochloric acid 50L of 3M is prepared, and adds 1g neopelexes, is transferred in the reaction kettle of 100L；Take out
Presoma is mixed, is slowly added into 100L reaction kettles, there are a large amount of bubbles to produce；Finish, obtain graphene dispersing solution；By
Filter, washing, dilution is scattered, obtains 5% graphene dispersing solution, the number of plies of graphene is at 5~15 layers；
(c) 100g graphene dispersing solutions are taken, add neopelex 5g, are dispersed with stirring uniformly, in ultrasound condition
Lower ultrasound 30min, power 300W；By washing, centrifuge, after drying, the powder of few layer graphene is obtained.
The number of plies for the graphene powder that the present embodiment obtains is 3~10 layers, conductivity 600S/cm.
Fig. 2 shows the TEM figures of graphene made from embodiment；Fig. 3 is the XPS for showing graphene made from embodiment
Figure.As can be seen that TEM tests show graphene in flake from Fig. 2 and Fig. 3, and there is the fold of part, be graphene
Characteristic feature, illustrate that the lamella of graphene is relatively thin；In addition, XPS test results show that impurity element is less in graphene, knot
Structure keeps preferable, and quality is higher.
Embodiment 2
A kind of preparation method of graphene, comprises the following steps：
(a) 325 mesh expanded graphite 50g are weighed, sodium carbonate 2000g, after mixing, is put into ball grinder, use is horizontal
Ball milling, ball milling 48h, ball milling finish, and obtain mixing presoma；
(b) the sulfuric acid 50L of 6M is prepared, and adds 0.5g neopelexes, is transferred in the reaction kettle of 100L；Take
Go out to mix presoma, be slowly added into 100L reaction kettles, there are a large amount of bubbles to produce；Finish, obtain the dispersion liquid of graphene；Through
Filtering, washing, dilution is scattered, obtains 5% graphene dispersing solution, the graphene number of plies is at 6~20 layers；
(c) 100g graphene dispersing solutions are taken, add polyvinylpyrrolidone 10g, are dispersed with stirring uniformly, under ultrasound condition
Ultrasonic 600min, power 500W；By washing, centrifuge, after drying, the powder of graphene is obtained.
The number of plies for the graphene powder that the present embodiment obtains is 3~10 layers, conductivity 750S/cm.
Embodiment 3
A kind of preparation method of graphene, comprises the following steps：
(a) 5000 mesh crystalline flake graphite 50g are weighed, sodium carbonate 5000g, after mixing, is put into ball grinder, using planet
Formula ball milling, ball milling 100h, ball milling finish, and obtain mixing presoma；
(b) the phosphoric acid 50L of 6M is prepared, and adds 1g neopelexes, is uniformly dispersed, is transferred to the reaction of 100L
In kettle；Mixing presoma is taken out, is slowly added into 100L reaction kettles, there are a large amount of bubbles to produce；Finish, obtain point of graphene
Dispersion liquid；By filtering, washing, dilution is scattered, obtains 5% graphene dispersing solution, the graphene number of plies is at 5~12 layers；
(c) 100g graphene dispersing solutions are taken, add polyvinylpyrrolidone 0.5g, are dispersed with stirring uniformly, in ultrasound condition
Lower ultrasound 1200min, power 3000W；By washing, centrifuge, after drying, the powder of graphene is obtained.
The number of plies for the graphene powder that the present embodiment obtains is 3~5 layers, conductivity 1000S/cm.
Embodiment 4
A kind of preparation method of graphene, comprises the following steps：
(a) 1000 mesh amorphous graphite 50g are weighed, sodium carbonate 250g, after mixing, is put into ball grinder, use is horizontal
Ball milling, ball milling 5h, ball milling finish, and obtain mixing presoma；
(b) the sulfuric acid 50L of 6M is prepared, and adds 1g neopelexes, is transferred in the reaction kettle of 100L；Take out
Presoma is mixed, is slowly added into 100L reaction kettles, there are a large amount of bubbles to produce；Finish, obtain the dispersion liquid of graphene；By
Filtering, washing, dilution is scattered, obtains 5% graphene dispersing solution, the number of plies of graphene is at 4~14 layers；
(c) 100g graphene dispersing solutions are taken, add polyvinylpyrrolidone 5g, are dispersed with stirring uniformly, under ultrasound condition
Ultrasonic 300min, power 5000W；By washing, centrifuge, after drying, the powder of graphene is obtained.
The number of plies for the graphene powder that the present embodiment obtains is 2~6 layers, conductivity 600S/cm.
Embodiment 5
A kind of preparation method of graphene, comprises the following steps：
(a) 2000 mesh Delanium 50g are weighed, sodium carbonate 2500g, after mixing, is put into ball grinder, using high energy
Ball milling, ball milling 10h, ball milling finish, and obtain mixing presoma；
(b) the sulfuric acid 50L of 1M is prepared, and adds 1g neopelexes, is transferred in the reaction kettle of 100L；Take out
Presoma is mixed, is slowly added into 100L reaction kettles, there are a large amount of bubbles to produce；Finish, obtain the dispersion liquid of graphene；By
Filtering, washing, dilution is scattered, obtains 5% graphene dispersing solution, the number of plies of graphene is at 5~12 layers；
(c) 100g graphene dispersing solutions are taken, add polyethylene glycol 10g, are dispersed with stirring uniformly, it is ultrasonic under ultrasound condition
600min, power 3000W；By washing, centrifuge, after drying, the powder of graphene is obtained.
The number of plies for the graphene powder that the present embodiment obtains is 3~5 layers, conductivity 800S/cm.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution described in foregoing embodiments, either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
- A kind of 1. preparation method of graphene, it is characterised in that the method prepares graphene by way of three rank strippings, Three rank peels off and is followed successively by single order graphite mechanical stripping and intercalation, second order solution expansion stripping and three ranks ultrasound is peeled off.
- 2. the preparation method of graphene according to claim 1, it is characterised in that the single order graphite mechanical stripping and insert Layer includes：By graphite powder and intercalator after mixing, using mechanical lapping mode, mixing presoma is obtained.
- 3. the preparation method of graphene according to claim 2, it is characterised in that the graphite powder include crystalline flake graphite, At least one of expanded graphite, amorphous graphite and Delanium, the size of graphite powder is 32~10000 mesh；Preferably, the intercalator is sodium salt, is preferably included in sodium carbonate, sodium acid carbonate, sodium sulfite and sodium hydrogensulfite It is at least one；Preferably, the mass ratio of the graphite powder and intercalator is 1：5~1：100.
- 4. the preparation method of graphene according to claim 2, it is characterised in that the mechanical lapping mode is using horizontal At least one of grinding, planetary grinding or high-energy ball milling, the time of mechanical lapping is preferably 0.5~100h.
- 5. the preparation method of graphene according to claim 1, it is characterised in that bag is peeled off in the second order solution expansion Include：Neopelex is added in certain density acid solution, obtains mixed liquor；The product of single order graphite mechanical stripping is slowly added into the mixed liquor, after anti-raw reaction, obtains graphene dispersion Liquid.
- 6. the preparation method of graphene according to claim 5, it is characterised in that the acid solution is molten for highly acid Liquid, preferably includes at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, the concentration of acid solution is preferably 1~6mol/L；Preferably, the addition of the neopelex is 0.5~2g.
- 7. the preparation method of graphene according to claim 1, it is characterised in that the three ranks ultrasound, which is peeled off, to be included：To Dispersant is added in the product that the expansion of second order solution is peeled off, after stirring evenly, ultrasound is peeled off, and is obtained three ranks and is peeled off product；Preferably, the step of three rank stripping product is washed, separated and be dried to obtain graphene powder is further included.
- 8. the preparation method of graphene according to claim 7, it is characterised in that the dispersant includes detergent alkylate At least one of sodium sulfonate, polyvinylpyrrolidone and polyethylene glycol, the mass concentration of dispersant is preferably 0.1%~ 20%.
- 9. the preparation method of graphene according to claim 7, it is characterised in that ultrasonic time is 30~1200min, is surpassed Acoustical power is 50~5000W.
- 10. a kind of graphene, it is characterised in that be made by the preparation method of claim 1~9 any one of them graphene.
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