CN106672954A - Method for preparing graphene two-dimensional material through liquid-phase stripping - Google Patents
Method for preparing graphene two-dimensional material through liquid-phase stripping Download PDFInfo
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- CN106672954A CN106672954A CN201710045865.3A CN201710045865A CN106672954A CN 106672954 A CN106672954 A CN 106672954A CN 201710045865 A CN201710045865 A CN 201710045865A CN 106672954 A CN106672954 A CN 106672954A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000007791 liquid phase Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 238000005520 cutting process Methods 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- -1 n-methlpyrrolidone Chemical compound 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006228 supernatant Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a method for preparing a graphene two-dimensional material through liquid-phase stripping. The method comprises the following steps: (1) dispersing graphite into water and/or an organic solvent, maintaining the mixture temperature at 20-80 DEG C, alternatively preforming emulsified cutting and strong ultrasonic, wherein the graphene concentration in the mixture is 0.15-10g/L; (2) separating the product in the step (1) by use of a centrifuging method, taking the separated supernatant as the graphene dispersion liquid, wherein the centrifuging rate is 1000-6000rpm, and the centrifuging time is 5-30min. The commercial graphite with low price is used as the raw material, the organic solvent with good graphene dispersion property is used as the solvent for liquid-phase stripping, the ethanol, the isopropanol and other organic solvents are pollution-free, low in cost and recyclable; by use of the method of combining the emulsified cutting and the strong ultrasonic, the production time is short, the period is 6-20h, the method is simple, and the efficiency is high; the obtained graphene yield is high and can achieve 2%.
Description
Technical field
The invention belongs to material with carbon element preparation field, and in particular to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of ultra-thin two-dimensional material, and because it has very high specific surface area, excellent is chemical, thermally-stabilised
Property, good electric conductivity and heat conductivility, the property such as excellent mechanical performance so that the material receives extensive research.
As people deepen continuously to grapheme material research, in the near future, Graphene will be in catalysis, electronics, energy etc.
Various fields obtain business-like application.And in some important fields, such as electronic printing, electrically-conducting paint, lithium ion battery,
The substantial amounts of Graphene for being capable of industrialized production will be may require that.For example in lithium ion battery, Graphene can be taken as performance excellent
Different, cheap electrode material, and this electrode is produced by slurry coating, this is just to Graphene suspension, stone
Black alkene ink or graphene dispersing solution propose demand in large quantities.So, liquid phase stripping prepares the method for Graphene will be become
A kind of important technological means.
At present the synthetic method of Graphene mainly has micromechanics stripping, the life of chemical vapor deposition (CVD), crystalline epitaxial
Length, oxidation-reduction method etc..The method that wherein micromechanics is peeled off is to peel off the method that graphite obtains Graphene repeatedly by photoresist,
The method is simple, and the Graphene quality for preparing is higher, but wastes time and energy, poor repeatability, it is difficult to precise control, is unsuitable for big
Scale prepares Graphene.CVD method is the method for being deposited on Graphene in solid film substrate by gas phase reaction under high temperature,
The method can prepare high-quality, large-area Graphene, but cost higher at this stage, complicated technique and accurate control
Processing conditionss processed constrain its development.Crystal epitaxy method removes Si, so as to obtain in SiC by heating monocrystalline 6H-SiC
The Graphene of surface extension, the Graphene prepared by the method is affected very big by SiC substrates, Graphene electrical conductivity it is relatively low or
It is difficult to be stripped down from substrate, it is difficult to accomplish scale production.At present most common method is oxide-reduction method, and its is basic
Principle is to process graphite by strong strong protonic acid, forms compound between graphite layers, is subsequently adding strong oxidizer and it is aoxidized,
Graphene oxide is formed, Graphene can be obtained by reduction, but the method has used had to chemical industry equipment in process of production
Severe corrosive, the strong acid of strong oxidizing property and strong oxidizer, there is larger harm to environment, and formed Graphene electronic structure and
Perfection of crystal is destroyed by serious, and electrical conductivity has significantly reduction, and (such as accurate is micro- in some fields to limit it
Electronic applications) in application and industrialization production.
Compared to additive method, liquid phase peels off the method for Graphene and represents high, production Graphene quality height of the rate of output etc.
Advantage, but limited by stripping means and solvent, at present still without it is a kind of can be with the liquid phase stripping means of large-scale production.
The content of the invention
The technical problem to be solved is to overcome the low yield of existing Graphene production method, pollute big, technique
The weak points such as complexity, there is provided a kind of low production cost, environmental friendliness, yield are high and be suitable to the liquid phase of industrialized production and peel off system
The method of standby Graphene.
The technical scheme for realizing the object of the invention is：
A kind of liquid phase peels off the method for preparing grapheme two-dimension material, including step：
(1) mixture temperature will be kept at 20~80 DEG C in graphite dispersion to water and/or organic solvent, emulsifying cutting with
Alternately, an emulsifying clipping time is 10min~6h to strong ultrasound, and once strong ultrasonic time is 10min~2h, alternately 3~
10 wheels, the wherein rotating speed of emulsifying cutting equipment are 6000~12000rpm, and strong ultrasonic power is 400~950W, and graphite is in mixing
Concentration in thing is 0.15~10g/L；
(2) product of step (1) is separated using the method for centrifugation, takes detached upper liquid for graphene dispersion
Liquid；Wherein centrifugation rate is 1000~6000rpm, and centrifugation time is 5~30min.
Wherein, the graphite is in the solid phase that crystalline flake graphite, graphite powder, expanded graphite, step (2) centrifugation go out
Kind.In raw material, from a cost perspective, preferred graphite powder.
Wherein, the organic solvent be selected from ethanol, isopropanol, nitrogen, nitrogen-dimethylformamide, n-methlpyrrolidone,
One or more in dimethyl sulfoxide solvent.It is comprehensive to consider from cost and environmental conservation angle in industrialized production, it is preferably different
Propanol.
Further, in step (1), by graphite dispersion to water and organic solvent, the volume ratio of water and organic solvent is 3
~7：7~3；Graphite concentration in the mixture is 1~3g/L.
It is highly preferred that in step (1), an emulsifying clipping time, once strong ultrasonic time was in 30~40min in 2~3h,
Alternately 4~6 take turns.Find in test, ultrasonic time has an impact to thickness；Alternate frequency also has certain impact on Graphene size.
Wherein, in step (1), emulsifying is cut with strong ultrasonic procedure, is controlled mixture temperature by water-bath and is maintained at 20
~60 DEG C；In 8000~10000rpm, strong ultrasonic power is 600~800W to the rotating speed of emulsifying cutting equipment.The temperature of solution exists
Emulsifying is cut and is constantly raised in strong ultrasonic procedure, and the setting of temperature can be controlled by water-bath, be found in test, rate of cutting
There is certain impact on the size of Graphene with ultrasonic temperature, in 6000~8000rpm, Graphene yield exists cutting rotating speed
0.5%~1.1%, when rotating speed is cut in 8000~12000rpm, Graphene yield is 1.1%~2.3%.
Wherein, in step (2), the rotating speed of centrifugation is 2000~4000rpm, and centrifugation time is 10~15min.Centrifugation
The solid phase isolated is graphite waste, is circulated in preparing for Graphene.
Find in test, centrifugal rotational speed has an impact to thickness：In centrifugal rotational speed in 2000~3000rpm, the stone isolated
In 1~50nm, centrifugal rotational speed isolates Graphene thickness in 1~20nm to black alkene thickness in 3000~4000rpm.
Wherein, after step (2), graphene dispersing solution is rotated, lyophilization, obtains solid product, as graphite
Alkene powder body.
Freeze-dried Medium can be one or more in water, ethanol, propanol, isopropanol, carbon dioxide.
The Graphene that method of the present invention is prepared.
The present invention has the advantage that compared with prior art：
(1) present invention adopts low-cost commercial graphite for raw material；(2) done using the good organic solvent of graphene dispersion
The solvent that liquid phase is peeled off, and these organic solvents such as ethanol, isopropanol etc. is pollution-free, price is low, recoverable；(3) adopt
The method in combination with strong ultrasound is cut in emulsifying, and the production time is short, and the cycle is 6~20h, and method is simple, efficiency high；(4) gained
The yield of Graphene is high, can reach 2%.(5), without chemical reaction, every time the remaining graphite of production is molten with organic for the method
The equal recoverable of agent.
To sum up, liquid phase stripping of the present invention prepares Graphene method, easy with method, environmental friendliness, low cost and other advantages,
The Graphene produced has ultra-thin thickness (1~20nm), and have superelevation yield (>2%), the grapheme material can be extensive
It is applied to the fields such as electronic printing, electrically-conducting paint, lithium ion battery；Additionally, the method is from cheap raw material, adopt
The little, energy consumption of pollution is low, yield is high, process is simple, time-consuming few technique, is suitable to industrialized production.
Description of the drawings
Fig. 1 is the characterization result of the Graphene suspension of embodiment 1, wherein (a) and (b) sweeping for Graphene different multiplying
Electron microscope (SEM) is retouched, is (c) transmission electron microscope (TEM) figure with (d).
Fig. 2 peels off X-ray diffraction (XRD) result of Graphene for the liquid phase of embodiment 1.
Fig. 3 peels off the characterization result of Graphene for the liquid phase of embodiment 2, wherein (a) and (b) is Graphene different multiplying
Scanning electron microscope (SEM) photograph (SEM), is (c) transmission electron microscope (TEM) figure with (d).
Specific embodiment
Detailed description below is used to illustrate the present invention, but should not be construed as limiting the invention.
In embodiment, emulsifying cuts through the realization of emulsifying cutting machine, and strong ultrasound is realized by biomixer.
In embodiment, if no special instructions, technological means used are this area conventional technique means.
Embodiment 1：
A kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, its method is implemented by following steps：
(1), graphite powder 5g, water 500mL, isopropanol 500mL are mixed in the beaker that capacity is 2L, by emulsifying cutting machine
Cutter head submerges under liquid level, under 40 DEG C of water bath conditions, keeps cutter head rotating speed 8000rpm, and to mixed liquor 2h is cut.
(2), will be put in biomixer through the mixed liquor of step (1), under 40 DEG C of water bath conditions, keep power
800w, to mixed liquor ultrasound 30min.
(3) the emulsifying cutting step and the ultrasound described in step (2) described in implementation steps (1), is replaced to mixed liquor
Step, alternately 5 takes turns altogether.
(4), will be centrifuged with rotating speed 3000rpm through the mixed liquor of step (3), 15min be centrifuged, collected upper liquid,
As graphene dispersing solution.The graphite waste of precipitation collects to recycle.
The pattern of gained Graphene is characterized, Fig. 1 is as a result seen.SEM is characterized and is confirmed that the Graphene prepared is horizontal
Size is that between 0.1~1 μm, (c) and (d) of Fig. 1 is transmission electron microscope (TEM) figure, further demonstrate that the above-mentioned horizontal stroke of Graphene
To size and its transparent, ultra-thin characteristic under Electronic Speculum.Fig. 2 is the X-ray diffraction result that liquid phase peels off Graphene.
Between 0.1~1 μm, between 1~20nm, yield is 2% to thickness to the average transverse of graphite ene product.
Embodiment 2
A kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, its method and step is different substantially with embodiment 1
It is that water feeds intake capacity ratio for 3 with isopropanol:7, the pattern of gained Graphene is characterized, the average transverse of Graphene
Between 0.1~3 μm, between 1~20nm, yield is 1% to thickness to size.
Fig. 3 peels off the characterization result of Graphene for the liquid phase of embodiment 2, it was demonstrated that the lateral dimension of Graphene is 0.1~3 μm
Between.(c) and (d) of Fig. 3 is transmission electron microscope (TEM) figure, further demonstrate that Graphene above-mentioned lateral dimension and its it is super
Thin characteristic.
Embodiment 3
A kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, its method and step is different substantially with embodiment 1
It is that water feeds intake capacity ratio for 7 with isopropanol:3, the pattern of gained Graphene is characterized, the average transverse of Graphene
Between 0.1~3 μm, between 1~20nm, yield is 0.5% to thickness to size.
Embodiment 4
A kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, its method is implemented by following steps：
(1), graphite powder 5g, water 500mL, isopropanol 500mL are mixed in the beaker that capacity is 2L, by emulsifying cutting machine
Cutter head submerges under liquid level, at 40 DEG C, keeps cutter head rotating speed 10000rpm, and to mixed liquor 2h is cut.
(2), will be put in biomixer through the mixed liquor of step (1), at 40 DEG C, power 700W is kept, to mixed
Close liquid ultrasound 30min.
(3) the emulsifying cutting step and the ultrasound described in step (2) described in implementation steps (1), is replaced to mixed liquor
Step, alternately 5 takes turns altogether.
(4), will be centrifuged with rotating speed 3000rpm through the mixed liquor of step (3), 15min be centrifuged, collected upper liquid,
As graphene dispersing solution.
(5), lyophilization obtains solid product, as graphene powder.
The pattern of gained Graphene is characterized, between 0.3~3 μm, thickness is 1 for the average transverse of Graphene
Between~20nm, yield is 1.5%.
Embodiment 5
A kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, its method and step is different substantially with embodiment 1
It is to replace graphite powder to characterize to the pattern of gained Graphene as raw material using expanded graphite, the average transverse chi of Graphene
It is very little between 0.3~3 μm, between 1~20nm, yield is 1% to thickness.
Impact of the different parameters of embodiment 1~5 to graphite ene product is shown in Table 1.
Table 1：Embodiment 1-5 technological parameter
| Numbering | Cutting speed | Raw material | Ultrasonic power | Water:IPA | The lateral dimension of product | Thickness | Yield |
| Embodiment 1 | 8000rpm | Graphite powder | 800W | 1:1 | 0.1~1 μm | 1~20nm | 2% |
| Embodiment 2 | 8000rpm | Graphite powder | 800W | 3:7 | 0.1~3 μm | 1~20nm | 1% |
| Embodiment 3 | 8000rpm | Graphite powder | 800W | 7:3 | 0.1~3 μm | 1~20nm | 0.5% |
| Embodiment 4 | 10000rpm | Graphite powder | 700W | 1:1 | 0.3~3 μm | 1~20nm | 1.5% |
| Embodiment 5 | 10000rpm | Expanded graphite | 700W | 1:1 | 0.3~3 μm | 1~20nm | 1% |
Comparative example 1
This example provides a kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, the substantially same embodiment of its method and step
1, except for the difference that, in the mixture of dispersed graphite, graphite inventory is 20g.The pattern of gained Graphene is characterized, shape
Looks are basically identical with the products therefrom pattern of embodiment 1, and at 0.1~1 μm, in 1~20nm, yield is 1.3% to thickness to lateral dimension.
Comparative example 2
This example provides a kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, the substantially same embodiment of its method and step
1, except for the difference that in step (1), the rotating speed of emulsifying machine cutter head is respectively 6000,8000,10000,12000rpm.
Product result of calculation to obtaining shows that rate of cutting has certain impact on the size of Graphene with ultrasonic temperature,
Cutting rotating speed in 6000~8000rpm, Graphene yield 0.5%~1.1%, when cutting rotating speed is in 8000~12000rpm
When, Graphene yield is 1.1%~2.3%.
Comparative example 3
This example provides a kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, the substantially same embodiment of its method and step
1, except for the difference that in step (2), will be put in biomixer through the mixed liquor of step (1), at 40 DEG C, keep power
700W, to mixed liquor ultrasound 10,20,30,40,50,60min.
Found by electron microscopic observation, before ultrasonic time is less than 30min, ultrasonic time is longer, and Graphene is thinner, ultrasound
Time more than 30min, gained Graphene thickness in~20nm, then extend ultrasonic time thickness change it is unobvious.
Comparative example 4
This example provides a kind of preparation method of the grapheme two-dimension material that liquid phase is peeled off, the substantially same embodiment of its method and step
1, except for the difference that in step (4), the rotating speed of centrifugation is 2000,3000,4000rpm, and centrifugation time is 15min.
Found by electron microscopic observation, in centrifugal rotational speed in 2000~3000rpm, the Graphene thickness isolated 1~
50nm, centrifugal rotational speed isolates Graphene thickness in 1~20nm in 3000~4000rpm.
The present invention is complicated for existing graphene preparation method step, low yield, existing for gained Graphene grade of poor quality
Deficiency, adjust preparation technology by changing liquid phase stripping media, final acquisition can prepare the liquid phase of high-quality graphene and peel off
New method.Little, energy consumption is low, yield is high, process is simple, time-consuming few technique using polluting for the method, is suitable to industrialized production,
It is significant to the commercial applications of following Graphene.
Example above is only that the specific embodiment to the present invention is described, and not the scope of the present invention is carried out
Limit, those skilled in the art can also do on the basis of existing technology numerous modifications and variations, without departing from present invention design
On the premise of spirit, various modifications and improvement that this area ordinary skill technical staff makes to technical scheme,
Should fall in the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of liquid phase peels off the method for preparing grapheme two-dimension material, it is characterised in that including step：
(1) mixture temperature in graphite dispersion to water and/or organic solvent, will be kept at 20~80 DEG C, emulsifying cutting is super with strong
Alternately, an emulsifying clipping time is 10min~6h to sound, and once strong ultrasonic time is 10min~2h, alternately 3~10 is taken turns,
Wherein the rotating speed of emulsifying cutting equipment is 6000~12000rpm, and strong ultrasonic power is 400~950W, and graphite is in the mixture
Concentration is 0.15~10g/L；
(2) product of step (1) is separated using the method for centrifugation, takes detached upper liquid for graphene dispersing solution；Its
Middle centrifugation rate is 1000~6000rpm, and centrifugation time is 5~30min.
2. method according to claim 1, it is characterised in that the graphite be crystalline flake graphite, graphite powder, expanded graphite,
One kind in the solid phase that step (2) centrifugation goes out.
3. method according to claim 1, it is characterised in that the organic solvent is selected from ethanol, isopropanol, nitrogen, nitrogen-two
One or more in methylformamide, n-methlpyrrolidone, dimethyl sulfoxide solvent.
4. method according to claim 3, it is characterised in that in step (1), by graphite dispersion to water and organic solvent
In, the volume ratio of water and organic solvent is 3~7：7~3；Graphite concentration in the mixture is 1~3g/L.
5. method according to claim 1, it is characterised in that in step (1), an emulsifying clipping time in 2~3h, one
Secondary strong ultrasonic time alternately 4~6 is taken turns in 30~40min.
6. in method according to claim 1, it is characterised in that in step (1), emulsifying cutting and strong ultrasonic procedure, lead to
Cross water-bath control mixture temperature and be maintained at 20~60 DEG C；The rotating speed of emulsifying cutting equipment is strong ultrasonic in 8000~10000rpm
Power is 600~800W.
7. method according to claim 1, it is characterised in that in step (2), the rotating speed of centrifugation is 2000~
4000rpm, centrifugation time is 10~15min；The solid phase that centrifugation goes out is graphite waste, is circulated in preparing for Graphene.
8. the method according to any one of claim 1~7, it is characterised in that after step (2), graphene dispersing solution is entered
Row revolving, lyophilization obtains solid product, as graphene powder.
9. the Graphene that the method described in any one of claim 1~8 is prepared.
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| CN201710045865.3A CN106672954B (en) | 2017-01-20 | 2017-01-20 | A kind of method of liquid phase removing preparation grapheme two-dimension material |
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| CN201710045865.3A CN106672954B (en) | 2017-01-20 | 2017-01-20 | A kind of method of liquid phase removing preparation grapheme two-dimension material |
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| CN106672954B CN106672954B (en) | 2019-02-01 |
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| CN109081315A (en) * | 2017-06-13 | 2018-12-25 | 天津大学 | A kind of preparation method of two-dimensional material telluride germanium |
| CN107579219A (en) * | 2017-08-23 | 2018-01-12 | 北京航空航天大学 | For graphene/zinc oxide negative material of secondary zinc base battery and its preparation |
| CN107579219B (en) * | 2017-08-23 | 2020-08-14 | 北京航空航天大学 | Graphene/zinc oxide negative electrode material for secondary zinc-based battery and preparation thereof |
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| CN107934947A (en) * | 2017-12-15 | 2018-04-20 | 广州中天联合高新技术发展有限公司 | A kind of graphene production method based on efficient surfactant |
| CN107934947B (en) * | 2017-12-15 | 2021-06-08 | 广州中天联合高新技术发展有限公司 | Graphene preparation method based on efficient surfactant |
| CN108417802A (en) * | 2018-03-08 | 2018-08-17 | 北京旭碳新材料科技有限公司 | Graphene ternary material compound and preparation method thereof |
| CN108706577A (en) * | 2018-06-19 | 2018-10-26 | 于峰 | A kind of method for separating and preparing of graphene nano material |
| CN108793140A (en) * | 2018-07-10 | 2018-11-13 | 清华大学深圳研究生院 | A kind of high quality large scale two-dimensional material and preparation method thereof |
| CN113772732A (en) * | 2021-09-26 | 2021-12-10 | 江南大学 | Method for preparing two-dimensional material nanosheet by DEET stripping |
| CN113772732B (en) * | 2021-09-26 | 2022-05-06 | 江南大学 | Method for preparing two-dimensional material nanosheet by DEET stripping |
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