CN106672954B - A kind of method of liquid phase removing preparation grapheme two-dimension material - Google Patents
A kind of method of liquid phase removing preparation grapheme two-dimension material Download PDFInfo
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- 239000007791 liquid phase Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 79
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 238000005520 cutting process Methods 0.000 claims abstract description 19
- 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
- 238000004945 emulsification Methods 0.000 claims abstract description 14
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- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
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- 239000003791 organic solvent mixture Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
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- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 238000010574 gas phase reaction Methods 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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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
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- 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
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- 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 present invention provides a kind of method of liquid phase removing preparation grapheme two-dimension material, comprising steps of (1) will be in graphite dispersion to water and/or organic solvent, keep mixture temperature at 20~80 DEG C, alternately with strong ultrasound, the concentration of graphite in the mixture is 0.15~10g/L for emulsification cutting；(2) product of step (1) is separated using the method for centrifugation, taking the upper liquid of separation is graphene dispersing solution；Wherein centrifugation rate is 1000~6000rpm, and centrifugation time is 5~30min.The present invention uses low-cost commercial graphite to make the solvent of liquid phase removing using the good organic solvent of graphene dispersion for raw material, and these organic solvents such as ethyl alcohol, isopropanol etc. are pollution-free, and price is low, recoverable；The method combined using emulsification cutting with strong ultrasound, the production time is short, and the period is 6~20h, and method is simple, high-efficient；The yield of gained graphene is high, can reach 2%.
Description
Technical field
The invention belongs to carbon material preparation fields, and in particular to a kind of preparation method of graphene.
Background technique
Graphene is a kind of ultra-thin two-dimensional material, since it has very high specific surface area, excellent chemistry, thermostabilization
Property, good electric conductivity and heating conduction, the properties 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 commercialized application.And in some important fields, such as electronic printing, conductive coating, lithium ion battery,
It will may require that the graphene for largely capableing of industrialized production.Such as 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 the method that liquid phase removing prepares graphene will become
A kind of important technological means.
The synthetic method of graphene mainly also has micromechanics removing, chemical vapor deposition (CVD), crystalline epitaxial raw at present
Length, oxidation-reduction method etc..Wherein the method for micromechanics removing is the method removed graphite repeatedly by photoresist and obtain graphene,
This method is simple, and the graphene quality prepared is higher but time-consuming and laborious, poor repeatability, it is difficult to which accurate 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,
This method can prepare the graphene of high quality, large area, but higher cost, complicated technique and accurate control at this stage
Processing conditions processed constrains its development.Crystal epitaxy method removes Si, to obtain in SiC by heating monocrystalline 6H-SiC
The graphene of surface extension, graphene prepared by this method influenced by SiC substrate it is very big, graphene conductivity it is lower or
It is difficult to peel off from the substrate, it is difficult to accomplish scale production.Most common method is oxide-reduction method, basic
Principle is to handle graphite by strong strong protonic acid, forms compound between graphite layers, and strong oxidizer is then added and aoxidizes to it,
Graphene oxide is formed, by restoring available graphene, but the method has used have to chemical industry equipment in process of production
The strong acid and strong oxidizer of strong corrosive, strong oxidizing property have biggish harm to environment, and formed graphene electronic structure and
For perfection of crystal by serious destruction, conductivity has apparent reduction, and limiting it, (such as accurate is micro- in certain fields
Electronic field) in application and industrialization production.
Compared to other methods, the method for liquid phase removing graphene shows high, graphene quality height of production of the rate of output etc.
Advantage, but limited by stripping means and solvent, the liquid phase stripping means that can be still mass produced without one kind at present.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the low yield of existing graphene production method, pollute big, technique
In place of the deficiencies of complicated, the liquid phase removing system that a kind of production cost is low, environmental-friendly, yield is high and suitable for industrialized production is provided
The method of standby graphene.
Realize the technical solution of the object of the invention are as follows:
A kind of method of liquid phase removing preparation grapheme two-dimension material, comprising steps of
(1) by graphite dispersion to water and/or organic solvent, keep mixture temperature at 20~80 DEG C, emulsification cutting with
Alternately, primary to emulsify clipping time be 10min~6h to strong ultrasound, and primary strong ultrasonic time is 10min~2h, alternately 3~
10 wheels, wherein the revolving speed of emulsification cutting equipment is 6000~12000rpm, strong ultrasonic power is 400~950W, and graphite is mixing
Concentration in object is 0.15~10g/L；
(2) product of step (1) is separated using the method for centrifugation, taking the upper liquid of separation is graphene dispersion
Liquid；Wherein centrifugation rate is 1000~6000rpm, and centrifugation time is 5~30min.
Wherein, one in solid phase that the graphite is crystalline flake graphite, graphite powder, expanded graphite, step (2) are centrifugated out
Kind.In raw material, from a cost perspective, preferred graphite powder.
Wherein, the organic solvent be selected from ethyl alcohol, isopropanol, nitrogen, nitrogen-dimethylformamide, n-methlpyrrolidone,
It is one or more in dimethyl sulfoxide solvent.It is comprehensive to consider from cost and environmental protection angle in industrialized production, it is preferably different
Propyl alcohol.
Further, in step (1), by graphite dispersion into water and organic solvent, the volume ratio of water and organic solvent is 3
~7:7~3；The concentration of graphite in the mixture is 1~3g/L.
It is primary to emulsify clipping time in 2~3h it is highly preferred that in step (1), primary strong ultrasonic time in 30~40min,
Alternately 4~6 wheel.It is found in test, ultrasonic time has an impact to thickness；Alternate frequency also has certain influence to graphene size.
Wherein, in step (1), emulsification cutting controls mixture temperature by water-bath and is maintained at 20 with strong ultrasonic procedure
~60 DEG C；The revolving speed of cutting equipment is emulsified in 8000~10000rpm, strong ultrasonic power is 600~800W.The temperature of solution exists
Emulsification is cut and is constantly increased 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 influence to the size of graphene with ultrasonic temperature, cuts revolving speed in 6000~8000rpm, graphene yield exists
0.5%~1.1%, when cutting revolving speed is in 8000~12000rpm, graphene yield is 1.1%~2.3%.
Wherein, in step (2), the revolving speed of centrifuge separation is 2000~4000rpm, and centrifugation time is 10~15min.Centrifugation
The solid phase isolated is graphite waste, and circulation is in graphene preparation.
It is found in test, centrifugal rotational speed has an impact to thickness: in centrifugal rotational speed in 2000~3000rpm, the stone isolated
Black alkene thickness isolates graphene thickness in 1~20nm in 3000~4000rpm in 1~50nm, centrifugal rotational speed.
Wherein, after step (2), graphene dispersing solution is rotated, is freeze-dried, obtains solid product, as graphite
Alkene powder.
Freeze-dried Medium can be one of water, ethyl alcohol, propyl alcohol, isopropanol, carbon dioxide or a variety of.
The graphene that method of the present invention is prepared.
The invention has the following advantages over the prior art:
(1) present invention uses low-cost commercial graphite for raw material；(2) it is done using the good organic solvent of graphene dispersion
The solvent of liquid phase removing, and these organic solvents such as ethyl alcohol, isopropanol etc. are pollution-free, price is low, recoverable；(3) it uses
The method that emulsification cutting is combined with strong ultrasound, the production time is short, and the period is 6~20h, and method is simple, high-efficient；(4) gained
The yield of graphene is high, can reach 2%.(5) this method is without chemical reaction, every time the remaining graphite of production with it is organic molten
The equal recoverable of agent.
To sum up, liquid phase removing of the present invention prepares graphene method, has the advantages that method is easy, environmental-friendly, at low cost,
The graphene produced has ultra-thin thickness (1~20nm), and has the yield (> 2%) of superelevation, which can be extensive
Applied to fields such as electronic printing, conductive coating, lithium ion batteries；In addition, this method is used from cheap raw material
The technique that small, low energy consumption, yield is high, process is simple, time-consuming is few is polluted, industrialized production is suitable for.
Detailed description of the invention
Fig. 1 is the characterization result of the graphene suspension of embodiment 1, wherein (a) and (b) is sweeping for graphene different multiplying
Electron microscope (SEM) is retouched, (c) and (d) is transmission electron microscope (TEM) figure.
Fig. 2 is that the liquid phase of embodiment 1 removes X-ray diffraction (XRD) result of graphene.
Fig. 3 is that the liquid phase of embodiment 2 removes the characterization result of graphene, wherein (a) and (b) is graphene different multiplying
Scanning electron microscope (SEM) photograph (SEM), (c) and (d) is transmission electron microscope (TEM) figure.
Specific embodiment
Following specific embodiments should not be construed as limiting the invention for illustrating the present invention.
In embodiment, emulsification cuts through emulsification cutting machine and realizes, strong ultrasound is realized by biomixer.
In embodiment, unless otherwise instructed, technological means used is this field conventional technology.
Embodiment 1:
A kind of preparation method of the grapheme two-dimension material of liquid phase removing, method are implemented by following steps:
(1), graphite powder 5g, water 500mL, isopropanol 500mL are mixed in the beaker that capacity is 2L, cutting machine will be emulsified
Cutter head submerges under liquid level, under 40 DEG C of water bath conditions, keeps cutter head revolving speed 8000rpm, cuts 2h to mixed liquor.
(2), it will be put into biomixer by the mixed liquor of step (1), under 40 DEG C of water bath conditions, keep power
800w, to mixed liquor ultrasound 30min.
(3), to ultrasound described in emulsification cutting step described in mixed liquor alternating implementation steps (1) and step (2)
Step alternately 5 is taken turns altogether.
(4), it will be centrifuged by the mixed liquor of step (3) with revolving speed 3000rpm, be centrifuged 15min, collect upper liquid,
As graphene dispersing solution.The graphite waste of precipitating is collected to be recycled.
The pattern of gained graphene is characterized, the result is shown in Figure 1.SEM characterization confirms that the graphene prepared is lateral
Between 0.1~1 μm, (c) and (d) of Fig. 1 is transmission electron microscope (TEM) figure, further demonstrates the above-mentioned cross of graphene
To size and its transparent, ultra-thin characteristic under Electronic Speculum.Fig. 2 is the X-ray diffraction result that liquid phase removes graphene.
The average transverse of graphite ene product is between 0.1~1 μm, and thickness is between 1~20nm, yield 2%.
Embodiment 2
A kind of preparation method of the grapheme two-dimension material of liquid phase removing, method and step are different substantially with embodiment 1
It is that the capacity ratio that feeds intake of water and isopropanol is 3:7, the pattern of gained graphene is characterized, the average transverse of graphene
Size is between 0.1~3 μm, and thickness is between 1~20nm, yield 1%.
Fig. 3 is that the liquid phase of embodiment 2 removes the characterization result of graphene, 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 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 of liquid phase removing, method and step are different substantially with embodiment 1
It is that the capacity ratio that feeds intake of water and isopropanol is 7:3, the pattern of gained graphene is characterized, the average transverse of graphene
Size is between 0.1~3 μm, and thickness is between 1~20nm, yield 0.5%.
Embodiment 4
A kind of preparation method of the grapheme two-dimension material of liquid phase removing, method are implemented by following steps:
(1), graphite powder 5g, water 500mL, isopropanol 500mL are mixed in the beaker that capacity is 2L, cutting machine will be emulsified
Cutter head submerges under liquid level, at 40 DEG C, keeps cutter head revolving speed 10000rpm, cuts 2h to mixed liquor.
(2), it will be put into biomixer by the mixed liquor of step (1), at 40 DEG C, power 700W kept, to mixed
Close liquid ultrasound 30min.
(3), to ultrasound described in emulsification cutting step described in mixed liquor alternating implementation steps (1) and step (2)
Step alternately 5 is taken turns altogether.
(4), it will be centrifuged by the mixed liquor of step (3) with revolving speed 3000rpm, be centrifuged 15min, collect upper liquid,
As graphene dispersing solution.
(5), solid product, as graphene powder are freeze-dried to obtain.
The pattern of gained graphene is characterized, the average transverse of graphene is between 0.3~3 μm, and thickness is 1
Between~20nm, yield 1.5%.
Embodiment 5
A kind of preparation method of the grapheme two-dimension material of liquid phase removing, method and step are different substantially with embodiment 1
It is that graphite powder is replaced as pattern of the raw material to gained graphene using expanded graphite and is characterized, the average transverse ruler of graphene
It is very little between 0.3~3 μm, thickness is between 1~20nm, yield 1%.
Influence of the Examples 1 to 5 different parameters to graphite ene product is shown in Table 1.
Table 1: embodiment 1-5 technological parameter
| Number | 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 of liquid phase removing, the substantially same embodiment of method and step
1, unlike, in the mixture of dispersed graphite, graphite inventory is 20g.The pattern of gained graphene is characterized, shape
Looks and 1 products therefrom pattern of embodiment are almost the same, and lateral dimension is at 0.1~1 μm, and thickness is in 1~20nm, yield 1.3%.
Comparative example 2
This example provides a kind of preparation method of the grapheme two-dimension material of liquid phase removing, the substantially same embodiment of method and step
1, the difference is that the revolving speed for emulsifying machine cutter head is respectively 6000,8000,10000,12000rpm in step (1).
Rate of cutting and ultrasonic temperature, which have certain influence to the size of graphene, to be shown to obtained product calculated result,
Revolving speed is cut in 6000~8000rpm, graphene yield is 0.5%~1.1%, when cutting revolving 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 of liquid phase removing, the substantially same embodiment of method and step
1, the difference is that will be put into biomixer by the mixed liquor of step (1) in step (2), and at 40 DEG C, keep power
700W, to mixed liquor ultrasound 10,20,30,40,50,60min.
By Electronic Speculum it has been observed that ultrasonic time is longer, and graphene is thinner, ultrasound in ultrasonic time lower than before 30min
Time is 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 of liquid phase removing, the substantially same embodiment of method and step
1, the difference is that the revolving speed of centrifuge separation is 2000,3000,4000rpm, centrifugation time 15min in step (4).
By Electronic Speculum it has been observed that in centrifugal rotational speed in 2000~3000rpm, the graphene thickness isolated 1~
50nm, centrifugal rotational speed isolate graphene thickness in 1~20nm in 3000~4000rpm.
The present invention is complicated for existing graphene preparation method step, low yield, present in gained graphene grade of poor quality
Deficiency, adjust preparation process by changing liquid phase stripping media, it is final to obtain the liquid phase removing that prepare high-quality graphene
New method.This method is suitable for industrialized production using the technique that small, low energy consumption, yield is high, process is simple, time-consuming is few is polluted,
It is of great significance to the commercial applications of the following graphene.
Above example is only that a specific embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, those skilled in the art can also do numerous modifications and variations on the basis of existing technology, not depart from design of the present invention
Under the premise of spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (2)
1. a kind of method of liquid phase removing preparation grapheme two-dimension material, which is characterized in that comprising steps of
(1) by graphite dispersion into water and organic solvent, emulsification is cut with strong ultrasound alternately, and primary emulsification clipping time exists
2~3h, primary strong ultrasonic time is in 30~40min, alternately 5 wheel, wherein the organic solvent is isopropanol, water and organic molten
The volume ratio of agent is 1:1；Disperse 5g graphite in every liter of water and ORGANIC SOLVENT MIXTURES；The graphite is graphite powder, expansion stone
One of the solid phase that ink, step (2) are centrifugated out；
Emulsification cutting controls mixture temperature by water-bath and is maintained at 40 DEG C with strong ultrasonic procedure；Emulsify turning for cutting equipment
For speed in 8000~10000rpm, strong ultrasonic power is 600~800W；
(2) product of step (1) is separated using the method for centrifugation, taking the upper liquid of separation is graphene dispersing solution；From
The revolving speed of heart separation is 2000~4000rpm, and centrifugation time is 10~15min；The solid phase being centrifugated out is graphite waste, is followed
Ring is in graphene preparation.
2. cold the method according to claim 1, wherein rotated after step (2) to graphene dispersing solution
It is lyophilized dry, obtains solid product, as graphene powder.
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| CN108706577B (en) * | 2018-06-19 | 2021-01-29 | 于峰 | Separation preparation method of graphene nano material |
| CN108793140B (en) * | 2018-07-10 | 2020-09-08 | 清华大学深圳研究生院 | High-quality large-size two-dimensional material and preparation method thereof |
| 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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| CN103771517B (en) * | 2014-01-17 | 2015-07-08 | 哈尔滨工业大学 | Method for preparing liquid phase dispersion-based two-dimensional MoS2 nanosheets |
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