CN110127679A - A kind of nitromethane intercalated graphite prepares the ball grinding method of graphene - Google Patents
A kind of nitromethane intercalated graphite prepares the ball grinding method of graphene Download PDFInfo
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- CN110127679A CN110127679A CN201910494446.7A CN201910494446A CN110127679A CN 110127679 A CN110127679 A CN 110127679A CN 201910494446 A CN201910494446 A CN 201910494446A CN 110127679 A CN110127679 A CN 110127679A
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- nitromethane
- graphite
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- ball milling
- graphene
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention provides the ball grinding method that a kind of nitromethane intercalated graphite prepares graphene.Binary graphite intercalation compound and dry ice are collectively disposed in ball milling kettle and sealed, dry ice, which absorbs heat, becomes CO2Gas, explosive decomposition of the nitromethane under the shock of steel ball, CO2Gas absorbs explosion heat and the heat of steel ball collision quickly enters supercriticality, and nitromethane, which is decomposed, removes graphite with ball milling and supercritical gas collective effect.Binary graphite intercalation compound makes graphite layers away from becoming larger in the method for the present invention, and nitromethane decomposes in knockout process, is conducive to promote ball milling charge stripping efficiency, FeCl3Play the role of guidance booster action in binary graphite intercalation compound forming process, plays the role of increasing interlamellar spacing in ball milling stripping process, playing after ball milling prevents graphene sheet layer to be superimposed.
Description
Technical field
The present invention relates to the nitromethane intercalated graphites that field of preparation of graphene more particularly to a kind of supercritical fluid assist
Ball-milling method prepare graphene.
Background technique
Graphene is the quasi- two dimension that the thickness that one kind is made of carbon atom completely is only monoatomic layer or several monoatomic layers
Crystalline material, special structure contain abundant and novel physical phenomenon, it is made to show many excellent properties, for example,
Most thin, most secured, high rigidity, high thermal conductivity coefficient, high electron mobility, almost transparent etc. characteristics, can be used to develop thinner
And conductive speed electronic component of new generation, transparent touch screen, gas sensor, composite material, field emmision material etc. faster,
It is widely used in the fields such as electronics, the energy, chemical industry, light industry, military project, space flight and national defence.
Currently, the preparation method of graphene mainly has physical method and chemical method two major classes, wherein physical method is main
Have mechanical stripping method, liquid phase or the direct stripping method of gas phase etc., chemical method mainly have chemical vapour deposition technique, oxidation-reduction method,
Epitaxial growth method, arc discharge method.The physics stripping method whole process of liquid phase or gas phase is not related to complicated chemical reaction substantially,
It is a kind of main method for preparing high-quality graphene.Ball-milling method is common a kind of technology in industrial production, can achieve stripping
From the effect with crushing.Ball milling both can produce shear stress, makes graphite removing at graphene, can also be produced by the effect of rolling of ball
Raw collision and vertical impact, graphite crystal is crushed.In addition, ball mill is as a kind of disintegrating apparatus, in grinding, most of machine
Tool can be changed into thermal energy, cause to grind interior temperature higher.It is long that traditional ball-milling method prepares the time used in graphene, and energy consumption is high, to stone
The quality of black alkene is affected, and needs to find the method that ball-milling method prepares graphene efficiency that improves.
Summary of the invention
Propose the ball grinding method that a kind of nitromethane intercalated graphite prepares graphene.Firstly, passing through preparation binary graphite
Intercalation compound introduces explosive nitromethane between graphite flake layer；Then, binary graphite intercalation compound and dry ice is common
It is placed in high pressure resistant ball milling kettle and seals, stand at room temperature, dry ice, which absorbs heat, becomes CO2Gas；Secondly, starting ball mill, nitre
Explosive decomposition of the methylmethane under the shock of steel ball, CO2The heat that gas absorbs explode heat and steel ball collision quickly enters super
Critical state, at this point, the loosening that nitromethane decomposes between ball action bring graphite flake layer can make supercritical gas more
Readily to enter inside graphite flake layer；Finally, ball mill is out of service, stand, by high pressure resistant ball milling kettle pressure release, remaining chlorine
Change iron adherency on the surface of graphene, graphene sheet layer can be prevented to be superimposed.
The present invention adopts the following technical scheme:
A kind of nitromethane intercalated graphite prepares the ball grinding method of graphene, includes the following steps:
(1) by anhydrous FeCl3It is dissolved in nitromethane, adds graphite, mix slowly constant temperature under state and flow back, preparation three
The binary graphite intercalation compound of iron chloride and the common intercalated graphite of nitromethane；
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stood at room temperature, done
Ice, which absorbs heat, becomes CO2Gas；
(3) start ball mill, explosive decomposition of the nitromethane under the shock of steel ball, CO2Gas absorb explosion heat and
The heat of steel ball collision quickly enters supercriticality；
(4) ball mill is out of service, stands, and by high pressure resistant ball milling kettle pressure release, collects product, obtains graphene.
Anhydrous FeCl in step (1)3It is 50: 1-10: 1 with graphite quality ratio, constant temperature reflux temperature is 20-80 DEG C, permanent
Warm return time is 24-144h.
Dry ice in step (2) answer it is enough, when being completely converted into gas, the CO in ball milling kettle2Pressure is higher than
7.38MPa。
Time of repose in step (2) is 0.5-24h.
Drum's speed of rotation in step (3) is 100-1000r/min, time 0.5-24h.
The present invention has the advantage that
(1) for nitromethane as explosive intercalated graphite, inflammable and explosive characteristic promotes it to decompose generation bulk gas,
Graphite flake layer can be effectively peeled off.
(2) binary graphite intercalation compound makes graphite layers away from becoming larger, and nitromethane decomposes in ball milling knockout process, has
Conducive to promotion ball milling charge stripping efficiency.
(3)CO2The heat that nitromethane decomposes the heat generated and steel ball hits generation is absorbed, is quickly entered overcritical
Fluid state is not necessarily to heating process using supercritical fluid own characteristic exfoliated graphite layer, in addition, nitromethane decomposition can
Generate CO2Gas can decrease in the additional amount of ice.
(4)FeCl3Guidance booster action is played in binary graphite intercalation compound forming process, in ball milling stripping process
In play the role of increase interlamellar spacing, played after ball milling prevent graphene sheet layer superposition.
Detailed description of the invention
Fig. 1 is the schematic diagram that the method for the present invention prepares binary graphite intercalation compound.
Fig. 2 is the schematic diagram that ball milling exfoliated graphite layer prepares graphene process under the method for the present invention supercriticality.
Fig. 3 is the transmission electron microscope picture that the method for the present invention prepares graphene.
Fig. 4 is the transmission electron microscope electron diffraction diagram that the method for the present invention prepares graphene.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) by the anhydrous FeCl of 10g3It is put into 50 milliliters of round-bottomed flasks with the nitromethane of 25mL, addition 0.2g expands stone
Ink mixes slowly, and temperature is 60 DEG C, constant temperature reflux 72h.
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stand 2h at room temperature,
Dry ice, which absorbs heat, becomes CO2Gas.
(3) ball grinder is symmetrically fixed on planetary ball mill, by rotating-speed modulation to 700r/m, continuous ball milling 2h.
(4) 2h is stood after ball mill is out of service, by high pressure resistant ball milling kettle pressure release, is collected product, is obtained graphene.
Embodiment 2
(1) by the anhydrous FeCl of 5g3It is put into 50 milliliters of round-bottomed flasks with the nitromethane of 25mL, addition 0.2g expands stone
Ink mixes slowly, and temperature is 60 DEG C, constant temperature reflux 48h.
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stand 2h at room temperature,
Dry ice, which absorbs heat, becomes CO2Gas.
(3) ball grinder is symmetrically fixed on planetary ball mill, by rotating-speed modulation to 700r/m, continuous ball milling 2h.
(4) 2h is stood after ball mill is out of service, by high pressure resistant ball milling kettle pressure release, is collected product, is obtained graphene.
Embodiment 3
(1) by the anhydrous FeCl of 10g3It is put into 50 milliliters of round-bottomed flasks with the nitromethane of 25mL, addition 0.2g expands stone
Ink mixes slowly, and temperature is 60 DEG C, constant temperature reflux 72h.
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stand 4h at room temperature,
Dry ice, which absorbs heat, becomes CO2Gas.
(3) ball grinder is symmetrically fixed on planetary ball mill, by rotating-speed modulation to 700r/m, continuous ball milling 2h.
(4) 2h is stood after ball mill is out of service, by high pressure resistant ball milling kettle pressure release, is collected product, is obtained graphene.
Embodiment 4
(1) by the anhydrous FeCl of 10g3It is put into 50 milliliters of round-bottomed flasks with the nitromethane of 25mL, addition 0.2g expands stone
Ink mixes slowly, and temperature is 60 DEG C, constant temperature reflux 72h.
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stand 2h at room temperature,
Dry ice, which absorbs heat, becomes CO2Gas.
(3) ball grinder is symmetrically fixed on planetary ball mill, by rotating-speed modulation to 400r/m, continuous ball milling 12h.
(4) 2h is stood after ball mill is out of service, by high pressure resistant ball milling kettle pressure release, is collected product, is obtained graphene.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (5)
1. a kind of nitromethane intercalated graphite prepares the ball grinding method of graphene, include the following steps:
(1) by anhydrous FeCl3It is dissolved in nitromethane, adds graphite, mix slowly constant temperature under state and flow back, prepare tri-chlorination
The binary graphite intercalation compound of iron and the common intercalated graphite of nitromethane；
(2) binary graphite intercalation compound is collectively disposed in high pressure resistant ball milling kettle with dry ice and is sealed, stood at room temperature, dry ice is inhaled
Receiving heat becomes CO2Gas；
(3) start ball mill, explosive decomposition of the nitromethane under the shock of steel ball, CO2Gas absorbs explosion heat and steel ball touches
The heat hit quickly enters supercriticality；
(4) ball mill is out of service, stands, and by high pressure resistant ball milling kettle pressure release, collects product, obtains graphene.
2. preparation method according to claim 1, which is characterized in that the anhydrous FeCl in step (1)3With graphite quality ratio
It is 50: 1-10: 1, constant temperature reflux temperature is 20-80 DEG C, and constant temperature return time is 24-144h.
3. preparation method according to claim 1, which is characterized in that the dry ice in step (2) is answered enough, is totally converted
When for gas, the CO in ball milling kettle2Pressure is higher than 7.38MPa.
4. preparation method according to claim 1, which is characterized in that the time of repose in step (2) is 0.5-24h.
5. preparation method according to claim 1, which is characterized in that the drum's speed of rotation in step (3) is 100-
1000r/min, time 0.5-24h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910494446.7A CN110127679A (en) | 2019-06-02 | 2019-06-02 | A kind of nitromethane intercalated graphite prepares the ball grinding method of graphene |
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| CN201910494446.7A CN110127679A (en) | 2019-06-02 | 2019-06-02 | A kind of nitromethane intercalated graphite prepares the ball grinding method of graphene |
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| CN110127679A true CN110127679A (en) | 2019-08-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11542166B2 (en) | 2021-05-04 | 2023-01-03 | TMTP Labs, Inc. | Apparatus and method for exfoliating graphite |
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2019
- 2019-06-02 CN CN201910494446.7A patent/CN110127679A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11542166B2 (en) | 2021-05-04 | 2023-01-03 | TMTP Labs, Inc. | Apparatus and method for exfoliating graphite |
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Application publication date: 20190816 |