CN106986329A - A kind of method for preparing graphene - Google Patents
A kind of method for preparing graphene Download PDFInfo
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- CN106986329A CN106986329A CN201610030508.5A CN201610030508A CN106986329A CN 106986329 A CN106986329 A CN 106986329A CN 201610030508 A CN201610030508 A CN 201610030508A CN 106986329 A CN106986329 A CN 106986329A
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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
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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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
Abstract
The present invention relates to a kind of method for preparing graphene, graphite raw material is placed in reactor, control reactor is warming up to 10 80 DEG C, and CO is pumped into thereto2Pressure into reactor reaches 8 60MPa；Open the cutter being connected with reactor, the rotating speed for adjusting rotor is 3500 9000rpm, the shearing, cavitation and the mechanical impact effect that are produced using rotor with stator in high speed relative motion couple insertion and the stabilization of CO 2 fluid, and graphite is carried out to peel off 1 5h；By the CO in reactor2Emptying, collects the graphene peeled off and obtained.Compared with prior art, present invention process flow is simple, and equipment investment is small, is a kind of environmentally friendly green technology, and the large-scale production of graphene can be achieved.
Description
Technical field
The present invention relates to a kind of two-dimension nano materials preparing technical field, more particularly, to a kind of CO 2 fluid
Couple the method that stator rotor cutter peels off preparing graphite alkene.
Background technology
Graphene is the most thin two-dimensional atomic crystal material found in the world at present, and it is with SP2Hydbridized carbon atoms
The hexa-atomic ring element of class of formation, and infinite expanding be in honeycomb lattice flat film, graphene have excellent electricity,
Calorifics, mechanical property, have a wide range of applications.High-quality, Large-scale graphene preparation is to realize graphene
Wide variety of premise.
At present, the preparation of graphene mainly has mechanical stripping method, chemical oxidation to peel off and reducing process, chemical vapor deposition
Area method etc..Wherein chemistry redox method is the method produced in batches at present, but is due to that chemistry redox method makes
With substantial amounts of strong acid and strong oxidizer, production process pollutes environment, while complex manufacturing, production cost is high,
Moreover, oxidizing process destroys the atomic structure of carbon of graphene, original structure is returned to it is difficult to be reduced, makes graphite
The quality of alkene especially electric property is by extreme influence.In order to solve the problem, mandate of the applicant in invention
In patent (ZL 201210001582.6, ZL 201210008133.4), supercritical CO has been invented2It is auxiliary with ultrasound
The method for peeling off preparing graphite alkene is helped, the graphene of high-quality large scale is obtained, with potentially applying valency
Value.But, it is necessary to carry out multiple boosting and decompression in patent (ZL 201210001582.6) method
Processing；In patent (ZL 201210008133.4) method, the supersonic generator amplification used is limited
System.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can it is low into
Originally, high-quality, scale CO 2 fluid coupling stator rotor cutter peels off the side of preparing graphite alkene
Method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method for preparing graphene, using following steps：
(1) graphite raw material is placed in reactor, control reactor is warming up to 10-80 DEG C, and CO is pumped into thereto2
Pressure into reactor reaches 8-60MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 3500-9000rpm, using turn
Shearing, cavitation and the mechanical impact effect that son is produced with stator in high speed relative motion couple CO 2 fluid
Insertion and stabilization, stripping 1-5h is carried out to graphite；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained.
Graphite includes natural flake graphite, expanded graphite or high starch breeding etc., but is not limited to above-mentioned several graphite
Raw material.
Preferably, the temperature in reactor is 20-60 DEG C, and pressure is 15-45MPa.The rotating speed of rotor is
4000-8000rpm,, can in system reactor when rotating speed is 4000-8000rpm to graphite lift-off processing 2-4h
Produce and accelerate to touch between sufficiently large energy, including stripping of the shearing force to graphite between rotor and stator, particle
Hit stripping and the CO of generation2The jet release effect that cavitation in fluid media (medium) is produced all is improved, this
Outside, when temperature is 20-60 DEG C, and pressure is 15-45MPa, CO2Density and viscosity be conducive to CO2As
The effect for the molecular separating force that intercalator inserts graphite layers to weaken graphite layers by scattering and permeating, while also right
The graphene of stripping has good stabilization.
Graphene is collected in the aqueous solution or organic solvent containing dispersant.Preferably, dispersant is polyvinyl alcohol,
Triton X-100 or sodium abietate, organic solvent are ethanol water or n- methyl pyrrolidones.
Preferably, the material being combined with graphene, the weight of graphene and material to be composite are additionally added in step (1)
Amount is than being 1-20:100, it is further preferred that being polyvinyl alcohol, poly-methyl methacrylate with the material that graphene is combined
Ester or polyaniline.
Preferably, when step (2) is peeled off to graphite, adjuvant can also be added, the adjuvant and graphite
Weight ratio be 1-20:100.It is further preferred that adjuvant is monomer or polymer containing big pi bond structure, bag
Include aniline, polyaniline or Triton X-100.
Compared with prior art, the present invention using rotor and stator produced in high speed relative motion shear, it is empty
Change and mechanical impact acts on the insertion for coupling CO 2 fluid and stabilization, in a level pressure of CO 2 fluid
Under certain rotating speed effect of power and temperature and rotor, by the stripping of certain time, from preparing graphite alkene
Method.In stripping process, it is properly added adjuvant and is conducive to the stripping of graphite and the stabilization of graphene.By this
Graphene prepared by method keeps original SP2Hydbridized carbon atoms structure, without oxy radical, with excellent conduction
Rate, less than 5 layers of graphene reaches 90%, and yield reaches more than 80%.
The present invention has a clear superiority, and the graphene quality obtained is high, zero defect, and oxy radical, does not have
Excellent conductance；Without using poisonous and hazardous organic solvent and strong acid, highly basic, not welding, green ring
Protect, be typical environment-friendly sustainable green technology；Technological process is simple, it is easy to industrialization amplification, enters
Row large-scale production.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the graphene high resolution transmission electron microscopy and electron diffraction diagram peeled off.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1,5 grams of expanded graphite powder are put into high-pressure reactor 5, control temperature of reactor reaches
45 DEG C, the carbon dioxide in carbon dioxide storage tank 1 is squeezed into high-pressure reactor 5 by high-pressure pump 2 through valve 3
It is interior, until pressure reaches 15MPa, cutter 4 is opened, 4000rpm is arrived in shear rate regulation, and shear time is
2 hours；After time to be stripped terminates, the pressure release of vent valve 6 is opened, sample is collected；After testing, less than 5 layers
Graphene yield is 45.6%.
Embodiment 2
As shown in figure 1,5 grams of expanded graphite powder are put into high-pressure reactor 5, control temperature of reactor reaches
60 DEG C, the carbon dioxide in carbon dioxide storage tank 1 is squeezed into high-pressure reactor 5 by high-pressure pump 2 through valve 3
It is interior, until pressure reaches 40MPa, cutter 4 is opened, 6500rpm is arrived in shear rate regulation, and shear time is
3 hours；After time to be stripped terminates, the pressure release of vent valve 6 is opened, sample is collected；After testing, less than 5 layers
Graphene yield is 81.6%.The transmission electron microscope picture of representational graphene sample as shown in fig. 2, it can be seen that
The graphene number of plies is 1 layer and 3 layers, while retaining complete SP2The carbon atom crystal structure of hydridization；Graphene (system
Into film) electrical conductivity reach 1.6 × 106S/m。
Embodiment 3
As shown in figure 1,30 grams of expanded graphite powder are put into high-pressure reactor 5, control temperature of reactor reaches
60 DEG C, the carbon dioxide in carbon dioxide storage tank 1 is squeezed into high-pressure reactor 5 by high-pressure pump 2 through valve 3
It is interior, until pressure reaches 45MPa, cutter 4 is opened, 8000rpm is arrived in shear rate regulation, and shear time is
4 hours；After time to be stripped terminates, the pressure release of vent valve 6 is opened, sample is collected；After testing, less than 5 layers
Graphene yield is 58.2%.
Embodiment 4
As shown in figure 1,5 grams of crystalline graphite powders are put into high-pressure reactor 5, control temperature of reactor reaches
25 DEG C, the carbon dioxide in carbon dioxide storage tank 1 is squeezed into high-pressure reactor 5 by high-pressure pump 2 through valve 3
It is interior, until pressure reaches 15MPa, cutter 4 is opened, 5000rpm is arrived in shear rate regulation, and shear time is
3 hours；After time to be stripped terminates, the pressure release of vent valve 6 is opened, sample is collected；After testing, less than 5 layers
Graphene yield is 35.3%.
Embodiment 5
As shown in figure 1,5 grams of crystalline graphite powders are put into high-pressure reactor 5, control temperature of reactor reaches
60 DEG C, the carbon dioxide in carbon dioxide storage tank 1 is squeezed into high-pressure reactor 5 by high-pressure pump 2 through valve 3
It is interior, until pressure reaches 40MPa, cutter 4 is opened, 6500rpm is arrived in shear rate regulation, and shear time is
3 hours；After time to be stripped terminates, the pressure release of vent valve 6 is opened, sample is collected；After testing, less than 5 layers
Graphene yield is 65.3%.
Embodiment 6
A kind of method for preparing graphene, using following steps：
(1) natural flake graphite raw material and polyvinyl alcohol are placed in reactor, graphene and polyvinyl alcohol
Weight ratio is 1：100, control reactor is warming up to 10 DEG C, and CO is pumped into thereto2Pressure into reactor reaches
To 60MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 3500rpm, using rotor and
The insertion of shearing, cavitation and mechanical impact effect coupling CO 2 fluid that stator is produced in high speed relative motion
And stabilization, stripping 5h is carried out to graphite；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained, and may collect in containing scattered
In the aqueous solution of agent polyvinyl alcohol.
Embodiment 7
A kind of method for preparing graphene, using following steps：
(1) stone is expanded into black raw material and polymethyl methacrylate is placed in reactor, graphene and poly- methyl-prop
The weight ratio of e pioic acid methyl ester is 20：100, control reactor is warming up to 20 DEG C, and CO is pumped into thereto2To reaction
Pressure in device reaches 45MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 4000rpm, using rotor and
The insertion of shearing, cavitation and mechanical impact effect coupling CO 2 fluid that stator is produced in high speed relative motion
And stabilization, stripping 4h is carried out to graphite；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained, and may collect in containing scattered
In the aqueous solution of agent Triton X-100.
Embodiment 8
A kind of method for preparing graphene, using following steps：
(1) high starch breeding raw material is placed in reactor, control reactor is warming up to 60 DEG C, is pumped into thereto
CO2Pressure into reactor reaches 15MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 8000rpm, using rotor and
The insertion of shearing, cavitation and mechanical impact effect coupling CO 2 fluid that stator is produced in high speed relative motion
And stabilization, stripping 2h is carried out to graphite, when being peeled off to graphite, adjuvant aniline can also be added,
The aniline of addition and the weight ratio of graphite are 1:100；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained, may collect in ethanol water-soluble
In liquid.
Embodiment 9
A kind of method for preparing graphene, using following steps：
(1) high starch breeding raw material is placed in reactor, control reactor is warming up to 80 DEG C, is pumped into thereto
CO2Pressure into reactor reaches 8MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 9000rpm, using rotor and
The insertion of shearing, cavitation and mechanical impact effect coupling CO 2 fluid that stator is produced in high speed relative motion
And stabilization, stripping 1h is carried out to graphite, when being peeled off to graphite, the poly- second two of adjuvant can also be added
Alcohol octyl phenyl ether, the Triton X-100 of addition and the weight ratio of graphite are 20:100；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained, may collect in n- methyl pyrroles
In pyrrolidone.
Claims (8)
1. a kind of method for preparing graphene, it is characterised in that this method uses following steps：
(1) graphite raw material is placed in reactor, control reactor is warming up to 10-80 DEG C, and CO is pumped into thereto2
Pressure into reactor reaches 8-60MPa；
(2) open the cutter that be connected with reactor, adjust the rotating speed of rotor for 3500-9000rpm, using turn
Shearing, cavitation and the mechanical impact effect that son is produced with stator in high speed relative motion couple CO 2 fluid
Insertion and stabilization, stripping 1-5h is carried out to graphite；
(3) by the CO in reactor2Emptying, collects the graphene peeled off and obtained.
2. a kind of method for preparing graphene according to claim 1, it is characterised in that described graphite
Including natural flake graphite, expanded graphite or high starch breeding.
3. a kind of method for preparing graphene according to claim 1, it is characterised in that described reaction
Temperature in device is preferably 20-60 DEG C, and pressure is preferably 15-45MPa.
4. a kind of method for preparing graphene according to claim 1, it is characterised in that described rotor
Rotating speed be preferably 4000-8000rpm, to graphite lift-off processing 2-4h.
5. a kind of method for preparing graphene according to claim 1, it is characterised in that in step (1)
The material being combined with graphene is additionally added, the weight ratio of graphene and above-mentioned material is 1-20：100.
6. a kind of method for preparing graphene according to claim 5, it is characterised in that described and stone
The compound material of black alkene is polyvinyl alcohol, polymethyl methacrylate or polyaniline.
7. a kind of method for preparing graphene according to claim 1, it is characterised in that step (2) is right
Graphite can also add adjuvant when being peeled off, and the weight ratio of the adjuvant and graphite is 1-20:100.
8. a kind of method for preparing graphene according to claim 7, it is characterised in that described auxiliary
Agent is monomer or polymer containing pi bond structure, including aniline, polyaniline or Triton X-100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610030508.5A CN106986329A (en) | 2016-01-18 | 2016-01-18 | A kind of method for preparing graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610030508.5A CN106986329A (en) | 2016-01-18 | 2016-01-18 | A kind of method for preparing graphene |
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| CN106986329A true CN106986329A (en) | 2017-07-28 |
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| CN201610030508.5A Pending CN106986329A (en) | 2016-01-18 | 2016-01-18 | A kind of method for preparing graphene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628610A (en) * | 2017-10-30 | 2018-01-26 | 北京万源工业有限公司 | A kind of method that mechanical stripping method prepares graphene and graphene conductive liquid |
| CN108975322A (en) * | 2018-09-05 | 2018-12-11 | 七台河宝泰隆石墨烯新材料有限公司 | The method for preparing graphene slurry |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583326A (en) * | 2012-01-11 | 2012-07-18 | 上海交通大学 | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance |
| CN103771401A (en) * | 2013-12-26 | 2014-05-07 | 中国石油大学(北京) | Preparation method for single-layered graphene |
-
2016
- 2016-01-18 CN CN201610030508.5A patent/CN106986329A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583326A (en) * | 2012-01-11 | 2012-07-18 | 上海交通大学 | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance |
| CN103771401A (en) * | 2013-12-26 | 2014-05-07 | 中国石油大学(北京) | Preparation method for single-layered graphene |
Non-Patent Citations (2)
| Title |
|---|
| LEI LI ET AL.: "Preparation of graphene nanosheets by shear-assisted supercritical CO2 exfoliation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| YING WEI ET AL.: "Liquid-phase exfoliation of graphite for mass production of pristine few-layer graphene", 《CURRENT OPINION IN COLLOID & INTERFACE SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628610A (en) * | 2017-10-30 | 2018-01-26 | 北京万源工业有限公司 | A kind of method that mechanical stripping method prepares graphene and graphene conductive liquid |
| CN108975322A (en) * | 2018-09-05 | 2018-12-11 | 七台河宝泰隆石墨烯新材料有限公司 | The method for preparing graphene slurry |
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Application publication date: 20170728 |