CN105819432B - A kind of method for preparing high-quality graphene material - Google Patents
A kind of method for preparing high-quality graphene material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 238000002525 ultrasonication Methods 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 54
- 239000010439 graphite Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
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- 239000004172 quinoline yellow Substances 0.000 claims description 13
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- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
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- 229910001172 neodymium magnet Inorganic materials 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 238000010008 shearing Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
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- 150000001336 alkenes Chemical class 0.000 description 6
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 description 6
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- BTMZHHCFEOXAAN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-dodecylbenzenesulfonic acid Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O BTMZHHCFEOXAAN-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 description 2
- JHPNTZAETISEHT-UHFFFAOYSA-N CCCCCCCCCCCCOS(=O)(=O)C1=C(C=CC2=CC=CC=C21)S(=O)(=O)O Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=C(C=CC2=CC=CC=C21)S(=O)(=O)O JHPNTZAETISEHT-UHFFFAOYSA-N 0.000 description 2
- WSVQZZFFMBFCKH-UHFFFAOYSA-N [Na].C(CCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O Chemical compound [Na].C(CCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O WSVQZZFFMBFCKH-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- 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
-
- 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
- C01B2204/32—Size or surface area
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of new method for preparing high-quality graphene material, the actual demand that graphene is produced to meet high-volume, high quality, low-cost industrial provides technical solution.The method of the present invention is to prepare principle within the specific limits to maintain the physical parameters such as mixed solution surface tension, viscosity always, it is adjusted at any time while the real time measure mixed solution surface tension and viscosity or adds various raw materials at random, and graphene dispersing solution is obtained using the shear mixing equipments such as emulsification pretreatment machine progress shear agitation and/ultrasonication.The present invention can obtain that lateral dimension is very big, graphene of the thickness of very high concentrations within 4 layers, since using non-oxide method, gained graphene electrical conductivity is higher；The method of the present invention is more simple, without complex process flow, is suitble to large-scale industrial production.
Description
Technical field
The invention belongs to technical field of graphene, and in particular to a kind of new method for preparing high-quality graphene material.
Background technology
Graphene is a kind of special two-dimensional material being made of carbon atom, because it is with high conductivity, high mechanical properties, super
The extremely excellent comprehensive physical performance such as bigger serface, highly thermally conductive, in the various field tools such as electronics, space flight military project, new energy
There is significant application value.
In order to realize and meet the large-scale industrial production of graphene and practical application request, prepared by the production of graphene
Method need at least meet three key factors：High quality, high-volume, low cost, although there are many on graphite both at home and abroad at present
The report of alkene preparation method, but from the point of view of the actual demands such as high quality, inexpensive volume production, prepared by most of graphenes reported
Method all has the defects of various.For example, vapour deposition process（CVD）Though it is high-quality to meet production with SiC thermal decomposition methods
The requirement of graphene is measured, but there is the defects of higher cost, complex process simultaneously；Coleman et al. (J. Am. Chem. Soc. 2009, 131, 3611-3620) and pass through the side of the supersound process graphite in the solution of neopelex and water
The graphene of better performances has been made in method, but obtained graphene dispersing solution concentration is extremely low (0.002~0.05g/L), it is difficult to
Scale of mass production, thus do not meet large batch of requirement；Oxidizing process is the current most common method for preparing graphene, this method
Relatively easy volume production and technique is relatively easy, but the physical property of the graphene obtained is due to the work of the substances such as strong oxidizer
With being subject to compared with havoc, although people are it is further proposed that oxidation-reduction method carrys out reduction treatment graphene oxide in recent years, make to be made
Graphene product performance have larger improvement, but the substances such as strong oxidizer, strong reductant used in this kind of method exist corruption
The shortcomings of corrosion is strong, toxicity is big, Environmental costs are high and problem；In addition, there is also many new graphene preparation methods, but it is logical
It a series of problems, such as Chang Douhui is related to such as preparation process complexity, is difficult to scale of mass production, is of high cost, environmental hazard is big, can be same
When to meet high quality, high-volume, the graphene preparation method of inexpensive three key factors relatively fewer at present.
Thus, in order to further meet the actual demand of graphene commercial application, seek it is a kind of it is simple for process, be produced into
This is low, and graphene comprehensive physical performance will not be greatly lowered simultaneously and the simple mass production method of higher Environmental costs is caused to have
It is significant.
The content of the invention
In view of the problems of the existing technology, it is an object of the invention to design, offer is a kind of to prepare high-quality graphene material
The technical solution of the new method of material.
A kind of new method for preparing high-quality graphene material, it is characterised in that comprise the following steps that：
1）Water is made to flow through magnetic field and carries out magnetization treatment, obtains the magnetization treatment water that surface tension is 50~60 mN/m, and will
The magnetization treatment water is added in into container；
2）Graphite and/or BN parameter regulations substance are added in into step 1）Container in form mixed solution, then to the mixing
Solution progress shear agitation and/or ultrasonication, the surface tension and viscosity of the real time measure mixed solution, and by this
Graphite, water and/or BN parameter regulation substances are added in mixed solution, the BN parameter values for making mixed solution always maintain 9~
In the range of 58000；
3）By step 2）To get to graphene product after the graphene dispersing solution removal solvent of gained.
A kind of new method for preparing high-quality graphene material, it is characterised in that the step 1）At middle magnetization
The magnetic field intensity of reason is 0.02~10 T.
A kind of new method for preparing high-quality graphene material, it is characterised in that the step 2）Middle BN parameters
By the surface tension of mixed solution and viscosity common definition：The numerical value of BN parameters=mixed solution surface tension numerical value × mixing is molten
Fluid viscosity value, surface tension numerical value in units of mN/m, viscosity in units of mPas, surface tension value range for 20~
61, viscosity value range is 0.3~1000.
A kind of new method for preparing high-quality graphene material, it is characterised in that the step 2）Middle BN parameters
Auto-regulator is polyethylene glycol, polyvinyl alcohol, sodium citrate, the red, quinoline yellow of temptation, famille rose, acid red, propylene glycol, glycerine,
Glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, triethanolamine, diethanol amine, alkylbenzenesulfonate, alkyl benzene sulphonate salt derivative,
Alkyl diphenyl ether disulfonate, alkyl diphenyl ether disulfonate derivative, alkylnaphthalene sulfonate, alkyl naphthalene sulfonic acid salt derivative,
Alkyl dinaphthyl ether sulfonate and one kind in Alkyl dinaphthyl ether sulfonate derivative or arbitrary several mixture.
A kind of new method for preparing high-quality graphene material, it is characterised in that the step 2）Middle graphite is
Native graphite, highly directional thermal cracking graphite, expanded graphite and one kind in crystallite Delanium or arbitrary several mixture.
A kind of new method for preparing high-quality graphene material, it is characterised in that the step 3）Middle removal is molten
One or more in agent method specially centrifugation, suction filtration, heating, drying, freeze-drying and spray drying.
A kind of new method for preparing high-quality graphene material, it is characterised in that unstripped remaining stone in raw material
Ink continues cycling through utilization as raw material.
Compared with prior art, the invention has the advantages that：
1）Present invention firstly provides graphene is prepared using magnetization treatment water, graphene preparation can be very effectively improved
Efficiency.People just have found the surface tension that can make water when water flows through magnetic field and the transverse cuts magnetic line of force a long time ago
It is greatly reduced, but rarely has using magnetized water the report for preparing graphene；And stone is prepared using magnetized water in the method for the present invention
Black alkene can be saved largely must be used for the dosage for adjusting the raw material for reducing mixed solution surface tension, such as surface-active originally
Agent etc., this has for industrializing scale of mass production graphene and has very important significance, and can substantially reduce cost.
2）Present invention firstly provides by BN parameters that the surface tension of mixed solution and viscosity is unified to formation connection together
Mechanism that is dynamic and conditioning each other, and surface tension, viscosity, temperature of monitoring mixed solution etc. can at any time in real time in process of production
Between continually changing physical parameter, so as to the addition of the various raw materials of correspondingly real-time monitoring, order, adding speed, shearing
The preparation parameters such as stir speed (S.S.) greatly improve graphene preparation efficiency, can effectively generate and stablize a large amount of high quality stones
The dispersion liquid of black alkene, the number of plies that be averaged of graphene obtained by preferred embodiment can be less than 4 layers.The graphene dispersing solution concentration for making acquisition is non-
Chang Gao, preferred embodiment is up to more than 11g/L, and the concentration system is so far in document report, using same mixture matter and similarity method
To prepare the rare high concentration of graphene.
3）Graphene product prepared by the present invention can have porous structure and lateral dimension is very big, up to microns up to a hundred with
On, the document report with similar results is few so far.
4）Strong oxidizer is not directed to use in the present invention, because without seriously destroying graphene knot as conventional oxidation method
Structure performance, so as to which the graphene that this method produces is made to possess higher physical property, graphene electrical conductivity obtained by preferred embodiment
The order of magnitude is 104~105S/m；In addition, be not directed to use in the method for the present invention other special intercalated material, strong reductants etc. into
This it is higher or can to environment generate seriously endanger chemical raw material, thus lower cost and environmental hazard it is small；Present invention side
The most of raw materials used in method are common chemical raw material, and method is very simple, are not related to extremely complex operative employee
Skill is very suitable for large-scale industrial production.
5）The preparation method of graphene in the present invention can meet large-scale industrial production and practical application simultaneously
Three required key factors：High quality, high-volume, low cost, can be produced on the basis of low cost be provided simultaneously with high concentration,
The graphene product of the excellent comprehensive characteristics such as low layer number, high conductance, large scale.
Description of the drawings
Fig. 1 is the atomic force microscopy diagram of graphene produced by the present invention.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 1.1T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 54mN/m and then add in container.
（2）By expanded graphite, native graphite, polyethylene glycol, quinoline yellow, famille rose, sodium citrate and dodecyl hexichol
Ether sodium disulfonate adds in step（1）Container in, with high-speed shearing emulsion machine with 3500rpm rotating speeds stirring 3.5 it is small when obtain stone
Black alkene dispersion liquid adjusts according to the surface tension and viscosity surveyed in the process or adds various raw materials at random（Raw material is swollen
Swollen graphite, native graphite, polyethylene glycol, quinoline yellow, famille rose, sodium citrate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, water）, make
The BN parameters of solution（The numerical value of BN parameters=mixed solution surface tension numerical value × mixed solution viscosity number, surface tension numerical value with
MN/m is unit, and for viscosity in units of mPas, surface tension value range is 20~61, viscosity value range for 0.3~
1000）Always maintain in the range of 98~101, it is high-quality then with 3000rpm rotating speeds centrifugal treating to obtain upper strata after 30 minutes again
Graphene dispersing solution is measured, which is 11.5g/L, and gained dispersion liquid obtains graphene product after suction filtration.
The graphene product learns graphene lateral dimension up to 105 μm or more through atomic force microscope observation, and the average number of plies is 3 layers,
As shown in Figure 1；The graphene electrical conductivity order of magnitude can be obtained after tested as 105s/m。
Embodiment 2：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.9T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 53mN/m and then add in container.
（2）By native graphite, expanded graphite, polyvinyl alcohol, dodecyl benzene sulfonic acid triethanolamine, quinoline yellow, dodecane
Base dinaphthyl ether sodium disulfonate, glycol and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate add in step（1）Container in, with high speed shear breast
Change machine with 3700rpm rotating speeds stirring 3 it is small when obtain graphene dispersing solution, in the process according to the surface tension and viscosity surveyed come
It adjusts or adds various raw materials at random（Raw material is native graphite, expanded graphite, polyvinyl alcohol, three ethyl alcohol of dodecyl benzene sulfonic acid
Amine, quinoline yellow, dodecyl dinaphthyl ether sodium disulfonate, glycol, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, water）, join the BN of solution
Number is maintained in the range of 158~161 always, then obtains upper strata high quality after 35 minutes again with 2800rpm rotating speeds centrifugal treating
Graphene dispersing solution, the graphene dispersing solution concentration are 12.4g/L, and gained dispersion liquid obtains graphene product after suction filtration.Through
Test understands that obtained graphene is averaged the number of plies as 3 layers, and for lateral dimension up to 110 μm or more, the electrical conductivity order of magnitude is 104s/m。
Embodiment 3：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.8T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 55mN/m or so and then add in container.
（2）By native graphite, expanded graphite, double disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, acid red 27, famille rose, 16
Sodium alkyl benzene sulfonate and propylene glycol add in step（1）Container in, with high-speed shearing emulsion machine with 3800rpm rotating speeds stir and it is same
When with 100W power ultrasonics processing 2 it is small when obtain graphene dispersing solution, in the process according to the surface tension and viscosity surveyed come
It adjusts or adds various raw materials at random（Raw material is native graphite, expanded graphite, double disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, acidity
Red 27, famille rose, cetyl benzenesulfonic acid sodium, propylene glycol, water）, the BN parameters of solution is made to maintain 277~280 scopes always
It is interior, upper strata high-quality graphene dispersion liquid, the graphene dispersion are then obtained after 38 minutes with 2700rpm rotating speeds centrifugal treating again
Liquid concentration is 11.1g/L, and gained dispersion liquid obtains graphene product after suction filtration.Understand that obtained graphene is averaged after tested
The number of plies is 4 layers, and lateral dimension is 121 μm or more, and the electrical conductivity order of magnitude is 104s/m。
Embodiment 4：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.7T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 57mN/m and then add in container.
（2）By expanded graphite, native graphite, quinoline yellow, acid red 27, carmine, double dodecyl diphenyl oxide disulfonic acid
Sodium, glycerine and triethanolamine add in step（1）Container in, with high-speed shearing emulsion machine with 3800rpm rotating speeds stirring 2.5 it is small when
Graphene dispersing solution is obtained, adjusts according to surface tension, the viscosity surveyed in the process or adds various raw materials at random（Raw material
For expanded graphite, native graphite, quinoline yellow, acid red 27, carmine, double disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, glycerine, three second
Alcohol, water）, the BN parameters of solution is made to maintain always in the range of 105~108, are then divided again with 2500rpm rotating speeds centrifugal treating 35
Upper strata high-quality graphene dispersion liquid is obtained after clock, which is 13.1g/L, and gained dispersion liquid is through filtering
Afterwards, graphene product is obtained.Understand that the obtained graphene number of plies that be averaged is 4 layers after tested, lateral dimension up to 105 μm or more,
The electrical conductivity order of magnitude is 104s/m。
Embodiment 5：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.4T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 56mN/m or so and then add in container.
（2）By native graphite, expanded graphite, polyvinyl alcohol, triethylene glycol, diethanol amine, acid red 27, cetyl hexichol
Ether sodium disulfonate and dodecyl naphthalene disulfonate add in step（1）Container in, with high-speed shearing emulsion machine with 4800rpm turn
Speed stirring 3 obtains graphene dispersing solution when small, each to adjust or add at random according to the surface tension, viscosity surveyed in the process
Kind raw material（Raw material is native graphite, expanded graphite, polyvinyl alcohol, triethylene glycol, diethanol amine, acid red 27, cetyl hexichol
Ether sodium disulfonate, dodecyl naphthalene disulfonate）, the BN parameters of solution is made to maintain always in the range of 311~314, Ran Houzai
Upper strata high-quality graphene dispersion liquid is obtained with 2600rpm rotating speeds centrifugal treating after twenty minutes, which is
11.3g/L, gained dispersion liquid obtain graphene product after suction filtration.Understand that the obtained graphene number of plies that be averaged is 3 after tested
Layer, for lateral dimension up to 116 μm or more, the electrical conductivity order of magnitude is 104s/m。
Embodiment 6：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.8T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 55mN/m or so and then add in container.
（2）By expanded graphite, native graphite, cetyl diphenyl ether sodium disulfonate, polyethylene glycol, quinoline yellow, hexadecane
Base benzene sulfonic acid sodium salt adds in step（1）Container in, with 180W power ultrasonics processing 3 it is small when obtain graphene dispersing solution, in the process
Surface tension, viscosity according to surveying adjust or add various raw materials at random（Raw material is expanded graphite, native graphite, gathers
Ethylene glycol, polyvinyl alcohol, sodium citrate, the red, quinoline yellow of temptation, famille rose, acid red, propylene glycol, glycerine, glycol, diethylene glycol (DEG),
Triethylene glycol, tetraethylene glycol, triethanolamine, diethanol amine, water）, the BN parameters of solution is made to maintain always in the range of 32~39, then
Upper strata high-quality graphene dispersion liquid is obtained after 15 minutes with 2000rpm rotating speeds centrifugal treating again, the graphene dispersing solution concentration
For 11g/L, gained dispersion liquid obtains graphene product after suction filtration.Understand that obtained graphene lateral dimension is reachable after tested
100 μm or more, the average number of plies is 3 layers；The graphene electrical conductivity order of magnitude can be obtained after tested as 105s/m。
Embodiment 7：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.8T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 58mN/m or so and then add in container.
（2）By expanded graphite, native graphite, neopelex, red, three ethyl alcohol of dodecyl benzene sulfonic acid of temptation
Amine, quinoline yellow add in step（1）Container in, with high-speed shearing emulsion machine with 3650rpm rotating speeds stirring 2.5 it is small when obtain graphite
Alkene dispersion liquid adjusts according to surface tension, the viscosity surveyed in the process or adds various raw materials at random（Raw material is expansion stone
Ink, native graphite, neopelex, red, the dodecyl benzene sulfonic acid triethanolamine of temptation, quinoline yellow, water）, make solution
BN parameters maintain always in the range of 122~125, upper strata is then obtained after 30 minutes with 3000rpm rotating speeds centrifugal treating again
High-quality graphene dispersion liquid, the graphene dispersing solution concentration are 12.2g/L, and gained dispersion liquid obtains graphene after suction filtration
Product.Understand that the obtained graphene number of plies that be averaged is 4 layers after tested, lateral dimension is up to 110 μm or more, the electrical conductivity order of magnitude
105s/m。
Embodiment 8：
（1）Water is flowed through to magnetic of the polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 1T in a manner of vertical magnetic field direction
Field areas makes the surface tension of water be down to 59mN/m or so and then add in container.
（2）By native graphite, expanded graphite, lure red, octadecyl benzenesulfonic acid sodium, dodecyl naphthalene diether disulfonic acid
Sodium, diethylene glycol (DEG) add in step（1）Container in, with high-speed shearing emulsion machine with 4500rpm rotating speeds stirring 3 it is small when obtain graphene
Dispersion liquid adjusts according to surface tension, the viscosity surveyed in the process or adds various raw materials at random（Raw material is natural stone
Ink, expanded graphite lure red, octadecyl benzenesulfonic acid sodium, dodecyl naphthalene diether sodium disulfonate, diethylene glycol (DEG), water）, make solution
BN parameters maintain always in the range of 41200~41400, then obtained again with 3100rpm rotating speeds centrifugal treating after 30 minutes
Upper strata high-quality graphene dispersion liquid, the graphene dispersing solution concentration are 13.6g/L, and gained dispersion liquid obtains stone after suction filtration
Black alkene product.Understand that the obtained graphene number of plies that be averaged is 3 layers after tested, lateral dimension is up to 35 μm or more, electrical conductivity quantity
Grade is 105s/m。
Embodiment 9：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 0.02T in a manner of vertical magnetic field direction
Field region, make water surface tension be down to 53mN/m or so and then add in container in.
（2）By highly directional native graphite, thermal cracking graphite, tetraethylene glycol, cetyl benzenesulfonic acid sodium, carmine addition step
（1）Container in, with high-speed shearing emulsion machine with 200W power ultrasonics processing 2 it is small when obtain graphene dispersing solution, root in the process
The surface tension that factually measures, viscosity adjust or add various raw materials at random（Raw material is native graphite, thermal cracking graphite, gathers
Ethylene glycol, polyvinyl alcohol, sodium citrate, the red, quinoline yellow of temptation, famille rose, acid red, propylene glycol, glycerine, glycol, diethylene glycol (DEG),
Triethylene glycol, tetraethylene glycol, triethanolamine, diethanol amine, alkylbenzenesulfonate, alkyl benzene sulphonate salt derivative, alkyl diphenyl ether two
Sulfonate, alkyl diphenyl ether disulfonate derivative, alkylnaphthalene sulfonate, alkyl naphthalene sulfonic acid salt derivative, alkyl dinaphthyl ether sulphur
Hydrochlorate, Alkyl dinaphthyl ether sulfonate derivative, water）, the BN parameters of solution is made to maintain always in the range of 223~225, Ran Houzai
Upper strata high-quality graphene dispersion liquid is obtained with 2000rpm rotating speeds centrifugal treating after ten minutes, which is
13.4g/L, gained dispersion liquid obtain graphene product after suction filtration.Understand that the obtained graphene number of plies that be averaged is 4 after tested
Layer, for lateral dimension up to 108 μm or more, the electrical conductivity order of magnitude is 104s/m。
Embodiment 10：
（1）Water is flowed through into polylith magnetic field intensity between the Nd-Fe-B permanent magnet of 10T in a manner of vertical magnetic field direction
Field region makes the surface tension of water be down to 56mN/m or so and then add in container.
（2）By expanded graphite, native graphite, crystallite Delanium, neopelex, polyvinyl alcohol, poly- second two
Alcohol, sodium citrate add in step（1）Container in, with high-speed shearing emulsion machine with 4200rpm rotating speeds stirring 3.5 it is small when obtain stone
Black alkene dispersion liquid adjusts according to surface tension, the viscosity surveyed in the process or adds various raw materials at random（Raw material is expansion
Graphite, native graphite, crystallite Delanium, neopelex, polyvinyl alcohol, polyethylene glycol, sodium citrate, water）, make
The BN parameters of solution are maintained in the range of 62~64 always, are then obtained again with 3000rpm rotating speeds centrifugal treating after 30 minutes
Floor height quality graphene dispersing solution, the graphene dispersing solution concentration are 12g/L, and gained dispersion liquid obtains graphene after suction filtration
Product.Understand that the obtained graphene number of plies that be averaged is 4 layers after tested, lateral dimension is up to 113 μm or more, the electrical conductivity order of magnitude
105s/m。
Claims (5)
- A kind of 1. method for preparing high-quality graphene material, it is characterised in that comprise the following steps that：1）Water is made to flow through magnetic field and carries out magnetization treatment, obtains the magnetization treatment water that surface tension is 50~60 mN/m, and by the magnetic Change processing water to add in into container；2）Graphite and BN parameter regulations substance are added in into step 1）Container in form mixed solution, then the mixed solution is carried out Shear agitation and/or ultrasonication, the surface tension and viscosity of the real time measure mixed solution, and by the mixed solution Middle addition graphite, water and/or BN parameter regulation substances, make the BN parameter values of mixed solution maintain 9~58000 scopes always Interior, the BN parameters are by the surface tension of mixed solution and viscosity common definition：The numerical value of BN parameters=mixed solution surface Power numerical value × mixed solution viscosity number, surface tension numerical value is in units of mN/m, and in units of mPas, surface tension takes viscosity It is 20~61 to be worth scope, and viscosity value range is 0.3~1000, and the BN parameter regulations substance is polyethylene glycol, polyethylene It is alcohol, sodium citrate, the red, quinoline yellow of temptation, famille rose, acid red, propylene glycol, glycerine, glycol, diethylene glycol (DEG), triethylene glycol, four sweet Alcohol, triethanolamine, diethanol amine, alkylbenzenesulfonate, alkyl benzene sulphonate salt derivative, alkyl diphenyl ether disulfonate, alkyl Diphenyl oxide disulfonates derivative, alkylnaphthalene sulfonate, alkyl naphthalene sulfonic acid salt derivative, Alkyl dinaphthyl ether sulfonate and alkyl two One kind or arbitrary several mixture in naphthalene ether sulfonate derivative；3）By step 2）To get to graphene product after the graphene dispersing solution removal solvent of gained.
- A kind of 2. method for preparing high-quality graphene material as described in claim 1, it is characterised in that the step 1） The magnetic field intensity of middle magnetization treatment is 0.02~10 T.
- A kind of 3. method for preparing high-quality graphene material as described in claim 1, it is characterised in that the step 2） Middle graphite is native graphite, highly directional thermal cracking graphite, expanded graphite and one kind or arbitrary several in crystallite Delanium Mixture.
- A kind of 4. method for preparing high-quality graphene material as described in claim 1, it is characterised in that the step 3） One or more in middle removal solvent method specially centrifugation, suction filtration, heating, drying, freeze-drying and spray drying.
- 5. a kind of method for preparing high-quality graphene material as described in claim 1, it is characterised in that unstripped in raw material Remaining graphite, continue cycling through utilization as raw material.
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| CN107585753B (en) * | 2017-08-23 | 2020-03-24 | 阮伟 | Production method of large-size graphene material |
| CN110386599A (en) * | 2018-04-20 | 2019-10-29 | 杭州万杵材料科技有限公司 | A kind of graphene composite material and preparation method thereof |
| CN113479875B (en) | 2019-08-22 | 2022-08-12 | 常州富烯科技股份有限公司 | Graphene oxide film and preparation method thereof |
| CN110746563B (en) * | 2019-10-24 | 2021-06-29 | 江苏理工学院 | PEG ball-milling intercalation h-BN modified polyurethane heat-conducting composite material and preparation method thereof |
| CN113135564B (en) * | 2021-05-11 | 2022-10-11 | 中钢集团南京新材料研究院有限公司 | Preparation method of stable graphene aqueous dispersion liquid |
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