CN106744878B - A kind of scale crushes the method for preparing large stretch of footpath graphene - Google Patents
A kind of scale crushes the method for preparing large stretch of footpath graphene Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 81
- 239000010439 graphite Substances 0.000 claims abstract description 81
- 239000000919 ceramic Substances 0.000 claims abstract description 42
- 230000000694 effects Effects 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000011229 interlayer Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 230000033001 locomotion Effects 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- 230000002687 intercalation Effects 0.000 claims description 18
- 238000009830 intercalation Methods 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000004227 thermal cracking Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000138 intercalating agent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- -1 stand 3-5 days Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000002604 ultrasonography Methods 0.000 abstract description 5
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- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B2204/32—Size or surface area
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention proposes that a kind of scale crushes the method for preparing large stretch of footpath graphene.Graphite powder is used as raw material, graphite powder is placed in mill, the surface of fixed millstone and movable grinding disc is the ceramic minute surface of wearability, by graphite powder under the mutually opposing crisscross motion effect of minute surface mill, peeling sheet layer by layer, the reduction of radial direction in graphite linings is effectively prevent, by introducing ultrasonic dither in mill, graphite flake interlayer is torn, obtains large stretch of footpath graphene.This method realizes continuous graphene production, cleaning, the technique effect of environmental protection, has promoted the industrialization continuous production of graphene.Further, a step completes shearing stripping in mill, the scattered process of ultrasound homogenization, the deck structure of graphene is not only remained to greatest extent, and grapheme material can be prepared with continuous-stable, the surface integrity and Topological Symmetry of graphene are not destroyed, ensure that the quality of graphene product.
Description
Technical field
The present invention relates to nano material manufacture field, and in particular to a kind of scale crushes the side for preparing large stretch of footpath graphene
Method.
Background technology
The plane carbon nanomaterial that graphene is made up of one layer of carbon atom, it is to be currently known most thin two-dimensional material, its
Thickness is only 0.335nm, and it is made up of the lattice of six sides.By σ key connections between carbon atom in graphene, graphene is imparted
Extremely excellent mechanical property and structural rigidity.Moreover, in graphene, each carbon atom has the p electronics of a non-bonding,
These p electronics can move freely in crystal, and movement velocity is up to the 1/300 of the light velocity, impart that graphene is good to lead
Electrically.In optics aspect, graphene is almost fully transparent, only absorbs 2.3% light.Graphene has peculiar mechanics, light
Learn and electrical properties, graphene possess very vast potential for future development.
The preparation method of graphene mainly includes chemical vapour deposition technique, oxidation intercalation restores method, liquid phase stripping method, machine
Tool stripping method.Wherein chemical vapour deposition technique can obtain the graphene of high quality, but low yield, require high to substrate, turn
Move and greatly difficulty be present；Oxidation intercalation, which restores method, can realize batch production graphene, but due to stone in oxidizing process
The structure of black alkene is destroyed, it is difficult to obtains the graphene product of high quality；Liquid phase stripping method is in a suitable solvent, to utilize
Ultrasonic energy dissociates to graphite flake layer, is difficult to remove asking for residual solvent however, solvent stripping method prepares graphene presence
Topic, and solvent stripping yield is general very low.By contrast, it is high-quality to be that one kind can be prepared with low cost for mechanical-physical stripping method
Measure the simple and easy method of graphene.But graphene size prepared by mechanical stripping method is generally smaller, therefore large scale stone
The preparation of black alkene turns into study hotspot.
Chinese invention patent application number 201210292680.X discloses a kind of preparation method of large-size monocrystal graphene,
It is characterized in that in environment more than 800 DEG C, by adjusting the flow velocity of organic gas, hydrogen and inert gas and point of flow field
Cloth prepares large-size monocrystal graphene in metal surface；The organic gas includes：Alkane, alkene, alkynes, aromatic hydrocarbon etc. contains
Carbon gas；The metal surface includes：The metal surfaces such as copper, platinum；The flow field includes：The flow velocity of various gases, flowing side
To and air pressure；Ambient pressure during heat treatment is normal pressure, and the time is in 20min-40min；The ambient pressure during growth is 1
Between Pa-300 Pa, the time is in 1 min-2h.But this method obtains activity using metallic high temperature reduction organic gas
Charcoal atom, it is costly using noble metal as growth substrates, growing film at high temperature is kept, to equipment and instrument requirement
Height, be not suitable for large-scale production.
Chinese invention patent application number 201510128458.X discloses one kind and prepares large-size high-quality graphene monocrystalline
Device and method.The device includes：Housing and top cover, the gas tip with gas distribution pipe is set in top cover, makes the high-purity gas of entrance
Body is uniformly distributed into reaction cavity；Reaction cavity is sent out by sealed silica envelope, the graphite being plugged among two sections of sealed silica envelopes
Hot body, the graphite crucible being placed on inside graphite heater composition, graphite crucible are used to place SiC wafer substrates；Graphite is sent out
Heat has cooling water system, intermediate frequency coil in vitro；Housing bottom has gas outlet.The present invention also provides to be served as a contrast using the device in SiC
The method that large-size high-quality graphene monocrystalline is prepared on bottom.Using the present apparatus and growing method, height is made on SiC substrates
The graphene crystal of quality, graphene prepared by its mobility ratio SiC high temperature pyrolysis method improve nearly 1~2 quantity
Level.But the main design thought of this method, from carbon atom is obtained, is arranged again still from the method for SiC high temperature pyrolysis
Row carbon atom obtains graphene, and using decomposition reaction under high-purity hydrogen and hot environment, equipment cost is high, and equipment is endangered during working
It is dangerous big.
Chinese invention patent application number 200910187298.0 discloses a kind of preparation method of big size graphene, is applicable
Prepared in the magnanimity of big size graphene.This method includes：(1) large scale graphite is used as raw material, utilizes modified Hummers
Method carries out weak oxide to graphite raw material；(2) graphite oxide that be will be dispersed in using weak ultrasound or oscillation method in water carries out temperature
And stripping, obtain graphene oxide；(3) multiple centrifugal method is used, by controlling centrifugal rotational speed and centrifugation time to aoxidize stone
Black alkene separation, obtains uniform large scale graphene oxide；(4) graphene oxide is deposited on matrix, utilizes hydrazine or hydration
Hydrazine reduces, and obtains high quality, big size graphene.Large-sized graphene is obtained using the present invention, maximum area up to 3 ×
104μm2, be graphene in nesa coating, display and electrode of solar battery, gas sensor, optical-electrical converter, film
The application in the flexible optoelectronic function film such as electronic device field is laid a good foundation.Although The method avoids high temperature shape before
The use of state and high-risk gas, still, limit there is to the size of graphene using large scale graphite as raw material in this method
System, can not obtain can directly apply large-sized graphene film.The reducing agent of this method is poisonous hydrazine or hydrazine hydrate, no
Only production cost is high, and environmental pollution, influences the health of operator.
In summary, at present using strong oxidizer to Graphitic pretreatment, the graphenic surface grafted polar of preparation can be made again
Group, it is detrimental to health and causes environmental pollution, destroy the perfection of lattice of graphene, reduces the conductive energy of system
Power.It is low that the charge stripping efficiency of graphene powder is prepared using mechanical stripping method, production process dust pollution is serious, it is impossible to realizes stone
The continuous production of black alkene, and the flour mill device due to using now does not all account for the radial dimension of reservation graphite, therefore,
The size of graphite prepared by mechanical stripping method is relatively small.If secondary to mill using ceramic minute surface, graphene is prepared, will be from basic
On solve the above problems.Therefore, from the point of view of the extensive industrialization of big size graphene, we are with greater need for one kind operation letter
List, scale, the graphene preparation method of no pollution.
The content of the invention
Low, the production process dust pollution for the charge stripping efficiency for preparing graphene powder with mechanical stripping method in the prior art
Seriously, it is impossible to realize the continuous production of graphene, and the flour mill device due to using now does not all account for retaining stone
The radial dimension of ink, therefore, the size of graphite prepared by mechanical stripping method are relatively small.The present invention proposes that a kind of scale crushes
The method for preparing large stretch of footpath graphene.Use graphite powder that graphite powder is placed in mill for raw material, the table of fixed millstone and movable grinding disc
Face is the ceramic minute surface of wearability, by graphite powder under minute surface mill mutually opposing crisscross motion effect, peeling sheet layer by layer,
The reduction of radial direction in graphite linings is effectively prevent, by introducing ultrasonic dither in mill, tears graphite flake interlayer
Split, obtain large stretch of footpath graphene.This method realizes continuous big size graphene production, cleaning, the technique effect of environmental protection, promotes
The industrialization continuous production of big size graphene.Further, a step completes shearing stripping in mill, and ultrasound homogenization is scattered
Process, not only remain the deck structure of graphene to greatest extent, and grapheme material can be prepared with continuous-stable, no
The surface integrity and Topological Symmetry of graphene are destroyed, ensure that the quality of graphene product.
To solve the above problems, the present invention, which provides a kind of scale, crushes the method for preparing large stretch of footpath graphene, using stone
Ink powder is raw material, uses the surface of fixed millstone and movable grinding disc to be used as the ceramic minute surface of wearability secondary to mill, peels off graphite layer by layer,
Ultrasonic system is introduced in mill simultaneously, dither, the tear of graphite flake interlayer, forms large stretch of footpath graphene, specific steps
Including：
（1）By graphite raw material, intercalation additive, water and surfactant according to mass ratio be 1:2-5:5-10:0.1-0.5
Ratio be configured to scattered suspension, 10-25min is dispersed with stirring with 300-500rpm rotating speed, to the graphite raw material molten
It is uniformly dispersed in agent, obtains scattered suspension, stand 3-5 days, intercalator is entered graphite layers；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 500-1000rpm,
The relative direction on the surface of fixed millstone and movable grinding disc is kept to move, graphite is by the ceramic minute surface mill mixing and peels off；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 500-1500kW, ultrasound are introduced
Frequency is 50-170kHz, under the dither effect of ultrasonic wave, tears graphite flake interlayer, interfloor distance increase, so
More preferable charge stripping efficiency is obtained under inside and outside collective effect, and without reduction graphite radial dimension.
Preferably, the graphite raw material is crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite, graphite oxide
At least one of, the graphite raw material particle diameter is less than or equal to 1 millimeter.
Preferably, the intercalation additive be sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, ammonium chloride, ammonium sulfate,
At least one of ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate.
Preferably, described surfactant is lauryl sodium sulfate, neopelex, polyvinylpyrrolidine
At least one of ketone, 1- pyridine acids.
Preferably, 100-500 KW ultrasonic power is used during the standing, graphite is ultrasonically treated, promotes intercalation
Additive is well into interlayer.
Preferably, the ceramic minute surface is aluminium oxide ceramics, and minute surface roughness is 0.5-2.3 μm.
Preferably, graphene collector is set in the end of ceramic minute surface mill, collects graphene.
In existing scheme mechanical stripping method prepare graphene powder charge stripping efficiency it is low, production process dust pollution is serious,
The continuous production of graphene can not be realized, and the flour mill device due to using now does not all account for the footpath of reservation graphite
To size, therefore, the size of graphite prepared by mechanical stripping method is relatively small.This method realizes big size graphene production and connected
Continuous, cleaning, the technique effect of environmental protection, have promoted the industrialization continuous production of big size graphene.Further, a step in mill
Complete shearing to peel off, the scattered process of ultrasound homogenization, not only remain the deck structure of graphene, Er Qieke to greatest extent
Grapheme material is prepared with continuous-stable, does not destroy the surface integrity and Topological Symmetry of graphene, ensure that graphene produces
The quality of product.
By big size graphene performance prepared by the present invention compared with tradition machinery stripping prepares graphene, in graphene matter
Amount, yield etc. have the advantage that as shown in table 1.
Table 1：
| Performance indications | The present invention |
| 90% graphene film radial dimension | 150-180μm |
| 90% graphene thickness | 0.5-4nm |
| Charge stripping efficiency | 85%- |
The present invention proposes that a kind of scale crushes the method for preparing large stretch of footpath graphene, and compared with prior art, it is protruded
The characteristics of and excellent effect be：
1st, the present invention uses graphite powder that graphite powder is placed in mill for raw material, and the surface of fixed millstone and movable grinding disc is resistance to
The ceramic minute surface of mill property, by graphite powder under minute surface mill mutually opposing crisscross motion effect, peeling sheet layer by layer, effectively
The reduction of radial direction in graphite linings is prevented, by introducing ultrasonic dither in mill, graphite flake interlayer is torn, obtains
Large stretch of footpath graphene.
2nd, this programme is prepared in a manner of pure physics, destruction of the chemical reaction avoided to graphene-structured, not only
The deck structure of graphene is remained to greatest extent, and grapheme material can be prepared with continuous-stable, does not destroy graphene
Surface integrity and Topological Symmetry, further ensure the quality of graphene finished product.
3rd, scheme preparation technology disclosed by the invention is simple, and raw material sources are extensive, and cost is low, the forerunner's volume property prepared
Stable, easily storage transports.
4th, operation equipment of the present invention is simple, portable high, it is easy to accomplish scale industrial production.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By crystalline flake graphite, intercalation Sodium Carbonate Additive, water and Surfactant SDS according to mass ratio
For 1:2:5:0.1 ratio is configured to scattered suspension, and 10min is dispersed with stirring with 300rpm rotating speed, to the graphite raw material
It is uniformly dispersed in a solvent, obtains scattered suspension, stand 3 days, 100 KW ultrasonic power is used during standing, to graphite
It is ultrasonically treated, promotes intercalation additive well into interlayer；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 500rpm, keeps fixed
The relative direction motion on the surface of mill and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off, the ceramic minute surface
It is 2.3 μm to grind as aluminium oxide ceramics, minute surface roughness；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 500kW are introduced, supersonic frequency is
50kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so inside and outside common
Effect is lower to obtain more preferable charge stripping efficiency, and without reduction graphite radial dimension.
After carrying out performance test to the graphene prepared in embodiment 1, it is as shown in table 2 to obtain data.
Embodiment 2
（1）By expanded graphite, intercalation additive potassium carbonate, water and Surfactant SDS according to mass ratio
For 1:2.5:6:0.3 ratio is configured to scattered suspension, and 15min is dispersed with stirring with 350rpm rotating speed, former to the graphite
Material is uniformly dispersed in a solvent, obtains scattered suspension, stands 3.5 days, and 250KW ultrasonic power is used during standing, right
Graphite is ultrasonically treated, and promotes intercalation additive well into interlayer；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 650rpm, keeps fixed
The relative direction motion on the surface of mill and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off, the ceramic minute surface
It is 2.0 μm to grind as aluminium oxide ceramics, minute surface roughness；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 700kW are introduced, supersonic frequency is
70kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so inside and outside common
Effect is lower to obtain more preferable charge stripping efficiency, and without reduction graphite radial dimension.
After carrying out performance test to the graphene prepared in embodiment 2, it is as shown in table 2 to obtain data.
Embodiment 3
（1）By highly oriented graphite, intercalation additive saleratus, water and surfactant polyvinylpyrrolidone according to matter
Amount is than being 1:4:8:0.3 ratio is configured to scattered suspension, and 20min is dispersed with stirring with 400rpm rotating speed, to the graphite
Raw material is uniformly dispersed in a solvent, obtains scattered suspension, stands 4 days, and 300 KW ultrasonic power is used during standing, right
Graphite is ultrasonically treated, and promotes intercalation additive well into interlayer；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 800rpm, keeps fixed
The relative direction motion on the surface of mill and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off, the ceramic minute surface
It is 1.5 μm to grind as aluminium oxide ceramics, minute surface roughness；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 1100kW, supersonic frequency are introduced
For 120kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so inside and outside
More preferable charge stripping efficiency is obtained under collective effect, and without reduction graphite radial dimension.
After carrying out performance test to the graphene prepared in embodiment 3, it is as shown in table 2 to obtain data.
Embodiment 4
（1）By thermal cracking graphite, intercalation additive ammonium sulfate, water and surfactant sodium dodecyl base benzene sulfonic acid sodium salt according to matter
Amount is than being 1:4:8:0.4 ratio is configured to scattered suspension, and 20min is dispersed with stirring with 450rpm rotating speed, to the graphite
Raw material is uniformly dispersed in a solvent, obtains scattered suspension, stands 4.5 days, 400 KW ultrasonic power is used during standing,
Graphite is ultrasonically treated, promotes intercalation additive well into interlayer；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 850rpm, keeps fixed
The relative direction motion on the surface of mill and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off, the ceramic minute surface
It is 1.0 μm to grind as aluminium oxide ceramics, minute surface roughness；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 1250kW, supersonic frequency are introduced
For 150kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so inside and outside
More preferable charge stripping efficiency is obtained under collective effect, and without reduction graphite radial dimension.
After carrying out performance test to the graphene prepared in embodiment 4, it is as shown in table 2 to obtain data.
Embodiment 5
（1）By crystalline flake graphite, intercalation additive ammonium hydrogen sulfate, water and surfactant sodium dodecyl base benzene sulfonic acid sodium salt according to matter
Amount is than being 1:5:10:0.5 ratio is configured to scattered suspension, and 25min is dispersed with stirring with 500rpm rotating speed, to the graphite
Raw material is uniformly dispersed in a solvent, obtains scattered suspension, stands 5 days, and 500 KW ultrasonic power is used during standing, right
Graphite is ultrasonically treated, and promotes intercalation additive well into interlayer；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 1000rpm, is kept
The relative direction motion on the surface of fixed millstone and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off, the ceramic mirror
Face mill is aluminium oxide ceramics, and minute surface roughness is 0.5 μm；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 1500kW, supersonic frequency are introduced
For 170kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so inside and outside
More preferable charge stripping efficiency is obtained under collective effect, and without reduction graphite radial dimension.
After carrying out performance test to the graphene prepared in embodiment 5, it is as shown in table 2 to obtain data.
Table 2
| Performance indications | 90% graphene film radial dimension | 90% graphene thickness | Charge stripping efficiency |
| Embodiment one | 150-160μm | 0.5-2nm | 81.0% |
| Embodiment two | 160-180μm | 1.5-2nm | 83.4% |
| Embodiment three | 150-178μm | 0.8-1.6nm | 80.8% |
| Example IV | 155-175μm | 2.9-4.0nm | 79.1% |
| Embodiment five | 160-180μm | 2.5-3.7nm | 85.0% |
Claims (7)
1. a kind of scale crushes the method for preparing large stretch of footpath graphene, graphite powder is used as raw material, using fixed millstone and dynamic mill
The surface of disk is used as to mill pair for the ceramic minute surface of wearability, peels off graphite layer by layer, while ultrasonic system is introduced in mill, high
Frequency vibration, graphite flake interlayer tear, forms large stretch of footpath graphene, specific steps include：
（1）By graphite raw material, intercalation additive, water and surfactant according to mass ratio be 1:2-5:5-10:0.1-0.5 ratio
Example is configured to scattered suspension, and 10-25min is dispersed with stirring with 300-500rpm rotating speed, to the graphite raw material in a solvent
It is uniformly dispersed, obtains scattered suspension, stand 3-5 days, intercalator is entered graphite layers；
（2）Scattered suspension solution is added into ceramic minute surface mill apparatus, the rotary speed for controlling movable grinding disc is 500-1000rpm, is kept
The relative direction motion on the surface of fixed millstone and movable grinding disc, graphite is by the ceramic minute surface mill mixing and peels off；
（3）While ceramic minute surface grinds and peeled off, ultrasonic dither, ultrasonic power 500-1500kW, supersonic frequency are introduced
For 50-170kHz, under the dither effect of ultrasonic wave, tear graphite flake interlayer, interfloor distance increase, so including
More preferable charge stripping efficiency is obtained under outer collective effect, and without reduction graphite radial dimension.
2. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that described
Graphite raw material is crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite, at least one of graphite oxide, the stone
Black raw material particle size is less than or equal to 1 millimeter.
3. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that described
Intercalation additive is sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbon
At least one of sour hydrogen ammonium, ammonium phosphate.
4. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that described
Surfactant be lauryl sodium sulfate, neopelex, polyvinylpyrrolidone, in 1- pyridine acids at least
It is a kind of.
5. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that described
100-500 KW ultrasonic power is used during standing, graphite is ultrasonically treated, promotes intercalation additive well into interlayer.
6. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that described
Ceramic minute surface is aluminium oxide ceramics, and minute surface roughness is 0.5-2.3 μm.
7. a kind of scale according to claim 1 crushes the method for preparing large stretch of footpath graphene, it is characterised in that is making pottery
The end of porcelain minute surface mill sets graphene collector, collects graphene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104609413A (en) * | 2015-02-11 | 2015-05-13 | 合肥微晶材料科技有限公司 | Machine-like stripping device for ton-scale production of graphene and production method of machine-like stripping device |
| CN105905888A (en) * | 2016-05-06 | 2016-08-31 | 成都新柯力化工科技有限公司 | Graphene composite microchips stripped by using turbine sander and preparation method for graphene composite microchips |
| CN106044761A (en) * | 2016-08-01 | 2016-10-26 | 邓仟菀 | High-shearing-force wear-resistant rubber grinding pan for preparing graphene and preparation method and application of high-shearing-force wear-resistant rubber grinding pan |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401971A (en) * | 2014-10-23 | 2015-03-11 | 江阴碳谷科技有限公司 | Graphene grinding and stripping device, graphene production system and production method |
| CN104609413A (en) * | 2015-02-11 | 2015-05-13 | 合肥微晶材料科技有限公司 | Machine-like stripping device for ton-scale production of graphene and production method of machine-like stripping device |
| CN105905888A (en) * | 2016-05-06 | 2016-08-31 | 成都新柯力化工科技有限公司 | Graphene composite microchips stripped by using turbine sander and preparation method for graphene composite microchips |
| CN106044761A (en) * | 2016-08-01 | 2016-10-26 | 邓仟菀 | High-shearing-force wear-resistant rubber grinding pan for preparing graphene and preparation method and application of high-shearing-force wear-resistant rubber grinding pan |
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