CN108622888B - A kind of method, apparatus of high-volume scale continuous production graphene and graphene prepared therefrom - Google Patents
A kind of method, apparatus of high-volume scale continuous production graphene and graphene prepared therefrom Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B2204/00—Structure or properties of graphene
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Abstract
The present invention provide a kind of high-volume scale continuous production graphene method, apparatus and graphene prepared therefrom.The described method comprises the following steps: a) sufficiently wetting: graphite and solvent are mixed, and are stirred at low speed processing or/and low velocity shear processing at least once, obtain graphite dispersing solution；B) graphite dispersing solution in step a) preliminary removing: is subjected to sanded treatment at least once, the graphene dispersing solution tentatively removed；C) secondary removing: carrying out high-pressure homogeneous processing or/and ultrasonic treatment at least once for the graphene dispersing solution tentatively removed in step b), obtains single layer or few layer graphene dispersing solution.The method can further obtain the graphene of high quality under the premise of environmental protection, reduce technology difficulty and cost；Device provided by the invention can solve current graphene and be difficult to scale quantity-produced problem.The graphene being prepared is with high purity, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few.
Description
Technical field
The invention belongs to the preparation technical fields of graphene, and in particular to a kind of high-volume scale continuous production graphene
Method, apparatus and by this method prepare graphene.
Background technique
2004, two professors of Univ Manchester UK successfully prepared graphene, and therefore obtained in 2010
The Nobel Prize.Graphene is a kind of two-dimensional material of only one carbon atom thickness, has excellent physical and chemical performance.Example
Such as, graphene specific surface area is 2630m2/ g, thermal coefficient are up to 5300W/mK, its electron mobility is more than under room temperature
15000cm2/ Vs, resistivity only have 10-8Ω cm, intensity are up to 1.01TPa.The superior function of graphene makes it have huge
Big application prospect.
Currently, the case where domestic and international market graphene production capacity is low, unstable quality is generally existing, people need to find one kind
Quickly, method efficiently, inexpensively prepares graphene.Currently, the preparation method of graphene is broadly divided into two kinds: chemical method and physics
Method.Chemical method mainly includes oxidation-reduction method, epitaxial growth method and chemical vapour deposition technique；Physical method is also referred to as mechanical stripping
Method mainly includes ultrasonic method and ball-milling method.The occupation rate of market that oxidation-reduction method prepares graphene is higher, but it is to graphene
Performance influence is very big, exists simultaneously serious environmental issue.Epitaxial growth method and chemical vapour deposition technique working condition harshness, work
Skill is complicated, the height that consumes energy, low output, at high cost, unsuitable batch production.Ultrasonic method is severely limited by material state and concentration, produces
Measure it is low, be used alone peeling effect it is general.Ball-milling method peeling effect is poor, it is difficult to obtain the less graphene of the number of plies, mostly 10
Layer or more graphite flake.Also there is the method for preparing graphene by high pressure homogenizer to occur in the recent period, still, peeling effect one
As, and it is similarly subjected to the influence of material state and concentration, yield is lower, and equipment damage is serious, does not have practical application value.With
Upper method is difficult to achieve the purpose that environmental protection, batch quickly, efficiently, inexpensive prepare high-quality graphene.
Summary of the invention
To improve the above problem, the present invention provide a kind of high-volume scale continuous production graphene method, apparatus and
Graphene prepared therefrom.Method provided by the invention can further obtain the graphene of high quality under the premise of environmental protection,
Technology difficulty is reduced, yield is improved, reduces cost, is a kind of high efficiency, high yield, easy to operate, inexpensive graphene production
Mode.Device production easy to automate provided by the invention can solve current high-quality graphene and be difficult to scale company
The problem of continuous production.The graphene purity is high of method preparation of the invention, thickness is thin, large specific surface area, resistivity is low, metal is miscellaneous
Matter content is few and piece diameter is controllable, the application suitable for the various fields such as electronics, energy storage, environment, biologic medical, composite material.
The first aspect of the present invention provides a kind of method of continuous production graphene, the described method comprises the following steps:
A) sufficiently wetting: graphite and solvent are mixed, stirred at low speed at processing or/and low velocity shear at least once
Reason, obtains graphite dispersing solution；
B) preliminary removing: the graphite dispersing solution in step a) is subjected to sanded treatment at least once, is tentatively removed
Graphene dispersing solution；
C) graphene dispersing solution tentatively removed in step b) secondary removing: is subjected to high-pressure homogeneous processing at least once
Or/and ultrasonic treatment, obtain single layer or few layer graphene dispersing solution.
The high-volume of graphene, scale ground continuous production may be implemented in method of the invention.
The second aspect of the present invention provides a kind of graphene prepared by the above method, and the number of plies of the graphene is
5 layers or less；D50It is 8-12 μm, specific surface area 600-800m2/g；The resistance of graphene≤10 Ω cm；Iron tramp content≤
10ppm。
Graphene of the invention is with high purity, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few and piece diameter
Controllably, the application suitable for the various fields such as electronics, energy storage, environment, biologic medical, composite material.
The third aspect of the present invention provides a kind of device of continuous production graphene, and described device includes the first dispersion dress
Set, sanding apparatus, high-pressure homogeneous device, in parallel with the high-pressure homogeneous device first surmount pipeline, ultrasonic processing apparatus, with
The second of the ultrasonic processing apparatus parallel connection surmounts pipeline and device for storing liquid；
Wherein, the outlet end of first dispersal device respectively with the high-pressure homogeneous device, the sanding apparatus and storage
The input end of liquid device is connected；The outlet end of the sanding apparatus respectively with the input end of first dispersal device and the storage
The input end of liquid device is connected；
The outlet end of the high-pressure homogeneous device is connected with the input end of the ultrasonic processing apparatus；The ultrasonic treatment dress
The outlet end set is connected with the input end of first dispersal device, or is connected with the input end of the device for storing liquid.
The high-volume of graphene, scale ground continuous production may be implemented in the device of the invention.
The fourth aspect of the present invention is to provide a kind of method of continuous production graphene, uses company described in the third aspect
The device of continuous production graphene is implemented.
Technical solution of the present invention has the following advantages and beneficial effects: compared with prior art
1. method and apparatus provided by the invention is mainly for industrialized production, to use physical method to shell graphite
From not causing to damage to the structure of graphene itself, ensure that the excellent physical and chemical performance of graphene.Be not related to intercalator and
The use of dispersing agent, Complicated Flow needed for reducing intercalator and dispersing agent removal, reduce may remaining intercalator and
Influence of the dispersing agent to product quality, while production cost is reduced, and the graphene of high-volume high quality can be obtained.
2. the present invention carries out scale continuous production graphene for high-pressure homogeneous device as one of core equipment for the first time, by
It is very high, the very fast equipment of a temperature rise in high pressure homogenizer, and lacks effective cooling measure in itself, is repeated 1 times temperature
It rises and can reach 30 DEG C.And high pressure homogenizer is more enervated, and it is perishable, it is therefore, equal when reducing access times and improving charging
Even property is extremely important, so high pressure homogenizer is not used really in the industrial production line of graphene at present.In the application, use
The cycle-index of high pressure homogenizer can be 1-4 times, hence it is evident that reduce number of repetition, extend the service life of equipment, product
Cost, producing line maintenance cost be greatly lowered.
3. due to it is high-pressure homogeneous or it is ultrasonic limited by equipment itself, directly processing is merely through the monodispersed graphite of letter
When, the concentration of graphite dispersing solution is lower, and production efficiency is low, and equipment attrition is serious, and the present invention improves this, is carrying out high pressure
(stir at low speed and/or low velocity shear) and preliminary removing (circulation sand milling) etc. are first sufficiently soaked before homogeneous or ultrasonic treatment
Step process, can make that material is more stable, piece diameter is more uniform, and not destroy the expansion structure of raw material, can significantly improve
The concentration of high-pressure homogeneous or ultrasonic product to be processed significantly improves production efficiency, reduces production cost.
4. the present invention passes through sufficiently wetting (stir at low speed and/or low velocity shear), preliminary removing (circulation is sanded), secondary stripping
From (high-pressure homogeneous and/or ultrasonic) and etc. be sequentially reduced graphite and graphene film diameter, progressive carry out graphite by easy stages
The removing of alkene can significantly promote the effect of graphene removing, reduce the defect of graphene, obtain high quality, high-ratio surface
The graphene of long-pending, high conductivity and high yield.
5. sanding apparatus, high-pressure homogeneous device and ultrasonic treatment dress can be made by the way that the second dispersal device is arranged in the present invention
Set all can be two cylinders circulation form, make all materials can by processing, improve single cylinder circulation caused by material unevenness
Even problem.
6. high-pressure homogeneous device and ultrasonic processing apparatus are equipped with and in parallel therewith surmount pipeline, that is to say, that Ke Yidan
The further removing of raw material is solely carried out by the two by high-pressure homogeneous device or separately through ultrasonic processing apparatus or simultaneously；Or
When the two one of them when something goes wrong, another is alternative, when raw material need simultaneously use high-pressure homogeneous device and surpass
When acoustic processing device, can also easily it realize.
7. device provided by the invention also further has cooling device, this is for there are at high-pressure homogeneous device and ultrasound
Reason device producing line be it is vital because the two temperature rise is exceedingly fast, increase with number of repetition, temperature rise is higher, if more than 100
DEG C, when without being equipped with cooling device, the low boiling point solvents such as water, ethyl alcohol are not available at all, the high boiling solvents such as NMP and DMF
It will form a large amount of dangerous vapors, cause serious harm to environment, to human body, while being more than that equipment high temperature limits, to equipment
Cause irreversible damage.The present invention is well understood that this point, individually increases cooling device in a device, so as to protect
The normal continuous production of card device.
8. present invention process process simply easily manipulates, at low cost, no pollution to the environment, with being suitable for high-volume scale even
The graphene of continuous preparation high quality.Device flexible design, process route are simple in the present invention, hermetically sealed design, and can basis
Practical situations increase automatic control system, realize automated production, save human cost, are also manually operable, and increase spirit
Activity realizes high-quality graphene large-scale production.
Detailed description of the invention
Fig. 1 is graphene preparation technology flow chart of the present invention；
Fig. 2 is the stereoscan photograph that the embodiment of the present invention 1 obtains graphene；
Fig. 3 is the low power transmission electron microscope photo that the embodiment of the present invention 1 obtains graphene；
Fig. 4 is the high power transmission electron microscope photo that the embodiment of the present invention 1 obtains graphene.
Fig. 5 is the process units schematic diagram of scale continuous production graphene powder of the present invention；
Wherein, powder charging device 1, liquid feed device 2, dispersal device 3, sanding apparatus 4, high-pressure homogeneous device 5, super
Acoustic processing device 6, cooling device 7, filter device 8, device for storing liquid 9, centrifugal spray drying device 10.
Specific embodiment
As previously mentioned, the first aspect of the present invention provides a kind of method of continuous production graphene, the method is able to achieve
The high-volume scale of graphene ground continuous production, the described method comprises the following steps:
A) sufficiently wetting: graphite and solvent are mixed, stirred at low speed at processing or/and low velocity shear at least once
Reason, obtains graphite dispersing solution；Wherein, stir at low speed at least once and/or low velocity shear by way of make graphite in solvent
In sufficiently wetting and tentatively reduction graphite piece diameter；
B) preliminary removing: the graphite dispersing solution in step a) is subjected to sanded treatment at least once, is tentatively removed
Graphene dispersing solution；Wherein, the piece diameter of graphite is further decreased by the processing such as being sanded at least once；
C) graphene dispersing solution tentatively removed in step b) secondary removing: is subjected to high-pressure homogeneous processing at least once
Or/and ultrasonic treatment, obtain single layer or few layer graphene dispersing solution.
In a specific embodiment of the invention, the method also includes following steps:
D) it post-processes: the single layer in step c) or less layer graphene dispersing solution is passed through at filtering, centrifugation, washing and drying
Reason obtains single layer or few layer graphene.
In a specific embodiment of the invention, processing or/and low velocity shear processing are stirred at low speed in step a)
Number is greater than 1.
In a specific embodiment of the invention, in step b), the number of sanded treatment is greater than 1.
Preferably, can with sanded treatment with stir at low speed processing and/or low velocity shear processing recycled after walked again
It is rapid c), i.e., at least circulation primary stir at low speed processing and/or low velocity shear processing, sanded treatment, stir at low speed processing and/or it is low
Step c) is carried out after fast shear treatment again.Circulation in this way, the material that sand milling can be made to come out further uniformly disperse,
Give material to carry out effective temperature-reducing simultaneously, improve the effect of sanded treatment, make before secondary removing raw graphite obtain it is uniform,
Adequately preliminary removing increases the consistency of preliminary removing product, lays the foundation to go on smoothly step c), can also reduce by
The strong temperature rise of high-pressure homogeneous device and ultrasonic processing apparatus caused by charging is uneven, guarantees drop while the quality of product
The probability of low equipment damage extends the service life of equipment.
In a specific embodiment of the invention, in step c), the number of high-pressure homogeneous processing or/and ultrasonic treatment is big
In 1, preferably more than 1 to less than or equal to 4 times.
Preferably, can high-pressure homogeneous processing or/and ultrasonic treatment with stir at low speed processing and/or low velocity shear handle into
Row circulation, i.e., at least circulation primary stir at low speed processing and/or low velocity shear processing, it is high-pressure homogeneous processing or/and ultrasonic treatment,
Single layer or few layer graphene dispersing solution are obtained after stirring at low speed processing and/or low velocity shear processing.Circulation in this way, can be with
Disperse the high-pressure homogeneous or ultrasonic material come out further uniformly, while carrying out effective temperature-reducing to material, improves high pressure
The effect of homogeneous or ultrasonic treatment obtains more uniform consistent product, increases lot stability.
In a specific embodiment of the invention, in step a), the graphite is expanded graphite.
Preferably, the expanded graphite is to be prepared by the methods of high-temperature expansion or microwave expansion, and expansion multiplying power is
150 or more, such as expansion multiplying power is 150-400.In the present invention, the reason of selecting such graphite, is that raw material can be made to shell
From the abundant wetting and intercalation for obtaining solvent before, enable subsequent first removing and secondary removing more sufficiently, to obtain
Obtain the graphene product of the number of plies≤5.
In a specific embodiment of the invention, in step a), the solvent is NMP, acetone, ethyl alcohol, DMF, isopropyl
The one or more of alcohol, chloroform, water.
In a specific embodiment of the invention, in step a), the graphite is in the mixture of graphite and solvent
Concentration is 0.1~10wt%.If concentration is lower than 0.1wt%, yield is too low, higher cost, does not have actual production meaning；If
Concentration is higher than 10wt%, and due to the powerful absorbency of expanded graphite, expanded graphite can not obtain sufficient wetting, subsequent step
It cannot go on smoothly, obtained product is extremely uneven, and there may be partially absolutely not remove or cannot sufficiently shell in product
From product.
In a specific embodiment of the invention, in step a), the stirring rate stirred at low speed is 10-41r/
min；The shear rate of the low velocity shear is 100-600r/min, and rate is adjustable.Select such rate, it is ensured that graphite
Intercalation is sufficiently soaked by solvent and does not destroy the expansion structure of graphite.
In a specific embodiment of the invention, in step a), the time sufficiently soaked is 0.2~3h, preferably
For 0.5~2h.
In a specific embodiment of the invention, in step b), the time tentatively removed is 0.5~10h, preferably
For 2~8h.
In a specific embodiment of the invention, in step c), the high-pressure homogeneous pressure is 30~90MPa, excellent
It is selected as 50~80MPa.If pressure is lower than 30MPa, material can not obtain sufficient removing, and the number of plies of products obtained therefrom is higher, one
As >=10 layers；If pressure is higher than 90MPa, for the existing big-flow high-pressure homogenizer of existing market, it is excessively high to will cause temperature rise,
Pressure instability generates biggish damage to high pressure homogenizer, not can guarantee the normal use of equipment.
In a specific embodiment of the invention, in step c), power >=1000W of the ultrasound, it is preferable that power
>=2000W, for example, power is 3000-6000W；Frequency >=20kHz, it is preferable that frequency >=40kHz, for example, frequency is 50-
80kHz.If power is less than 1000W, frequency is less than 20kHz, is then difficult to handle the material of high concentration.
In a specific embodiment of the invention, in step c), the high-pressure homogeneous discharging flow is 500-
2000L/h.As it can be seen that by means of the invention it is also possible to high-pressure homogeneous discharging flow is significantly increased, to improve production
Amount, reduces cost.
In a specific embodiment of the invention, in step c), the high-pressure homogeneous processing or/and ultrasonic treatment when
Between be 1h~4h.
In a specific embodiment of the invention, in step d), the method for the drying is spray drying, vacuum is dry
At least one of drying modes such as dry, freeze-drying.
The second aspect of the present invention provides a kind of graphene prepared by the above method, and the number of plies of the graphene is
5 layers or less；D50It is 8-12 μm, specific surface area 600-800m2/g；The resistance of graphene≤10 Ω cm；Iron tramp content≤
10ppm。
Graphene of the invention is with high purity, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few and piece diameter
Controllably, the application suitable for the various fields such as electronics, energy storage, environment, biologic medical, composite material.
The third aspect of the present invention provides a kind of device of continuous production graphene, and described device includes the first dispersion dress
Set, sanding apparatus, high-pressure homogeneous device, in parallel with the high-pressure homogeneous device first surmount pipeline, ultrasonic processing apparatus, with
The second of the ultrasonic processing apparatus parallel connection surmounts pipeline and device for storing liquid；
Wherein, the outlet end of first dispersal device respectively with the high-pressure homogeneous device, the sanding apparatus and storage
The input end of liquid device is connected；The outlet end of the sanding apparatus respectively with the input end of first dispersal device and the storage
The input end of liquid device is connected；
The outlet end of the high-pressure homogeneous device is connected with the input end of the ultrasonic processing apparatus；The ultrasonic treatment dress
The outlet end set is connected with the input end of first dispersal device, or is connected with the input end of the device for storing liquid.
In a specific embodiment of the invention, described device further includes cooling device, the ultrasonic processing apparatus
Outlet end is connected with the input end of the outlet end of the sanding apparatus and the cooling device respectively.
In a specific embodiment of the invention, described device further includes filter device, the outlet of the cooling device
End is connected with the input end of the filter device.
In a specific embodiment of the invention, described device further includes the second dispersal device, the filter device
Outlet end is connected with the input end of the input end of first dispersal device and second dispersal device respectively；Described second point
The outlet end in bulk set is connected with the input end of the input end of the high-pressure homogeneous device and sanding apparatus respectively.
In a specific embodiment of the invention, described device further includes centrifugal spray drying device, the liquid storage dress
The outlet end set is connected with the centrifugal spray drying device.The present invention is using centrifugal spray drying device to treated object
Material is spray-dried, is granulated, and subsequent product packaging and transport are conducive to.
In a specific embodiment of the invention, described device further includes powder charging device and liquid feed device,
The outlet end of the powder charging device and liquid feed device is connected with the input end of first dispersal device respectively.
In a specific embodiment of the invention, setting in the tank body of first dispersal device and the second dispersal device
Agitating paddle and/or dispersion impeller.Agitating paddle therein has the function of stirring and dispersed material, and agitating paddle can be with frequency conversion tune
Speed.Dispersion impeller therein can be sheared (such as carrying out low velocity shear) to material.
Preferably, the tank body is double-layer structure, and outer layer is cooling layer, can cool down the material in tank body.
Preferably, the tank interior is equipped with and scrapes wall device.The wall device of scraping can will be bonded in inner tank wall
Slurry scrapes off.
It will be appreciated by those skilled in the art that the material of the tank body and agitating paddle etc. and the material of material contact can basis
Actual conditions are selected or are carried out coating design.
In a specific embodiment of the invention, the powder charging device uses Seal Design.The Seal Design
For a kind of Environmental Design, it can prevent solvent from evaporateing into air；And it can guarantee due to waving solvent by high temperature
Hair, caused by technique it is unstable.
It will be appreciated by those skilled in the art that the size of the powder charging device can be according to raw material packaged form, institute
State that tank body and space are too small to be designed.
In a specific embodiment of the invention, the high-pressure homogeneous device includes pump and high pressure homogenizer.
Preferably, the pump can select centrifugal pump, screw pump or other pump housings according to the concentration or viscosity of material.
Preferably, the rated pressure of the high pressure homogenizer is 30~90MPa.
In a specific embodiment of the invention, the ultrasonic processing apparatus can be two or more processor for ultrasonic wave
Serial or parallel connection.
In a specific embodiment of the invention, the type of cooling of the cooling device includes external cooler, pipeline
One or more of types of cooling such as cooling jacket.
In a specific embodiment of the invention, described device further includes weighing device, and the weighing device setting exists
It is respectively set before the tank body or before the liquid feed device and powder charging device.
In a specific embodiment of the invention, the single producing line graphene yield of described device is up to 600 tons/year.
It will be appreciated by those skilled in the art that the device of the continuous production graphene can also include matching with described device
The devices such as cooling-water machine, air compressor machine, connecting pipe and the valve of set.The connecting tube of the cooling-water machine, air compressor machine, each device of connection
The corollary apparatus such as road and valve can carry out type selecting according to the demand of practical producing line.
The fourth aspect of the present invention is to provide a kind of method of continuous production graphene, and the method uses third aspect institute
The device for the continuous production graphene stated is implemented.
In a specific embodiment of the invention, the method includes the continuous production graphenes described in first aspect
Step in method.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Embodiment 1
Step 1: by way of stirring at low speed, expanded graphite sufficiently being soaked in a solvent and subtracted small flake diameter, expands stone
Ink is prepared by high-temperature expansion method, expansion multiplying power 150, solvent NMP, mixture of the expanded graphite in expanded graphite and solvent
In concentration be 0.1wt%, mixing time 0.2h obtains expanded graphite dispersion liquid.
Step 2: the expanded graphite dispersion liquid sufficiently soaked in step 1 is further subtracted piece diameter by way of sand milling
It is small, obtain the uniform and stable rubble ink alkene dispersion liquid tentatively removed.The sand milling time is 0.5h.
Step 3: the stable rubble ink alkene dispersion liquid tentatively removed in step 2 being subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersing solution.High-pressure homogeneous pressure is 30MPa, time 1h.
Step 4: the single layer in step 3 or less layer graphene dispersing solution being passed through into filtering, centrifugation, carrying out washing treatment and sprayed
Mist is dry, can be obtained single layer or few layer graphene.
Embodiment 2
Step 1: by way of low velocity shear, expanded graphite sufficiently being soaked in a solvent and subtracted small flake diameter, expands stone
Ink is prepared by high-temperature expansion method, and expansion multiplying power 250, solvent is acetone, mixing of the expanded graphite in expanded graphite and solvent
Concentration in object is 2.5wt%, and mixing time 1h obtains expanded graphite dispersion liquid.
Step 2: the expanded graphite dispersion liquid sufficiently soaked in step 1 is further subtracted piece diameter by way of sand milling
It is small, obtain the uniform and stable rubble ink alkene dispersion liquid tentatively removed.The sand milling time is 1h.
Step 3: the stable rubble ink alkene dispersion liquid tentatively removed in step 2 being subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersing solution.High-pressure homogeneous pressure is 65MPa, time 2h.
Step 4: the single layer in step 3 or less layer graphene dispersing solution being passed through into filtering, centrifugation, carrying out washing treatment and carried out cold
It is lyophilized dry, can be obtained single layer or few layer graphene.
Embodiment 3
Step 1: by way of stirring at low speed and combining low velocity shear, expanded graphite sufficiently being soaked and reduced in a solvent
Piece diameter, expanded graphite are the preparation of microwave expansion method, and expansion multiplying power 300, solvent is ethyl alcohol, expanded graphite expanded graphite with
Concentration in the mixture of solvent is 5wt%, and mixing time 2h obtains expanded graphite dispersion liquid.
Step 2: the expanded graphite dispersion liquid sufficiently soaked in step 1 is further subtracted piece diameter by way of sand milling
It is small, obtain the uniform and stable rubble ink alkene dispersion liquid tentatively removed.The sand milling time is 3h.
Step 3: the stable rubble ink alkene dispersion liquid tentatively removed in step 2 being ultrasonically treated, single layer is obtained
Or few layer graphene dispersing solution.Time 3h.
Step 4: the single layer in step 3 or less layer graphene dispersing solution being passed through into filtering, centrifugation, carrying out washing treatment and carried out very
Sky is dry, can be obtained single layer or few layer graphene.
Embodiment 4
Step 1: by way of stirring at low speed, expanded graphite sufficiently being soaked in a solvent and subtracted small flake diameter, expands stone
Ink is prepared by microwave expansion method, and expansion multiplying power 400, solvent is water, mixture of the expanded graphite in expanded graphite and solvent
In concentration be 3wt%, mixing time 3h obtains expanded graphite dispersion liquid.
Step 2: the expanded graphite dispersion liquid sufficiently soaked in step 1 is further subtracted piece diameter by way of sand milling
It is small, obtain the uniform and stable rubble ink alkene dispersion liquid tentatively removed.The sand milling time is 6h.
Step 3: the stable rubble ink alkene dispersion liquid tentatively removed in step 2 being ultrasonically treated, single layer is obtained
Or few layer graphene dispersing solution.Time 3h.
Step 4: the single layer in step 3 or less layer graphene dispersing solution being passed through into filtering, centrifugation, carrying out washing treatment and sprayed
Mist is dry, can be obtained single layer or few layer graphene film.
Embodiment 5
Step 1: by way of low velocity shear, expanded graphite sufficiently being soaked in a solvent and subtracted small flake diameter, expands stone
Ink is prepared by microwave expansion method, expansion multiplying power 200, solvent DMF, mixture of the expanded graphite in expanded graphite and solvent
In concentration be 10wt%, mixing time 3h obtains expanded graphite dispersion liquid.
Step 2: the expanded graphite dispersion liquid sufficiently soaked in step 1 is further subtracted piece diameter by way of sand milling
It is small, obtain the uniform and stable rubble ink alkene dispersion liquid tentatively removed.The sand milling time is 10h.
Step 3: the stable rubble ink alkene dispersion liquid tentatively removed in step 2 being subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersing solution, high-pressure homogeneous pressure are 90MPa, time 4h.
Step 4: the single layer in step 3 or less layer graphene dispersing solution being passed through into filtering, centrifugation, carrying out washing treatment and carried out cold
It is lyophilized dry, can be obtained single layer or few layer graphene.
Embodiment 6
As shown in figure 5, a kind of device of continuous production graphene, described device include powder charging device and liquid feed
Device, the first dispersal device, sanding apparatus, high-pressure homogeneous device, in parallel with the high-pressure homogeneous device first surmount pipeline,
Ultrasonic processing apparatus, in parallel with the ultrasonic processing apparatus second surmount pipeline, cooling device, filter device, the second dispersion
Device, device for storing liquid and centrifugal spray drying device；
Wherein, the outlet end of the powder charging device and liquid feed device respectively with first dispersal device into
Mouth end is connected；
Wherein, the outlet end of first dispersal device respectively with the high-pressure homogeneous device and the sanding apparatus into
Mouth end is connected；The outlet end of the sanding apparatus is connected with the input end of the cooling device；
The outlet end of the high-pressure homogeneous device is connected with the input end of the ultrasonic processing apparatus；The ultrasonic treatment dress
The outlet end set is connected with the input end of the cooling device；
Wherein, the outlet end of cooling device is connected with the input end of the filter device；
Wherein, the outlet end of the filter device disperses with the input end of first dispersal device, described second respectively
The input end of device is connected with the input end of device for storing liquid；The outlet end of second dispersal device respectively with it is described high-pressure homogeneous
The input end of device is connected with the input end of sanding apparatus；
Wherein, the outlet end of the device for storing liquid is connected with the centrifugal spray drying device.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (23)
1. a kind of method of continuous production graphene, which is characterized in that the described method comprises the following steps:
A) sufficiently wetting: graphite and solvent are mixed, and are stirred at low speed processing or/and low velocity shear processing at least once, obtained
To graphite dispersing solution；
B) graphite dispersing solution in step a) preliminary removing: is subjected to sanded treatment at least once, the graphite tentatively removed
Alkene dispersion liquid；
C) secondary removing: by the graphene dispersing solution tentatively removed in step b) carry out at least once it is high-pressure homogeneous processing or/and
Ultrasonic treatment obtains single layer or few layer graphene dispersing solution；
Wherein, sanded treatment and stir at low speed processing and/or low velocity shear processing recycled after carry out step c) again, i.e., at least
Circulation primary stirs at low speed processing and/or low velocity shear processing, sanded treatment, stirs at low speed processing and/or low velocity shear processing
Carry out step c) again afterwards；
In step a), concentration of the graphite in the mixture of graphite and solvent is 0.1~10wt%；
In step a), the stirring rate stirred at low speed is 10-41r/min；The shear rate of the low velocity shear is 100-
600r/min；The time sufficiently soaked is 0.2~3h；
In step c), the high-pressure homogeneous pressure is 30~90MPa；
In step c), power >=1000W of the ultrasound；Frequency >=20kHz.
2. the method according to claim 1, wherein the method also includes following steps:
D) it post-processes: the single layer in step c) or less layer graphene dispersing solution is passed through into filtering, centrifugation, washing and drying process,
Obtain single layer or few layer graphene.
3. the method according to claim 1, wherein stirring at low speed processing or/and low velocity shear in step a)
Number of processing is greater than 1；In step b), the number of sanded treatment is greater than 1；In step c), at high-pressure homogeneous processing or/and ultrasound
The number of reason is greater than 1.
4. according to the method described in claim 3, it is characterized in that, the number of high-pressure homogeneous processing or/and ultrasonic treatment is greater than 1
To less than or equal to 4 times.
5. method according to claim 1-4, which is characterized in that in step a), the graphite is expanded graphite.
6. method according to claim 1-4, which is characterized in that in step b), the time tentatively removed
For 0.5~10h.
7. method according to claim 1-4, which is characterized in that in step c), the power of the ultrasound >=
2000W, frequency >=40kHz.
8. the method according to the description of claim 7 is characterized in that the power of the ultrasound is 3000-6000W in step c)；
Frequency is 50-80kHz.
9. method according to claim 1-4, which is characterized in that in step c), the high-pressure homogeneous discharging
Flow is 500-2000L/h.
10. method according to claim 1-4, which is characterized in that in step c), the high-pressure homogeneous processing
Or/and the time of ultrasonic treatment is 1h~4h.
11. a kind of graphene being prepared by any one of claim 1-10 the method, which is characterized in that the graphene
The number of plies be 5 layers or less；D50It is 8-12 μm, specific surface area 600-800m2/g；The resistance of graphene≤10 Ω cm；Iron is miscellaneous
Matter content≤10ppm.
12. a kind of device of continuous production graphene, which is characterized in that described device include the first dispersal device, sanding apparatus,
High-pressure homogeneous device, in parallel with the high-pressure homogeneous device first surmount pipeline, ultrasonic processing apparatus and the ultrasonic treatment
The second of device parallel connection surmounts pipeline and device for storing liquid；
Wherein, the outlet end of first dispersal device is filled with the high-pressure homogeneous device, the sanding apparatus and liquid storage respectively
The input end set is connected；The outlet end of the sanding apparatus is filled with the input end of first dispersal device and the liquid storage respectively
The input end set is connected；
The outlet end of the high-pressure homogeneous device is connected with the input end of the ultrasonic processing apparatus；The ultrasonic processing apparatus
Outlet end is connected with the input end of first dispersal device, or is connected with the input end of the device for storing liquid.
13. device according to claim 12, which is characterized in that described device further includes cooling device, at the ultrasound
The outlet end of reason device is connected with the input end of the outlet end of the sanding apparatus and the cooling device respectively.
14. device according to claim 13, wherein described device further includes filter device, and the cooling device goes out
Mouth end is connected with the input end of the filter device.
15. device according to claim 14, which is characterized in that described device further includes the second dispersal device, the mistake
The outlet end of filter device is connected with the input end of the input end of first dispersal device and second dispersal device respectively；Institute
The outlet end for stating the second dispersal device is connected with the input end of the input end of the high-pressure homogeneous device and sanding apparatus respectively.
16. the described in any item devices of 2-15 according to claim 1, which is characterized in that described device further includes centrifugal spray dryer
Dry device, the outlet end of the device for storing liquid are connected with the centrifugal spray drying device.
17. the described in any item devices of 2-15 according to claim 1, which is characterized in that described device further includes that powder feeds intake dress
Set with liquid feed device, the outlet end of the powder charging device and liquid feed device respectively with first dispersal device
Input end be connected.
18. device according to claim 17, which is characterized in that the powder charging device uses Seal Design.
19. device according to claim 15, which is characterized in that the tank of first dispersal device and the second dispersal device
Setting agitating paddle and/or dispersion impeller in vivo.
20. device according to claim 19, which is characterized in that the tank of first dispersal device and the second dispersal device
Body is double-layer structure, and outer layer is cooling layer.
21. device according to claim 20, which is characterized in that the tank of first dispersal device and the second dispersal device
Internal portion, which is equipped with, scrapes wall device.
22. the described in any item devices of 2-15 according to claim 1, which is characterized in that the ultrasonic processing apparatus be two with
Upper processor for ultrasonic wave serial or parallel connection.
23. a kind of method of continuous production graphene, which is characterized in that the method is using any one of claim 12-22 institute
The device stated is implemented, and the method includes the steps in the method for the described in any item continuous production graphenes of claim 1-10
Suddenly.
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| CN105217612A (en) * | 2015-09-29 | 2016-01-06 | 北京航空航天大学 | A kind of ultrasonic assistant sand mill peels off the method preparing Graphene and the device peeling off Graphene processed |
| CN106185895A (en) * | 2016-07-06 | 2016-12-07 | 青岛华高墨烯科技股份有限公司 | A kind of graphene dispersion liquid and preparation method thereof |
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| CN107585757A (en) * | 2017-08-25 | 2018-01-16 | 广州臻晨新材料科技有限公司 | A kind of graphene, nano graphite flakes and preparation method |
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| CN105217612A (en) * | 2015-09-29 | 2016-01-06 | 北京航空航天大学 | A kind of ultrasonic assistant sand mill peels off the method preparing Graphene and the device peeling off Graphene processed |
| CN106185895A (en) * | 2016-07-06 | 2016-12-07 | 青岛华高墨烯科技股份有限公司 | A kind of graphene dispersion liquid and preparation method thereof |
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