CN108622888A - 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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- C01B2204/00—Structure or properties of graphene
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Abstract
The present invention provides a kind of method, apparatus of high-volume scale continuous production graphene and graphene prepared therefrom.It the described method comprises the following steps：A) fully wetting：Graphite and solvent are mixed, stirring at low speed processing at least once or/and low velocity shear processing is carried out, obtains graphite dispersing solution；B) preliminary stripping：Graphite dispersing solution in step a) is subjected to sanded treatment at least once, the graphene dispersing solution tentatively removed；C) secondary stripping：The graphene dispersing solution tentatively removed in step b) is subjected to high-pressure homogeneous processing or/and supersound process at least once, obtains single layer or few layer graphene dispersion liquid.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 purity that is prepared is high, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few.
Description
Technical field
The invention belongs to the preparing 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 technology
2004, two professors of Univ Manchester UK successfully prepared graphene, and are therefore obtained in 2010
The Nobel Prize.Graphene is a kind of, and there are one the two-dimensional materials of carbon atom thickness, have 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 generally existing, people need to find a kind of
Quickly, method efficiently, cheap prepares graphene.Currently, the preparation method of graphene is broadly divided into two kinds：Chemical method and physics
Method.Chemical method includes mainly oxidation-reduction method, epitaxial growth method and chemical vapour deposition technique；Physical is also referred to as mechanical stripping
Method includes mainly 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 complexity, energy consumption height, low output, of high cost, unsuitable batch production.Ultrasonic method is severely limited by material state and concentration, production
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 relatively low, and equipment damage is serious, does not have actual application value.With
Upper method is difficult to achieve the purpose that environmental protection, batch quickly, efficiently, inexpensive prepare high-quality graphene.
Invention content
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, the production of easy to operate, inexpensive graphene
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 of the method preparation of the present invention is high, thickness is thin, large specific surface area, resistivity is low, metal is miscellaneous
Matter content is few and piece diameter is controllable, is suitable for the application in 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) fully wetting：Graphite and solvent are mixed, carried out at stirring at low speed processing at least once or/and low velocity shear
Reason, obtains graphite dispersing solution；
B) preliminary stripping：Graphite dispersing solution in step a) is subjected to sanded treatment at least once, is tentatively removed
Graphene dispersing solution；
C) secondary stripping：The graphene dispersing solution tentatively removed in step b) is subjected to high-pressure homogeneous processing at least once
Or/and be ultrasonically treated, obtain single layer or few layer graphene dispersion liquid.
The high-volume of graphene, scale ground continuous production may be implemented in the method for the present invention.
The second aspect of the present invention provides a kind of graphene being 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 Ω cm of the resistance of graphene≤10；Iron tramp content≤
10ppm。
The graphene purity of the present invention is high, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few and piece diameter
Controllably, it is suitable for the application in 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 that the first dispersion fills
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 supersound process 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 the 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 effect compared with prior art：
1. method and apparatus provided by the invention is mainly for industrialized production, to use Physical 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 dispersant reduces the Complicated Flow needed for intercalator and dispersant removal, reduce may remaining intercalator and
Influence of the dispersant 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 using high-pressure homogeneous device as one of core equipment for the first time, by
It is that a temperature rises very high, very fast equipment, and lacks effective cooling measure in itself in high pressure homogenizer, 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 safeguard 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 relatively low, and low production efficiency, equipment attrition is serious, and the present invention is improved this, into horizontal high voltage
It first carries out fully soaking (stirring at low speed and/or low velocity shear) and preliminary stripping (recycle and be sanded) etc. before homogeneous or supersound process
Step process can make material more stabilization, piece diameter more uniform, and not destroy the expansion structure of raw material, can significantly improve
The concentration of high-pressure homogeneous or ultrasonic pending product significantly improves production efficiency, reduces production cost.
4. the present invention is by fully soaking (stirring at low speed and/or low velocity shear), preliminary stripping (cycle 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 stripping of alkene can significantly promote the effect of graphene stripping, reduce the defect of graphene, obtain high quality, high-ratio surface
The graphene of product, high conductivity and high yield.
5. can make sanding apparatus, high-pressure homogeneous device and be ultrasonically treated to fill by the way that the second dispersal device is arranged in the present invention
Set all can be two cylinders cycle form, make all materials can by processing, improve single cylinder cycle 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 stripping 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, also can easily it realize.
7. device provided by the invention also further carry cooling device, this for there are high-pressure homogeneous device and ultrasound at
The producing line for managing device is vital, because the two Wen Sheng is exceedingly fast, is increased with number of repetition, Wen Shengyue high, if more than 100
DEG C, when without being equipped with cooling device, the low boiling point solvents such as water, ethyl alcohol can not use at all, the high boiling solvents such as NMP and DMF
A large amount of dangerous vapors can be formed, are caused serious harm to environment, to human body, while being limited more than equipment high temperature, 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 flow simply easily manipulates, at low cost, environmentally safe, with being suitable for high-volume scale even
The continuous graphene for preparing 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.
Description of the drawings
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 implementation mode
As previously mentioned, the first aspect of the present invention provides a kind of method of continuous production graphene, the method can be realized
The high-volume scale of graphene ground continuous production, the described method comprises the following steps：
A) fully wetting：Graphite and solvent are mixed, carried out at stirring at low speed processing at least once or/and low velocity shear
Reason, obtains graphite dispersing solution；Wherein, make graphite in solvent by way of stirring at low speed at least once and/or low velocity shear
In fully wetting and tentatively reduction graphite piece diameter；
B) preliminary stripping：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) secondary stripping：The graphene dispersing solution tentatively removed in step b) is subjected to high-pressure homogeneous processing at least once
Or/and be ultrasonically treated, obtain single layer or few layer graphene dispersion liquid.
In a specific implementation mode of the invention, the method is further comprising the steps of：
D) it post-processes：By in step c) single layer or few layer graphene dispersion liquid by filtering, centrifugation, washing and it is dry at
Reason obtains single layer or few layer graphene.
In a specific implementation mode of the invention, what stirring at low speed processing or/and low velocity shear in step a) were handled
Number is more than 1.
In a specific implementation mode of the invention, in step b), the number of sanded treatment is more than 1.
Preferably, it is walked again after being recycled with stirring at low speed processing and/or low velocity shear processing with sanded treatment
It is rapid c), i.e., at least circulation primary stirring at low speed processing and/or low velocity shear processing, sanded treatment, stirring at low speed handle and/or it is low
Step c) is carried out after fast shear treatment again.Cycle in this way can be such that the material that sand milling comes out further uniformly disperses,
Give material to carry out effective temperature-reducing simultaneously, improve the effect of sanded treatment, make before secondary stripping raw graphite obtain it is uniform,
Adequately preliminary stripping increases the consistency of preliminary stripping product, lays the foundation to be smoothed out step c), can also reduce by
In feed it is uneven caused by high-pressure homogeneous device and ultrasonic processing apparatus strong Wen Sheng, the quality for ensureing product while drops
The probability of low equipment damage extends the service life of equipment.
In a specific implementation mode of the invention, in step c), the number of high-pressure homogeneous processing or/and supersound process is big
In 1, preferably more than 1 to less than or equal to 4 times.
Preferably, can it is high-pressure homogeneous processing or/and supersound process with stirring at low speed processing and/or low velocity shear handle into
Row cycle, i.e., at least circulation primary stirring at low speed processing and/or low velocity shear processing, it is high-pressure homogeneous processing or/and supersound process,
Single layer or few layer graphene dispersion liquid are obtained after stirring at low speed processing and/or low velocity shear processing.Cycle in this way, can be with
So that high-pressure homogeneous or ultrasonic material out is further uniformly disperseed, while effective temperature-reducing is carried out to material, improves high pressure
The effect of homogeneous or supersound process obtains more uniform product, increases lot stability.
In a specific implementation mode 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 graphite as selection, is that raw material can be made to shell
From the abundant wetting and intercalation for obtaining solvent before, enable subsequent first stripping and secondary stripping more fully, to obtain
Obtain the graphene product of the number of plies≤5.
In a specific implementation mode 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 implementation mode of the invention, in step a), the graphite is in the mixture of graphite and solvent
A concentration of 0.1~10wt%.If concentration is less than 0.1wt%, yield is too low, and cost is higher, 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 be smoothed out, obtained product is extremely uneven, and there may be partly completely without removing or cannot fully shell in product
From product.
In a specific implementation mode of the invention, in step a), the stir speed (S.S.) of the stirring at low speed is 10-41r/
min；The shear rate of the low velocity shear is 100-600r/min, and rate is adjustable.The such rate of selection, it is ensured that graphite
Intercalation is fully soaked by solvent and does not destroy the expansion structure of graphite.
In a specific implementation mode of the invention, in step a), the time fully soaked is 0.2~3h, preferably
For 0.5~2h.
In a specific implementation mode of the invention, in step b), the time tentatively removed is 0.5~10h, preferably
For 2~8h.
In a specific implementation mode of the invention, in step c), the high-pressure homogeneous pressure is 30~90MPa, excellent
It is selected as 50~80MPa.If pressure is less than 30MPa, material can not obtain sufficient stripping, 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, temperature can be caused to rise excessively high,
Pressure instability generates high pressure homogenizer larger damage, can not ensure the normal use of equipment.
In a specific implementation mode 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 implementation mode 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 implementation mode of the invention, in step c), the high-pressure homogeneous processing or/and supersound process when
Between be 1h~4h.
In a specific implementation mode of the invention, in step d), the method for the drying is spray drying, vacuum is done
At least one of drying modes such as dry, freeze-drying.
The second aspect of the present invention provides a kind of graphene being 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 Ω cm of the resistance of graphene≤10；Iron tramp content≤
10ppm。
The graphene purity of the present invention is high, thickness is thin, large specific surface area, resistivity is low, metals content impurity is few and piece diameter
Controllably, it is suitable for the application in 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 that the first dispersion fills
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 supersound process 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 implementation mode 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 implementation mode 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 implementation mode 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 implementation mode 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 implementation mode 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 implementation mode 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 become frequency modulation
Speed.Dispersion impeller therein can shear material (such as carrying out low velocity shear).
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 implementation mode 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 ensure due to by high temperature and so that solvent is waved
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 implementation mode 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 implementation mode of the invention, the ultrasonic processing apparatus can be two or more processor for ultrasonic wave
Serial or parallel connection.
In a specific implementation mode 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 implementation mode 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 implementation mode 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 implementation mode 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 defined by the present invention and protect
Within the scope of.
Embodiment 1
Step 1：By way of stirring at low speed, expanded graphite is fully soaked to and subtracted small flake diameter in a solvent, 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 a concentration of 0.1wt%, mixing time 0.2h obtains expanded graphite dispersion liquid.
Step 2：The expanded graphite dispersion liquid fully 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 rubble ink alkene dispersion liquid of stabilization in step 2 tentatively removed is subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersion liquid.High-pressure homogeneous pressure is 30MPa, time 1h.
Step 4：By in step 3 single layer or few layer graphene dispersion liquid by filtering, centrifugation, carrying out washing treatment and spray
Mist is dried, you can obtains single layer or few layer graphene.
Embodiment 2
Step 1：By way of low velocity shear, expanded graphite is fully soaked to and subtracted small flake diameter in a solvent, 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
A concentration of 2.5wt% in object, mixing time 1h obtain expanded graphite dispersion liquid.
Step 2：The expanded graphite dispersion liquid fully 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 rubble ink alkene dispersion liquid of stabilization in step 2 tentatively removed is subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersion liquid.High-pressure homogeneous pressure is 65MPa, time 2h.
Step 4：By in step 3 single layer or few layer graphene dispersion liquid by filtering, centrifugation, carrying out washing treatment and carry out cold
It is lyophilized dry, you can obtain single layer or few layer graphene.
Embodiment 3
Step 1：By way of stirring at low speed combination low velocity shear, expanded graphite is fully soaked and reduced in a solvent
Piece diameter, expanded graphite are prepared by microwave expansion method, and expansion multiplying power 300, solvent is ethyl alcohol, expanded graphite expanded graphite with
A concentration of 5wt% in the mixture of solvent, mixing time 2h obtain expanded graphite dispersion liquid.
Step 2：The expanded graphite dispersion liquid fully 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 rubble ink alkene dispersion liquid of stabilization in step 2 tentatively removed is ultrasonically treated, single layer is obtained
Or few layer graphene dispersion liquid.Time 3h.
Step 4：By in step 3 single layer or few layer graphene dispersion liquid by filtering, centrifugation, carrying out washing treatment and carry out true
Sky is dry, you can obtains single layer or few layer graphene.
Embodiment 4
Step 1：By way of stirring at low speed, expanded graphite is fully soaked to and subtracted small flake diameter in a solvent, 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 a concentration of 3wt%, mixing time 3h obtains expanded graphite dispersion liquid.
Step 2：The expanded graphite dispersion liquid fully 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 rubble ink alkene dispersion liquid of stabilization in step 2 tentatively removed is ultrasonically treated, single layer is obtained
Or few layer graphene dispersion liquid.Time 3h.
Step 4：By in step 3 single layer or few layer graphene dispersion liquid by filtering, centrifugation, carrying out washing treatment and spray
Mist is dried, you can obtains single layer or few layer graphene piece.
Embodiment 5
Step 1：By way of low velocity shear, expanded graphite is fully soaked to and subtracted small flake diameter in a solvent, 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 a concentration of 10wt%, mixing time 3h obtains expanded graphite dispersion liquid.
Step 2：The expanded graphite dispersion liquid fully 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 rubble ink alkene dispersion liquid of stabilization in step 2 tentatively removed is subjected to high-pressure homogeneous processing, is obtained
Single layer or few layer graphene dispersion liquid, high-pressure homogeneous pressure are 90MPa, time 4h.
Step 4：By in step 3 single layer or few layer graphene dispersion liquid by filtering, centrifugation, carrying out washing treatment and carry out cold
It is lyophilized dry, you can obtain 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 supersound process 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 the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of method of continuous production graphene, which is characterized in that the described method comprises the following steps：
A) fully wetting：Graphite and solvent are mixed, stirring at low speed processing at least once or/and low velocity shear processing is carried out, obtains
To graphite dispersing solution；
B) preliminary stripping：Graphite dispersing solution in step a) is subjected to sanded treatment at least once, the graphite tentatively removed
Alkene dispersion liquid；
C) secondary stripping：By the graphene dispersing solution tentatively removed in step b) carry out at least once it is high-pressure homogeneous processing or/and
It is ultrasonically treated, obtains single layer or few layer graphene dispersion liquid.
Preferably, the method is further comprising the steps of：
D) it post-processes：By in step c) single layer or few layer graphene dispersion liquid by filtering, centrifugation, washing and be dried,
Obtain single layer or few layer graphene.
2. according to the method described in claim 1, it is characterized in that, the stirring at low speed processing in step a) or/and low velocity shear
Number of processing is more than 1.
Preferably, in step b), the number of sanded treatment is more than 1.
Preferably, sanded treatment is handled with stirring at low speed and/or low velocity shear handles after being recycled and carries out step c) again, i.e., extremely
At few circulation primary stirring at low speed processing and/or low velocity shear processing, sanded treatment, stirring at low speed processing and/or low velocity shear
Step c) is carried out after reason again.
Preferably, in step c), it is high-pressure homogeneous processing or/and supersound process number be more than 1, preferably more than 1 to be less than etc.
In 4 times.
Preferably, high-pressure homogeneous processing or/and supersound process are recycled with stirring at low speed processing and/or low velocity shear processing,
I.e. at least circulation primary stirring at low speed processing and/or low velocity shear processing, high-pressure homogeneous processing or/and supersound process, low speed stir
Single layer or few layer graphene dispersion liquid are obtained after mixing processing and/or low velocity shear processing.
3. method according to claim 1 or 2, which is characterized in that in step a), the graphite is expanded graphite.
Preferably, in step a), a concentration of 0.1~10wt% of the graphite in the mixture of graphite and solvent.
Preferably, in step a), the stir speed (S.S.) of the stirring at low speed is 10-41r/min；The shear rate of the low velocity shear
For 100-600r/min.
Preferably, in step a), the time fully soaked is 0.2~3h, preferably 0.5~2h.
Preferably, in step b), the time tentatively removed is 0.5~10h, preferably 2~8h.
Preferably, in step c), the high-pressure homogeneous pressure is 30~90MPa, preferably 50~80MPa.
Preferably, 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.
Preferably, in step c), the high-pressure homogeneous discharging flow is 500-2000L/h.
Preferably, in step c), the time of the high-pressure homogeneous processing or/and supersound process is 1h~4h.
4. a kind of graphene being prepared by any one of claim 1-3 the methods, which is characterized in that the graphene
The number of plies is 5 layers or less；D50It is 8-12 μm, specific surface area 600-800m2/g；The Ω cm of the resistance of graphene≤10；Iron tramp
Content≤10ppm.
5. 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 supersound process
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.
6. device according to claim 5, which is characterized in that described device further includes cooling device, the supersound process
The outlet end of device is connected with the input end of the outlet end of the sanding apparatus and the cooling device respectively.
Preferably, described device further includes filter device, the input end of the outlet end of the cooling device and the filter device
It is connected.
7. device according to claim 5 or 6, 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.
8. according to claim 5-7 any one of them devices, which is characterized in that described device further includes centrifugal spray drying dress
It sets, the outlet end of the device for storing liquid is connected with the centrifugal spray drying device.
Preferably, described device further includes powder charging device and liquid feed device, and the powder charging device and liquid are thrown
The outlet end of material device is connected with the input end of first dispersal device respectively.
Preferably, the powder charging device uses Seal Design.
9. device according to claim 7 or 8, which is characterized in that first dispersal device and the second dispersal device
Setting agitating paddle and/or dispersion impeller in tank body.
Preferably, the tank body is double-layer structure, and outer layer is cooling layer.
Preferably, the tank interior is equipped with and scrapes wall device.
Preferably, the ultrasonic processing apparatus is two or more processor for ultrasonic wave serial or parallel connections.
10. a kind of method of continuous production graphene, which is characterized in that the method is using described in claim any one of 5-9
Device implement.
Preferably, the method includes the steps in the method for claim 1-4 any one of them continuous production graphenes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020416A (en) * | 2018-10-26 | 2018-12-18 | 新奥石墨烯技术有限公司 | High-performance graphene concrete and preparation method thereof |
| CN109652014A (en) * | 2018-12-26 | 2019-04-19 | 宁波杉元石墨烯科技有限公司 | A kind of graphene dispersion grinding aid and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107117603A (en) * | 2017-06-16 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of utilization pulse ultrasonic wave peels off grading system for the method for graphene |
| 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 |
-
2018
- 2018-03-08 CN CN201810190887.3A patent/CN108622888B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107117603A (en) * | 2017-06-16 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of utilization pulse ultrasonic wave peels off grading system for the method for graphene |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020416A (en) * | 2018-10-26 | 2018-12-18 | 新奥石墨烯技术有限公司 | High-performance graphene concrete and preparation method thereof |
| CN109020416B (en) * | 2018-10-26 | 2021-04-30 | 新奥石墨烯技术有限公司 | High-performance graphene concrete and preparation method thereof |
| CN109652014A (en) * | 2018-12-26 | 2019-04-19 | 宁波杉元石墨烯科技有限公司 | A kind of graphene dispersion grinding aid and preparation method thereof |
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