CN107840326A - A kind of method for preparing graphene - Google Patents
A kind of method for preparing graphene Download PDFInfo
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- CN107840326A CN107840326A CN201610838764.7A CN201610838764A CN107840326A CN 107840326 A CN107840326 A CN 107840326A CN 201610838764 A CN201610838764 A CN 201610838764A CN 107840326 A CN107840326 A CN 107840326A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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Abstract
The present invention relates to field of graphene, specifically, it is related to a kind of method for preparing graphene, this method includes lamellar graphite is scattered in a solvent, then the dispersion liquid for making to obtain flows through minitype channel and enters horizontal high voltage extrusion process, the feed end pressure ratio discharging end pressure of the high pressure extrusion process up to lacks 1MPa, obtains graphene dispersing solution.Lamellar graphite can not only be effectively peeled off by this method, but also can improve the production efficiency of graphene, simple efficient, low for equipment requirements, be the Perfected process for preparing graphene on a large scale.Produce cavitation realization stripping in addition, this method need not be shaken by using ultrasonic probe and disperse, metal impurities, great prospects for commercial application will not be produced.
Description
Technical field
The present invention relates to field of graphene, in particular it relates to a kind of method for preparing graphene.
Background technology
Graphene is individual layer or few layer graphite, is the elementary cell for forming lamellar graphite.It is thousands of in lamellar graphite
Graphene layer between be combined into one by intermolecular van der Waals interaction.Graphite layers Van der Waals force is weaker, can be with
By external energy by graphite layer open, and then obtain the graphene of individual layer or few layer.
The method for preparing graphene at present mainly has Physical and chemical method.Wherein, Physical includes mechanical stripping method, liquid
Phase stripping method, direct growth method, chemical method include oxidation-reduction method, organic synthesis method, solvent-thermal process method.And liquid phase stripping method
It is divided into ultrasound to peel off and supercritical fluid stripping two ways.In major way such as the A1 of US 20110017585 that ultrasound is peeled off
It is mentioned, it is specially that lamellar graphite (crystalline flake graphite, intercalated graphite or graphite worm etc.) is scattered in a solvent, by Ultrasound Instrument
Height concussion caused by device and the effect of solvent (or surfactant) are by graphite layer open.And supercritical fluid stripping method is near
Year start rise a kind of method, its general principle be by graphite dispersion small molecule HTHP supercritical fluid (such as
CO2) in, supercritical fluid is obtained by high-pressure pump and heater in high-pressure bottle, by the low surface of supercritical fluid
Power effect small molecule quickly penetrates into graphite layers, then reduces pressure and temperature, supercritical fluid volume through apparatus for supercooling
Graphite layer open is obtained the graphene film of individual layer or few layer by rapid expansion, impact graphite layers Van der Waals force.
Had the disadvantages that however, preparing graphene using ultrasonic stripping method：Charge stripping efficiency is slow, usually the single treatment time
Reach more than 10 hours；Low yield, the yield of single treatment is only 10% or so；Metals content impurity is high, ultrasonic probe work
During occur that cavitation erosion causes ultrasonic probe metal to come off, contaminated material.And graphite is prepared using supercritical fluid stripping method
Alkene then needs hyperpressure and temperature, requires higher to device parameter, equipment cost is higher.
The content of the invention
The invention aims to overcome prior art to prepare stone using ultrasonic stripping method and supercritical fluid stripping method
The drawbacks described above of black alkene, and a kind of new method for preparing graphene is provided.
Specifically, the invention provides a kind of method for preparing graphene, wherein, this method includes disperseing lamellar graphite
In a solvent, the dispersion liquid for then making to obtain flows through minitype channel and enters horizontal high voltage extrusion process, and the high pressure extrusion process is entered
Expect that end pressure is up to fewer 1MPa than discharging end pressure, obtains graphene dispersing solution.
The method provided by the invention for preparing graphene is scattered in a solvent by lamellar graphite material first, and solvent passes through profit
Wet osmosis enters graphite layers, then solution (dispersion liquid) is pressurizeed to enter horizontal high voltage extrusion process, and controls the height
The feed end pressure ratio discharging end pressure of extrusion process is pressed up to lack 1MPa, highly pressurised liquid is squeezed through one section of miniature duct,
Flow rate of liquid moment improves to 1-2000m/s, Fluid pressure and drastically declined in minitype channel, and pressure is less than full under corresponding temperature
And vapour pressure, solvent gasify rapidly, graphite layers and intergranular solvent moment produce air pocket, and dispersion liquid goes out from minitype channel
After coming, speed moment is slack-off, air pocket tight-face blasting under external pressure, produces powerful stripping impulsive force, by graphene from layer
Peeled off in shape graphite and scattered, meanwhile, the current difference in minitype channel produces the aquashear effect of strength, and graphene is entered into one
Step is peeled off and disperseed, and obtains graphene dispersing solution.Lamellar graphite can not only be carried out using method provided by the invention effective
Peel off, but also production efficiency can be improved, it is simple efficient, it is low for equipment requirements, it is the ideal side for preparing graphene on a large scale
Method.
In addition, compared with ultrasonic stripping method, method provided by the invention produces gas without being shaken by using ultrasonic probe
Cavitation, which is realized, to be peeled off and disperses, therefore will not produce metal impurities.And compared with supercritical fluid method, side provided by the invention
Method can produce large-scale air pocket demolition effect, substantially increase charge stripping efficiency, and processing procedure can produce simultaneously it is higher
Aquashear effect, can carry out graphene fully dispersed, and dispersion efficiency is higher, lower to equipment requirement.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the transmission electron microscope photo of the graphene dispersing solution obtained by embodiment 1；
Fig. 2 is the transmission electron microscope photo of the graphene dispersing solution obtained by embodiment 2；
Fig. 3 is the transmission electron microscope photo of the graphene dispersing solution obtained by embodiment 3；
Fig. 4 is the cross-sectional view of sandwich-type minitype channel；
Fig. 5 is the top view of sandwich-type minitype channel；
Fig. 6 is the cross-sectional view of pipe type micro passage；
Fig. 7 is the top view of pipe type micro passage；
Fig. 8 is the cross-sectional view of Leo formula minitype channel difficult to understand；
Fig. 9 is the top view of Leo formula minitype channel difficult to understand.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The method provided by the invention for preparing graphene includes disperseing lamellar graphite in a solvent, then to make obtained point
Dispersion liquid flows through minitype channel and enters horizontal high voltage extrusion process, and the feed end pressure ratio discharging end pressure of the high pressure extrusion process is up to
Few 1MPa, obtains graphene dispersing solution.
The present invention is not particularly limited to the species of the solvent, can be that existing various can act as peptizaiton
Inertia liquid, such as can be existing various alcohols solvents, esters solvent, ether solvent, amide solvent, water
Deng, but enter graphite layers to be more beneficial for the solvent by wetting action to promote the stripping of graphene, it is preferable that institute
State solvent be selected from 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide, alcohol, acetone, water, toluene, dimethylbenzene,
At least one of methyl acetate and ethyl acetate, it is more preferably selected from 1-METHYLPYRROLIDONE, dimethylformamide, alcohol, third
At least one of ketone and water.In addition, relative to the layered graphite of 100 parts by weight, the dosage of the solvent is preferably
100-10000 parts by weight, more preferably 200-10000 parts by weight, most preferably 1000-10000 parts by weight.
Layered graphite can be existing various by being combined between graphene layer by intermolecular van der Waals interaction
The graphite formed, its instantiation include but is not limited to crystalline flake graphite, intercalated graphite, graphite worm, graphite oxide and pyrolysis stone
At least one of ink, it is preferably selected from least one of crystalline flake graphite, intercalated graphite and graphite worm.Wherein, the scale
Graphite is natural phenocrystalline graphite, and its shape is like fish scale-shaped, in layer structure.It is certain that the layer structure of graphite make it that interlayer is present
Space, therefore under certain condition, the atom (or molecule) of some reactants (such as acid, alkali, halogen) can enter interlayer
Gap, and intercalation compound is formed with carbon net, this graphite for being inserted with intercalation compound is intercalated graphite." graphite is compacted for term
Worm " is also known as expanded graphite, refers to be obtained through intercalation, washing, drying, high temperature puffing by native graphite a kind of loose porous compacted
Worm shape material.Term " graphite oxide " formal name is graphite oxide or graphitic acid, is a kind of indefinite by the ratio between amount of substance
The compound that carbon, hydrogen, oxygen element are formed, it can handle graphite to prepare by using strong oxidizer, in resulting product,
Degree of oxidation highest product is a kind of yellow solid of carbon, oxygen ratio of number between 2.1 to 2.9, and still retains stone
The layer structure of ink, but structure becomes more sophisticated.The pyrolytic graphite is a kind of new carbon material, is that high-purity hydrocarbon gas exist
The pyrolytic carbon of the higher crystalline orientation gone out on 1800-2000 DEG C of graphite matrix through chemical vapor deposition.
According to the method provided by the invention for preparing graphene, in order to be more beneficial for point of layered graphite in a solvent
Dissipate, it is preferable that described be dispersed in the presence of dispersant is carried out.The dispersant can be that existing various can promote stratiform
The material of graphite dispersion in a solvent, it is preferably selected from polyvinylpyrrolidone, Kynoar, ten acid dimethyl sodium, ten
At least one of dimethyl sulfate sodium, op emulsifying agents, tween and polyethylene glycol, particularly preferably selected from polyvinylpyrrolidone,
At least one of Kynoar, ten acid dimethyl sodium, op emulsifying agents and polyethylene glycol.In addition, relative to 100 weight
The layered graphite of part, the dosage of the dispersant is preferably 1-80 parts by weight, more preferably 10-40 parts by weight, most preferably
For 10-30 parts by weight.
A preferred embodiment of the invention, the preparation method of the graphene, which is additionally included in into horizontal high voltage, to be extruded
Before processing, the mixture of lamellar graphite, solvent and optional dispersant is subjected to high-speed stirred (stir speed (S.S.) 10-
20000 revs/min) to viscosity be 10-10000cP.
According to the method provided by the invention for preparing graphene, make the dispersion liquid flow through minitype channel purpose be in order to
Powerful stripping impulsive force is produced to separate graphene from layered graphite.According to one kind side of being preferable to carry out of the present invention
Formula, the minitype channel are at least one of sandwich-type minitype channel, pipe type micro passage and Leo formula minitype channel difficult to understand.
As shown in Figure 4 and Figure 5, the sandwich-type minitype channel includes overhead gage layer, intermediate fluid layer and lower block flaggy, institute
State dispersion liquid and introduce intermediate fluid layer from one end of the sandwich-type minitype channel, the intermediate fluid layer is flowed through, then from institute
The other end for stating sandwich-type minitype channel is drawn, so as to complete the high pressure extrusion process.The horizontal stroke of the sandwich-type minitype channel
The narrow hem width degree in section is preferably 1-2000 μm, more preferably 10-1000 μm, most preferably 50-500 μm；The broadside of cross section
Width is preferably 5-30mm, more preferably 8-20mm, most preferably 10-15mm；Axial length is preferably 0.1-10mm, more preferably
For 1-5mm, most preferably 1-3mm.In the present invention, term " narrow hem width degree " refers to the sandwich-type minitype channel cross section
The width of shorter edge, i.e. the width of overhead gage and lower baffle plate, the width of intermediate fluid layer.Term " broadside width " refers to described
The width of the longer sides of sandwich-type minitype channel, i.e. the distance between overhead gage and lower baffle plate, the height of intermediate fluid layer.Art
Language " axial length " refers to the length of minitype channel.
As shown in Figure 6 and Figure 7, the cross-sectional aperture of the pipe type micro passage is preferably 1-2000 μm, more preferably 10-
1000 μm, most preferably 50-500 μm；Axial length is preferably 0.1-10mm, more preferably 1-5mm, most preferably 1-3mm.
As shown in Figure 8 and Figure 9, the Leo formula minitype channel difficult to understand includes overhead gage layer, intermediate fluid layer and lower block flaggy,
And the overhead gage layer includes liquid hand-hole.The dispersion liquid introduces from the liquid hand-hole of the overhead gage layer, flows through institute
Intermediate fluid layer is stated, and enters horizontal high voltage extrusion process in the intermediate fluid layer, then from the surrounding of the intermediate fluid layer
Outflow.The aperture of the liquid hand-hole is preferably greater than 3mm, more preferably higher than 4mm, most preferably 4-15mm；The centre
The highly preferred of fluid layer is 1-2000 μm, more preferably 10-1000 μm, most preferably 50-500 μm.In addition, the liquid note
The center for entering hole is preferably placed at the center of the Leo formula minitype channel difficult to understand.
In addition, in order to improve efficiency, it can also use and carry out a plurality of minitype channel (such as 2-10 bars) parallel form
High pressure extrusion molding.In the present invention, unless otherwise specified, otherwise minitype channel used is a passage.The present invention
The material for forming the minitype channel is not particularly limited, for example, can be stainless steel, ceramics, glass, metal alloy,
Composite etc..In addition, the minitype channel can be molded to be formed by mould.
The charging end pressure of the high pressure extrusion process refers to that dispersion liquid flows through the pressure before minitype channel, discharge end
Pressure refers to that dispersion liquid flows through the pressure after minitype channel, i.e., both refer respectively to the pressure positioned at minitype channel both sides.
Pressure can be with identical used by multiplicating is handled, can also be different.As described above, the feed end of the high pressure extrusion process
Pressure ratio discharging end pressure up to lacks 1MPa, preferably high 5-120MPa, more preferably high 70-110MPa.In addition, the high pressure extrusion
The charging end pressure and discharging end pressure of processing preferably control in 80-300MPa and 0.01-100MPa respectively, more preferably control respectively
System is in 80-150MPa and 0.01-50MPa.Wherein, the charging end pressure of the high pressure extrusion process can be by high-pressure pump to dividing
Dispersion liquid is pressurizeed and is controlled, and the discharging end pressure of the high pressure extrusion process can be controlled by discharge valve
System.In the present invention, the pressure refers both to gauge pressure.
According to the method provided by the invention for preparing graphene, it is preferable that this method is also included the graphene dispersion
Liquid repeats above-mentioned high pressure extrusion process, can so improve the yield of graphene.As a rule, the number of the repetition is excellent
Elect as 1-20 times, more preferably 1-10 times, most preferably 1-5 times.
According to the method provided by the invention for preparing graphene, it is preferable that this method is also included the graphene dispersion
Liquid and/or the dispersion liquid for repeating to obtain after the high pressure extrusion process are dried to obtain the step of graphene powder
Suddenly, the graphene so obtained is powder shaped rather than solution shape, so as to be more beneficial for transporting and store.
The present invention is not particularly limited to the mode of the drying, such as can be vacuum drying, spray drying etc., excellent
Elect spray drying as.A preferred embodiment of the invention, the condition of the spray drying are 50-300 including temperature
DEG C, more preferably 90-200 DEG C；Spray rate is 10-200kg/h, more preferably 20-50kg/h.
According to a kind of embodiment of the present invention, the preparation method of the graphene comprises the following steps：1. in room
Under temperature, by dispersant by stirring and dissolving in solvent, be subsequently added into lamellar graphite and continue to stir, then cut using height
Cut equipment by lamellar graphite it is fully dispersed to viscosity be 10-10000cP, obtain dispersion liquid；2. dispersion liquid is added using high-pressure pump
Be depressed into 80-300MPa, and it is pressed through miniature duct, discharge end by valve by Stress control in 0.01-100MPa, obtain
To graphene dispersing solution；3. optionally repeat step 2., the graphene dispersing solution further peeled off；4. optionally by step
3. obtained graphene dispersing solution is spray-dried, graphene powder is obtained.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is used to illustrate the method provided by the invention for preparing graphene.
(1) it is formulated：
The composition and part by weight of the present embodiment formula used are as follows：Graphite worm (also known as expanded graphite, it is new purchased from Yichang
Into graphite Co., Ltd, trade mark Kp80, similarly hereinafter) 100 parts, PVP (polyvinylpyrrolidone, molecular formula (C6H9NO) n, number
Average molecular weight is 1000) 10 parts, alcohol (ethanol, molecular formula C2H5OH, concentration are 95 weight %) 1000 parts.
(2) preparation of graphene：
1. alcohol water-bath is heated into 50 DEG C, PVP is added into alcohol in two batches under magnetic stirring, treats that PVP is complete
After dissolving, room temperature is down to, graphite worm is added to PVP wine under high-speed stirred (stir speed (S.S.) is 100 revs/min, similarly hereinafter)
In smart solution, it is 10000cP to continue stirring to viscosity, obtains dispersion liquid.2. dispersion liquid is forced into 80MPa by high-pressure pump,
And it is set to be pressed through pipe type micro passage (aperture in the pipe type micro duct is 50 μm, axial length 1mm), miniature duct
The other end by discharge valve by Stress control in 0.01MPa, obtain graphene dispersing solution Y1.Whole preparation process spent when
Between be 3 hours.Determination of transmission electron microscopy graphene dispersing solution Y1 is used according to method specified in JY/T 010-1996
The microscopic appearance of middle graphene, as a result as shown in Figure 1.Can be seen that it from Fig. 1 result is sheet thin graphene.
Embodiment 2
The embodiment is used to illustrate the method provided by the invention for preparing graphene.
(1) it is formulated：
The composition and part by weight of the present embodiment formula used are as follows：Crystalline flake graphite (newly has purchased from Yichang into graphite responsibility
Limit company, the trade mark are XCF 500) 100 parts, PVDF (Kynoar, molecular formula (CH9CF2)n, number-average molecular weight 900) and 30
Part, NMP (1-METHYLPYRROLIDONE, molecular formula C5H9NO) 10000 parts.
(2) preparation of graphene：
1. NMP heating water baths are under magnetic stirring disposably added PVDF into NMP to 50 DEG C.Treat that PVDF is complete
After dissolving, room temperature is down to, is added crystalline flake graphite in PVDF nmp solution under high velocity agitation.Continuing stirring to viscosity is
100cP, obtain dispersion liquid.2. dispersion liquid is forced into 150MPa by high-pressure pump, and it is pressed through Ao Liao and decline type
(the Leo formula minitype channel difficult to understand includes overhead gage layer, intermediate fluid layer and lower block flaggy to passage, and the overhead gage layer includes position
Liquid hand-hole in center, and the aperture of liquid hand-hole is 10mm, the height of the intermediate fluid layer is 300 μm, liquid
The center of hand-hole to the distance that fluid interlayer exports be 20mm), the outlet of the intermediate fluid layer of minitype channel passes through discharge valve
By Stress control in 50MPa, the graphene dispersing solution tentatively peeled off.3. according to step 2. recycling processing 5 times, entered
The graphene dispersing solution Y2 that one step is peeled off, it is 2.5 hours the time spent in whole preparation process.According in JY/T 010-1996
Defined method uses the microscopic appearance of graphene in determination of transmission electron microscopy graphene dispersing solution Y2, as a result such as Fig. 2
It is shown.Can be seen that it from Fig. 2 result is sheet thin graphene.
Embodiment 3
The embodiment is used to illustrate the method provided by the invention for preparing graphene.
(1) it is formulated：
The composition and part by weight of the present embodiment formula used are as follows：Intercalated graphite (has purchased from Shanghai tiger composite advanced in years
Limit company, trade mark KP425) 100 parts, polyethylene glycol (molecular formula HO (CH2CH2O)nH, number-average molecular weight 2000) 20 parts, water
5000 parts.
(2) preparation of graphene：
1. polyethylene glycol is added into water to 50 DEG C using heating water bath, wait to gather by water in three batches under magnetic stirring
After ethylene glycol is completely dissolved, room temperature is down to, is added intercalated graphite in PVP nmp solution under high velocity agitation, continues stirring extremely
Viscosity is 200cP, obtains dispersion liquid.2. dispersion liquid is forced into 120MPa by high-pressure pump, and it is micro- it is pressed through tubular type
Type passage (aperture of the pipe type micro passage is 300 μm, axial length 2mm), the minitype channel other end passes through discharge valve
By Stress control in 20MPa, the graphene dispersing solution tentatively peeled off.3. according to step 2. recycling processing 3 times, entered
The graphene dispersing solution Y3 that one step is peeled off, it is 2.5 hours the time spent in whole preparation process.According in JY/T 010-1996
Defined method uses the microscopic appearance of graphene in determination of transmission electron microscopy graphene dispersing solution Y3, as a result such as Fig. 3
It is shown.Can be seen that it from Fig. 3 result is sheet thin graphene.
Embodiment 4
The embodiment is used to illustrate the method provided by the invention for preparing graphene.
(1) it is formulated：
It is same as Example 2.
(2) preparation of graphene：
1. NMP heating water baths are under magnetic stirring disposably added PVDF into NMP to 50 DEG C, treat that PVDF is complete
After dissolving, room temperature is down to, is added crystalline flake graphite in PVDF nmp solution under high velocity agitation, continuing stirring to viscosity is
100cP, obtain dispersion liquid.2. dispersion liquid is forced into 10MPa by high-pressure pump, and it is set to be pressed through sandwich-type minitype channel
(the sandwich-type minitype channel includes overhead gage layer, intermediate fluid layer and lower block flaggy, and the narrow hem width degree of cross section be 800 μm,
The broadside width of cross section is 8mm, axial length 10mm), the minitype channel other end is existed Stress control by discharge valve
1MPa, the graphene dispersing solution tentatively peeled off.3. according to step 2. recycling processing 8 times, the stone further peeled off
Black alkene dispersion liquid.4. 3. graphene dispersing solution that step is obtained obtains graphene powder Y4 after being dried by spray dryer,
Wherein, the condition of spray drying include drying temperature be 220 DEG C, spray rate 10kg/h, whole preparation process spent when
Between be 2 hours.According to method specified in JY/T 010-1996, using determination of transmission electron microscopy, the graphene divides powder Y4
The microscopic appearance of middle graphene, it is compared with slab-like graphene.
Embodiment 5
The embodiment is used to illustrate the method provided by the invention for preparing graphene.
Method according to embodiment 1 prepares graphene, unlike, the aperture of minitype channel is 5000 μm, and length is
15mm, obtains graphene dispersing solution Y5, is 2 hours the time spent in whole preparation process.According to being provided in JY/T 010-1996
Method use determination of transmission electron microscopy graphene dispersing solution Y5 in graphene microscopic appearance, its be compared with slab-like stone
Black alkene.
Comparative example 1
The comparative example is used for the preparation method for illustrating the graphene of reference.
(1) it is formulated：
It is same as Example 1.
(2) preparation of graphene：
1. alcohol water-bath is heated into 50 DEG C, PVP is added into alcohol in two batches under magnetic stirring, treats that PVP is complete
After dissolving, room temperature is down to, graphite worm is added to PVP wine under high-speed stirred (stir speed (S.S.) is 100 revs/min, similarly hereinafter)
In smart solution, it is 10000cP to continue stirring to viscosity, obtains dispersion liquid.2. dispersion liquid is handled into 10h using Ultrasonic Cell Disruptor,
Obtain graphene dispersing solution DY1, be 11 hours the time spent in whole preparation process.According to specified in JY/T 010-1996
Method uses determination of transmission electron microscopy graphene dispersing solution DY1 microscopic appearance, and it is compared with slab-like graphene.
Comparative example 2
The comparative example is used for the preparation method for illustrating the graphene of reference.
Method according to embodiment 5 prepares graphene, unlike, the charging end pressure and discharge end of high pressure extrusion process
Pressure is respectively 0.05MPa and 0MPa, obtains graphene dispersing solution DY2, is 2 hours the time spent in whole preparation process.Press
Graphene in determination of transmission electron microscopy graphene dispersing solution DY2 is used according to method specified in JY/T 010-1996
Microscopic appearance, it is compared with slab-like graphene.
Test case
Test case is used for the test for the graphene performance that explanation is prepared by above example and comparative example.
(dosage is with graphene content for the graphene dispersing solution or graphene powder that above example and comparative example are obtained
Meter), LiFePO 4, PVP binding agents (number-average molecular weight 6000) and aqueous solvent according to 1: 47.5: 1.5: 50 weight than mixing
Close uniformly, and smearing into the film of 100 μ m-thicks, drying, is obtaining battery just on PI films (thickness is 125 μm) by obtained slurry
Very thin films.Then the resistivity of anode film, acquired results such as table 1 are determined using GB/T6615-1986 method of testing
It is shown.
Table 1
| Project | Graphene | Resistivity (Ω cm) |
| Embodiment 1 | Y1 | 37 |
| Embodiment 2 | Y2 | 32 |
| Embodiment 3 | Y3 | 35 |
| Embodiment 4 | Y4 | 43 |
| Embodiment 5 | Y5 | 58 |
| Comparative example 1 | DY1 | 62 |
| Comparative example 2 | DY2 | 89 |
As a rule, resistivity is more low, illustrates that the graphite number of plies is fewer, specific surface area is bigger, and quality is more excellent.From the above
As a result as can be seen that when preparing graphene using method provided by the invention, lamellar graphite can be effectively peeled off, is obtained
The performance of the graphene arrived is more excellent, and shorter the time required to whole process, simple efficient, low for equipment requirements, is big
Scale prepares the Perfected process of graphene.
In addition, compared with ultrasonic stripping method, method provided by the invention produces gas without being shaken by using ultrasonic probe
Cavitation, which is realized, to be peeled off and disperses, therefore will not produce metal impurities.And compared with supercritical fluid method, side provided by the invention
Method can produce large-scale air pocket demolition effect, substantially increase charge stripping efficiency, and processing procedure can produce simultaneously it is higher
Aquashear effect, can carry out graphene fully dispersed, and dispersion efficiency is higher, lower to equipment requirement.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. method for preparing graphene, it is characterised in that this method includes disperseing in a solvent, then to make by lamellar graphite Obtained dispersion liquid flows through minitype channel and enters horizontal high voltage extrusion process, the feed end pressure ratio discharge end of the high pressure extrusion process Pressure height at least 1MPa, obtains graphene dispersing solution.
- 2. according to the method for claim 1, wherein, the feed end pressure ratio discharging end pressure of the high pressure extrusion process is high 5-120MPa, preferably high 70-110MPa；Preferably, the charging end pressure of the high pressure extrusion process and discharging end pressure difference For 80-300MPa and 0.01-100MPa, preferably respectively 80-150MPa and 0.01-50MPa.
- 3. according to the method for claim 1, wherein, the minitype channel is sandwich-type minitype channel, pipe type micro passage At least one of with Leo formula minitype channel difficult to understand；The sandwich-type minitype channel includes overhead gage layer, intermediate fluid layer and lower block flaggy, and the dispersion liquid is from the interlayer One end of formula minitype channel introduces intermediate fluid layer, flows through the intermediate fluid layer, and height is carried out in the intermediate fluid layer Extrusion process is pressed, is then drawn from the other end of the sandwich-type minitype channel；The cross section of the sandwich-type minitype channel Narrow hem width degree is 1-2000 μm, and the broadside width of cross section is 5-30mm, axial length 0.1-10mm；The cross-sectional aperture of the pipe type micro passage is 1-2000 μm, axial length 0.1-10mm；The Leo formula minitype channel difficult to understand includes overhead gage layer, intermediate fluid layer and lower block flaggy, and the overhead gage layer includes Liquid hand-hole, the dispersion liquid introduce from the liquid hand-hole of the overhead gage layer, flow through the intermediate fluid layer, and in institute State and enter horizontal high voltage extrusion process in intermediate fluid layer, then flowed out from the surrounding of the intermediate fluid layer；The liquid hand-hole Aperture be more than 3mm, the height of the intermediate fluid layer is 1-2000 μm.
- 4. according to the method described in any one in claim 1-3, wherein, relative to the layered graphite of 100 parts by weight, The dosage of the solvent is 100-10000 parts by weight.
- 5. according to the method described in any one in claim 1-3, wherein, layered graphite is selected from crystalline flake graphite, intercalation At least one of graphite, graphite worm, graphite oxide and pyrolytic graphite；The solvent is selected from 1-METHYLPYRROLIDONE, diformazan At least one in base formamide, dimethyl acetamide, alcohol, acetone, water, toluene, dimethylbenzene, methyl acetate and ethyl acetate Kind.
- 6. according to the method described in any one in claim 1-3, wherein, described be dispersed in the presence of dispersant is carried out, The dispersant is selected from polyvinylpyrrolidone, Kynoar, ten acid dimethyl sodium, ten dimethyl sulfate sodium, op breasts At least one of agent, tween and polyethylene glycol.
- 7. according to the method for claim 6, wherein, relative to the layered graphite of 100 parts by weight, the dispersant Dosage is 1-80 parts by weight.
- 8. according to the method for claim 1, wherein, this method is also above-mentioned including the graphene dispersing solution is repeated High pressure extrusion process；Preferably, the number of the repetition is 1-20 times.
- 9. the method according to claim 1 or 8, wherein, this method is also included the graphene dispersing solution and/or repetition The step of dispersion liquid obtained after the high pressure extrusion process is dried to obtain graphene powder.
- 10. according to the method for claim 9, wherein, the drying is is spray-dried, and the condition bag of the spray drying It is 50-300 DEG C to include temperature, spray rate 10-200kg/h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535900A (en) * | 2018-10-16 | 2019-03-29 | 深圳市信维通信股份有限公司 | A kind of shielding piece and preparation method thereof |
| CN109761228A (en) * | 2019-03-29 | 2019-05-17 | 广州大学 | The method and apparatus of two-dimensional material are efficiently removed under a kind of low reynolds number |
| CN113845327A (en) * | 2021-10-27 | 2021-12-28 | 中国科学院过程工程研究所 | Graphene alkali-free liquid accelerator and preparation method and application thereof |
| CN114196934A (en) * | 2021-11-26 | 2022-03-18 | 中国科学技术大学 | Method for rapidly and nondestructively transferring two-dimensional layered material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003372A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN105271210A (en) * | 2015-11-27 | 2016-01-27 | 成都新柯力化工科技有限公司 | Method for preparing graphene from thermoplastic graphite material |
| CN105502376A (en) * | 2016-02-04 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing large-sized thin film by mechanically exfoliating graphene nanoplatelets and solar cell |
| CN105849040A (en) * | 2013-12-26 | 2016-08-10 | 株式会社Lg化学 | Production method for graphene |
-
2016
- 2016-09-21 CN CN201610838764.7A patent/CN107840326A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003372A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
| CN105849040A (en) * | 2013-12-26 | 2016-08-10 | 株式会社Lg化学 | Production method for graphene |
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN105271210A (en) * | 2015-11-27 | 2016-01-27 | 成都新柯力化工科技有限公司 | Method for preparing graphene from thermoplastic graphite material |
| CN105502376A (en) * | 2016-02-04 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing large-sized thin film by mechanically exfoliating graphene nanoplatelets and solar cell |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535900A (en) * | 2018-10-16 | 2019-03-29 | 深圳市信维通信股份有限公司 | A kind of shielding piece and preparation method thereof |
| CN109535900B (en) * | 2018-10-16 | 2020-12-22 | 深圳市信维通信股份有限公司 | Shielding sheet and manufacturing method thereof |
| CN109761228A (en) * | 2019-03-29 | 2019-05-17 | 广州大学 | The method and apparatus of two-dimensional material are efficiently removed under a kind of low reynolds number |
| CN109761228B (en) * | 2019-03-29 | 2023-09-15 | 广州大学 | Method and device for efficiently stripping two-dimensional material under low Reynolds number |
| CN113845327A (en) * | 2021-10-27 | 2021-12-28 | 中国科学院过程工程研究所 | Graphene alkali-free liquid accelerator and preparation method and application thereof |
| CN114196934A (en) * | 2021-11-26 | 2022-03-18 | 中国科学技术大学 | Method for rapidly and nondestructively transferring two-dimensional layered material |
| CN114196934B (en) * | 2021-11-26 | 2022-10-28 | 中国科学技术大学 | Method for rapidly and nondestructively transferring two-dimensional layered material |
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