CN106542524B - A kind of graphene dispersion body and preparation method thereof - Google Patents
A kind of graphene dispersion body and preparation method thereof Download PDFInfo
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- CN106542524B CN106542524B CN201610918000.9A CN201610918000A CN106542524B CN 106542524 B CN106542524 B CN 106542524B CN 201610918000 A CN201610918000 A CN 201610918000A CN 106542524 B CN106542524 B CN 106542524B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The present invention provides a kind of graphene dispersion body and preparation method thereof, by (1) by wax material heating melting；(2) graphite raw material is added in wax material and is stirred evenly, obtain melting behaviors；(3) melting behaviors are removed by high-energy ultrasonic, obtains removing body；(4) solvent is added into removing body, it is made to be separated into oily drop in solvent；(5) the emulsion cooling that will be formed after step (4), solid particle is all condensed into wax-like materials therein, a kind of graphene dispersion body wrapped up by wax material is obtained, rubber, plastics can be added, in coating in the dispersion, play the role of increasing the strength of materials, toughness, thermal conductivity.
Description
Technical field
The present invention relates to grapheme material fields, and in particular to the technical field of graphene is prepared by Mechanical Method.
Background technique
2004, two scientists of Univ Manchester UK had found graphene using the method that micromechanics is removed,
And Nobel Prize in physics was obtained in 2010.Graphene is a kind of single atomic thickness and the carbon original with sp2 bond
The slab construction of son theoretically has perfect hexagonal reticulated structure, present excellent electronic stability, thermal conductivity, optical property,
Mechanical property etc..Since graphene was discovered, since its excellent performance and huge market application prospect have caused object
The research boom in the fields such as reason and material science.It is also most hard nano material that graphene, which is most thin at present, is provided simultaneously with
The performance that numerous common materials such as photosensitiveness is good, thermal coefficient is high, electron mobility is high, resistivity is low, mechanical strength is high do not have,
Future is expected to numerous in electrode, battery, transistor, touch screen, solar energy, sensor, super light material, medical treatment, sea water desalination etc.
Field is widely applied, and is one of most promising advanced material.However there is presently no effective methods can volume production high quality stone
Black alkene.
Mainly include at present mechanical stripping method in the preparation method of graphene: being removed graphite for single layer by mechanism
Atomic structure of carbon；Epitaxial growth method is heated at high temperature large area monocrystal SiC, makes graphene growth thereon, then at ultrahigh vacuum or
Si is removed under normal pressure and leaves C, then obtains the graphene thin layer with the similar area of SiC, the material as graphene substrate point
For non-metal kind substrate (such as SiC, SiO2, GaAs etc.) and metal substrate (such as Cu, Ni, Co, Ru, Au, Ag), epitaxial growth method
Graphene obtained is still unable to reach homogeneous thickness；Metal catalysed processes: by solid-state or gaseous carbon source in certain temperature, pressure
And the method for directly generating graphene under the action of catalyst in substrate, including chemical vapour deposition technique and metal catalysed processes two
Kind；Quenching method: by be quickly cooled down in caused by internal-external temperature difference generate stress, make graphene from graphite surface be detached from, further include
Direct combustion method, electrochemical process, in-situ authigenic template etc..
Common dispersed graphite alkene majority is made from graphene oxide reduction method, i.e., first by natural stone currently on the market
Ink oxidation is prepared into graphene oxide, then is made into graphene oxide dispersion, then in the liquid phase by graphene oxide also
Original is at graphene.Since this method has used a large amount of strong oxidizer and reducing agent during the preparation process, graphene is destroyed
Phenyl ring conjugated structure, and the reduction effect of this method is also not ideal enough.Reducing agent used can not remove all oxygen-containing
Functional group, therefore the structure for the graphene being destroyed can not be repaired thoroughly, and the various excellent performances of graphene is caused to be affected.
In addition, easily reuniting also due to graphene is in nanoscale even if obtaining graphene, losing due performance.Also have graphite
The direct prepared composition dispersion liquid of alkene saves, but use scope is restricted.
To solve phenomena such as graphene is reunited, and application range and storage application effect are widened, has been taken in portion of techniques
Using the method for other carriers separation graphene, such as:
Wax liquor of a kind of load nano-graphene and preparation method thereof is disclosed in Chinese patent CN103468004B and is used
On the way, one kind has been obtained by the way that the superfine nano graphite powder particle of 20 ~ 40nm to be carried on the Wax particles of 200 ~ 800nm of partial size
The wax dispenser of graphene is loaded, and is applied in the covering with paint of coating, ink or leather.
The part prior art is further defined the specific structure of the graphene containing carrier, and illustrates that it is suitable
Range, such as:
A kind of heat-conductive coating is disclosed in Chinese utility model patent CN202898300, which includes coating ontology, this
Contain paraffin layer in body, be enclosed with graphite linings in paraffin layer, the thermal conductivity of heat-conductive coating can be improved.
It is similar with above-mentioned patent, it is in the prior art by preparing first about the combination between graphene and carrier wax
Graphene, and then it is connected by reaction physically or chemically with carrier, it achieves the goal.
Summary of the invention
It is an object of the invention to propose a kind of can obtain during preparing graphene by wax material package
The preparation method of graphene dispersion body.
Technical scheme is as follows:
A kind of preparation method of graphene dispersion body, comprising the following steps: (1) by wax material heating melting；(2) by stone
Black raw material is added in wax material and stirs evenly, and obtains melting behaviors；(3) melting behaviors are removed by high-energy ultrasonic, is obtained
To removing body；(4) solvent is added into removing body, it is made to be separated into oily drop in solvent；(5) will after step (4) shape
At emulsion cooling, to wax-like materials therein be all condensed into solid particle to get arrive the graphene dispersion body.
In the above-mentioned technical solutions, graphite and waxy materials melt can not only ultimately form the graphene of wax material package
Dispersion, while because of the adhesive force of wax material, when graphite is removed in stirring or high-energy ultrasonic, wax material also can
The graphite of adherency therebetween is removed, so that the removing of graphite does not only rely on high-energy ultrasonic, while can also be obtained by separation
The help of wax material.The removing body obtained in step (3) is the mixing that thin layer graphite and thin layer wax material fuse into one
Removing body can be separated into oily drop because of it by object, the solvent being added in step (4), it is clear that it, which needs to meet, is unable to dissolving wax
The property of material, graphene dispersion body obtained in step (5) can be used in a variety of industrial goods such as plastics, rubber, coating, rise
To enhancing, toughening, increase the effects of thermal conductivity.
High-energy ultrasound to the removing of melting behaviors mainly by its cavitation, make by high-energy ultrasound in the technical scheme
When for melt, there are positive or negative high voltages to replace period of change, and positive phase molecular melt is squeezed, minus phase molecular melt by
There is hole as the enhancing of ultrasonic wave is close and is more than the critical molecular distance of its stable state in tearing, intermolecular average distance,
Hole constantly vibrates, and finally ruptures, and the removing of material is realized with this, because viscosity is larger in melt, the ultrasonic wave of needs
Intensity should be greater than ultrasonic intensity of general action when liquid, it is therefore desirable to high-energy ultrasound.
Preferably: the viscosity of the melting behaviors is 50 ~ 300mPa.s at 50 ~ 200 DEG C.
The viscosity of melting behaviors influences whether the peeling effect of graphite raw material in the technical scheme, if viscosity is excessive, high energy
Ultrasonic wave acts on it limited, it is difficult to obtain the graphene of thin layer.
It is also preferred that: the wax material is selected from one of paraffin, polyethylene wax or a variety of.
It is also preferred that: the graphite raw material is selected from highly directional thermal cracking graphite, thermal expansion graphite, crystallite artificial stone
One of ink is a variety of.
It is also preferred that: the solvent is selected from one of deionized water, methanol, ethyl alcohol, propyl alcohol, butanol or more
Kind.
In the technical scheme because polar solvent will not generally generate obvious dissolution, it is preferable to use polarity is molten to wax material
The effects of agent, segment polarity solvent can generate swelling to wax material, in this case, obtained graphene dispersion body can pass through
The removal residual solvent such as washing, vacuum distillation.
It is also preferred that: the mass ratio of the wax material and the graphite raw material is 2 ~ 30:1.
It is also preferred that: the mass ratio of the solvent and the melting behaviors is 3 ~ 30:1.
It is also preferred that: the frequency of the high-energy ultrasonic is 40 ~ 80kHz.
It is also preferred that: high-energy ultrasonic described in the step (3) act on the melting behaviors time be 60 ~
200s。
Present invention further proposes a kind of graphene dispersion bodies, are prepared by any of the above-described kind of preparation method.
The dispersion can direct or modified addition rubber, plastics, in coating, play and increase the strength of materials, toughness, thermally conductive
The effect of property.
Graphene has been made by simple step by graphite raw material in the present invention, passes through wax material and graphite raw material
Melting, removing, during graphene generates, by avoiding the reunion of graphene, the graphene dispersion body being prepared
It can store for a long time, can be used as enhancing, toughening, the filler use for improving thermal conductivity.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) by paraffin at 50 ~ 60 DEG C heating melting；
(2) highly directional thermal cracking graphite is added in paraffin in the mass ratio of paraffin for the ratio of 1:5, carries out high-speed stirring
It mixes, obtains melting behaviors after mixing evenly, melting phase viscosity is 300mPa.s；
(3) after carrying out processing 100s to the high-energy ultrasonic that melting behaviors frequency of use is 80kHz, removing body is obtained；
(4) deionized water that quality is 15 times of melting behaviors is added into removing body, after persistently stirring 40min, formation contains
The emulsion of oily drop of uniform size；
(5) emulsion is cooled to 5 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 60 μm, tested after stripping graphene therein be averaged the number of plies be 3 ~ 6 layers.
Embodiment 2
(1) by paraffin at 60 ~ 80 DEG C heating melting；
(2) graphite will be thermally expanded to be added in paraffin in the mass ratio of paraffin for the ratio of 1:10, carries out high-speed stirred, stirs
Melting behaviors are obtained after mixing uniformly, melting phase viscosity is 200mPa.s；
(3) after carrying out processing 100s to the high-energy ultrasonic that melting behaviors frequency of use is 70kHz, removing body is obtained；
(4) mixture of ethyl alcohol and water that quality is 20 times of melting behaviors is added into removing body, after persistently stirring 40min,
Form oily drop of uniform size；
(5) emulsion is cooled to 10 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 70 μm, tested after stripping graphene therein be averaged the number of plies be 1 ~ 5 layer.
Embodiment 3
(1) by paraffin at 80 ~ 100 DEG C heating melting；
(2) crystallite artificial graphite is added in paraffin in the mass ratio of paraffin for the ratio of 1:20, carries out high-speed stirred,
Melting behaviors are obtained after mixing evenly, and melting phase viscosity is 100mPa.s；
(3) after carrying out processing 200s to the high-energy ultrasonic that melting behaviors frequency of use is 40kHz, removing body is obtained；
(4) mixture of water and ethyl alcohol that quality is 30 times of melting behaviors is added into removing body, after persistently stirring 30min,
Form the emulsion for being dispersed with oily drop of uniform size；
(5) emulsion is cooled to 10 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 50 μm, tested after stripping graphene therein be averaged the number of plies be 2 ~ 8 layers.
Embodiment 4
(1) by molecular weight be 4000 polyethylene wax at 100 ~ 120 DEG C heating melting；
(2) highly directional thermal cracking graphite is added in polyethylene wax in polyethylene wax mass ratio for the ratio of 1:2, is carried out
High-speed stirred, obtains melting behaviors after mixing evenly, and melting phase viscosity is 50mPa.s；
(3) after carrying out processing 60s to the high-energy ultrasonic that melting behaviors frequency of use is 40kHz, removing body is obtained；
(4) ethyl alcohol that quality is 3 times of melting behaviors is added into removing body, after persistently stirring 60min, formation is dispersed with size
The emulsion of uniform oily drop；
(5) emulsion is cooled to 5 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 30 μm, tested after stripping graphene therein be averaged the number of plies be 5 ~ 11 layers.
Embodiment 5
(1) by molecular weight be 5000 polyethylene wax at 100 ~ 120 DEG C heating melting；
(2) graphite will be thermally expanded to be added in polyethylene wax in polyethylene wax mass ratio for the ratio of 1:10, carries out high speed
Stirring, obtains melting behaviors after mixing evenly, and melting phase viscosity is 55mPa.s；
(3) after carrying out processing 100s to the high-energy ultrasonic that melting behaviors frequency of use is 60kHz, removing body is obtained；
(4) propyl alcohol that quality is 10 times of melting behaviors is added into removing body, after persistently stirring 1h, it is equal that formation is dispersed with size
The emulsion of even oily drop；
(5) emulsion is cooled to 5 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 35 μm, tested after stripping graphene therein be averaged the number of plies be 5 ~ 10 layers.
Embodiment 6
It (1) is that 6000 polyethylene waxes heating melting and are uniformly mixed at 150 ~ 200 DEG C by molecular weight；
(2) crystallite artificial graphite is added in polyethylene wax in polyethylene wax mass ratio for the ratio of 1:20, is carried out high
Speed stirring, obtains melting behaviors after mixing evenly, and melting phase viscosity is 60mPa.s；
(3) after carrying out processing 200s to the high-energy ultrasonic that melting behaviors frequency of use is 80kHz, removing body is obtained；
(4) deionized water that quality is 20 times of melting behaviors is added into removing body, after persistently stirring 1h, formation is dispersed with big
The emulsion of small uniform oily drop；
(5) emulsion is cooled to 5 DEG C, oily liquids therein is condensed into solid particle all to get the graphite is arrived
Alkene dispersion.
The graphene dispersion body partial size be 30 μm, tested after stripping graphene therein be averaged the number of plies be 6 ~ 10 layers.
Claims (6)
1. a kind of preparation method of graphene dispersion body, it is characterised in that: melted the following steps are included: (1) heats wax material
Melt；(2) graphite raw material is added in wax material and is stirred evenly, obtain melting behaviors；The wax material and the graphite are former
The mass ratio of material is 2~30:1；(3) melting behaviors are removed by high-energy ultrasonic, obtains removing body；The high-energy ultrasonic
Frequency is 40~80kHz, and action time is 60~200s；(4) solvent is added into removing body, it is made to be separated into oil in solvent
Shape drop；The mass ratio of the solvent and the melting behaviors is 3~30:1；(5) the emulsion drop that will be formed after step (4)
Temperature, until wax-like materials therein are condensed into solid particle all to get the graphene dispersion body is arrived.
2. the preparation method of graphene dispersion body according to claim 1, it is characterised in that: the viscosity of the melting behaviors exists
It is 50~300mPa.s at 50~200 DEG C.
3. the preparation method of graphene dispersion body according to claim 1, it is characterised in that: the wax material be selected from
One of paraffin, polyethylene wax are a variety of.
4. the preparation method of graphene dispersion body according to claim 1, it is characterised in that: the graphite raw material be selected from
One of highly directional thermal cracking graphite, thermal expansion graphite, crystallite artificial graphite are a variety of.
5. the preparation method of graphene dispersion body according to claim 1, it is characterised in that: the solvent be selected from go from
One of sub- water, methanol, ethyl alcohol, propyl alcohol, butanol are a variety of.
6. a kind of graphene dispersion body, it is characterised in that: preparation method preparation according to any one of claims 1 to 5
It obtains.
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| CN105731440A (en) * | 2016-02-01 | 2016-07-06 | 成都新柯力化工科技有限公司 | Method for achieving stripping preparation of graphene nanoplatelets by means of phase change material |
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| "石墨烯/石蜡复合材料的热物理性能研究";郭美茹等;《工程热物理学报》;20140630;第35卷(第6期);第1200-1205页 |
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