CN106744881A - A kind of method that utilization ultrasonic continuous prepare Graphene - Google Patents
A kind of method that utilization ultrasonic continuous prepare Graphene Download PDFInfo
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- CN106744881A CN106744881A CN201611225104.8A CN201611225104A CN106744881A CN 106744881 A CN106744881 A CN 106744881A CN 201611225104 A CN201611225104 A CN 201611225104A CN 106744881 A CN106744881 A CN 106744881A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
The present invention provides a kind of method that utilization ultrasonic continuous prepare Graphene, it is characterized in that physical blowing agent is immersed into graphite layers in the case where high pressure is acted on, foaming agent makes graphite layers ftracture in a heated condition, ultrasonic cavitation is peeled off in continuous ultrasound device, so as to realize that serialization ultrasound stripping prepares Graphene.It is different from traditional action breaks down graphite layers structure that ultrasonic wave is utilized under liquid-phase condition, it is impossible to which continuous large-scale production, efficiency is low.The method is adapted to large-scale continuous production, not only increases the yield of Graphene, and preparative capacibility significantly reduces production cost, and nontoxic in preparation process, safe operation, and technical process is simple, post-processes simple and easy to apply, safety and environmental protection.
Description
Technical field
The invention belongs to functional material and field of nanometer material technology, and in particular to a kind of side of large-scale production grapheme material
Method.
Background technology
Graphene（Graphene）Be one kind by carbon atom with sp2The cellular flat film that hybrid form is formed, is one
The quasi- two-dimensional material of only one of which atomic layer level thickness is planted, so be called doing monoatomic layer graphite.Its thickness is about
, there are different fluctuatings according to the difference of preparation method in 0.335nm, generally in height about 1nm or so of vertical direction, water
It is all carbon crystals in addition to diamond square to width about 10nm to 25nm（Zero dimension fullerene, one-dimensional CNT, three
Dimension body is to graphite）Basic structural unit.The Graphene of broad sense is really multilayer or thick-layer Graphene, and thickness is more than 10 layers
Below 10nm benzene ring structures（That is hexagonal honeycomb structure）Periodically closelypacked carbon atom is with different way of stacking（Including
ABC stackings, ABA stackings etc.）A kind of two-dimentional carbon material that stacking is constituted.
Graphene is most thin, most light, maximum intensity, most hard, carrier mobility highest, the current density having now been found that
The maximum new material of patience.Graphene has good thermal property, mechanical property, crystal property, and extremely excellent electricity
Property is learned, is current electric conductivity material outstanding, application prospect is quite varied, can be used as molecule detecting, super capacitor
Device, thermal interfacial material, integrated circuit, biological devices, antibacterial material etc..
At present, graphene preparation method mainly has：Micromechanics stripping method, chemistry redox method, chemical vapour deposition technique,
Carborundum pyrolysismethod and cut CNT method.The advantage of micromechanics stripping method is that the product for obtaining has perfect crystal structure,
Defect is less, but the product for obtaining not exclusively is single-layer graphene, and produces the less efficient of Graphene, and size is not easily-controllable
System, majority is small size Graphene, is not suitable for large-scale industrial production, is only suitable for carrying out laboratory theoretical research, is limited
Its practical application.Graphene prepared by chemical vapour deposition technique is often in uneven thickness, and the active force between Graphene and substrate
The property of carbon-coating can be influenceed.Carborundum pyrolysismethod prepares that Graphene technology is also immature, resulting Graphene number of plies fluctuation compared with
Greatly, defect is a lot, and the physical property difference of the Graphene of the silicon carbide substrate preparation of opposed polarity is larger.Cut CNT method process
It is uncontrollable, and product homogeneity is poor.Oxidation intercalation restores method and realizes batch production Graphene, but due to oxidizing process
The structure of middle Graphene is destroyed, it is difficult to obtain high-quality graphene product.And, it is first to use the dense sulphur of strong oxidizer
, by graphite oxidation into graphite oxide, oxidizing process is to intert some oxygen-containing functions in graphite layers for acid, concentrated nitric acid, potassium permanganate etc.
Group, so as to increase graphite layers away from graphene oxide then is reduced into stone with strong reductant hydrazine hydrate, sodium borohydride etc. again
Black alkene.Substantial amounts of waste water, spent acid can be produced, severe contamination is caused to environment, limit the industrialized development of Graphene.
Having been reported the vibration produced using ultrasonic wave can realize the stripping of Graphene, and ultrasonic wave peels off Graphene will be subtracted
The impact of few mechanical force, the quality of graphene for obtaining is higher.But because ultrasonic wave peels off finite energy, it is necessary to be filled to graphite
The treatment such as intercalation, oxidation for dividing could be peeled off, and the Graphene after stripping is still needed to by repeatedly washing.And ultrasound splitting time is long,
It is difficult to serialization.In view of this, the present invention proposes a kind of method that utilization ultrasonic continuous prepare Graphene, in high pressure conditions
Physical blowing agent is immersed into graphite layers with ultrasonic wave or so, foaming agent makes graphite layers ftracture in a heated condition, super
Quickly peeled off under sound wave cavitation, so as to realize that serialization ultrasound stripping prepares Graphene.Further, the stone that the method is obtained
Black alkene structural damage is small, and excellent electrical property is suitable for conductive agent.
The content of the invention
It is an object of the invention to propose a kind of method that utilization ultrasonic continuous prepare Graphene, it is characterized in height
Physical blowing agent is immersed into graphite layers under pressure effect, foaming agent makes graphite layers ftracture in a heated condition, in continuous ultrasound
Ultrasonic cavitation is peeled off in device, so as to realize that serialization ultrasound stripping prepares Graphene.Further, the Graphene that the method is obtained
Structural damage is small, excellent electrical property, is suitable for conductive agent.
To achieve the above object, specific technical scheme is：
A kind of method that utilization ultrasonic continuous prepare Graphene, is characterized in physical blowing agent in the case where high pressure low temperature is acted on
Graphite layers are immersed, foaming agent makes graphite layers ftracture in a heated condition, is peeled off through ultrasonic cavitation in continuous ultrasound device, obtains
To Graphene, comprise the following steps：
（1）Open booster pump and physical blowing agent is pumped into reaction tube high pressure low temperature section, open feed arrangement and load graphite raw material
Reaction tube high pressure low temperature section, graphite linings gap is immersed by physical blowing agent；
（2）Bring the graphite of reaction tube high pressure section low temperature leaching physical blowing agent into high-temperature low-pressure area, graphite linings under screw acting
Volume rapidly becomes big to foaming agent at high temperature in gap so that graphite linings gap spacing becomes big, and Van der Waals force reduces, and continues through ultrasound
Device is quickly peeled off and obtains Graphene；Gas recovery；
（3）The Graphene of stripping enters grader, mixed surfactant dispersion in classification process, storage.
The reaction tube is the reaction tube of Liang Duan UNICOMs, and one section is high pressure low temperature section, and one section is high-temperature low-pressure section, high pressure section
Two ends and low pressure stage two ends set pressure-regulating device, and the pressure value of two sections of control sets worm propeller, high-temperature low-pressure section in pipe
Outer wall installs heater.
The Vltrasonic device is arranged on high-temperature low-pressure reaction tube rear end, manages built-in ultrasonic width bar.
The physical blowing agent includes liquid gas, low-boiling point liquid, preferably liquid carbon dioxide, liquid nitrogen, liquefied ammonia, fluorine profit
One kind in high, methyl alcohol, graphite linings gap is easily entered under high pressure effect.
The graphite raw material is selected to one or more in thermal cracking graphite, thermal expansion graphite, crystallite Delanium.
The ultrasonic frequency of the ultrasonic wave is preferably 20 50kHz.
, in 10 ~ 20MPa, temperature is without regulation for the high pressure section low-temperature working pressure.
High-temperature low-pressure section temperature control is more than foaming agent volatilization point, namely temperature needed for different foaming agents is different.
Graphite composite powder is under screw rod drive in high-temperature low-pressure section, phase mutual friction and mixing, and the temperature for improving graphite is equal
Even property
Surfactant is at least one in lauryl sodium sulfate, neopelex, APES.
The present invention be different from it is traditional prepare Graphene under liquid-phase condition, it is necessary to by graphite dispersion in solvent, then profit
With the action breaks down graphite layers structure of ultrasonic wave, solvent is peeled off into graphite layers, prepare Graphene, although its
The dilute structure of graphite will not be destroyed as oxidation-reduction method, but yield is extremely low, and single treatment amount is minimum, it is impossible to continuous scale
Metaplasia produces Graphene, and physical blowing agent is immersed graphite layers by the present invention, and foaming agent opens graphite layers in a heated condition
Split, quickly peeled off under ultrasonic cavitation effect, so as to realize that serialization ultrasound stripping prepares Graphene.The method is adapted to big rule
Mould continuous prodution, not only increases the yield of Graphene, and preparative capacibility significantly reduces production cost, and preparing
Nontoxic in journey, safe operation, technical process is simple, post-processes simple and easy to apply, safety and environmental protection.Further, the method is obtained
Graphene-structured damage it is small, conductance is up to 1000S/cm, is suitable for conductive agent.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
1st, opening device, reaction tube cryogenic high pressure section is pumped into booster pump by physical blowing agent carbon dioxide, and operating pressure reaches
10MPa, opens feed arrangement and loads thermal cracking graphite, opens helical screw agitator, and physical blowing agent is immersed into graphite linings gap.
2nd, high-temperature low-pressure section unlatching heater, temperature is set as, will soak physical blowing agent in reaction tube cryogenic high pressure section
Graphite take lower entrance high-temperature low-pressure area in screw rod, open ultrasonic generator in high-temperature low-pressure section, frequency density control exists
1.5w/cm2, volume rapidly becomes big to foaming agent at high temperature in graphite linings gap, volatilization so that graphite linings gap spacing becomes big, Fan De
Magnificent power reduces, and is quickly peeled off under ultrasonic cavitation effect.
3rd, the Graphene peeled off takes lower entrance grader in screw rod, and surfactant-dispersed is added after classification, stores standby
With.Surfactant is lauryl sodium sulfate, is 1 with the weight ratio of Graphene:1.
Test is obtained Graphene content and reaches 70%, and wherein single-layer graphene reaches 35%.Conductance is 669S/cm.
Embodiment 2
1st, opening device, reaction tube cryogenic high pressure section is pumped into booster pump by physical blowing agent liquid nitrogen, and operating pressure reaches
12.5MPa, opens feed arrangement and loads native graphite, opens ultrasonic generator, and frequency density is controlled in 1.5w/cm2.Open
Helical screw agitator, graphite linings gap is immersed by physical blowing agent.
2nd, high-temperature low-pressure section unlatching heater, temperature is set as, will soak physical blowing agent in reaction tube cryogenic high pressure section
Graphite take lower entrance high-temperature low-pressure area in screw rod, open ultrasonic generator in high-temperature low-pressure section, frequency density control exists
2.0w/cm2, volume rapidly becomes big to foaming agent at high temperature in graphite linings gap, volatilization so that graphite linings gap spacing becomes big, Fan De
Magnificent power reduces, and is quickly peeled off under ultrasonic cavitation effect.
3rd, the Graphene peeled off takes lower entrance grader in screw rod, and surfactant is added after classification, stores for future use.Table
Face activating agent is neopelex, and the weight ratio with Graphene is：1:1.
4th, the prepared Graphene content of last test reaches 72%, and wherein single-layer graphene reaches 39%.Conductance is 781S/
cm。
Embodiment 3
1st, opening device, reaction tube cryogenic high pressure section is pumped into booster pump by physical blowing agent liquefied ammonia, and operating pressure reaches
15MPa, opens feed arrangement and loads thermal expansion graphite, opens helical screw agitator, and physical blowing agent is immersed into graphite linings gap.
2nd, high-temperature low-pressure section unlatching heater, temperature is set as, will soak physical blowing agent in reaction tube cryogenic high pressure section
Graphite take lower entrance high-temperature low-pressure area in screw rod, open ultrasonic generator in high-temperature low-pressure section, frequency density control exists
2.5w/cm2, volume rapidly becomes big to foaming agent at high temperature in graphite linings gap, volatilization so that graphite linings gap spacing becomes big, Fan De
Magnificent power reduces, and is quickly peeled off under ultrasonic cavitation effect.
3rd, the Graphene peeled off takes lower entrance grader in screw rod, and surfactant is added after classification, stores for future use.Table
Face activating agent is APES, is 1 with the weight ratio of Graphene:1.
Test is obtained Graphene content and reaches 65%, and wherein single-layer graphene reaches 41%.Conductance is 752S/cm.
Embodiment 4
1st, opening device, reaction tube cryogenic high pressure section is pumped into booster pump by physical blowing agent freon, and operating pressure reaches
17.5MPa, opens feed arrangement and loads thermal expansion graphite, opens helical screw agitator, and physical blowing agent is immersed into graphite linings gap.
2nd, high-temperature low-pressure section unlatching heater, temperature is set as, will soak physical blowing agent in reaction tube cryogenic high pressure section
Graphite take lower entrance high-temperature low-pressure area in screw rod, open ultrasonic generator in high-temperature low-pressure section, frequency density is controlled in 3w/
Cm2, volume rapidly becomes big to foaming agent at high temperature in graphite linings gap, volatilization so that graphite linings gap spacing becomes big, and Van der Waals force subtracts
It is small, quickly peeled off under ultrasonic cavitation effect.
3rd, the Graphene peeled off takes lower entrance grader in screw rod, and surfactant is added after classification, stores for future use.Table
Face activating agent is APES, and the weight ratio with Graphene is：1:2.
Test is obtained Graphene content and reaches 79%, and wherein single-layer graphene reaches 67%.Conductance is 1029S/cm.
Embodiment 5
1st, opening device, reaction tube cryogenic high pressure section is pumped into booster pump by physical blowing agent methyl alcohol, and operating pressure reaches
20MPa, opens feed arrangement and loads thermal expansion graphite, opens helical screw agitator, and physical blowing agent is immersed into graphite linings gap.
2nd, high-temperature low-pressure section unlatching heater, temperature is set as, will soak physical blowing agent in reaction tube cryogenic high pressure section
Graphite take lower entrance high-temperature low-pressure area in screw rod, open ultrasonic generator in high-temperature low-pressure section, frequency density control exists
3.5w/cm2, volume rapidly becomes big to foaming agent at high temperature in graphite linings gap, volatilization so that graphite linings gap spacing becomes big, Fan De
Magnificent power reduces, and is quickly peeled off under ultrasonic cavitation effect.
3rd, the Graphene peeled off takes lower entrance grader in screw rod, and surfactant is added after classification, stores for future use.Table
Face activating agent is APES, neopelex, is 1 with the weight ratio of Graphene:0.5:1.5.
Test is obtained Graphene content and reaches 86%, and wherein single-layer graphene reaches 52%.Conductance is 953S/cm.
Claims (6)
1. a kind of method that utilization ultrasonic continuous prepare Graphene, is characterized in physical blowing in the case where high pressure low temperature is acted on
Graphite layers are immersed in agent, and foaming agent makes graphite layers ftracture in a heated condition, is peeled off through ultrasonic cavitation in continuous ultrasound device,
Graphene is obtained, is comprised the following steps：
（1）Open booster pump and physical blowing agent is pumped into reaction tube high pressure low temperature section, open feed arrangement and load graphite raw material
Reaction tube high pressure low temperature section, graphite linings gap is immersed by physical blowing agent；
（2）Bring the graphite of reaction tube high pressure section low temperature leaching physical blowing agent into high-temperature low-pressure area, graphite linings under screw acting
Volume rapidly becomes big to foaming agent at high temperature in gap so that graphite linings gap spacing becomes big, and Van der Waals force reduces, and continues through ultrasound
Device is quickly peeled off and obtains Graphene；Gas recovery；
（3）The Graphene of stripping enters grader, mixed surfactant dispersion in classification process, storage；
The reaction tube is the reaction tube of Liang Duan UNICOMs, and one section is high pressure low temperature section, and one section is high-temperature low-pressure section, high pressure section two ends
Pressure-regulating device is set with low pressure stage two ends, the pressure value of two sections of control sets worm propeller, high-temperature low-pressure section outer wall in pipe
Heater is installed；The Vltrasonic device is arranged on high-temperature low-pressure reaction tube rear end, manages built-in ultrasonic width bar.
2. a kind of method that utilization ultrasonic continuous prepare Graphene according to claim 1, it is characterised in that：The thing
Haircut infusion is the one kind in liquid carbon dioxide, liquid nitrogen, liquefied ammonia, freon, methyl alcohol.
3. a kind of method that utilization ultrasonic continuous prepare Graphene according to claim 1, it is characterised in that：The stone
Black raw material is one or more in thermal cracking graphite, thermal expansion graphite, crystallite Delanium.
4. a kind of method that utilization ultrasonic continuous prepare Graphene according to claim 1, it is characterised in that：It is described super
The ultrasonic frequency of sound wave is 20 50kHz.
5. a kind of method that utilization ultrasonic continuous prepare Graphene according to claim 1, it is characterised in that：The height
, in 10 ~ 20MPa, temperature is without regulation for pressure section low-temperature working pressure.
6. a kind of method that utilization ultrasonic continuous prepare Graphene according to claim 1, it is characterised in that：The table
Face activating agent is at least one in lauryl sodium sulfate, neopelex, APES.
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| CN109108524A (en) * | 2018-08-30 | 2019-01-01 | 桂林电子科技大学 | A kind of diamond-nano mattisolda Heat Conduction Material and preparation method thereof |
| CN110182908A (en) * | 2019-05-13 | 2019-08-30 | 浙江大学 | A kind of expanded graphite electrode and its preparation method and application for the removal of heavy metal ions in wastewater electrochemistry |
| CN110482532A (en) * | 2019-08-22 | 2019-11-22 | 董恬纲 | Graphite liquid CO2Suspension produces graphene diaphragm approach |
| CN112778729A (en) * | 2020-12-30 | 2021-05-11 | 西北大学 | Preparation method of graphene reinforced SMC composite material |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
| US11459240B2 (en) | 2018-10-29 | 2022-10-04 | Lms Co., Ltd | Method of manufacturing graphene and apparatus therefor |
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| CN112778729A (en) * | 2020-12-30 | 2021-05-11 | 西北大学 | Preparation method of graphene reinforced SMC composite material |
| CN112778729B (en) * | 2020-12-30 | 2021-09-28 | 西北大学 | Preparation method of graphene reinforced SMC composite material |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
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