CN111470498A - Preparation method and application of water-phase graphene - Google Patents
Preparation method and application of water-phase graphene Download PDFInfo
- Publication number
- CN111470498A CN111470498A CN201910979593.3A CN201910979593A CN111470498A CN 111470498 A CN111470498 A CN 111470498A CN 201910979593 A CN201910979593 A CN 201910979593A CN 111470498 A CN111470498 A CN 111470498A
- Authority
- CN
- China
- Prior art keywords
- product
- preparation
- graphite
- graphene
- laser irradiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004945 emulsification Methods 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims description 86
- 238000010008 shearing Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001133 acceleration Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 230000017525 heat dissipation Effects 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 230000020169 heat generation Effects 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 14
- 238000000265 homogenisation Methods 0.000 abstract description 12
- 239000012071 phase Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002679 ablation Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method and application of water-phase graphene. The invention provides a preparation method of water-phase graphene, which comprises the following steps: purification, dispersion, laser irradiation, ultrasonic emulsification, shear homogenization and purification. The invention also provides an application of the aqueous phase graphene product obtained by the preparation method. According to the invention, the interlayer spacing of the graphite can be enlarged and the original surface structure of the graphite can be maintained by a laser pulse liquid phase corrosion technology, so that the graphite is dispersed; meanwhile, substances such as a surfactant and the like are not introduced in the preparation process; furthermore, the product prepared by the technical scheme provided by the invention has the yield of 87-95% and good stability through detection. The preparation method and the application of the aqueous phase graphene provided by the invention solve the technical defects of low yield and poor stability of graphene dispersion by a physical dispersion method in the prior art.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method and application of water-phase graphene.
Background
Graphene is a two-dimensional carbon nanomaterial consisting of a layer of carbon atoms, is the thinnest two-dimensional material known at present, and has unique properties in the aspects of mechanics, electricity, heat and the like. Due to the unique properties of graphene, the graphene has great potential application in the fields of conductive materials, antistatic materials, electromagnetic shielding materials of electronic products, microwave absorbing materials, gas sensors, optoelectronic devices, chemical energy solar cells, lithium ion batteries, catalyst electrodes and the like.
At present, the dispersion methods of graphene mainly include two main types, namely physical dispersion methods and chemical dispersion methods. The physical dispersion method can break up large graphene aggregates, but due to the hydrophobic property of graphene, the dispersed graphene is easy to aggregate together; the chemical dispersion method can enable graphene to adsorb a dispersing agent, the graphene is mutually repelled through electrostatic acting force or steric hindrance acting force, stable graphene dispersion liquid is obtained, a surfactant is often adsorbed on the surface of the graphene dispersed by the chemical method, and the surfactant is difficult to remove, so that the adverse effect which cannot be eliminated is generated on a produced device in actual use. However, the graphene is dispersed by a single physical means, so that the yield is low, the stability is poor, and the industrial demand cannot be met.
Therefore, a preparation method and an application of aqueous phase graphene are developed to solve the technical defects of low yield and poor stability of graphene dispersion by a physical dispersion method in the prior art, and thus the problem to be solved by the technical staff in the field is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method and an application of aqueous phase graphene, which are used for solving the technical defects of low yield and poor stability of graphene dispersed by a physical dispersion method in the prior art.
The invention provides a preparation method of water-phase graphene, which comprises the following steps:
step one, purification: purifying graphite in a protective atmosphere to obtain a first product;
step two, dispersing: mixing the first product with the dispersion liquid, and stirring and dispersing to obtain a second product;
step three, laser irradiation: carrying out laser irradiation on the second product under the ultrasonic condition to obtain a third product;
step four, ultrasonic emulsification: cooling the third product after ultrasonic emulsification to obtain a fourth product;
step five, shearing and homogenizing: sequentially shearing and homogenizing the fourth product in a water bath environment to obtain a fifth product;
step six, purification: and centrifuging the fifth product, and collecting supernatant to obtain a water-phase graphene product.
Preferably, in step one, the protective atmosphere is selected from: a mixed atmosphere of any one or more of argon, nitrogen, and helium;
in step one, the graphite is selected from: any one or more of natural graphite, artificial graphite, flake graphite, expandable graphite and expanded graphite, wherein the particle size of the graphite is less than 1 mm.
Preferably, in the first step, the purification method is: heating and purifying for 1-2 h at 2000-3000 ℃.
Preferably, in the second step, the dispersion liquid is ethanol and/or isopropanol;
the feeding ratio of the first product to the dispersion liquid is as follows by mass: 1 (500-20000).
Preferably, in the second step, the stirring speed is 6000 to 10000r/min, the stirring time is 2 to 30min, and the stirring temperature is 25 to 30 ℃ at room temperature.
Preferably, in the third step, the laser energy of the laser irradiation is 300-400 mJ, the pulse frequency of the laser irradiation is 10Hz, and the laser irradiation time is 0.5-1 h.
Preferably, in step four, the method of ultrasonic emulsification is: performing ultrasonic action for 5-12 h in a pulse mode of 2s on and 2s off under the condition of 30-60% of amplitude;
in the fourth step, the cooling temperature is 15-65 ℃, and the cooling method is water bath cooling.
Preferably, in the fifth step, the shearing speed is 4000-12000 r/min, the single action time of the shearing is 20-60 min, and the shearing frequency is 3-5 times;
in the fifth step, the temperature of the water bath is 15-65 ℃;
in the fifth step, the homogenizing pressure is 80-160 MPa, and the homogenizing times are 10-15 times
Preferably, in the sixth step, the centrifugal acceleration is 500-6000G, and the centrifugal time is 5-120 min.
The invention also provides an application of the water-phase graphene product obtained by the preparation method in the fields of catalyst preparation, heat dissipation, heating and preparation of lithium ion batteries or antistatic coatings.
In summary, the invention provides a preparation method of aqueous phase graphene, which comprises the following steps: purification, dispersion, laser irradiation, ultrasonic emulsification, shear homogenization and purification. The invention also provides an application of the aqueous phase graphene product obtained by the preparation method. In the technical scheme provided by the invention, the interlayer spacing of the graphite can be enlarged and the original surface structure of the graphite is kept by a laser pulse liquid phase corrosion technology, so that the graphite is dispersed; meanwhile, substances such as a surfactant and the like are not introduced in the preparation process; furthermore, the product prepared by the technical scheme provided by the invention has the yield of 87-95% and good stability through detection. The preparation method and the application of the aqueous phase graphene provided by the invention solve the technical defects of low yield and poor stability of graphene dispersion by a physical dispersion method in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic flow chart of a preparation method of aqueous phase graphene provided by the invention;
fig. 2 is a graph of the ultraviolet absorption spectrum of the graphene prepared in example 1 and the graphene dispersion of the control substance diluted in the same proportion in example 6.
Detailed Description
The invention provides a preparation method and application of aqueous phase graphene, which are used for solving the technical defects of low yield and poor stability of graphene dispersed by a physical dispersion method in the prior art.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to illustrate the present invention in more detail, the following describes a preparation method and an application of the aqueous phase graphene provided by the present invention in detail with reference to examples.
Example 1
Step one, 1000g of natural graphite is heated and purified for 2 hours at 2600 ℃ in the argon protective atmosphere to obtain a first product 1; wherein the particle size of the natural graphite is less than 1 mm.
And step two, mixing 10g of the first product 1 with 10000ml of dispersion liquid ethanol, and stirring and dispersing for 30min at 90r/min at room temperature (25-30 ℃) to obtain a second product 1.
Step three, carrying out laser irradiation on the second product 1 under the ultrasonic condition to obtain graphite turbid liquid, namely a third product 1; wherein the laser energy of laser irradiation is 400mJ, the pulse frequency of the laser irradiation is 10Hz, and the laser irradiation time is 1 h.
Step four, cooling the third product 1 after ultrasonic emulsification to obtain a fourth product 1; the ultrasonic emulsification method comprises the following steps: performing ultrasonic action for 6h in a pulse mode of 2s on and 2s off under the condition of 60% of amplitude; the ultrasonic emulsification is cooled in water bath in the whole process, and the cooling temperature is 30 ℃.
Step five, sequentially shearing and homogenizing the fourth product 1 in a water bath environment at 40 ℃ to obtain a fifth product 1; wherein the shearing speed is 10000r/min, the single action time of shearing is 30min, and the shearing frequency is 3 times; the pressure of homogenization is 120MPa, the single action time of homogenization is 5min, and the times of homogenization are 15 times.
And step six, centrifuging the fifth product 1, and collecting supernatant to obtain a water-phase graphene product. Wherein the centrifugal acceleration is 1200G, and the centrifugal time is 100 min. In this example, the yield of the aqueous phase graphene product was 92%.
Example 2
Step one, 800g of artificial graphite is heated and purified for 1h at 2200 ℃ in a high-purity nitrogen protective atmosphere to obtain a first product 2; wherein the particle size of the artificial graphite is less than 1 mm.
And step two, mixing 1g of the first product 2 with 20000ml of dispersion liquid ethanol, and stirring and dispersing for 20min at 120r/min at room temperature (25-30 ℃) to obtain a second product 2.
Step three, carrying out laser irradiation on the second product 2 under the ultrasonic condition to obtain graphite turbid liquid, namely a third product 2; wherein the laser energy of laser irradiation is 360mJ, the pulse frequency of the laser irradiation is 10Hz, and the laser irradiation time is 0.5 h.
Step four, cooling the third product 2 after ultrasonic emulsification to obtain a fourth product 2; the ultrasonic emulsification method comprises the following steps: performing ultrasonic action for 10 hours in a pulse mode of 2s on and 2s off under the condition of 30 percent of amplitude; the ultrasonic emulsification is cooled in water bath in the whole process, and the cooling temperature is 15 ℃.
Step five, sequentially shearing and homogenizing the fourth product 2 in a water bath environment at 15 ℃ to obtain a fifth product 2; wherein the shearing speed is 12000r/min, the single action time of the shearing is 40min, and the shearing frequency is 4 times; the pressure for homogenization is 160MPa, the single action time for homogenization is 6min, and the number of times for homogenization is 11.
And step six, centrifuging the fifth product 2, and collecting supernatant to obtain a water-phase graphene product. Wherein the centrifugal acceleration is 500G, and the centrifugal time is 120 min. In this example, the yield of the aqueous phase graphene product was 95%.
Example 3
Step one, heating and purifying 500g of a mixture of flake graphite and expandable graphite for 1.5h at 3000 ℃ in an argon protective atmosphere to obtain a first product 3; wherein the grain size of the crystalline flake graphite is less than 1 mm.
And step two, mixing 10g of the first product 3 with 5000ml of dispersion liquid ethanol, and stirring and dispersing for 2min at the room temperature at the speed of 150r/min to obtain a second product 3.
Step three, carrying out laser irradiation on the second product 3 under the ultrasonic condition to obtain graphite turbid liquid, namely a third product 3; wherein the laser energy of laser irradiation is 300mJ, the pulse frequency of the laser irradiation is 10Hz, and the laser irradiation time is 0.7 h.
Step four, cooling the third product 3 after ultrasonic emulsification to obtain a fourth product 3; the ultrasonic emulsification method comprises the following steps: performing ultrasonic action for 5h in a pulse mode of 2s on and 2s off under the condition of 45% of amplitude; the ultrasonic emulsification is cooled in water bath in the whole process, and the cooling temperature is 65 ℃.
Step five, sequentially shearing and homogenizing the fourth product 3 in a water bath environment at 50 ℃ to obtain a fifth product 3; wherein the shearing speed is 6000r/min, the single action time of the shearing is 60min, and the shearing frequency is 3 times; the homogenizing pressure is 100MPa, the single action time of homogenizing is 8min, and the homogenizing times are 10 times.
And step six, centrifuging the fifth product 3, and collecting supernatant to obtain a water-phase graphene product. Wherein the centrifugal acceleration is 6000G, and the centrifugal time is 40 min. In this example, the yield of the aqueous phase graphene product was 92%.
Example 4
Step one, 50g of expanded graphite is heated and purified for 1.2h at 2000 ℃ in a helium protective atmosphere to obtain a first product 4; wherein the particle size of the expanded graphite is less than 1 mm.
And step two, mixing 5g of the first product 4 with 3000ml of dispersion liquid ethanol, and stirring and dispersing at the room temperature (25-30 ℃) for 15min at the speed of 150r/min to obtain a second product 4.
Step three, carrying out laser irradiation on the second product 4 under the ultrasonic condition to obtain graphite turbid liquid, namely a third product 4; wherein the laser energy of laser irradiation is 350mJ, the pulse frequency of the laser irradiation is 10Hz, and the laser irradiation time is 0.6 h.
Step four, cooling the third product 4 after ultrasonic emulsification to obtain a fourth product 4; the ultrasonic emulsification method comprises the following steps: performing ultrasonic action for 12h in a pulse mode of 2s on and 2s off under the condition of 50% of amplitude; the ultrasonic emulsification is cooled in water bath in the whole process, and the cooling temperature is 60 ℃.
Step five, sequentially shearing and homogenizing the fourth product 4 in a water bath environment at 65 ℃ to obtain a fifth product 4; wherein the shearing speed is 4000r/min, the single action time of shearing is 30min, and the shearing frequency is 5 times; the pressure of homogenization is 80MPa, the single action time of the homogenization is 5min, and the times of the homogenization are 12 times.
And step six, centrifuging the fifth product 4, and collecting supernatant to obtain a water-phase graphene product. Wherein the centrifugal acceleration is 3000G, and the centrifugal time is 5 min. In this example, the yield of the aqueous phase graphene product was 95%.
In embodiments 1 to 4, the used pulsed laser liquid phase ablation technique is a technique that can be used for material surface modification, nano-film preparation, and nano-material growth, and has the advantages of being controllable in a certain range, being capable of operating at normal temperature and pressure, having very low impurity content in the reaction environment, and the like. The action principle is as follows: the pulse laser is irradiated on the surface of the material, the surface of the material absorbs the laser energy, the temperature is rapidly increased to generate melting, and the melted atoms or clusters are condensed again near the surface under the cooling and compressing action of the surrounding liquid to form the nano particles. When the energy of the incident pulse laser is very low, the laser irradiates the surface of the material, and the polarization enhancement effect increases the light field intensity of the surface of the material, so that the temperature of the material is rapidly increased; further, if the material is a layered material, the low-energy laser irradiation can expand the interlayer spacing and maintain the original surface structure of the material, thereby providing a high-quality precursor material for the subsequent stripping operation.
Example 5
This example is a specific example of performing bright field observation with a transmission electron microscope on the aqueous phase graphene products prepared in examples 1 to 4.
The aqueous phase graphene products prepared in the embodiments 1 to 4 are observed respectively, and can be seen in a microscope lens, the prepared aqueous phase graphene products are graphite sheets with holes, the diameter of each hole is 10-30 nm, and effective dispersion of graphite is realized.
Example 6
This example is a specific example for measuring the concentration and stability of the aqueous phase graphene products prepared in examples 1 to 4. In this example, the reference material used was a commercial graphene product.
The detection principle is that the detection is obtained by applying Lambert beer law A- α lC, wherein α is an absorption coefficient, A is an absorbance value at 660nm in an ultraviolet spectrum, l is a sample cell length (generally 0.01m), and C is the concentration of the graphene dispersion.
Firstly, a curve of concentration and absorbance is made through graphene with known volume concentration, then a specific numerical value of an extinction coefficient is calculated through the slope of a fitting straight line, and finally the concentration of the graphene is calculated by utilizing the absorbance of a sample to be measured at 660 nm.
Through dilution with the same multiple, the concentration of the graphene dispersion liquid prepared by the technical scheme provided by the invention is higher than the extinction coefficient of the dispersion liquid of a proportion by more than 1 time, which shows that the concentration of the graphene dispersion liquid prepared by the technical scheme provided by the invention is higher, and further shows that the concentration stability of the aqueous phase graphene product prepared by the embodiment is better.
When the graphene prepared in example 1 and a reference substance are allowed to stand for 30 days and then observed, the graphene prepared in example 1 is not layered, and the reference substance is obviously layered and cannot be used.
In view of the fact that the technical scheme provided by the invention is simple in proportion, other impurities except the solvent are not introduced, and the prepared product is good in stability, so that the preparation method can be widely applied to the field of catalyst preparation, the field of heat dissipation, the field of heating, and the preparation of lithium ion batteries or antistatic coatings.
In summary, the invention provides a preparation method of aqueous phase graphene, which comprises the following steps: purification, dispersion, laser irradiation, ultrasonic emulsification, shear homogenization and purification. The invention also provides an application of the aqueous phase graphene product obtained by the preparation method. In the technical scheme provided by the invention, the interlayer spacing of the graphite can be enlarged and the original surface structure of the graphite is kept by a laser pulse liquid phase corrosion technology, so that the graphite is dispersed; meanwhile, substances such as a surfactant and the like are not introduced in the preparation process; furthermore, the product prepared by the technical scheme provided by the invention has the yield of 87-95% and good stability through detection. The preparation method and the application of the aqueous phase graphene provided by the invention solve the technical defects of low yield and poor stability of graphene dispersion by a physical dispersion method in the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of water-phase graphene is characterized by comprising the following steps:
step one, purification: purifying graphite in a protective atmosphere to obtain a first product;
step two, dispersing: mixing the first product with the dispersion liquid, and stirring and dispersing to obtain a second product;
step three, laser irradiation: carrying out laser irradiation on the second product under the ultrasonic condition to obtain a third product;
step four, ultrasonic emulsification: cooling the third product after ultrasonic emulsification to obtain a fourth product;
step five, shearing and homogenizing: sequentially shearing and homogenizing the fourth product in a water bath environment to obtain a fifth product;
step six, purification: and centrifuging the fifth product, and collecting supernatant to obtain a water-phase graphene product.
2. The method according to claim 1, wherein in step one, the protective atmosphere is selected from the group consisting of: any one or more of argon, nitrogen, and helium;
in step one, the graphite is selected from: any one or more of natural graphite, artificial graphite, flake graphite, expandable graphite and expanded graphite, wherein the particle size of the graphite is less than 1 mm.
3. The method according to claim 1, wherein in step one, the purification method comprises: heating and purifying for 1-2 h at 2000-3000 ℃.
4. The method according to claim 1, wherein in the second step, the dispersion is ethanol and/or isopropanol;
the feeding ratio of the first product to the dispersion liquid is as follows by mass: 1 (500-20000).
5. The preparation method according to claim 1, wherein in the second step, the stirring speed is 6000 to 10000r/min, the stirring time is 2 to 30min, and the stirring temperature is room temperature.
6. The preparation method according to claim 1, wherein in the third step, the laser energy of the laser irradiation is 300-400 mJ, the pulse frequency of the laser irradiation is 10Hz, and the time of the laser irradiation is 0.5-1 h.
7. The method of claim 1, wherein in step four, the method of ultrasonic emulsification is: performing ultrasonic action for 5-12 h in a pulse mode of 2s on and 2s off under the condition of 30-60% of amplitude;
in the fourth step, the cooling temperature is 15-65 ℃, and the cooling method is water bath cooling.
8. The preparation method according to claim 1, wherein in the fifth step, the shearing speed is 4000-12000 r/min, the single action time of the shearing is 20-60 min, and the shearing frequency is 3-5 times;
in the fifth step, the temperature of the water bath is 15-65 ℃;
in the fifth step, the homogenizing pressure is 80-160 MPa, and the homogenizing times are 10-15 times.
9. The preparation method according to claim 1, wherein in the sixth step, the acceleration of the centrifugation is 500-6000G, and the time of the centrifugation is 5-120 min.
10. The application of the water-phase graphene product obtained by the preparation method of any one of claims 1 to 9 in the fields of catalyst preparation, heat dissipation, heat generation, lithium ion batteries or antistatic coating preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910979593.3A CN111470498A (en) | 2019-10-15 | 2019-10-15 | Preparation method and application of water-phase graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910979593.3A CN111470498A (en) | 2019-10-15 | 2019-10-15 | Preparation method and application of water-phase graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111470498A true CN111470498A (en) | 2020-07-31 |
Family
ID=71744979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910979593.3A Pending CN111470498A (en) | 2019-10-15 | 2019-10-15 | Preparation method and application of water-phase graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111470498A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477156A (en) * | 2022-03-11 | 2022-05-13 | 易会球 | Environment-friendly energy-saving graphene rotary-cut equipment |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057622A1 (en) * | 2002-01-08 | 2003-07-17 | Japan Science And Technology Corporation | Porous carbon nanostructure and method for preparation thereof |
| CN101327946A (en) * | 2008-06-05 | 2008-12-24 | 中山大学 | Micro-nanoparticle having special morphology, preparation and use thereof |
| CN102502613A (en) * | 2011-11-25 | 2012-06-20 | 北京工业大学 | Method for directly preparing graphene by aid of laser radiation of silicon carbide |
| US20130323158A1 (en) * | 2012-06-05 | 2013-12-05 | Purdue Research Foundation | Method of Laser Direct Synthesis of Graphene |
| CN103508451A (en) * | 2013-10-09 | 2014-01-15 | 江苏大学 | Method and device for nanosecond pulse laser-assisted preparation of nano-diamond |
| CN106044755A (en) * | 2016-05-31 | 2016-10-26 | 中国人民解放军装甲兵工程学院 | Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers |
| CN106365151A (en) * | 2016-08-29 | 2017-02-01 | 江苏大学 | Controllable graphene nanolayer preparation method |
-
2019
- 2019-10-15 CN CN201910979593.3A patent/CN111470498A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057622A1 (en) * | 2002-01-08 | 2003-07-17 | Japan Science And Technology Corporation | Porous carbon nanostructure and method for preparation thereof |
| CN101327946A (en) * | 2008-06-05 | 2008-12-24 | 中山大学 | Micro-nanoparticle having special morphology, preparation and use thereof |
| CN102502613A (en) * | 2011-11-25 | 2012-06-20 | 北京工业大学 | Method for directly preparing graphene by aid of laser radiation of silicon carbide |
| US20130323158A1 (en) * | 2012-06-05 | 2013-12-05 | Purdue Research Foundation | Method of Laser Direct Synthesis of Graphene |
| CN103508451A (en) * | 2013-10-09 | 2014-01-15 | 江苏大学 | Method and device for nanosecond pulse laser-assisted preparation of nano-diamond |
| CN106044755A (en) * | 2016-05-31 | 2016-10-26 | 中国人民解放军装甲兵工程学院 | Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers |
| CN106365151A (en) * | 2016-08-29 | 2017-02-01 | 江苏大学 | Controllable graphene nanolayer preparation method |
Non-Patent Citations (2)
| Title |
|---|
| L. ESCOBAR‑ALARCON ET AL: ""Two-dimensional carbon nanostructures obtained by laser ablation in liquid: effect of an ultrasonic field"", 《APPLIED PHYSICS A MATERIALS SCIENCE&PROCESSING》 * |
| 张颖: ""我国石墨烯产业化发展研究"", 《中国优秀硕士学位论文全文数据库 经济与管理科学辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477156A (en) * | 2022-03-11 | 2022-05-13 | 易会球 | Environment-friendly energy-saving graphene rotary-cut equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ganash et al. | The synthesis of carbon-based nanomaterials by pulsed laser ablation in water | |
| Komarov | Nano-and microstructuring of solids by swift heavy ions | |
| Shende et al. | Nitrogen doped hybrid carbon based composite dispersed nanofluids as working fluid for low-temperature direct absorption solar collectors | |
| Huang et al. | Bifunctional Au@ TiO2 core–shell nanoparticle films for clean water generation by photocatalysis and solar evaporation | |
| Alaferdov et al. | Size-controlled synthesis of graphite nanoflakes and multi-layer graphene by liquid phase exfoliation of natural graphite | |
| CN109110750B (en) | Method for preparing graphene by using expanded graphite | |
| EP3279138B1 (en) | Carbon film and method for producing same | |
| Uda et al. | Production and characterization of graphene from carbonaceous rice straw by cost-effect extraction | |
| CN111470498A (en) | Preparation method and application of water-phase graphene | |
| Yang et al. | Large-scale and green production of multi-layer graphene in deep eutectic solvents | |
| Zheng et al. | Encapsulation of graphene oxide/metal hybrids in nanostructured sol–gel silica ORMOSIL matrices and its applications in optical limiting | |
| Inoue et al. | Aqueous dispersion of hexagonal boron nitride via plasma processing in a hydroquinone solution | |
| Han et al. | Mechanical behaviours of penta-graphene and effects of hydrogenation | |
| Qian et al. | A large scale of CuS nano-networks: Catalyst-free morphologically controllable growth and their application as efficient photocatalysts | |
| Wang et al. | Synthesis of hollow ZnSnO3 nanospheres with high ethanol sensing properties | |
| CN106744878A (en) | The method for preparing large stretch of footpath Graphene is crushed in a kind of scale | |
| DE19904082A1 (en) | Process for the production of solar cells | |
| Liu et al. | A novel porous composite structure of titania nanowires grown on titanium foam for electrochemical degradation of methyl orange in water | |
| CN109824035A (en) | A kind of method that cellulose prepares graphene quantum dot | |
| Uchino et al. | Improvement of solvent affinity for graphene derivatives by solution plasma process | |
| Akbaba | Proton and electron irradiation effects on multi-walled carbon nanotubes | |
| Li et al. | Control of the size and luminescence of carbon nanodots by adjusting ambient pressure in laser ablation process | |
| Miao et al. | Enrichment of semiconducting single-walled carbon nanotubes by simple equipment and solar radiation | |
| Leng et al. | Effect of Cr@ RGO structure on microstructure and properties of RGO/CuCr25 composite | |
| Yan et al. | An abnormal non-incubation effect in femtosecond laser processing of freestanding reduced graphene oxide paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200731 |