CN113104842B - Functionalized graphene and preparation method and application thereof - Google Patents
Functionalized graphene and preparation method and application thereof Download PDFInfo
- Publication number
- CN113104842B CN113104842B CN202110296643.5A CN202110296643A CN113104842B CN 113104842 B CN113104842 B CN 113104842B CN 202110296643 A CN202110296643 A CN 202110296643A CN 113104842 B CN113104842 B CN 113104842B
- Authority
- CN
- China
- Prior art keywords
- ball
- reaction
- functionalized graphene
- preparation
- milling
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003801 milling Methods 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 238000009830 intercalation Methods 0.000 claims abstract description 21
- 230000002687 intercalation Effects 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- -1 amine salt Chemical class 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004299 exfoliation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000000498 ball milling Methods 0.000 description 67
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 23
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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
-
- 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
- C01B32/194—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses functionalized graphene and a preparation method and application thereof, and the preparation method comprises the following steps: adding the flake graphite powder, the intercalation auxiliary agent and the stripping auxiliary agent into reaction mill equipment, and sealing; introducing carbon dioxide gas into the reaction mill equipment to carry out reaction milling; and taking out the sample, screening, removing impurities and drying to obtain the functionalized graphene. According to the invention, by improving the preparation method, the functionalized graphene material with excellent performance can be obtained, and the preparation method can save the preparation cost and has an application prospect.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to functionalized graphene and a preparation method and application thereof.
Background
Graphene (Graphene) is sp 2 The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure, the new material has an ideal 2D structure, and the monoatomic thickness of the new material makes the new material the thinnest material in the world at present. Graphene has excellent optical, electrical and mechanical properties, and the excellent properties enable the graphene to be widely applied to multiple fields, such as materials science, micro-nano processing, energy, biomedicine, drug delivery and the like.
The preparation methods of graphene up to now mainly include two major types, namely a physical method and a chemical method, wherein the physical method mainly includes a mechanical stripping method, a liquid-phase or gas-phase direct stripping method and the like, and the chemical method mainly includes a chemical vapor deposition method, an oxidation-reduction method, a crystal epitaxial growth method, an arc discharge method and the like, wherein the oxidation-reduction method is one of the most common methods for preparing graphene at present due to the characteristics of low cost, simple and easily-controlled preparation process and the like.
Generally, graphene with a complete structure has a large aromatic conjugated structure, when a large number of graphene sheets are aggregated together, large van der waals force exists among the graphene sheets, so that the graphene is easy to aggregate and difficult to dissolve in water and other common organic solvents, which limits the exertion and application of excellent performance of the graphene, but the functionalized graphene becomes a main path for breaking through the application of the graphene, which is because the electrochemical performance and compatibility with other media are improved by introducing the functionalized functional group while the excellent performance of the graphene is maintained to the maximum extent by the functionalized graphene, so that the problem of easy aggregation of the graphene is effectively improved.
The Chinese patent application with the application number of 201510613444.7 discloses a method for preparing carboxyl functionalized graphene by a one-step method, which comprises the steps of adding natural crystalline flake graphite powder into a ball milling tank, introducing carbon dioxide gas, sealing and ball milling, and preparing the carboxyl functionalized graphene which contains a large amount of carboxyl functional groups on the surface and is in a lamellar structure by a one-step method; chinese patent with application number 201710862809.9 discloses a method for preparing edge carboxylated graphene and graphene by a reaction milling method, wherein graphite powder is placed in reaction milling equipment, the reaction milling equipment is sealed, carbon dioxide gas is flushed into the reaction milling equipment, the reaction milling equipment is started, and after a period of reaction milling, the edge carboxylated graphene is obtained; burning and reducing the edge carboxylated graphene in inert gas to obtain the edge carboxylated graphene. However, the two methods have single functionalization and relatively less amount of introduced carboxyl groups, and in addition, the problems of relatively thicker prepared graphene layer, longer preparation time, large energy consumption, high cost and unsatisfied environmental protection requirements exist.
Disclosure of Invention
In view of the above, the present invention needs to provide a functionalized graphene and a preparation method thereof, the preparation method is simple, the adopted raw materials are safe and environment-friendly, the surface of the obtained functionalized graphene contains a large number of oxygen-containing groups and has a relatively thin layer number, the functionalized graphene has excellent properties of graphene itself, the problem of agglomeration of graphene in a solvent can be improved, the dispersibility of graphene can be improved, and the preparation method has low energy consumption and meets the requirement of environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of functionalized graphene, which comprises the following steps:
adding the flake graphite powder, the intercalation auxiliary agent and the stripping auxiliary agent into reaction mill equipment, and sealing;
introducing carbon dioxide gas into the reaction mill equipment to carry out reaction milling;
and taking out the sample, screening, removing impurities, and drying to obtain the functionalized graphene.
Furthermore, the purity of the crystalline flake graphite powder is not lower than 99.98%, and the particle size of the crystalline flake graphite powder is not lower than 200 meshes.
Further, the intercalation auxiliary agent is selected from quaternary ammonium salt, organic amine salt and FeCl 3 At least one of EC, acetic acid and organic amide;
the stripping assistant is at least one selected from potassium permanganate, ammonium perchlorate, ammonium nitrate, mineral oil emulsion intercalation agent and polysiloxane.
Further, the mass ratio of the flake graphite powder to the intercalation assistant to the stripping assistant is 100: (1-5): (0.5 to 1);
the proportion of the flake graphite powder to the carbon dioxide gas is 1 g/(30-50) mL.
Further, the reaction mill equipment is filled with a reaction mill medium, the reaction mill medium accounts for 1/4-1/2 of the volume of the reaction mill equipment, the reaction mill medium is composed of a first ball and a second ball, and the number ratio of the first ball to the second ball is 1: (5-10), the particle diameter of the first ball is 2-5 mm, and the particle diameter of the second ball is 0.5-1 mm.
Furthermore, the rotating speed of the reaction mill is 500-1200 rpm, and the time is 5-9 h.
Further, the step of removing impurities specifically comprises: screening a sample to obtain a product, and washing the product with deionized water to be neutral;
the drying adopts freeze drying, and specifically comprises the following steps: after freeze drying at-20 to-10 ℃ for 2 to 5 hours, linearly heating to 15 to 25 ℃.
The invention also provides functionalized graphene prepared by adopting the preparation method of any one of the above.
Further, it has a C-O/C-O-C functional group content of not less than 5%, a COOH functional group content of not less than 16%, a specific surface area of not less than 760m 2 /g。
Further, the functionalized graphene is applied to a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention obtains high-purity non-agglomerated functionalized graphene containing various functional groups through a simple preparation process, wherein the functionalized graphene is in a lamellar structure, and the surface of the functionalized graphene contains a large number of oxygen-containing functional groups. The functionalized graphene not only has the excellent performance of graphene, but also improves the agglomeration problem of the graphene in a solvent, so that the graphene has good dispersibility. In addition, the invention avoids adopting high-risk and environment-unfriendly raw materials, and is safe and environment-friendly.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of functionalized graphene, which comprises the following steps:
adding the flake graphite powder, the intercalation auxiliary agent and the stripping auxiliary agent into reaction mill equipment, and sealing;
introducing carbon dioxide gas into the reaction mill equipment to carry out reaction milling;
and taking out the sample, screening, removing impurities, washing and drying to obtain the functionalized graphene.
The invention directly uses the crystalline flake graphite as a precursor, adds the intercalation auxiliary agent and the peeling auxiliary agent, and can obtain the functionalized graphene containing various functional groups by one-step reaction. The functionalized graphene prepared by the method disclosed by the invention is high in quality, simple to operate, easy to realize large-scale production, economic and environment-friendly.
Further, the flake graphite powder in the present invention is not particularly limited, and preferably, the flake graphite powder has a purity of not less than 99.98% and a particle size of not less than 200 mesh, and more preferably, a particle size of 325 mesh.
Further, the intercalation auxiliary agent is selected from quaternary ammonium salt, organic amine salt and FeCl 3 At least one of EC, acetic acid and organic amide;
the stripping assistant is at least one selected from potassium permanganate, ammonium perchlorate, ammonium nitrate, mineral oil emulsion intercalation agent and polysiloxane.
Further, the reaction mill apparatus described in the present invention is not particularly limited, and may be any apparatus capable of performing a reaction mill in the art, and specific examples include, but are not limited to, a self-propelled star ball mill, a horizontal ball mill, a high energy ball mill, a sand mill, and the like. The reaction mill equipment is filled with a reaction mill medium, the reaction mill medium accounts for 1/4-1/2 of the volume of the reaction mill equipment, and more preferably, the reaction mill medium accounts for 2/5 of the volume of the reaction mill equipment. The reaction grinding medium is composed of a first ball and a second ball, wherein the number ratio of the first ball to the second ball is 1: (5-10), the particle size of the first ball is larger than that of the second ball, and the reaction grinding is performed by adopting the balls with different particle sizes, so that the reaction grinding is performed more sufficiently, more oxygen-containing functional groups can be obtained on the surface of the graphene more easily, and the performance of the functionalized graphene is further improved. In the present invention, the particle diameter and material of the first and second balls are not particularly limited, and the material may be a reaction milling medium conventionally used in the art, such as stainless steel or zirconium dioxide, and the particle diameter may be adjusted according to the volume of the reaction milling equipment and the filling degree of the reaction milling medium, preferably, the particle diameter of the first ball is 2 to 5mm, the particle diameter of the second ball is 0.5 to 1mm, more preferably, the particle diameter of the first ball is 3mm, and the particle diameter of the second ball is 0.7mm.
Further, the mass ratio of the flake graphite powder to the intercalation auxiliary agent to the exfoliation auxiliary agent is 100: (1-5): (0.5 to 1); the ratio of the crystalline flake graphite powder to the carbon dioxide gas is 1 g/(30-50) mL, and preferably, in some specific embodiments of the invention, the ratio of the crystalline flake graphite powder to the carbon dioxide gas is 1g/40mL.
Further, the rotation speed and time of the reaction mill may be adjusted as needed, and are not particularly limited, and in some specific embodiments of the present invention, the rotation speed of the reaction mill is preferably 500 to 1200rpm, and the time is preferably 5 to 9 hours.
Further, the impurity removal in the present invention is mainly to remove impurities in the product, the removal method may adopt conventional means in the art, and since different reaction mill apparatuses or reaction mill media are adopted, the generated impurities are different and can be adjusted as required, and therefore are not limited specifically, in some specific embodiments of the present invention, when the reaction mill media adopt stainless steel balls, the impurity removal step specifically comprises: screening a sample to obtain a product, dissolving and diluting the product with deionized water, adding dilute hydrochloric acid to remove introduced iron impurities, removing impurities, and washing with water to be neutral. Preferably, in some embodiments of the present invention, the reaction milling medium is preferably made of zirconium dioxide, and in this case, the step of removing impurities is performed by only performing centrifugal washing until the reaction milling medium is neutral.
Further, the drying adopts freeze drying, and specifically comprises the following steps: after freeze drying at-20 to-10 ℃ for 2 to 5 hours, linearly heating to 15 to 25 ℃.
The second aspect of the invention discloses functionalized graphene prepared by the preparation method of the first aspect of the invention.
Further, the functionalized graphene prepared by the first aspect of the present invention maintains excellent properties of graphene, and has a surface containing a large amount of oxygen-containing functional groups, a C-O/C-O-C functional group content of not less than 5%, a-COOH functional group content of not less than 16%, and a specific surface area of not less than 760m 2 The functionalized graphene has excellent dispersibility, and the problem of easy agglomeration in a solvent can be obviously improved.
In a third aspect of the present invention, the application of the functionalized graphene according to the second aspect of the present invention in a lithium ion battery is disclosed. The functionalized graphene has excellent dispersibility, so that the problem of easy agglomeration of the graphene is greatly improved, and the functionalized graphene can be well dispersed in conductive slurry of a lithium ion battery, so that the prepared lithium ion battery has excellent performance.
The technical solution of the present invention will be more clearly and completely described below with reference to specific examples and comparative examples.
Example 1
The preparation method of the functionalized graphene in the embodiment specifically comprises the following steps:
50 zirconium dioxide ball-milling balls with the diameter of 3mm and 350 zirconium dioxide ball-milling balls with the diameter of 0.7mm are added into a 50L ball-milling tank, the zirconium dioxide ball-milling balls account for 2/5 of the volume of the ball-milling tank, and then 5000g of high-purity flake graphite powder (the purity is not lower than 99.98 percent) with the specification of 325 meshes and 60g of FeCl are added 3 Adding an intercalation assistant and 25g of ammonium perchlorate stripping assistant into a ball milling tank, and sealing;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/50mL;
opening a ball milling tank, carrying out ball milling reaction for 7h at the rotating speed of 700r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 3h, and linearly heating the freeze-dried sample from-10 ℃ to 15 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 2
Adding 60 zirconium dioxide ball-milling balls with the diameter of 3mm and 300 zirconium dioxide ball-milling balls with the diameter of 0.6mm into a 50L ball-milling tank, wherein the zirconium dioxide ball-milling balls account for 2/5 of the volume of the reaction milling tank, adding 5000g of high-purity flake graphite powder (the purity is not lower than 99.98%) with the specification of 350 meshes, 65g of organic ammonium salt intercalation auxiliary agent and 30g of potassium permanganate stripping auxiliary agent into the ball-milling tank, and sealing;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/50mL;
opening a ball milling tank, performing ball milling reaction for 8 hours at the rotating speed of 800r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separating sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 4 hours, and linearly heating the freeze-dried sample from-15 ℃ to 20 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 3
50 zirconium dioxide ball-milling balls with the diameter of 4mm and 320 zirconium dioxide ball-milling balls with the diameter of 1mm are added into a 50L ball-milling tank, the zirconium dioxide ball-milling balls account for 2/5 of the volume of the reaction milling tank, and 5000g of high-purity crystalline flake graphite powder (the purity is not lower than 99.98%) with the specification of 400 meshes, 70g of organic amide intercalation auxiliary agent and 40g of ammonium nitrate stripping auxiliary agent are added into the ball-milling tank and sealed;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/50mL;
opening a ball milling tank, carrying out ball milling reaction for 6h at the rotating speed of 900r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 4h, and linearly heating the freeze-dried sample from-15 ℃ to 25 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 4
Adding 60 zirconium dioxide ball-milling balls with the diameter of 4mm and 400 zirconium dioxide ball-milling balls with the diameter of 0.5mm into a 50L ball-milling tank, wherein the zirconium dioxide ball-milling balls account for 2/5 of the volume of the reaction milling tank, adding 5000g of high-purity flake graphite powder (the purity is not lower than 99.98 percent) with the specification of 425 meshes, 80g of EC intercalation auxiliary agent and 35g of polysiloxane stripping auxiliary agent into the ball-milling tank, and sealing;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/50mL;
opening a ball milling tank, carrying out ball milling reaction for 8h at the rotating speed of 850r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 4h, and linearly heating the freeze-dried sample from-10 ℃ to 15 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 5
Adding 55 zirconium dioxide ball-milling balls with the diameter of 3mm and 320 zirconium dioxide ball-milling balls with the diameter of 0.6mm into a 50L ball-milling tank, wherein the zirconium dioxide ball-milling balls account for 2/5 of the volume of the reaction milling tank, adding 5000g of high-purity flake graphite powder (the purity is not lower than 99.98%) with the specification of 425 meshes, 75g of quaternary ammonium salt intercalation auxiliary agent and 60g of mineral oil emulsion stripping auxiliary agent into the ball-milling tank, and sealing;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/50mL;
opening a ball milling tank, carrying out ball milling reaction for 6h at the rotating speed of 750r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 5h, and linearly heating the freeze-dried sample from-10 ℃ to 25 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 6
Adding 50 zirconium dioxide ball-milling balls with the diameter of 2mm and 500 zirconium dioxide ball-milling balls with the diameter of 0.5mm into a ball-milling tank, wherein the zirconium dioxide ball-milling balls account for 1/4 of the volume of the reaction milling tank, adding 5000g of high-purity crystalline flake graphite powder with the specification of 400 meshes (the purity is not lower than 99.98%), 50g of acetic acid intercalation aid and 50g of mineral oil emulsion stripping aid into the ball-milling tank, and sealing;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/30mL;
opening a ball milling tank, carrying out ball milling reaction for 9h at the rotating speed of 1000r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 3h, and linearly heating the freeze-dried sample from-20 ℃ to 15 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Example 7
30 zirconium dioxide ball-milling balls with the diameter of 5mm and 300 zirconium dioxide ball-milling balls with the diameter of 1mm are added into a ball-milling tank, wherein the zirconium dioxide ball-milling balls account for 1/2 of the volume of the reaction milling tank, and then 5000g of high-purity crystalline flake graphite powder with the specification of 350 meshes (the purity is not lower than 99.98%), 250g of acetic acid intercalation aid and 35g of ammonium nitrate stripping aid are added into the ball-milling tank and sealed;
filling carbon dioxide gas into the ball milling tank, wherein the proportion of the crystalline flake graphite powder to the carbon dioxide gas is 1g/40mL;
opening a ball milling tank, carrying out ball milling reaction for 5h at the rotating speed of 1200r/min to obtain a functionalized graphene sample, separating the sample from ball milling balls through a sample separation sieve, centrifugally washing the product to be neutral, removing impurities, freeze-drying for 2h, and linearly heating the freeze-dried sample from-15 ℃ to 20 ℃ at the heating rate of 0.5 ℃/min to obtain functionalized graphene powder.
Test example
The functionalized graphene obtained in examples 1 to 7 was dried in a vacuum environment at 80 ℃ for 3 hours, and then dissolved in absolute ethanol respectively for 0.5 hour by ultrasound to obtain uniform graphene dispersions, which were then subjected to specific surface area and xps tests respectively. The information on the surface element composition and the distribution of carbon-containing type of the functionalized graphene prepared in the examples is shown in table 1.
Specific surface area and surface functional group type distribution of functionalized graphene in table 1 example
As can be seen from Table 1, the functionalized graphene prepared in examples 1-7 has an average C-O/C-O-C functional group content of 6.59%, an average COOH functional group content of 17.26%, and an average specific surface area of 790.7m after ball milling for 5-9h 2 The preparation method has the advantages of short preparation time and excellent performance of the obtained functionalized graphene.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of functionalized graphene is characterized by comprising the following steps:
adding flake graphite powder, an intercalation assistant and a stripping assistant into reaction mill equipment, and sealing, wherein the intercalation assistant is selected from quaternary ammonium salt, organic amine salt and FeCl 3 At least one of acetic acid and organic amide; the stripping auxiliary agent is at least one selected from potassium permanganate, ammonium perchlorate, ammonium nitrate, mineral oil emulsion intercalation agent and polysiloxane;
introducing carbon dioxide gas into the reaction milling equipment and carrying out reaction milling, wherein the reaction milling equipment is filled with a reaction milling medium, the reaction milling medium accounts for 1/4 to 1/2 of the volume of the reaction milling equipment, and the reaction milling medium consists of a first ball and a second ball, wherein the number ratio of the first ball to the second ball is 1: (5-10), the particle diameter of the first ball is 2-5 mm, and the particle diameter of the second ball is 0.5-1 mm;
and taking out the sample, screening, removing impurities, and drying to obtain the functionalized graphene.
2. The method of claim 1, wherein the crystalline flake graphite powder has a purity of not less than 99.98% and a particle size of not less than 200 mesh.
3. The preparation method according to claim 1, wherein the mass ratio of the flake graphite powder, the intercalation aid and the exfoliation aid is 100: (1-5): (0.5 to 1);
the proportion of the scale graphite powder to the carbon dioxide gas is 1 g/(30-50) mL.
4. The method of claim 1, wherein the reaction mill is rotated at 500-1200 rpm for 5-9 hours.
5. The preparation method according to claim 1, wherein the step of removing impurities comprises: screening a sample to obtain a product, and washing the product with deionized water to be neutral;
the drying adopts freeze drying, and specifically comprises the following steps: after freeze drying at-20 to-10 ℃ for 2 to 5 hours, linearly heating to 15 to 25 ℃.
6. A functionalized graphene prepared by the preparation method according to any one of claims 1 to 5.
7. The functionalized graphene according to claim 6, wherein the content of C-O/C-O-C functional groups is not less than 5%, the content of-COOH functional groups is not less than 16%, and the specific surface area is not less than 760m 2 /g。
8. Use of the functionalized graphene according to claim 6 or 7 for the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110296643.5A CN113104842B (en) | 2021-03-19 | 2021-03-19 | Functionalized graphene and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110296643.5A CN113104842B (en) | 2021-03-19 | 2021-03-19 | Functionalized graphene and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113104842A CN113104842A (en) | 2021-07-13 |
| CN113104842B true CN113104842B (en) | 2022-10-11 |
Family
ID=76712055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110296643.5A Active CN113104842B (en) | 2021-03-19 | 2021-03-19 | Functionalized graphene and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113104842B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735101B (en) * | 2021-09-23 | 2024-04-09 | 上海烯望新材料科技有限公司 | Method for preparing lipophilic few-layer graphene by stripping method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| WO2015167113A1 (en) * | 2014-04-29 | 2015-11-05 | 국립대학법인 울산과학기술대학교 산학협력단 | Method for preparing graphite with functionalized edge from lower grade graphite through mechanical and chemical method, and graphene nanoplate manufactured thereby |
| CN105271188A (en) * | 2015-09-23 | 2016-01-27 | 合肥国轩高科动力能源有限公司 | Method for preparing carboxyl functionalized graphene by one-step method |
| CN106115679A (en) * | 2016-07-04 | 2016-11-16 | 济南大学 | A kind of low cost prepares the method for Graphene |
| CN107651669A (en) * | 2017-09-22 | 2018-02-02 | 北京化工大学 | A kind of method reacted mill method and prepare edge carboxylated graphene and graphene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529606B (en) * | 2017-03-03 | 2020-12-29 | 江苏天奈科技股份有限公司 | High-stability graphene slurry and preparation method thereof |
| CN107089655A (en) * | 2017-06-16 | 2017-08-25 | 青岛大学 | A kind of method that utilization Mechanical Method prepares single-layer graphene |
-
2021
- 2021-03-19 CN CN202110296643.5A patent/CN113104842B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| WO2015167113A1 (en) * | 2014-04-29 | 2015-11-05 | 국립대학법인 울산과학기술대학교 산학협력단 | Method for preparing graphite with functionalized edge from lower grade graphite through mechanical and chemical method, and graphene nanoplate manufactured thereby |
| CN105271188A (en) * | 2015-09-23 | 2016-01-27 | 合肥国轩高科动力能源有限公司 | Method for preparing carboxyl functionalized graphene by one-step method |
| CN106115679A (en) * | 2016-07-04 | 2016-11-16 | 济南大学 | A kind of low cost prepares the method for Graphene |
| CN107651669A (en) * | 2017-09-22 | 2018-02-02 | 北京化工大学 | A kind of method reacted mill method and prepare edge carboxylated graphene and graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113104842A (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108706575B (en) | Preparation method of liquid-phase ball-milling stripped graphene | |
| CN108298541B (en) | Preparation method of two-dimensional layered MXene nanosheet | |
| CN108736007B (en) | Preparation method of high-compaction-density lithium ion battery silicon-carbon negative electrode material | |
| WO2017084561A1 (en) | Preparation method for large-size graphene oxide or graphene | |
| CN113104842B (en) | Functionalized graphene and preparation method and application thereof | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN108529606B (en) | High-stability graphene slurry and preparation method thereof | |
| JP2015105200A (en) | Flaky graphite dispersion and production method of flaky graphite | |
| CN110272038A (en) | A kind of method of Mechanical Driven rubber molecule Boli scale preparing graphite alkene | |
| CN112008086B (en) | Antimonene nanosheet effectively stripped through physical modification and preparation method thereof | |
| CN113443620B (en) | Preparation method and application of few-layer graphene powder | |
| US20210164114A1 (en) | Precursor materials and methods for the preparation of nanostructured carbon materials | |
| CN106276881B (en) | A kind of preparation method of graphene | |
| CN105197918A (en) | High-quality graphene and quick preparation method thereof | |
| Wang et al. | Preparation of natural microcrystalline graphite with high sphericity and narrow size distribution | |
| JP2013100219A (en) | Method for producing flake-shaped fine graphite particles | |
| CN113753870A (en) | GeP nanosheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof | |
| JP2013163620A (en) | Method for producing high purity graphite powder | |
| CN106311581A (en) | Manufacturing method for efficient composite heat sink for electronic product | |
| CN105633382A (en) | Preparation method for cobalt oxide/graphene composite negative electrode material of lithium ion battery | |
| CN106531996A (en) | Negative electrode material for lithium-ion battery and preparation method of negative electrode material | |
| CN110028070B (en) | Single crystal silicon carbide/graphene core-shell structure nanofiber and preparation method and application thereof | |
| CN113817927B (en) | Method for efficiently preparing arsenic-alkene nanosheets | |
| CN108584919A (en) | A kind of non-destructive dispersing method of carbon nanotube | |
| Li et al. | Fabrication and electrochemical performance of graphene—ZnO nanocomposites |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |