CN113620280A - Graphene powder gas-phase physical stripping method and produced graphene - Google Patents
Graphene powder gas-phase physical stripping method and produced graphene Download PDFInfo
- Publication number
- CN113620280A CN113620280A CN202110999210.6A CN202110999210A CN113620280A CN 113620280 A CN113620280 A CN 113620280A CN 202110999210 A CN202110999210 A CN 202110999210A CN 113620280 A CN113620280 A CN 113620280A
- Authority
- CN
- China
- Prior art keywords
- graphene
- ball
- stainless steel
- powder
- magnesium
- 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
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B2204/02—Single layer graphene
-
- 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
- C01B2204/04—Specific amount of layers or specific thickness
-
- 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
- C01B2204/32—Size or surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of graphene production, in particular to a graphene powder gas-phase physical stripping method, which comprises the following steps: high-purity flaky graphite is selected as a raw material for producing graphene, the flaky graphite and a ball-milling stripping medium are mixed and sent into a ball mill, polyvinylpyrrolidone, polyvinyl alcohol and oleamide are added to carry out ball-milling stripping under the protection of inert gas, and graphene sheets stripped by the ball mill are separated by air flow classification under the protection of inert gas after stripping is finished. The production of the graphene is completed by a physical method, the graphene sheets exist in a complete powder form, the storage and use environment is not limited, the industrial production cost is low, and the graphene is conveniently and widely applied to various industries.
Description
Technical Field
The invention relates to the technical field of graphene production, in particular to a graphene powder gas-phase physical stripping method and produced graphene.
Background
The graphene is a two-dimensional crystal, carbon atoms are arranged in a hexagon and are connected with each other to form a carbon molecule, and the structure of the graphene is very stable; as the number of carbon atoms attached increases, the two-dimensional carbon molecule plane increases and the molecule size increases. The thickness of a single-layer graphene is only one carbon atom, namely 0.335 nm, which is equivalent to 20 ten-thousandth of the thickness of one hair, and about 150 ten thousand layers of graphene exist in 1 mm thick graphite. Graphene is the thinnest material known, and has the advantages of extremely high specific surface area, super conductivity and strength. The above advantages exist in that the method has good market prospect.
However, the method for industrial production in the prior art is mainly realized by a redox method and a Chemical Vapor Deposition (CVD), the redox method is simple in production, but is easy to cause waste liquid pollution, and the produced graphene has structural defects;
the graphene film with a small number of layers, which is large in area, continuous, transparent and high in conductivity, can be prepared by a chemical vapor deposition method, is mainly used for an anode of a photovoltaic device, and obtains the energy conversion efficiency of up to 1.71%; about 55.2% of its energy conversion efficiency compared to elements made with indium tin oxide material; but the defects are that the production difficulty is high, the production cost is high, and the application of the graphene is difficult to be widely developed; the graphene is obtained by repeatedly sticking and tearing the adhesive tape, and the graphene is low in efficiency or high in production cost in a friction method and a CVD method, so that the application popularization of the graphene is not facilitated.
Based on the method, the research on the process for producing the graphene by a low-cost physical method has revolutionary significance and needs further research, development and treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a graphene powder gas-phase physical stripping method.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a graphene powder gas-phase physical stripping method, which comprises the following steps:
high-purity flaky graphite is selected as a raw material for producing graphene, the flaky graphite and a ball-milling stripping medium are mixed and sent into a ball mill, polyvinylpyrrolidone, polyvinyl alcohol and oleamide are added to carry out ball-milling stripping under the protection of inert gas, and graphene sheets stripped by the ball mill are separated by air flow classification under the protection of inert gas after stripping is finished.
Preferably, the ball milling stripping medium is a composition of stainless steel balls, stainless steel powder and aluminum-magnesium-silicon alloy powder.
Preferably, the stainless steel ball is a 304 stainless steel ball; the stainless steel powder is spherical; the shape of the aluminum-magnesium-silicon alloy powder is spherical;
the diameter of the stainless steel ball is 0.3-10mm, and the weight of the stainless steel ball accounts for 3-50% of the ball-milling stripping medium;
the grain size range of the stainless steel powder is 5-150 mu m, and the weight of the stainless steel powder accounts for 15-90% of that of the ball-milling stripping medium;
the grain size range of the aluminum-magnesium-silicon alloy powder is 7-70 mu m, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 10-80% of the ball milling stripping medium;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 40-90%, the mass percentage of magnesium is 10-60%, and the mass percentage of silicon is 3-20%;
the average grain diameter D50 of the flake graphite is 1-50 μm, D100 is less than 20-100 μm, the impurity content is less than or equal to 0.1%, and the weight of the flake graphite is less than 7% of that of the ball-milling stripping medium.
Preferably, the diameter of the stainless steel ball is 0.4-1.0 mm; the weight of the stainless steel balls accounts for 5-45% of the ball-milling stripping medium;
the grain size range of the stainless steel powder is 10-100 μm, and the weight of the stainless steel powder accounts for 20-85% of the ball milling stripping medium;
the grain size range of the aluminum-magnesium-silicon alloy powder is 10-50 mu m, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 20-60% of the ball-milling stripping medium;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 50-80%, the mass percentage of magnesium is 20-50%, and the mass percentage of silicon is 5-15%;
the average particle size D50 of the flaky graphite is 2-30 μm; the weight of the flaky graphite is 2-5% of that of the ball-milling stripping medium;
preferably, the diameter of the stainless steel ball is 0.6-0.8mm, and the weight of the stainless steel ball accounts for 8-12% of the ball-milling stripping medium;
the grain size range of the stainless steel powder is 20-40 μm, and the weight of the stainless steel powder accounts for 30-60% of the ball-milling stripping medium;
the grain size range of the aluminum-magnesium-silicon alloy powder is 18-45 mu m, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 28-48% of that of the ball-milling stripping medium;
the stainless steel powder is 304 or 316 stainless steel powder for 3D printing;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 60-70%, the mass percentage of magnesium is 20-30%, and the mass percentage of silicon is 8-12%;
the average particle size D50 of the flaky graphite is 3-8 μm; the weight of the flaky graphite is 3.5 percent of that of the ball-milling stripping medium.
Preferably, the mixing ratio of the polyvinylpyrrolidone, the polyvinyl alcohol and the oleamide is 2: 5: 3, adding 1-3% of flaky graphite by mass; the polyvinyl pyrrolidone, the polyvinyl alcohol and the oleamide are matched and used for mainly reducing the agglomeration of the graphene and facilitating the dispersion.
Preferably, the inert gas protection is in an inert gas atmosphere with an oxygen content of less than 0.5 vol%, and the inert gas is nitrogen.
Preferably, the ball milling stripping temperature is 100-; the oxygen content of the atmosphere in the ball mill is controlled between 0.1 and 0.5 volume percent, and the protective pressure of nitrogen is 30 to 50 KPa.
The graphene produced by the stripping method has the average particle size of 0.6-5 mu m, the average thickness of 0.33-3nm and 1-10 layers of graphene, and is completely transparent; the average particle size of the graphene sheet is 0.8-4 μm, and the average thickness of the graphene sheet is 0.33-2 nm; the average particle size of the graphene sheet is 1-3 μm, and the average thickness is 0.33-1.5 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, stainless steel powder and aluminum-magnesium-silicon alloy spherical powder are added into a ball mill to serve as most of ball milling stripping media, a small amount of traditional steel ball media is added to increase kinetic energy, the shortage of kinetic energy of alloy powder is made up, the specific gravity difference between the three types of stripping media is large, the characteristic of large specific gravity difference is utilized in the stripping process, the main steel ball and the stainless steel powder play a main role in the stripping process within the first 150 plus 250 hours, the main role is played by the stainless steel powder and the aluminum-magnesium-silicon alloy powder within the later 250 plus 400 hours, friction and relative movement among the aluminum-magnesium-silicon alloy powder, the stainless steel powder, the steel ball and flake graphite continuously reduce flake graphite sheets, and a graphene thin layer material is obtained;
the processing technology is changed into nanoscale processing, the aluminum-magnesium-silicon alloy powder has the characteristics of good fluidity, light specific gravity and good strength, and as the graphene sheets are very easy to fall off, one or more layers of graphene can be stripped off every time the stainless steel powder and the aluminum-magnesium-silicon alloy powder are contacted with the kinetic energy of flake graphite along with the driving of the kinetic energy of the steel ball, the situation of stripping again for several times can occur in the stripping process, the graphene sheets can continuously wrap the surfaces of the stainless steel powder and the aluminum-magnesium-silicon alloy powder and continuously separate from the surfaces of the stainless steel powder and the aluminum-magnesium-silicon alloy powder to suspend on the uppermost layer of the space of the ball mill, and after the plurality of graphene sheets stripped before are contacted with the alloy powder again, the number of layers can be reduced again to form single-layer or few-layer graphene sheets.
(2) The graphene sheets can be peeled off again for several times in the peeling process, when the peeled multilayer graphene sheets are contacted with the alloy powder again, the number of layers can be reduced again to form single-layer or few-layer graphene sheets, the specific surface area of the micron-sized stainless steel powder and the aluminum-magnesium-silicon alloy powder used for ball milling and peeling is large, the peeling efficiency is high, the service life is long, the alloy powder can be repeatedly used, the phenomena of crushing and abrasion basically do not occur, and the alloy powder can be replaced once in 4-6 months;
the method is completely different from the existing graphene production process and is completed by a physical method, the graphene sheets exist in a complete powder form, the storage and use environment is not limited, the industrial production cost is low, the graphene is conveniently and widely applied to various industries, and the method is a revolution of the graphene processing industry.
Drawings
Fig. 1 is a graph showing the effect of the purity of flaky graphite on the thickness of graphene flakes.
FIG. 2 is a graph of the effect of stainless steel powder thickness on graphene sheet thickness;
FIG. 3 is an SEM image of a raw material high purity flaky graphite;
FIG. 4 is an SEM image of layer sampling in a ball mill after 50 hours;
FIG. 5 is an SEM image of layer sampling in a ball mill after 150 hours;
FIG. 6 is an SEM image of layer sampling in a ball mill after 380 hours;
fig. 7 is a graph showing the effect of the thickness of the si-mg-al alloy powder on the thickness of the graphene sheet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The graphene powder gas-phase physical stripping method of the embodiment comprises the following steps:
high-purity flaky graphite is selected as a raw material for producing graphene, the flaky graphite and a ball-milling stripping medium are mixed and sent into a ball mill, polyvinylpyrrolidone, polyvinyl alcohol and oleamide are added to carry out ball-milling stripping under the protection of inert gas, and graphene sheets stripped by the ball mill are separated by air flow classification under the protection of inert gas after stripping is finished.
The ball milling stripping medium of the embodiment is a composition of stainless steel balls, stainless steel powder and aluminum-magnesium-silicon alloy powder.
The stainless steel ball of the embodiment is a 304 stainless steel ball; the stainless steel powder is spherical; the shape of the aluminum-magnesium-silicon alloy powder is spherical;
the diameter of the stainless steel ball is 0.3-10mm, and the weight of the stainless steel ball accounts for 3-50% of the ball-milling stripping medium;
the grain size range of the stainless steel powder is 5-150 mu m, and the weight of the stainless steel powder accounts for 15-90% of that of the ball-milling stripping medium;
the grain size range of the aluminum-magnesium-silicon alloy powder is 7-70 mu m, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 10-80% of the ball milling stripping medium;
the aluminum mass percentage in the aluminum-magnesium-silicon alloy powder is 40-90%, the magnesium mass percentage is 10-60%, and the silicon mass percentage is 3-20%;
the average grain diameter D50 of the flake graphite is 1-50 μm, D100 is less than 20-100 μm, the impurity content is less than or equal to 0.1%, and the weight of the flake graphite is less than 7% of that of the ball-milling stripping medium.
The mixing ratio of polyvinylpyrrolidone, polyvinyl alcohol and oleamide in this example is 2: 5: 3, the addition amount of the flaky graphite is 1-3% by mass.
The inert gas blanket of this example was under an atmosphere of an inert gas having an oxygen content of less than 0.5% by volume, the inert gas being nitrogen.
The ball milling stripping temperature is 100-; controlling the oxygen content of the atmosphere in the ball mill to be 0.1-0.5 volume percent, and the protective pressure of nitrogen is 30-50 KPa; the airflow classification adopts 4 30KW four-linkage airflow classifiers, the rotating speed of a classification wheel of each classifier is kept at 9000 rpm, the wind speed is kept at 22-25 m/s, 1-2 layers of graphene sheets are separated into superior products, 2-5 layers of graphene sheets are separated out to be used as superior products, 4-10 layers of graphene sheets are used as secondary products, and more than 10 layers of graphene sheets are separated into inferior products;
in the graphene produced by the stripping method of the embodiment, the average particle size of the graphene sheet is 0.6-5 μm, the average thickness is 0.33-3nm, the graphene sheet has 1-10 layers of graphene, and the graphene sheet is completely transparent; the average particle size of the graphene sheet is 0.8-4 μm, and the average thickness of the graphene sheet is 0.33-2 nm; the average particle size of the graphene sheet is 1-3 μm, and the average thickness is 0.33-1.5 nm.
The ball mill is made of 1800mm 2800mm stainless steel (304), the rotating speed of the ball mill is 60-80 r/min, and the ball mill is used for ball milling and stripping under the pressure of 30-50 KPa.
Example 1
The graphene powder gas-phase physical stripping method of the embodiment comprises the following steps:
adding flaky graphite with the average particle diameter D50 of 2-7 mu m, D100 of less than 25 mu m and impurity content of less than or equal to 0.1 percent and stripping medium consisting of 18-45 mu m aluminum-magnesium-silicon alloy powder (aluminum content is 65wt percent, magnesium content is 25wt percent and silicon content is 10wt percent in aluminum-magnesium-silicon alloy) and stainless steel balls with the diameter of 0.5-0.9 mm and stainless steel powder with the diameter of 20-40 mu m into a ball mill, wherein the weight of the stainless steel balls, the stainless steel powder and the aluminum-magnesium-silicon alloy powder accounts for the following table 1, the weight of the flaky graphite is 3.5 percent of the ball milling stripping medium (the sum of the steel balls, the stainless steel powder and the aluminum-magnesium-silicon alloy powder), the ball mill rotates at 60-80 r/min and the temperature of 100 DEG, the ball milling stripping is carried out in a nitrogen atmosphere with the oxygen content of 0.1-0.5 percent, the nitrogen pressure is 30-50KPa, the ball milling stripping time is 300-400 hours, graphene sheets stripped by ball milling are separated in a grading manner through airflow under the protection of inert gas after the ball milling stripping is finished, then accurate grading is performed for multiple times through airflow, a grading system is a closed system, 4 30KW four-linked airflow grading machines are adopted, the rotating speed of a grading wheel of each grading machine is kept at 9000 r/min, the wind speed is kept at 22-25 m/s, 1-2 layers of graphene sheets can be separated out independently to serve as special products, 2-5 layers of graphene sheets are separated to serve as superior products, 4-10 layers of graphene sheets serve as second products, and finally the graphene sheets larger than 10 layers are divided into inferior products. The average particle size and average thickness of the obtained graphene platelet product are shown in the following table.
TABLE 1
As can be seen from table 1, the matching effect of 10% of steel balls, 48% of stainless steel powder and 42% of aluminum-magnesium-silicon alloy powder is the best, the graphene sheets are peeled to the best state, the single layer rate is the highest, the proper range is 30-60% of the weight of the stainless steel powder, 28-60% of the weight of the aluminum-magnesium-silicon alloy powder and 8-12% of the weight of the steel balls.
Example 2
Adding flaky graphite with the average particle size D50 of 2-7 mu m, the D100 of less than 25 mu m and the impurity content of less than or equal to 0.1 percent, and a ball milling stripping medium consisting of spherical aluminum-magnesium-silicon alloy powder with the particle size of 18-45 mu m, stainless steel balls with the diameter of 0.5-0.9 mm and stainless steel powder with the particle size of 20-40 mu m into a ball mill, wherein the ball milling stripping medium comprises 10 percent of the weight of the steel balls, 42 percent of the weight of the stainless steel powder, 48 percent of the weight of the aluminum-magnesium-silicon alloy powder, 65 percent of aluminum, 25 percent of magnesium and 10 percent of silicon in the aluminum-magnesium-silicon alloy. The weight ratio of the scaly graphite to the weight of the ball-milling exfoliation medium (the sum of the steel balls, the stainless steel powder, and the aluminum-magnesium-silicon alloy powder) is shown in table 2, in which polyvinylpyrrolidone, polyvinyl alcohol, and oleamide are added to the ball mill to perform ball-milling exfoliation under the protection of inert gas, and after the exfoliation is completed, the working conditions of separating the graphene flakes after ball-milling exfoliation by air classification under the protection of inert gas are the same as those in example 1.
TABLE 2
As can be seen from table 2, the amount of the flaky graphite material added is preferably about 4.5% by weight based on the total weight of the ball-milling exfoliation medium, and preferably 2%, 3%, 3.5%, 4.5% and 7%.
Example 3
Adding flaky graphite with the average particle diameter D50 of 2-7 mu m, D100 of less than 25 mu m and impurity content of less than or equal to 0.1 percent and stripping medium consisting of 18-45 mu m aluminum-magnesium-silicon alloy powder (aluminum content is 65wt percent, magnesium content is 25wt percent and silicon content is 10wt percent in aluminum-magnesium-silicon alloy) and stainless steel balls with the diameter of 0.5-0.9 mm and stainless steel powder with the diameter of 20-40 mu m into a ball mill, wherein the weight of the steel balls is 10 percent, the weight of the stainless steel powder is 48 percent and the weight of the aluminum-magnesium-silicon alloy powder is 42 percent relative to the total weight of the ball milling medium, the mass of the aluminum-magnesium-silicon in the aluminum-magnesium-silicon alloy accounts for example as shown in the following table 3, the weight of the flaky graphite is about 3.5 percent of the ball milling stripping medium (the sum of the steel balls, the stainless steel powder and the aluminum-magnesium-silicon alloy powder), adding polyvinylpyrrolidone, polyvinyl alcohol and oleamide into the ball mill for ball milling stripping under the protection of inert gas, the working conditions of separating the graphene sheets after the ball milling and peeling by air flow classification under the protection of inert gas after the peeling are the same as those of the example 1.
TABLE 3
As can be seen from Table 3, the ratio of aluminum, magnesium and silicon in the aluminum-magnesium-silicon alloy powder is preferably 40-90:10-60:3-20, 60-70: 20-30: the best effect is obtained when the temperature is between 8 and 12.
Example 4
Similar to example 1, except that 10% of steel balls and 42% of Al-Mg-Si alloy powder were mixed, the grain size of Al-Mg-Si alloy in the ball-milling separation medium was changed, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the ball-milled exfoliated Al-Mg-Si alloy particles having a size of 18-45 μm are most effective, preferably 5-55 μm, and the stainless steel powder particles having a size of 20-40 μm are most effective, preferably 10-50 μm.
Example 5
Similar to example 1, except that 10% of steel balls, 48% of stainless steel powder and 42% of AlMgSiAu powder were mixed, the thickness of the raw material flake graphite was changed, and the results are shown in Table 4.
TABLE 4
As seen from Table 4, the average particle diameter D50 of the flake graphite is preferably 2 to 9 μm, more preferably 3 to 6 μm, and the flake graphite having a D100 < 25 μm is used as the starting material, and the processed graphene flakes have the highest monolayer rate.
Example 6
The results are shown in FIG. 1, which are similar to those of example 1, except that the proportions of the steel balls of 10%, the stainless steel powder of 48% and the AlMgSiAu powder of 42% are changed to change the purity of the raw material, namely, the flaky graphite.
It is seen from fig. 1 that the higher the purity of the flaky graphite, the higher the single-layer rate of the graphene sheet, and the impurity content of the flaky graphite is less than or equal to 0.5%, and more preferably less than or equal to 0.1%.
The graphene is produced by a complete dry method, the whole production process is protected by inert gas, ball milling and stripping are carried out by a physical method, no pollutant is discharged during production, and the finished graphene has a wide application range and can become a representative new material in the future new energy and photoelectric industries.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A graphene powder gas-phase physical stripping method is characterized by comprising the following steps:
high-purity flaky graphite is selected as a raw material for producing graphene, the flaky graphite and a ball-milling stripping medium are mixed and sent into a ball mill, polyvinylpyrrolidone, polyvinyl alcohol and oleamide are added to carry out ball-milling stripping under the protection of inert gas, and graphene sheets stripped by the ball mill are separated by air flow classification under the protection of inert gas after stripping is finished.
2. The graphene powder gas-phase physical stripping method according to claim 1, wherein the ball-milling stripping medium is a composition of stainless steel balls, stainless steel powder and aluminum-magnesium-silicon alloy powder.
3. The graphene powder gas-phase physical stripping method according to claim 2, wherein the stainless steel ball is a 304 stainless steel ball; the stainless steel powder is spherical; the shape of the aluminum-magnesium-silicon alloy powder is spherical;
the diameter of the stainless steel ball is 0.3-10mm, and the weight of the stainless steel ball accounts for 3-50% of the ball-milling stripping medium;
the D50 average grain diameter range of the stainless steel powder is 5-150 μm, and the weight of the stainless steel powder accounts for 15-90% of the ball milling stripping medium;
the D50 average grain diameter range of the aluminum-magnesium-silicon alloy powder is 7-70 μm, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 10-80% of the ball milling stripping medium;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 40-90%, the mass percentage of magnesium is 10-60%, and the mass percentage of silicon is 3-20%;
the average grain diameter D50 of the flake graphite is 1-50 μm, D100 is less than 20-100 μm, the impurity content is less than or equal to 0.1%, and the weight of the flake graphite is less than 7% of that of the ball-milling stripping medium.
4. The graphene powder gas-phase physical stripping method according to claim 3, wherein the diameter of the stainless steel ball is 0.4-1.0 mm; the weight of the stainless steel balls accounts for 5-45% of the ball-milling stripping medium;
the average grain diameter range of D50 of the stainless steel powder is 10-100 μm, and the weight of the stainless steel powder accounts for 20-85% of the ball milling stripping medium;
the D50 average grain diameter range of the aluminum-magnesium-silicon alloy powder is 10-50 μm, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 20-60% of the ball milling stripping medium;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 50-80%, the mass percentage of magnesium is 20-50%, and the mass percentage of silicon is 5-15%;
the average particle size D50 of the flaky graphite is 2-30 μm; the weight of the flaky graphite is 2-5% of that of the ball-milling stripping medium.
5. The graphene powder gas-phase physical stripping method according to claim 4, wherein the diameter of the stainless steel ball is 0.6-0.8mm, and the weight of the stainless steel ball accounts for 8-12% of the ball-milling stripping medium;
the D50 particle size range of the stainless steel powder is 20-40 μm, and the weight of the stainless steel powder accounts for 30-60% of the ball milling stripping medium;
the D50 particle size range of the aluminum-magnesium-silicon alloy powder is 18-45 mu m, and the weight of the aluminum-magnesium-silicon alloy powder accounts for 28-48% of the ball milling stripping medium;
the stainless steel powder is 304 or 316 stainless steel powder for 3D printing;
in the aluminum-magnesium-silicon alloy powder, the mass percentage of aluminum is 60-70%, the mass percentage of magnesium is 20-30%, and the mass percentage of silicon is 8-12%;
the average particle size D50 of the flaky graphite is 3-8 μm; the weight of the flaky graphite is 3.5 percent of that of the ball-milling stripping medium.
6. The graphene powder gas-phase physical stripping method according to claim 1, wherein the mixing ratio of polyvinylpyrrolidone, polyvinyl alcohol and oleamide is 2: 5: 3, the addition amount of the flaky graphite is 1-3% by mass.
7. The graphene powder gas-phase physical exfoliation method according to claim 1, wherein the inert gas protection is performed in an inert gas atmosphere containing less than 0.5 vol% of oxygen, and the inert gas is nitrogen.
8. The method for physically stripping graphene powder in a gas phase according to claim 1, wherein the ball-milling stripping temperature is 100-; the oxygen content of the atmosphere in the ball mill is controlled between 0.1 and 0.5 volume percent, and the protective pressure of nitrogen is 30 to 50 KPa.
9. Graphene produced by the exfoliation method of claims 1-8, wherein the graphene is graphene flakes having an average particle size of 0.6-5 μm and an average thickness of 0.33-3nm, wherein the graphene flakes are 1-10 layers of graphene, wherein the graphene flakes are completely transparent; the average particle size of the graphene sheet is 0.8-4 μm, and the average thickness of the graphene sheet is 0.33-2 nm; the average particle size of the graphene sheet is 1-3 μm, and the average thickness is 0.33-1.5 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110999210.6A CN113620280A (en) | 2021-08-28 | 2021-08-28 | Graphene powder gas-phase physical stripping method and produced graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110999210.6A CN113620280A (en) | 2021-08-28 | 2021-08-28 | Graphene powder gas-phase physical stripping method and produced graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113620280A true CN113620280A (en) | 2021-11-09 |
Family
ID=78388272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110999210.6A Pending CN113620280A (en) | 2021-08-28 | 2021-08-28 | Graphene powder gas-phase physical stripping method and produced graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113620280A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
| CN105883763A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Efficient preparation method of graphene |
| CN107930778A (en) * | 2017-10-30 | 2018-04-20 | 李文辉 | A kind of graphene physics peels off production method and the graphene produced |
| CN110015655A (en) * | 2019-01-22 | 2019-07-16 | 复旦大学 | A kind of ultra-high throughput stripping means of graphene |
| CN110040729A (en) * | 2019-05-22 | 2019-07-23 | 大同墨西科技有限责任公司 | A kind of method that physics removing prepares graphene metal nanoparticle complex |
| CN110078062A (en) * | 2019-05-22 | 2019-08-02 | 大同墨西科技有限责任公司 | A kind of graphene energetic catalytic physics strip preparation method |
-
2021
- 2021-08-28 CN CN202110999210.6A patent/CN113620280A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
| CN105883763A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Efficient preparation method of graphene |
| CN107930778A (en) * | 2017-10-30 | 2018-04-20 | 李文辉 | A kind of graphene physics peels off production method and the graphene produced |
| CN110015655A (en) * | 2019-01-22 | 2019-07-16 | 复旦大学 | A kind of ultra-high throughput stripping means of graphene |
| CN110040729A (en) * | 2019-05-22 | 2019-07-23 | 大同墨西科技有限责任公司 | A kind of method that physics removing prepares graphene metal nanoparticle complex |
| CN110078062A (en) * | 2019-05-22 | 2019-08-02 | 大同墨西科技有限责任公司 | A kind of graphene energetic catalytic physics strip preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111900353B (en) | Composite material, preparation method, lithium ion battery negative electrode material containing composite material and lithium ion battery | |
| CN106044758B (en) | A kind of method and device preparing graphene using disc type airflow milling | |
| CN111710845A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN106077622A (en) | The gas-phase deposition process for preparing of graphene coated metal-based compound powder | |
| CN103757569A (en) | Ordered carbon nano-tube reinforced aluminum matrix composite material and preparation method thereof | |
| CN111559743B (en) | Preparation method and application of graphene powder | |
| CN107930778B (en) | Graphene physical stripping production method and produced graphene | |
| CN111014719A (en) | High-purity silver nanowire, preparation method thereof and silver nanowire conductive film | |
| CN106276881B (en) | A kind of preparation method of graphene | |
| Zheng et al. | Microstructure engineered silicon alloy anodes for lithium‐ion batteries: advances and challenges | |
| CN113620280A (en) | Graphene powder gas-phase physical stripping method and produced graphene | |
| CN100446900C (en) | Cutting production technology of metal nanometer powder zero boundry particle | |
| JP5191663B2 (en) | Manufacturing method of silver conductive film | |
| JP2011117080A5 (en) | ||
| CN101837949A (en) | In-situ carbon nanotube/nano graphite sheet composite powder and preparation method thereof | |
| Yang et al. | Recent advances in ball-milling-based silicon anodes for lithium-ion batteries | |
| CN106629687B (en) | A kind of method and graphene preparing graphene using airslide disintegrating mill | |
| CN110155943A (en) | Super-active hydrolytic hydrogen production aluminum matrix composite and preparation method thereof | |
| CN101821819A (en) | Transparent conducive film and method for producing the same | |
| CN108736006A (en) | A method of preparing silico-carbo composite material | |
| CN115287488A (en) | Diamond-graphene hybrid reinforced copper-based composite material and preparation method thereof | |
| CN111850489B (en) | Intermediate material of target material, forming method thereof and device for realizing forming method | |
| CN110040729B (en) | Method for preparing graphene metal nanoparticle complex through physical stripping | |
| CN109437170B (en) | Equipment and method for preparing graphene and graphene prepared by equipment and method | |
| CN1219696C (en) | Method for preparing nanometer carbon black powder |
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 |