CN114057188A - Graphene preparation method - Google Patents
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- C01B32/00—Carbon; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention relates to the technical field of graphene, and relates to a graphene preparation method, which comprises the steps of promoting a graphite raw material to generate friction collision with grinding medium resonance in a resonance mode to obtain graphene powder; the friction collision of the graphite raw material and the grinding medium resonance sequentially comprises dry friction and wet friction, and after wet friction, the graphene powder and the grinding medium are separated sequentially in a screening and magnetic separation mode, so that the graphene powder is finally obtained; the preparation method effectively solves the technical problems of low yield and high energy consumption of the graphene prepared in the prior art.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of graphene.
Background
Graphene (Graphene) is an sp2 hybridized two-dimensional honeycomb-shaped novel carbon nano material, in 2004, Anderson, Constantine and the like successfully prepare the Graphene by tearing graphite through adhesive tapes, and the research on the Graphene is one of hot spots at home and abroad; it has been found that graphene has many excellent properties such as excellent optical properties, excellent electrical conductivity, excellent mechanical properties, high thermal conductivity, etc., and is widely used in many fields such as optics, electronics, materials science, and biology.
Therefore, the preparation method of the lamellar graphene is always one of the hot spots in graphene research, and can be divided into a bottom-up method (chemical deposition method, molecular beam epitaxy method and the like) and a top-down method (mechanical exfoliation, oxidation-reduction method, intercalation exfoliation and the like). The chemical vapor deposition method and the molecular beam epitaxy method have high cost and complex process, large-scale production has certain technical threshold and too high cost, and compared with the bottom-up method, the top-down method is easier to realize the large-scale production of the graphene. However, the use of a large amount of chemicals in the redox method and the intercalation peeling method easily causes serious environmental pollution, so the mechanical peeling method is widely considered to be one of the technologies expected to realize high efficiency and scale production.
The synthesis methods of graphene quantum dots can be roughly divided into two categories: one is a method of using graphite-based bulk materials as carbon sources (such as crystalline flake graphite, expanded graphite, carbon nanofibers, coal, etc.) and obtaining nano-sized graphene quantum dots by physical or chemical "cutting", which is called a top-down method; the other method is a method for preparing the graphene quantum dots (such as a hydrothermal method and a microwave method) by using carbon-based small molecular substances (such as fructose, glucose, citric acid, cyclodextrin and the like) as precursors through aryl oxidation polymerization and final cracking, and is called as a bottom-up method. Most of the methods for preparing the graphene quantum dots from bottom to top are controllable, but the experimental process has complicated operation steps, and carbon quantum dots are easily mixed in the product and are not easy to purify; the traditional top-down method for preparing the graphene quantum dots has the advantages of easily available raw materials, simplicity in operation and easiness in mass production, but the preparation process still has the defects of high cost, complex process, difficulty in realizing large-scale production and the like in a chemical vapor deposition method.
Based on the fact that the prior art cannot rapidly, continuously, low in cost and environmentally friendly carry out production of the lamellar graphene or the graphene quantum dots, the graphene preparation method which is low in cost, environmentally friendly and suitable for large-scale production is developed, and the method has great technical significance and broad prospects.
Disclosure of Invention
The embodiment of the application provides a graphene preparation method, a physical preparation mode of a top-down method is adopted, and the method is environment-friendly and does not involve chemical substances such as strong acid, strong alkali and the like; the method has the advantages of low cost, no pollution, easy operation and the like, is suitable for industrial large-scale preparation of the graphene powder, and solves the technical problems of low yield and high energy consumption of the prepared graphene in the prior art.
The graphene preparation method provided by the invention comprises the step of promoting the graphite raw material and the grinding medium to generate friction collision by adopting a resonance mode to obtain graphene powder.
According to the technical scheme, the grinding medium comprises a main grinding medium and an auxiliary grinding medium, and the size of the main grinding medium is larger than that of the auxiliary grinding medium; the size of the main grinding medium is millimeter level, and the size of the auxiliary grinding medium is nanometer level.
As an improved technical scheme of the application, the graphene powder is lamellar graphene and/or graphene quantum dots.
As the improved technical scheme of the application, the auxiliary grinding medium is made of a magnetic material.
As an improved technical scheme of the application, the graphite raw material is one or more of bulk graphite, scale graphite, flake graphite and expanded graphite.
As an improved technical scheme of the application, the friction and collision of the graphite raw material and the grinding medium resonance sequentially comprise dry friction and wet friction;
the dry friction is that the graphite raw material and the grinding medium are subjected to first resonance collision in a resonance grinding machine, and the time of the first resonance collision is 2-48 h; and the wet friction is to use deionized water as a dispersion medium, the dry-rubbed graphite raw material and a grinding medium are subjected to second resonance collision in a resonance grinding machine, and the time of the second resonance collision is 10-30 min.
As the improved technical scheme, the method also comprises the steps of separating the graphene powder from the grinding medium in a screening and magnetic separation mode in sequence;
the screening process comprises the steps of separating a graphene powder mixed solution obtained after wet rubbing from a main grinding medium by using a sieve, and drying or freeze-drying the obtained graphene powder mixed solution to obtain a mixed powder; and the magnetic separation process comprises the steps of dispersing the mixed powder in a polyvinylpyrrolidone solvent, standing on a magnet frame, filtering to remove auxiliary grinding media, and centrifuging supernatant to obtain graphene powder.
As an improved technical scheme of the application, the main grinding medium is a zirconia ball with the diameter of 1-10mm, and the auxiliary grinding medium is ferroferric oxide particles with the particle size of 5-1000 nm.
As the improved technical scheme of the application, the screen adopted for screening is a 100-mesh stainless steel screen.
The technical scheme of the graphene preparation method disclosed by the invention has the following beneficial effects:
1. because the resonance mode is adopted to promote the graphite raw material to separate the sheet graphene or graphene quantum dots in the resonance friction collision with the grinding medium, the huge energy in the resonance process is mainly utilized to promote the physical bonds in the graphite raw material to break, and because of the existence of the grinding medium, the graphite raw material can overcome the acting force between the graphene layers in the resonance process, realize the forward collision of forward stripping, promote the graphite interlayer to slide, realize the shear collision of shear stripping; therefore, the problems that the traditional bottom-up method for preparing the lamellar graphene and the graphene quantum dot is complex in process, high in production cost and incapable of realizing large-scale production are effectively solved. In addition, the mode of resonance with a molar medium is adopted to effectively avoid the agglomeration of the prepared graphene powder.
2. Due to physical resonance, the resonance time or the resonance frequency and the resonance amplitude can be controlled, so that the product obtained after controlling the resonance of the graphite raw material is the lamellar graphene or the graphene quantum dot, and the technical purpose of obtaining different products by using the same process is achieved.
3. The invention controls the sizes of the main grinding medium and the auxiliary grinding medium, wherein the main grinding medium is realized by millimeter level to provide main power for the graphite raw material, and the main grinding medium collide with each other and the main grinding medium and the graphite raw material collide with each other, so that the graphite raw material can be rapidly reduced from large to small; the auxiliary grinding medium is in a nano-scale, so that lubrication between large particles (the main grinding medium and the large-particle graphite raw material) is promoted, and the graphite raw material is further crushed into a lamellar or quantum dot shape.
4. According to the invention, the auxiliary grinding medium is selected to be a magnetic material, so that the graphene product and the auxiliary grinding medium are separated in a magnetic screening mode after resonance friction is finished.
5. The method for preparing the graphene powder has the advantages of simple and easily obtained raw materials, rich sources and low cost, and can be one or more of massive graphite, flaky graphite, flake graphite and expanded graphite.
6. According to the method for preparing the graphene powder, no chemical substance is introduced in the process, only the graphite flake is mechanically stripped by using a physical method, the prepared graphene quantum dot does not introduce a surface group, and specific surface treatment can be carried out according to actual application requirements during application, so that the graphene quantum dot has a specific function, and has a wide application range and an important application value.
7. The graphene powder preparation method disclosed by the invention is simple in used instrument and equipment, simple to operate and applicable to production of large-scale graphene.
In conclusion, compared with the existing method, the method for preparing the graphene has the advantages of rapidness, continuity, low cost and environmental friendliness, and can be used for large-scale production of the graphene, so that the method plays a great role in promoting numerous applications and industrialization of the graphene.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below are contemplated as being part of the claimed subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present disclosure, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the specific embodiments in accordance with the teachings of the present disclosure.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present application will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a TEM characterization test chart of a sample obtained in example 1;
FIG. 2 is a TEM characterization test chart of a sample obtained in example 2;
FIG. 3 is a TEM characterization test chart of a sample obtained in example 3;
FIG. 4 is a TEM characterization test chart of a sample obtained in example 4;
FIG. 5 is a TEM characterization test chart of a sample obtained in example 5;
FIG. 6 is a TEM characterization test chart of the sample obtained in example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings of the embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the application without any inventive step, are within the scope of protection of the application. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as is understood by one of ordinary skill in the art to which this application belongs.
Based on the problems that the preparation of the lamellar graphene and the graphene quantum dot by the bottom-up method in the prior art is complex in process, high in production cost and incapable of large-scale production, the preparation of the lamellar graphene and the graphene quantum dot by the redox method and the intercalation peeling method in the top-down method can easily cause serious environmental pollution by using a large amount of chemical substances; therefore, the invention aims to disclose a graphene preparation method, which belongs to a mechanical stripping method for preparing graphene powder, has low cost, no pollution and easy operation, can be suitable for industrial large-scale preparation of graphene powder, and fully solves the technical problems of preparation of lamellar graphene and graphene quantum dots by a bottom-up method, an oxidation-reduction method and an intercalation stripping method.
The following describes the preparation method of graphene disclosed in the present application with reference to specific embodiments and drawings.
The technical scheme in the embodiment of the application solves the technical problems of the preparation method of the lamellar graphene and the graphene quantum dot, and the general idea is as follows: expanded graphite, flaky graphite, flake graphite or blocky graphite is used as a graphite raw material, and the raw material is promoted to be subjected to forward collision, shearing collision and the like under the assistance of a grinding medium, so that fragmentation is realized, and the aim of obtaining target product lamellar graphene or graphene quantum dots is fulfilled.
The specific process of the graphene preparation method disclosed by the embodiment of the application is as follows:
a preparation method of graphene takes one or more of massive graphite, flaky graphite, flake graphite and expanded graphite as a graphite raw material, and uses a main grinding medium and an auxiliary grinding medium for assistance in a resonance mill to promote the graphite raw material and the grinding medium to generate friction collision by adopting a resonance mode, so as to obtain the lamellar graphene or graphene quantum dots. Wherein, the size of the main grinding medium is millimeter level, the size of the auxiliary grinding medium is nanometer level, and the material of the auxiliary grinding medium is magnetic material.
The friction collision of the graphite raw material and the grinding medium by resonance sequentially comprises dry friction and wet friction, wherein the dry friction is that the graphite raw material and the grinding medium are subjected to first resonance collision in a resonance grinding machine, and the time of the first resonance collision is 2-48 h; and wet friction is to use deionized water as a dispersion medium, and the dry-friction graphite raw material and the grinding medium are subjected to second resonance collision in a resonance grinding machine, wherein the time of the second resonance collision is 10-30 min. The addition amount of deionized water in wet rubbing is 10-40% of the volume of the inner cavity of the grinding cylinder of the resonance grinding machine, and the aim is to separate powder from a main grinding medium after dispersion and collision.
The resonance time is selected differently when the resonance mill with the same frequency is used for preparing different target objects. For example, when preparing lamellar graphene, the time of the first resonance collision of the resonance mill is selected to be 2-10 h; and when the graphene quantum dots are prepared, the time of the second resonance collision of the resonance mill is selected to be 6-48 h.
In order to enable the graphite raw material to have a positive collision acting force, a shearing collision acting force and a certain lubricating property, the grinding medium is set to comprise a main grinding medium and an auxiliary grinding medium; meanwhile, in order to obtain different target products, the main grinding medium and the auxiliary grinding medium are different in size selection, for example, when the main grinding medium is used for preparing the lamellar graphene, the main grinding medium is zirconia balls with the diameter of 1-10mm, and the auxiliary grinding medium is ferroferric oxide magnetic particles with the particle size of 5-1000 nm; when the graphene quantum dot is used for preparing graphene quantum dots, the main grinding medium can be a 1-10mm spherical body, and the spherical body is any one or more of zirconia, silicon nitride or alumina; the auxiliary grinding medium is 5-1000nm magnetic particles, such as ferroferric oxide magnetic particles, iron powder or ferric oxide. Preferably, in the graphene preparation method designed by the application, the main grinding medium is a zirconia ball with the diameter of 1-10mm, the auxiliary grinding medium is a ferroferric oxide particle with the particle size of 5-1000nm, the zirconia ball with the diameter of 4mm and the zirconia ball with the diameter of 6mm are preferably in a mass ratio of 3:1, and the particle size of the ferroferric oxide particle is 100 nm.
Meanwhile, in the preparation process of the lamellar graphene and the preparation process of the graphene quantum dots, the amount of grinding media is critical, too small amount of grinding media is not enough to promote the formation of graphene split bodies, and too much amount of grinding media cannot form effective shearing friction among the graphite raw materials. In practical application, when the amount of the graphite raw material is 1-30g, the total amount of the grinding media occupies 50-90%, preferably 70% of the volume of the inner cavity of the grinding cylinder. Wherein, the dosage of the main grinding medium is between 1.6kg and 2.4kg, and the dosage of the auxiliary grinding medium is between 1g and 5g so as to reach the resonance frequency state or the near resonance frequency state of the resonance grinding machine and to reach the resonance frequency state or the near resonance frequency state of the resonance grinding machine for collision.
In order to separate graphene powder, firstly, after resonance friction, deionized water is added to continue resonance to realize wet friction, and after resonance collision for a plurality of times, a main grinding medium and the graphene powder mixed liquid obtained after wet friction are separated through a 100-mesh stainless steel sieve, and the obtained graphene powder mixed liquid is dried or freeze-dried to obtain mixed powder. And dispersing the prepared mixed powder in a polyvinylpyrrolidone (NMP) solvent, standing for more than 24h on a magnet frame, filtering to remove auxiliary grinding media, centrifuging 80% of supernate at 500rpm to remove large particles, centrifuging 80% of supernate at more than 10000rpm to obtain precipitate, and drying to obtain the graphene powder.
In order to perform the characterization test of the product in practical application, the following steps are further continued: and (3) ultrasonically dispersing 0.05g of the obtained graphene powder in 50ml of NMP solvent for 30-60min, and taking the liquid for TEM characterization.
Example one
A graphene preparation method comprises the following specific operation steps:
weighing 20g of expanded graphite powder and 2.5g of 100nm ferroferric oxide auxiliary grinding aid, mixing and putting into an annular spring type resonance mill shown in figure 1, wherein the volume of a cavity of the resonance mill is about 3L, and simultaneously weighing 1.2kg of zirconia balls with the diameter of 4mm and 0.4kg of zirconia balls with the diameter of 6mm, wherein the mass ratio of the two balls is 3: 1.
The vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, and the vibration mode is vibration of a spiral spring. The resonance collision time of the mill is 6h, after the resonance collision is finished, 300ml (10%) of deionized water is added into the inner cavity of the resonance mill, the resonance collision is carried out for 30min again, then the separation of the milling media and the collision powder is carried out by passing through a 100-mesh sieve, and the powder dispersion liquid is directly dried or freeze-dried to obtain the graphene-containing powder material. Dispersing the prepared powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet frame for more than 24h to remove ferroferric oxide particles, centrifuging 80% of the upper layer liquid at 500rpm to remove large particles, centrifuging 80% of the upper layer liquid at 10000rpm to obtain precipitate, and drying to obtain the graphene powder.
0.004g of graphene powder is weighed and dissolved in 40ml of polyvinylpyrrolidone (NMP) solvent, ultrasonic dispersion is carried out for 60min, and TEM characterization test is carried out on the liquid, and the result is shown in figure 1.
Example two
A graphene preparation method comprises the following specific operation steps:
weighing 1g of flake graphite powder and 1g of 5nm iron powder auxiliary grinding aid, mixing, placing into an annular spring type resonance mill shown in figure 1, wherein the volume of a cavity of the resonance mill is about 3L, and simultaneously weighing 1.8kg of silicon nitride pellets with the diameter of 1mm and 0.6kg of silicon nitride pellets with the diameter of 10mm, wherein the mass ratio of the two pellets is 3: 1.
The vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, and the vibration mode is vibration of a spiral spring. The resonance collision time of the mill is 2 hours, 600ml (20%) of deionized water is added into a cavity in the resonance mill after the resonance collision is finished, resonance collision is carried out for 20 minutes again, then the separation of the milling medium and the collision powder is carried out by passing through a 100-mesh sieve, and the powder dispersion liquid is directly dried or freeze-dried to obtain the graphene-containing powder material. And drying to obtain the powder containing the graphene. And dispersing the prepared powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet frame for more than 24h to remove iron powder nano particles, centrifuging 80% of the upper layer liquid at 500rpm to remove large particles, centrifuging 80% of the upper layer liquid at 10000rpm to obtain precipitate, and drying the precipitate to obtain the graphene powder.
0.004g of graphene powder is weighed and dissolved in 40ml of polyvinylpyrrolidone (NMP) solvent, ultrasonic dispersion is carried out for 60min, and TEM characterization test is carried out on the liquid, and the result is shown in figure 2.
EXAMPLE III
A graphene preparation method comprises the following specific operation steps:
30g of scaly graphite powder and 4g of 1000nm ferric oxide auxiliary grinding aid are weighed and mixed in an annular spring type resonance grinding machine shown in figure 1, the volume of a cavity of the resonance grinding machine is about 3L, 1.5kg of alumina globules with the diameter of 2mm and 0.5kg of alumina globules with the diameter of 8mm are weighed simultaneously, and the mass ratio of the two globules is 3: 1.
The vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, and the vibration mode is vibration of a spiral spring. The resonance collision time of the mill is 10 hours, 1200ml (40%) of deionized water is added into a cavity in the resonance mill after the resonance collision is finished, the resonance collision is carried out for 10min again, then the separation of the milling medium and the collision powder is carried out by passing through a 100-mesh sieve, and the powder dispersion liquid is directly dried or freeze-dried to obtain the graphene-containing powder material. And drying to obtain the powder containing the graphene. And dispersing the prepared powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet frame for more than 24h to remove ferric oxide nano particles, centrifuging 80% of the upper layer liquid at 500rpm to remove large particles, centrifuging 80% of the upper layer liquid at more than 10000rpm to obtain precipitate, and drying the precipitate to obtain the graphene powder.
0.004g of graphene powder is weighed and dissolved in 40ml of polyvinylpyrrolidone (NMP) solvent, ultrasonic dispersion is carried out for 60min, and the liquid is taken for TEM/HRTEM and other characterization tests, and the result is shown in figure 3.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages: the TEM of the graphene prepared in the embodiments 1 to 3 is shown in FIGS. 1 to 3, and the transparency of the morphology of the sample indicates that the graphene is successfully obtained in a resonance mode, which indicates that resonance collision has a good stripping effect. Therefore, the scheme has the advantages of simple and easily obtained raw materials, abundant sources, low cost, simple instruments and equipment, simple operation and suitability for large-scale production.
Example four
A preparation method of graphene quantum dots comprises the following specific operation steps:
weighing 1g of expanded graphite powder and 1g of 100nm ferroferric oxide auxiliary grinding aid, mixing and putting into an annular spring type resonance mill shown in figure 1, wherein the volume of a cavity in the resonance mill is about 3L, and simultaneously weighing 1.5kg of zirconia balls with the diameter of 4mm and 0.5kg of zirconia balls with the diameter of 6mm, wherein the mass ratio of the two balls is 3: 1. The vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, the vibration mode is vibration of a spiral spring, and the resonance collision time of the mill is 6 h.
And after the resonance collision is finished, 600ml of deionized water (accounting for 20% of the volume of the grinding cylinder) is added into the inner cavity of the resonance grinding machine, resonance collision is carried out for 30min again, grinding media and powder suspension liquid are separated through a 100-mesh stainless steel sieve, and the obtained powder dispersion liquid is directly dried or freeze-dried to obtain the powder containing the graphene quantum dots. Ultrasonically dispersing the obtained powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet for more than 24 hours to remove ferroferric oxide particles, centrifuging the upper layer solution at a high speed of 5000-10000rmp to remove large lamellar blocks, and drying 80% of the upper layer clear solution again to obtain the graphene quantum dot powder.
Taking 0.005g of the obtained graphene quantum dot powder to be ultrasonically dispersed in 50ml of NMP solution for 30min, taking liquid to perform TEM characterization, and obtaining the result shown in figure 4, wherein the average particle size of the prepared graphene quantum dot is about 1.43 nm.
EXAMPLE five
A preparation method of graphene quantum dots comprises the following specific operation steps:
weighing 10g of flake graphite powder and 4g of 1000nm iron powder auxiliary grinding aid, mixing the flake graphite powder and the iron powder auxiliary grinding aid, putting the mixture into an annular spring type resonance mill shown in figure 1, wherein the volume of a cavity in the resonance mill is about 3L, and simultaneously weighing 1.5kg of alumina globules with the diameter of 4mm and 0.5kg of alumina globules with the diameter of 6mm, wherein the mass ratio of the globules with the two diameters is 3: 1. The vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, the vibration mode is vibration of a spiral spring, and the ball milling time of the mill is 10 h.
And after the resonance collision is finished, adding 300ml of deionized water (accounting for 10% of the volume of the grinding cylinder) into the inner cavity of the resonance grinding machine, performing resonance collision for 20min again, separating grinding media from powder suspension liquid through a 100-mesh stainless steel sieve, and directly drying or freeze-drying the obtained powder dispersion liquid to obtain the powder containing the graphene quantum dots. Ultrasonically dispersing the obtained powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet for more than 24h to remove iron powder, centrifuging the upper layer solution at a high speed of 5000-10000rmp to remove large lamellar blocks, taking 80% of the upper layer clear solution, and drying again to obtain the graphene quantum dot powder.
Taking 0.005g of the obtained graphene quantum dot powder to be ultrasonically dispersed in 50ml of NMP solution for 30min, taking liquid to perform TEM characterization, and obtaining the result shown in figure 5, wherein the average particle size of the prepared graphene quantum dot is about 2.81 nm.
EXAMPLE six
A preparation method of graphene quantum dots comprises the following specific operation steps:
weighing 30g of expanded graphite powder and 3g of 5nm ferric oxide auxiliary grinding aid, mixing and placing the mixture into an annular spring type resonance mill shown in figure 1, wherein the volume of a cavity in the resonance mill is about 3L, weighing 1.8kg of silicon nitride pellets with the diameter of 1mm and 0.6kg of silicon nitride pellets with the diameter of 10mm, the mass ratio of the two kinds of pellets is 3:1, the vibration amplitude of the mill is 11mm, the vibration frequency is 16Hz, the vibration excitation mode is vibration of a vibration motor, the vibration mode is vibration of a spiral spring, and the ball milling time of the mill is 48 h.
After the resonance collision is finished, 1200ml of deionized water (accounting for 40% of the volume of the mill barrel) is added into the inner cavity of the resonance mill, resonance collision is carried out for 10min again, the separation of the milling medium and the powder suspension is carried out through a 100-mesh stainless steel sieve, and the obtained powder dispersion is directly dried or freeze-dried to obtain the powder containing the graphene quantum dots. Ultrasonically dispersing the obtained powder in a polyvinylpyrrolidone (NMP) solvent, standing on a magnet for more than 24h to remove ferric oxide particles, centrifuging the upper layer solution at a high speed of 5000-10000rmp to remove large lamellar blocks, taking 80% of the upper layer clear solution, and drying again to obtain the graphene quantum dot powder.
Taking 0.005g of the obtained graphene quantum dot powder to be ultrasonically dispersed in 50ml of NMP solution for 30min, taking the liquid to perform TEM AFM characterization, and obtaining the result shown in FIG. 6, wherein the average particle size of the prepared graphene quantum dot is about 3.30 nm.
The technical scheme of the graphene quantum dot in the embodiment of the application at least has the following technical effects or advantages: the preparation method has the advantages of simple and easily-obtained raw materials, rich sources, low cost, simple instruments and equipment, simple operation and suitability for large-scale production, and the TEM characterization of the graphene quantum dots prepared in the embodiments 4-6 is shown in figures 4-6, which shows that the quantum dots have uniform particle sizes, and the average particle sizes are 1.43nm, 2.81nm and 3.30nm respectively. The prepared graphene quantum dots do not introduce surface groups, can be subjected to specific surface treatment according to actual application requirements, have specific functions, and have wide application range and important application value.
The embodiment and the accompanying drawings are integrated to show that compared with the existing graphene preparation method, the graphene preparation method disclosed by the invention has the advantages of simplicity, rapidness, continuity, low cost and environmental friendliness, can be applied to large-scale production of graphene, plays a great role in promoting numerous applications and industrialization of graphene, and has remarkable practicability.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the present application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
Claims (10)
1. The preparation method of the graphene is characterized by comprising the step of promoting a graphite raw material to generate friction collision with grinding medium resonance in a resonance mode to obtain graphene powder.
2. The method according to claim 1, wherein the grinding medium comprises a main grinding medium and an auxiliary grinding medium, and the size of the main grinding medium is larger than that of the auxiliary grinding medium.
3. The graphene preparation method according to claim 1, wherein the graphene powder is lamellar graphene and/or graphene quantum dots.
4. The method according to claim 2, wherein the primary grinding medium has a size of millimeter level and the secondary grinding medium has a size of nanometer level.
5. The method according to claim 2, wherein the auxiliary grinding medium is made of a magnetic material.
6. The method for preparing graphene according to claim 1, wherein the graphite raw material is one or more of bulk graphite, flake graphite, and expanded graphite.
7. The graphene preparation method according to claim 5, wherein the frictional collision of the graphite raw material with the grinding medium resonance sequentially comprises dry friction and wet friction;
the dry friction is that the graphite raw material and the grinding medium are subjected to first resonance collision in a resonance grinding machine, and the time of the first resonance collision is 2-48 h;
and the wet friction is to use deionized water as a dispersion medium, the dry-friction graphite raw material and a grinding medium are subjected to second resonance collision in a resonance grinding machine, and the time of the second resonance collision is 10-30 min.
8. The graphene preparation method according to claim 7, further comprising separating graphene powder from the grinding medium by sequentially adopting a screening and magnetic separation manner;
the screening process comprises the steps of separating a graphene powder mixed solution obtained after wet rubbing from a main grinding medium by using a sieve, and drying or freeze-drying the obtained graphene powder mixed solution to obtain a mixed powder;
and the magnetic separation process comprises the steps of dispersing the mixed powder in a polyvinylpyrrolidone solvent, standing on a magnet frame, filtering to remove auxiliary grinding media, and centrifuging supernatant to obtain graphene powder.
9. The graphene preparation method according to claim 7, wherein the main grinding medium is zirconia balls with the diameter of 1-10mm, and the auxiliary grinding medium is ferroferric oxide particles with the particle size of 5-1000 nm.
10. The method for preparing graphene according to claim 8, wherein the screen used for screening is a 100-mesh stainless steel screen.
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