KR20170032656A - A method for manufacturing graphene using abandoned graphite - Google Patents
A method for manufacturing graphene using abandoned graphite Download PDFInfo
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- KR20170032656A KR20170032656A KR1020150130275A KR20150130275A KR20170032656A KR 20170032656 A KR20170032656 A KR 20170032656A KR 1020150130275 A KR1020150130275 A KR 1020150130275A KR 20150130275 A KR20150130275 A KR 20150130275A KR 20170032656 A KR20170032656 A KR 20170032656A
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- 239000010439 graphite Substances 0.000 title claims abstract description 112
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
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Images
Classifications
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- C01B31/0476—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- C01B31/043—
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Abstract
The present invention relates to a process for producing graphene using process graphite, and a process for producing graphene using process graphite according to the present invention is a process for producing a sintered product comprising diamond and unreacted graphite by sintering a mixed powder containing metal and graphite ; A second step of immersing the sintered body in a strong acid aqueous solution and electrolysis to convert it into a mixture containing diamond and graphite; A third step of adding an aqueous solution of potassium permanganate (KMnO 4 ) to the mixture and stirring the mixture; A fourth step of peeling the graphite in the mixture; A fifth step of recovering the removed graphene oxide; And a sixth step of reducing the exfoliated graphene grains.
According to the present invention, it is possible to reduce the cost of manufacturing graphene by using recycled graphite as a by-product of graphene, which is a by-product, which is discarded after the diamond manufacturing process, .
In addition, according to the present invention, the risk of explosion can be minimized by minimizing the reaction between sulfuric acid (H 2 SO 4 ) and potassium permanganate (KMnO 4 ) by treating graphite in a slurry state in which sulfuric acid solution remaining in graphite is minimized.
Description
The present invention relates to a process for producing graphene using process graphite, and more particularly, to a process for producing graphene using process graphite that can recycle process graphite, which is a byproduct produced during diamond manufacturing, as a raw material for producing graphene will be.
Graphene is a two-dimensional material made of carbon atoms and has a honeycomb structure. The types of graphene include single-layer graphene, two-layer graphene, and multi-layer graphene. Graphene or Graphite). The thickness of the single-layer graphene is extremely thin, about 0.34 nm, which is one carbon atom. However, if the graphene sheet is stacked to a thickness of mm, the strength enough to support a 2-ton automobile is extremely high. Also, graphene is transparent and absorbs only 2.3% of light. It has a higher thermal conductivity than silver at room temperature, and electrons can move as if there is no mass, so electricity flow faster than existing semiconductors. Be in the spotlight.
As such, graphene is one of the most outstanding materials with various characteristics such as strength, thermal conductivity and electron mobility. It is applied to various fields such as display, rechargeable battery, solar cell, automobile and lighting, It is recognized as a core material.
Graphene manufacturing techniques using various methods such as mechanical peeling, chemical peeling, non-oxidative peeling, chemical vapor deposition, and epitaxy are currently used as methods for producing graphene. Examples of the method for producing graphene include a method of separating a graphene layer from graphite crystal, a chemical vapor deposition method of synthesizing graphene using a transition metal that adsorbs carbon well at a high temperature as a catalyst layer, In particular, the chemical stripping method, in which graphite is oxidized and separated in solution and then reduced, is capable of hybridization with other materials because of the possibility of mass production and easy chemical modification. A lot of research is going on because of its merits.
The chemical peeling can be easily accomplished by ultrasonic milling after inserting an intergranular oxygen functional group in the process of producing graphite oxide. However, in the process of inserting the oxygen functional group between the graphene layers, there is a risk of explosion due to the generation of high temperature. Although the risk of explosion can be evaluated relatively small when the graphene is manufactured in a laboratory unit through chemical detachment, the cost for the control for removal of the explosion hazard is consumed in the factory process for mass production In the event of an accident, the damage can be unpredictable.
On the other hand, graphite used as a raw material in the production of graphene is used for electrodes such as pencil lead, crucible, electric furnace, arc, etc., and is also used as a raw material and used for manufacturing synthetic diamond. In recent years, synthetic diamond has been increasingly used in precision electronics and semiconductor fields as demand for processing precision materials such as printed circuit boards (PCBs), light emitting diodes (LEDs) and solar panels for industrial applications has increased. In addition, industrial diamond is used as a basic abrasive for precision machining of various kinds of machinery, and is used as a cutting material and processing material for high strength materials, and its value as a strategic material is becoming increasingly important.
Generally, particles smaller than 104 μm are called industrial powdered diamond, and such powdered synthetic diamond is manufactured using a high-temperature and high-pressure process. The synthetic diamond high temperature and high pressure process is produced by sintering graphite and metals such as cobalt, nickel, and iron at 1500 ° C and 50,000 bar. After the sintering process, the graphite is left as a process byproduct after sorting diamond and noble metal. The process graphite generated at this time is disposed of, and environmental pollution and cost loss resulting therefrom are a problem.
The present invention provides a process for producing graphene using process graphite which can recycle process graphite, which is a by-product of the discarded diamond manufacturing process, as an industrial material of high added value.
The present invention also provides a method for producing graphene using process graphite including unit processes capable of reducing the risk of explosion in the process of inserting an intergranular oxygen functional group.
Also, the present invention provides a method of manufacturing graphene using process graphite which is eco-friendly and cost-effective by using process graphite, which is a by-product that is discarded in the diamond manufacturing process.
A method for producing graphene using process graphite according to the present invention comprises the steps of: preparing a sintered body containing diamond and unreacted graphite by sintering a mixed powder containing metal and graphite; A second step of immersing the sintered body in a strong acid aqueous solution and electrolysis to convert it into a mixture containing diamond and graphite; A third step of adding an aqueous solution of potassium permanganate (KMnO 4) to the mixture and stirring the mixture; A fourth step of peeling the graphite in the mixture; A fifth step of recovering the exfoliated graphene grains; And a sixth step of reducing the recovered graphene oxide.
Also, after the second step and before the third step, an acid removing step for partially removing the strong acid such that the weight ratio of the strong acid remaining in the graphite to the total strong acid not absorbed by the graphite is within 5% Step < / RTI >
The graphite in the mixture may also be in the form of a slurry.
And a recovery step of recovering the diamond from the mixture after the second step.
Further, the noble metal can be further recovered in the recovery step.
The method may further include the step of purifying graphite in the mixture after the recovering step.
Further, the third step may further include adding 5% sulfuric acid (H 2 SO 4 ) to the byproduct.
The sulfuric acid (H 2 SO 4 ) may be added to the by-product in a state mixed with the potassium permanganate aqueous solution.
In the third step, the potassium permanganate (KMnO 4 ) aqueous solution may further contain sodium nitrate (NaNO 3 ).
The acid added in the second step may include at least one of sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), and hydrochloric acid (HCl).
The metal powder may include at least one of iron, nickel, and cobalt.
In the first step, the sintering may be performed at a temperature of 500 to 3000 ° C.
Also, in the first step, the sintering may be performed at a pressure of 40000 atm to 60,000 atm.
Also, in the first step, the sintering may be performed for 40 to 80 minutes.
The fourth step may be performed through heat treatment or ultrasonic irradiation.
In the sixth step, the reducing agent is added to at least one of hydrazine, sodium hydride, hydroquinone, sodium borohydride, ascorbic acid, and glucose. Lt; / RTI >
According to the present invention, it is possible to reduce the cost of manufacturing graphene by using recycled graphite as a by-product of graphene as a by-product, which is a by-product after the diamond manufacturing process, and to reduce additional costs such as waste disposal cost for disposing process graphite .
Also, according to the present invention, by recycling the process graphite, which is a by-product, which is discarded after the diamond manufacturing process, the problem of environmental pollution occurring in the process of disposing graphite can be minimized, thereby being eco-friendly.
According to the present invention, the risk of explosion can be minimized by minimizing the rapid exothermic reaction between sulfuric acid (H 2 SO 4 ) and potassium permanganate (KMnO 4 ) by treating graphite in a slurry state in which sulfuric acid solution remaining in graphite is minimized have.
According to the present invention, graphite is treated in a slurry state in which sulfuric acid solution remaining in graphite is minimized to minimize the reaction between sulfuric acid (H 2 SO 4 ) and potassium permanganate (KMnO 4 ) It is possible to obtain an effect of improving the process efficiency as well as eliminating the risk of explosion.
1 is a flowchart showing a method of manufacturing graphene according to an embodiment of the present invention.
2 is a flowchart showing a method of manufacturing graphene according to another embodiment.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the absence of special definitions or references, the terms used in this description are based on the conditions indicated in the drawings. The same reference numerals denote the same members throughout the embodiments. For the sake of convenience, the thicknesses and dimensions of the structures shown in the drawings may be exaggerated, and they do not mean that the dimensions and the proportions of the structures should be actually set.
First, a method of manufacturing graphene according to an embodiment of the present invention will be described with reference to FIG. 1 is a flowchart showing a method of manufacturing graphene according to an embodiment of the present invention.
The method of manufacturing graphene according to the present embodiment includes a first step (S100) of producing a sintered body including diamond and unreacted graphite by sintering metal powder and graphite powder, dipping the sintered body in an acid solution, and a fourth step of separating the process of graphite in the third step of stirring by introducing the potassium permanganate (KMnO 4) aqueous solution of step 2 (S200), the mixture (S300), the mixture (S400 to convert a mixture containing graphite A fifth step S500 of recovering the separated graphene oxide, and a sixth step S600 of reducing the recovered oxidized graphene.
In the first step S100, metal powder and graphite powder are produced in the form of pellets and sintered under high temperature and high pressure to form a sintered body. At this time, the metal powder may contain at least one of iron, nickel, and cobalt as a catalyst. Put graphite, iron, nickel, and cobalt powder in a cell of a certain size and sinter at high temperature and high pressure. In this case, the sintering can be carried out at a temperature of 500 to 3000 DEG C and a pressure of 40,000 to 60,000 atm for 40 to 80 minutes.
In the second step S200, the sintered body is immersed in an acid solution and electrolyzed. The sintered body described above is formed in a state in which diamonds, unreacted graphite, catalytic metals, and the like are mixed. In this case, the sintered body is difficult to separate into diamond, graphite and catalytic metal by a physical method. Therefore, in the second step, the sintered body is separated into diamond, graphite and catalytic metal, respectively, . At this time, only 10% of the initial amount of graphite is present as diamond, and 90% of unreacted graphite and metal powder are present in the mixture. Particularly, in the case of process graphite, the graphite interlayer expansion occurred due to the treatment at high temperature and high pressure, which is advantageous for the graphene oxide peeling process.
The acid solution used herein may be any one of sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), and hydrochloric acid (HCl). In the present invention, sulfuric acid (H 2 SO 4 ) is preferably used, but not always limited thereto.
Next, in a third step (S300), an aqueous solution of potassium permanganate (KMnO 4 ) is added to the acid-treated process graphite slurry or a process graphite slurry subjected to an acid treatment in an aqueous solution of potassium permanganate (KMnO 4 ) / RTI > At this time, the reaction rate with sulfuric acid (H 2 SO 4 ) can be controlled by controlling the concentration of potassium permanganate (KMnO 4 ) aqueous solution and injecting into the graphite oxide slurry. For example, by forming an aqueous solution of potassium permanganate (KMnO 4 ) into a graphite oxide slurry, or by injecting graphite oxide slurry into an aqueous solution of potassium permanganate (KMnO 4 ), the process according to the third step is carried out with or without the risk of explosion. You can proceed.
Meanwhile, the potassium permanganate (KMnO 4 ) aqueous solution may further contain sodium nitrate in the third step. And further adding 5% sulfuric acid (H 2 SO 4 ) as an additive (reaction activation). When 5% sulfuric acid (H 2 SO 4 ) is added as an additive and potassium permanganate (KMnO 4 ) solution is added, the insertion of oxygen functional group between graphene layers can be performed more smoothly and stably. Speed control of the motor.
Next, in a fourth step (S400), graphene is peeled by heat treatment or ultrasonic wave irradiation to the graphitized pulsed process graphite.
In the fifth step S500, the separated graphene oxide grains are recovered by centrifugation, filtration, or the like.
Oxidized graphene itself can be used as it is, but in order to utilize the electrical and physical properties inherent to graphene, it is necessary to reduce the graphene oxide by physicochemical methods. In general, a high temperature heat treatment process using a hydrazine reducing agent and / or hydrogen is performed to reduce the graphene oxide.
In the sixth step S600, the graphene oxide is reduced to improve the electrical characteristics and the like in accordance with the purpose of use. However, the graphene production method according to the present invention can be applied to various known reduction methods without any particular limitation.
The reagents used in the chemical reduction method are mainly hydrazine based. It is known that when hydrazine or sodium hydride is used as a reducing agent, it effectively removes the epoxy group or hydroxy group on the surface of graphene but does not remove the carbonyl group or carboxyl group located at the edge. These residual functional groups can be removed by sulfuric acid treatment or high temperature heat treatment. The thermal reduction is carried out at a temperature of 200 degrees or more in an inert gas or reduced gas environment. The desorption of oxygen from oxidized graphene occurs rapidly at high temperatures above 200 degrees Celsius and progressively at temperatures below 200 degrees Celsius.
Hydroquinone and sodium borohydride have been studied as substitutes for hydrazine-based reducing agents. Reducing agents such as ascorbic acid and glucose have been reported as eco-friendly reducing agents. It is also possible to induce deoxidation reaction in an organic solvent such as a basic aqueous solution, distilled water, dimethylformamide (DMF), methyl acetamide or n-methylpyrrolidinone (NMP) And a method of reducing the reaction time in a short time of about 15 minutes is being studied. The reduction of the graphene oxide can be performed in a base solution, a supercritical aqueous solution, or even in a solvent, so care must be taken in analyzing the chemical structure of the oxidized graphene. And can be effectively reduced by a hydrogen plasma treatment. In addition, there are an electrochemical reduction method, a photocatalytic reduction method, and a flash conversion method.
A method of manufacturing graphene using process graphite according to another embodiment will be described with reference to FIG. 2 is a flowchart showing a method of manufacturing graphene using process graphite according to another embodiment.
In the conventional graphene production process, graphite powder is added to an aqueous solution of sulfuric acid (H 2 SO 4 ) to disperse the graphite oxide powder in an aqueous solution to form an oxide graphite thin plate, then potassium permanganate (KMnO 4 ) powder is gradually added Oxygen functional groups were inserted between the pin layers. However, this method is a technique to prevent the rapid rise of temperature by controlling the amount of input and the rate of input due to the risk of explosion due to a rapid exothermic reaction with sulfuric acid in the process of inserting the oxygen functional group into the graphene layer by using potassium permanganate (KMnO 4 ) powder There is a drawback in that graphene must be manufactured by the method. In addition, this method can be easily managed in a small-scale manufacturing of a laboratory unit. However, when mass production is carried out at a factory unit, there is a risk of explosion, so that the safety of workers may be threatened. In case of an accident, There is a need for a more manageable method of managing the explosion risk.
The graphite in the mixture is present in a slurry state that absorbs sulfuric acid (H 2 SO 4 ) in the second step. Therefore, the excess sulfuric acid remaining in the by-product can be filtered or partially removed without using a separate washing or drying process to remove the acid from the graphite. Sulfuric acid present in the mixture is more steps (S600) to minimize the residual acid solution by any or remove all of the rate of sulfuric acid (H 2 SO 4) that is not absorbed by the sulfate whole, based on the weight of the process of graphite in the mixture such that less than 5% .
If the residual sulfuric acid (H 2 SO 4 ) solution is minimized, the step of controlling the concentration of surplus sulfuric acid in the by-product is controlled to be within 5%. In the third step (S300), an aqueous solution of potassium permanganate (KMnO 4 ) The temperature can be easily controlled and the risk of explosion can be reduced. That is, it is possible to minimize the amount of the sulfuric acid and potassium permanganate instantaneously brought into contact with, potassium permanganate (KMnO 4) solution is in proportion to the time to penetrate between the plate-like structure of graphite of sulfuric acid (H 2 SO 4) and potassium permanganate (KMnO 4 ), The problem of rapid temperature rise can be solved. Also, in the production of graphene, graphite used as a raw material is replaced with process graphite discharged as a by-product of a diamond manufacturing process, and reused, thereby reducing raw material costs.
Meanwhile, as described above, in the second step S200, the sintered body is dipped in an aqueous sulfuric acid solution and then separated by electrolysis so that diamond, graphite, and catalyst metals are easily recovered or separated from each other through a physical method .
The step S800 of recovering the diamond or the like from the mixture thus converted through the second step S200 can be performed at any step after the second step S200. That is, it is also possible to recover the diamond at any stage after the second step (S200), further to separate and recover the noble metal, and to separate the process graphite from the mixture (S900). That is, oxidized graphite is produced in the form of a brown viscous slurry and is formed of oxidized graphite, a stripped thin film oxidation plate, unoxidized graphite pieces, and residues of an oxidizing agent. Therefore, graphite oxide can improve the quality and yield of graphene by removing precipitated impurities through purification process (S900) through centrifugation and selectively filtering oxidized graphite to obtain purified graphite oxide. The process of separating the process graphite from the mixture can be variously applied to known filtration methods such as gravity filtration, pressure filtration, vacuum filtration, centrifugal filtration, osmosis filtration, and there is no particular limitation on the filtration method.
Thereafter, hydrogen peroxide (H 2 O 2 ) treatment (S700) can be performed as a general process for washing.
Hereinafter, specific preferred embodiments of the graphene fabrication method using the process graphite according to the present invention and each unit process according to the embodiment will be described in detail.
Graphite powder and metal powder such as iron, nickel, and cobalt powder are put into a cell of a certain size and sintered at a temperature of 1500 ° C. and a pressure of 50,000 atm for 60 minutes according to the process of producing graphene using the process graphite according to this embodiment. The sintered product is immersed in dilute sulfuric acid and electrolyzed. After electrolysis, the diamond and unreacted by-products are separated by gravity filtration in the converted mixture.
In the second step, sulfuric acid is preferably used as the acid solution for immersing the metal powder and the sintered graphite, but at least one of phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ) and hydrochloric acid It is possible.
Thereafter, the ratio of sulfuric acid remaining in the graphite to the total weight of the sulfuric acid contained in the by-product is not absorbed into the graphite is controlled to be within 5% so that the by-product forms a slurry form. If the ratio of sulfuric acid (H 2 SO 4 ) not absorbed in the graphite exceeds 5% and the sulfuric acid solution remains outside the graphite, the aqueous solution of potassium permanganate (KMnO 4 ) is added and stirred at the fourth step There is a problem that the risk of explosion due to a sudden rise of the explosion control system is increased. However, as in the present invention, if the residual sulfuric acid remaining in the process graphite is minimized, the interlayer expansion of the graphite sufficiently occurs, while the risk of explosion is minimized even if the potassium permanganate (KMnO 4 ) aqueous solution is added in the third step .
Next, an aqueous solution of potassium permanganate (KMnO 4 ) is added to the graphite slurry after the second step (S200) and stirred. Potassium permanganate (KMnO 4 ) is preferably an aqueous solution of potassium permanganate (KMnO 4 ) rather than powder particles, and is added to process graphite in the form of an acid-treated slurry and stirred.
Conventional graphene manufacturing process using potassium permanganate (KMnO 4) is when the input of potassium permanganate (KMnO 4), in particular a powder form of permanganate knife (KMnO 4) of cerium to the mixture of graphite and sulfuric acid (H 2 SO 4), It was not possible to apply it to mass production because of the troublesome operation of adjusting the temperature by a small amount due to the risk of explosion due to the temperature rise of the mixture. However, sulfuric acid remaining living quarters the filtration is insufficient number of sulfuric acid to have a range of 5% sulfuric acid the time of preparation of potassium permanganate (KMnO 4) by reducing the amount of (H 2 SO 4) to a minimum (H 2 SO 4) and The risk of temperature rise and explosion due to abrupt reaction of aqueous potassium permanganate (KMnO 4 ) solution can be remarkably reduced. As described above, the method for manufacturing graphene using the graphite of the present invention is suitable for mass production of graphene.
On the other hand, graphite oxide is produced in the form of a brown viscous slurry and is formed of oxide graphite, a stripped thin film oxidation plate, unoxidized graphite pieces, and residues of an oxidizing agent. The oxidized graphite can be subjected to a purification process by centrifugation, in which the precipitated impurities are removed and the suspended graphite oxide can be selectively filtered out.
Next, the process graphite is ultrasonically pulverized and separated into graphite oxide. The purified graphite oxide is dispersed in a basic aqueous solution or an organic solvent through ultrasonic pulverization and is peeled off in the form of graphene grains. Oxidized graphene grains with a more uniform monolayer and area are obtained through a density gradient-centrifugation process after ultrasonication.
It is also possible to separate the graphene grains by applying shear stress using a high-pressure homogenizer.
Thereafter, the graphene oxide which has been stripped is reduced. Although it is possible to use oxidized graphenes for specific applications, oxidized graphenes can be regarded as graphenes that have lost their electrical and thermal properties. Thus, to restore the lost electrical and thermal properties of graphene, the graphene graphene is reduced to finally form a reduced graphene. As described above, hydrazine and the like can be used as a reducing agent for reducing oxidized graphite.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. have.
Claims (16)
A second step of immersing the sintered body in a strong acid aqueous solution and electrolysis to convert it into a mixture containing diamond and graphite;
A third step of adding an aqueous solution of potassium permanganate (KMnO 4) to the mixture and stirring the mixture;
A fourth step of peeling the graphite in the mixture;
A fifth step of recovering the exfoliated graphene grains; And
A sixth step of reducing the exfoliated graphene grains;
Wherein the graphene is a graphene.
An acid removing step for partially removing the strong acid such that the weight ratio of the strong acid remaining in the graphite to the total strong acid contained in the mixture is not more than 5% after the second step and the third step, The method of manufacturing graphene using process graphite according to claim 1,
Wherein the graphite in the mixture is in the form of a slurry.
And recovering the diamond from the mixture after the second step.
And recovering the noble metal in the recovering step.
Further comprising the step of purifying graphite in the mixture after the recovering step.
And further adding 5% sulfuric acid (H2SO4) in the third step.
The sulfuric acid (H2SO4) is graphene production method using a process the graphite added in a state of being mixed with the potassium permanganate (KMnO 4) solution.
Wherein the potassium permanganate aqueous solution further comprises sodium nitrate (NaNO 3 ) in the third step.
The acid introduced in the second step may be at least one selected from the group consisting of graphite using process graphite containing at least one of sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ) and hydrochloric acid / RTI >
Wherein the metal powder comprises at least one of iron, nickel, and cobalt.
Wherein the sintering is performed at a temperature of 500 to 3000 in the first step.
Wherein the sintering in the first step is performed at a pressure of 40,000 to 60,000 atm.
Wherein the sintering is performed for 40 to 80 minutes in the first step.
Wherein the fourth step is performed by heat treatment or ultrasonic irradiation.
The sixth step is a step of adding at least one reducing agent selected from the group consisting of hydrazine, sodium hydride, hydroquinone, sodium borohydride, ascorbic acid, and glucose. Process for producing graphene using graphite.
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| KR101358883B1 (en) * | 2012-03-19 | 2014-02-07 | 인하대학교 산학협력단 | Manufacturing method of novel hybrid composites composed with metal-loaded graphene oxide and metal-organic frameworks for hydrogen storage |
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