CN113023712A - High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding - Google Patents
High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding Download PDFInfo
- Publication number
- CN113023712A CN113023712A CN202010414044.4A CN202010414044A CN113023712A CN 113023712 A CN113023712 A CN 113023712A CN 202010414044 A CN202010414044 A CN 202010414044A CN 113023712 A CN113023712 A CN 113023712A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- graphene oxide
- biocatalyst
- reduction
- 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.)
- Withdrawn
Links
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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- 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
- C01B2204/22—Electronic properties
-
- 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)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing graphene in large batch under high pressure and application thereof in electromagnetic shielding, which comprises the steps of taking graphene oxide gel as a precursor, adding a biocatalyst material, carrying out ultrasonic oscillation treatment, and then carrying out magnetic stirring pre-reduction to obtain a pre-reduction solution mixed by graphene oxide and a biocatalyst; the reducing material is used as a secondary reducing agent and a doping agent, a simple pressure cooker is adopted for cooking, high-pressure and high-temperature reaction is adopted, the graphene oxide is subjected to secondary reduction, and a target material is prepared in a large scale; meanwhile, the prepared graphene material has good water dispersibility, can be used for preparing conductive ink, and can be used for preparing a graphene electrode film with high conductivity and uniformity.
Description
Technical Field
The invention relates to the field of novel electronic materials, in particular to a method for preparing graphene on a large scale at high pressure and application of the graphene in electromagnetic shielding.
Background
Graphene is a novel carbon material having a single-layer sheet structure, which is composed of sp2 hybridized carbon atoms in a two-dimensional plane. Since GN has a single atomic layer structure, it has excellent properties in electrical and optical properties that many common carbon materials do not have. The surface area of the conductive material can reach 2675m2/g, and the maximum conductivity is 106S/cm. And GN has excellent mechanical properties, and tensile strength and elastic modulus thereof are 125GPa and 1.1TPa respectively, so that graphene has a wide application prospect in the fields of energy storage materials, sensor materials, biological materials, conductive ink, semiconductor materials, electronic components, electromagnetic compatibility, electromagnetic shielding and the like, and particularly, with the increasingly miniaturized development of electronic equipment, higher requirements are put forward in the field of electromagnetic compatibility, and the graphene material is more and more attracted more attention as a graphene material which can be applied to electromagnetic interference shielding/electrostatic protection (EM I/ESD) components.
However, graphene has a stable six-membered benzene ring, and a strong pi-pi bond effect exists between graphene sheets, so that the graphene is easy to re-accumulate or agglomerate, and the theoretical high specific surface area and other excellent properties of the graphene cannot be fully embodied. Meanwhile, graphene is difficult to prepare into a uniform electrode, which also limits the application of graphene in the fields of electronic components, electromagnetic shielding and the like.
In recent years, there have been many studies on graphene, and how to prepare graphene into a uniform electrode is important for the research. The existing main methods comprise the following steps:
(1) the graphene material is prepared by a mechanical stripping method, a seal cutting and transferring method and the like, and the method can be used for preparing the graphene material
The preparation of the single-layer graphene is difficult to form uniform electrodes, and obviously does not have the possibility of industrial production.
(2) The graphene electrode film is prepared by adopting a chemical vapor deposition method, an epitaxial growth method and the like, the graphene electrode film with better uniformity can be prepared by the method, but the chemical vapor deposition method and the epitaxial growth method have higher requirements on equipment, and the prepared graphene electrode film is thinner, has small area and is difficult to be applied on a large scale.
(3) The graphene material is prepared by adopting an organic chemical synthesis method, and the graphene has the advantages of high yield, complete structure, strong adjustability and the like. The design and synthesis of the precursor polycyclic aromatic hydrocarbon are key steps for obtaining high-performance and high-yield graphene, so that the requirement on the precursor is high. And the prepared graphene material is difficult to form a uniform electrode.
(4) The method has the advantages of simplicity, feasibility, low cost and the like, and particularly can modify the graphene according to actual requirements in the preparation process to obtain various functionalized graphene materials such as oxygen-doped graphene, nitrogen-doped graphene, sulfur-doped graphene, phosphorus-doped graphene and the like. The bifunctional graphene contains specific groups, can be stably dispersed in various solvents, can be uniformly coated on any substrate to form a uniform electrode, and is further applied to the fields of flexible devices, organic devices and the like.
However, the prior redox electrode materials and/or methods for preparing the same have more disadvantages, such as: although the composite material generated by adopting the oxidation-reduction method is easy to prepare a uniform electrode, toxic reducing agents such as hydrazine hydrate and the like are commonly used in the reduction process, and volatile solvents which are easy to pollute the environment such as DMF (dimethyl formamide) and NMP (N-methyl pyrrolidone) and the like are used, so that the environment is greatly damaged; large scale use is not recommended. Meanwhile, the flammable organic solvent needs to be under a high-temperature and high-pressure condition by adopting solvent heat, so that the method has certain explosion danger and has high requirements on equipment and operation.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for preparing graphene at high pressure on a large scale, which is characterized in that graphene oxide gel and a biocatalyst material are pre-reduced, then a reducing material is used as a secondary reducing agent and a dopant, a simple autoclave is adopted for cooking and high-temperature reaction, graphene oxide is secondarily reduced, and a target material is prepared on a large scale.
The second purpose of the invention is to provide a reduced graphene oxide material prepared by the method of the invention, which not only effectively inhibits the characteristic of easy agglomeration of the graphene material, but also has excellent conductivity; and simultaneously has good water dispersibility.
The third purpose of the present invention is to provide an electromagnetic shielding application, wherein the reduced graphene oxide material is used for manufacturing electronic components.
In order to achieve the above object, the present invention provides a method for preparing graphene at high pressure and high volume, the method comprising the following steps:
the method comprises the following steps: taking a biocatalyst material, dissolving or dispersing the biocatalyst material, and then performing ultrasonic oscillation treatment to obtain a biocatalyst solution;
step two: adding the graphene oxide gel into the biocatalyst solution, and performing ultrasonic oscillation treatment to obtain a dispersion solution mixed by the graphene oxide gel and the biocatalyst solution; performing magnetic stirring pre-reduction on the dispersion solution to obtain a pre-reduction solution mixed by graphene oxide gel and a biocatalyst solution;
step three: dissolving a reducing material, and then performing ultrasonic oscillation treatment to obtain a reducing solution;
step four: mixing the pre-reduction solution and the reducing solution, and then carrying out ultrasonic oscillation treatment to obtain a mixed solution;
step five: and (3) placing the mixed solution into a pressure cooker for cooking, carrying out secondary reduction, and repeatedly cleaning to obtain the reduced graphene oxide material.
Further, the biocatalyst material comprises one or more of L-ascorbic acid, L-glutathione, tea polyphenols, glucose, fructose, sucrose, chitosan, gallic acid, yeast, amino acids, and plant extracts containing ketones.
Further, the reducing material comprises one or more of ammonium thiocyanate, lithium aluminum hydride, urea, ammonia water, sodium borohydride, sodium hydroxide, potassium hydroxide, aluminum powder, zinc powder, sodium citrate and iodine hydrogen acid.
Further, the mass ratio of the biocatalyst solution to the graphene oxide gel in the pre-reduction solution is 2: 1-10: 1. Further, the temperature of the magnetic stirring pre-reduction in the second step is normal temperature, and the time is 8 to 24 hours.
Further, in the fourth step, the mass ratio of the graphene oxide gel in the pre-reduction solution to the reducing material in the reducing solution is 1: 10-1: 30.
Further, the second reduction in the fifth step is a high-temperature high-pressure reaction in an autoclave, and is maintained at a constant pressure for 0.5 to 5 hours.
In order to achieve the purpose, the invention further provides a reduced graphene oxide material and graphene prepared by the method.
Further, the graphene comprises a six-membered carbocyclic ring, wherein one or more heteroatoms are doped in the six-membered carbocyclic ring, and hydrophilic groups are introduced on carbon atoms in the six-membered carbocyclic ring.
In order to achieve the above object, the present invention further provides an electronic component including the reduced graphene oxide material.
The technical scheme at least has the following beneficial effects:
(1) the preparation method is simple, high in yield, low in equipment cost, easy to prepare, capable of realizing industrial mass production, and safe and pollution-free in preparation process;
(2) the reduced graphene oxide material has excellent comprehensive performance, one or more heteroatoms are doped in the six-membered carbon ring, the characteristic of easy agglomeration of the graphene material is effectively inhibited, and the advantages of excellent conductivity, high specific surface area and the like of the graphene material can be fully exerted; meanwhile, a hydrophilic group is introduced to carbon atoms in the six-membered carbon ring, so that the reduced graphene oxide material has good water dispersibility under the action of the hydrophilic group, and can be used for preparing graphene conductive ink.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The invention is further described below.
According to the method for preparing the graphene at high pressure and large scale, firstly, graphene oxide gel and a biocatalyst solution are prepared, wherein the graphene oxide gel adopts an improved Hummer method, and the method is widely used in the industry. And then, fully mixing a certain amount of graphene oxide gel with a certain amount of biocatalyst solution, then carrying out ultrasonic oscillation treatment to ensure that the graphene oxide gel is fully contacted with the biocatalyst solution, and carrying out magnetic stirring pre-reduction at room temperature to obtain a pre-reduction solution mixed by the graphene oxide gel and the biocatalyst solution. Taking the reducing material as a secondary reducing agent and a doping agent, dissolving the reducing material, then performing ultrasonic oscillation treatment to obtain a reducing solution, mixing the pre-reducing solution and the reducing solution, performing ultrasonic oscillation treatment to obtain a mixed solution, cooking the mixed solution by using a simple pressure cooker, performing high-pressure high-temperature reaction, and performing secondary reduction on graphene oxide gel to obtain heteroatom-doped pressure cooker reduced graphene oxide (pc-R graphene oxide gel), wherein the pc-R graphene oxide gel material has the characteristics of excellent conductivity, high specific surface area, good water dispersibility and the like, and the specific steps and flows are as follows:
the method comprises the following steps: taking a biocatalyst material, dissolving or dispersing the biocatalyst material, and then performing ultrasonic oscillation treatment to obtain a biocatalyst solution; in the step, the biocatalyst material is a mixed catalytic material of one or more of natural materials such as L-ascorbic acid, L-glutathione, tea polyphenol, glucose, fructose, sucrose, chitosan, gallic acid, yeast, amino acid, plant extracts containing ketones and the like, and the solution for dissolving or dispersing the biocatalyst material is preferably deionized water; the ultrasonic vibration treatment is carried out at the temperature of 0-10 ℃, the time of the ultrasonic vibration treatment is controlled to be 0.5-1 hour, and a dispersion solution with the concentration of the biocatalyst material being 2-50 mg/ml is preferably obtained;
step two: adding the graphene oxide gel into the biocatalyst solution, and performing ultrasonic oscillation treatment to obtain a dispersion solution mixed by the graphene oxide gel and the biocatalyst solution; performing magnetic stirring pre-reduction on the dispersion solution to obtain a pre-reduction solution mixed by graphene oxide gel and a biocatalyst solution; firstly, a proper amount of graphene oxide gel is measured, and the mass ratio of a biocatalyst solution to the graphene oxide gel in the measured graphene oxide gel is 2: 1-10: 1; the ultrasonic oscillation treatment is preferably carried out under the ice bath condition, more preferably, the temperature of the ice bath is controlled to be 0-5 ℃, and the time of the ultrasonic treatment is controlled to be 1-4 hours; the temperature of the magnetic stirring pre-reduction is normal temperature, and the time is 8 hours to 24 hours.
Step three: dissolving a reducing material, and then performing ultrasonic oscillation treatment to obtain a reducing solution; in this step, the mixed solution is first magnetically stirred at a high speed of 3000 rpm for 10-30 minutes at 2000-.
Step four: mixing the pre-reduction solution and the reducing solution, and then carrying out ultrasonic oscillation treatment to obtain a mixed solution; in the step, firstly, a proper amount of reducing material is measured, and the mass ratio of the graphene oxide gel in the pre-reduction solution to the reducing material in the reducing solution is 1: 10-1: 30. The ultrasonic treatment is carried out at room temperature, and the time of the ultrasonic treatment is controlled to be 1-2 h; further, the reducing material includes, but is not limited to, one or more mixed reducing materials of chemical reducing raw materials such as ammonium thiocyanate, lithium aluminum hydride, urea, ammonia water, sodium borohydride, sodium hydroxide, potassium hydroxide, aluminum powder, zinc powder, sodium citrate, and iodine hydrogen acid, and the solution for dissolving or dispersing the reducing material is preferably deionized water, and the volume of the reducing solution is the same as that of the pre-reducing solution; further, the mixed solution was magnetically stirred at a high speed of 2000-3000 rpm for 5-60 minutes.
Step five: and (3) placing the mixed solution into a pressure cooker for cooking, carrying out secondary reduction, and repeatedly cleaning to obtain the reduced graphene oxide material. In this step, the second reduction is carried out in an autoclave at high temperature and pressure, and is maintained at a constant pressure for 0.5 to 5 hours. Firstly, adding a mixed solution into a pressure cooker, and controlling the amount of the mixed solution to be 30-60% of the capacity of the pressure cooker; then closing the upper pot cover of the pressure cooker, closing the air valve, setting the constant temperature time, and reacting for 0.5-5 h at high temperature and high pressure; then, the pressure cooker is powered off to naturally cool; finally, washing for 5-10 times by using deionized water or ethanol to finally obtain a product;
the graphene is prepared by adopting the high-pressure large-batch graphene preparation method, and comprises a six-membered carbon ring, wherein one or more heteroatoms are doped in the six-membered carbon ring; a hydrophilic group is introduced to a carbon atom in a six-membered carbocyclic ring.
Specifically, the reaction results of the raw materials are as follows:
(1) under high temperature and high pressure, the graphene oxide (graphene oxide gel) is reduced for the second time to be the reduced graphene oxide (pc-R graphene oxide gel) in the pressure cooker.
(2) Meanwhile, under the conditions of high temperature and high pressure, heteroatoms in the reducing agent can replace carbon atoms in a six-membered carbon ring of the pc-R graphene oxide gel, and the heteroatoms are introduced into the pc-R graphene oxide gel or hydrophilic groups are introduced onto the carbon atoms in the six-membered carbon ring, so that the pc-R graphene oxide gel has the characteristics of excellent conductivity, high specific surface area, good water dispersibility and the like.
Therefore, the method adopts simple autoclave cooking (high-pressure high-temperature reaction) to reduce the graphene oxide for the second time, and prepares the target material in large batch. The preparation method has the advantages of simple operation steps, easy preparation, high yield, suitability for industrial mass production, safe preparation process and no pollution.
Further, the steps of the method of the present invention can be specifically referred to as follows:
(1) dissolving or dispersing a biocatalyst material, such as one or more of L-ascorbic acid, L-glutathione, tea polyphenol, glucose, fructose, sucrose, chitosan, gallic acid, yeast, amino acid, ketone-containing plant extracts and the like, in deionized water, and performing ultrasonic oscillation treatment for 0.5-1 h under the ice bath condition of 0-10 ℃ to obtain 2-50 mg/ml biocatalyst solution A;
(2) adding graphene oxide gel into the biocatalyst solution A according to a ratio of 1: 2-1: 10 (mass ratio of graphene oxide gel to the biomass catalyst), and performing ultrasonic vibration treatment for 1-4 hours under an ice bath condition at 0-5 ℃ to obtain a graphene oxide/biocatalyst dispersed solution B;
(3) at room temperature, magnetically stirring the graphene oxide/biocatalyst B at a high speed (3000 r/min) for 10-30 min, and then magnetically stirring the mixed solution at a low speed (600 r/min) for 8-24h to obtain a graphene oxide/biocatalyst pre-reduction solution C;
(4) according to the ratio of 1: 10-1: 30 (graphene oxide gel and reducing material), taking the reducing material, for example: dissolving one or more of ammonium thiocyanate, lithium aluminum hydride, urea, ammonia water, sodium borohydride, sodium hydroxide, potassium hydroxide, aluminum powder, zinc powder, sodium citrate, iodine hydrogen acid and the like in deionized water with the same volume as that of the graphene oxide/biocatalyst pre-reduction solution C, and magnetically stirring at a high speed (2000-3000 r/min) for 5-60 minutes at room temperature to obtain a reduction solution D;
(5) mixing the graphene oxide/biocatalyst pre-reduction solution C and the reducing solution D according to the volume ratio of 1:1, and then carrying out ultrasonic oscillation treatment for 1-2 h at room temperature to obtain a graphene oxide/biocatalyst/reducing agent mixed solution E;
(6) placing the graphene oxide/biocatalyst/reducing agent mixed solution E into an autoclave, and controlling the amount of the mixed solution E to be 30-60% of the capacity of the autoclave; then closing the upper pot cover of the pressure cooker, closing the air valve, setting the constant temperature time, and reacting for 0.5-5 h at high temperature and high pressure;
(7) after the reaction is finished, the pressure cooker is powered off and naturally cooled; finally, washing for 5-10 times by using deionized water or ethanol to finally obtain a reduced graphene oxide material F;
the pressure cooker reduced graphene oxide material prepared by the method has an obvious porous graphene fold structure on a microstructure, and has a large specific surface area (1500 m 2/g); and the graphene conductive ink has good hydrophilicity and can be used for preparing graphene conductive ink.
Furthermore, the graphene electrode prepared by spraying the graphene conductive ink has higher conductivity (> 200S/cm).
Furthermore, the reduced graphene oxide material provided by the invention can also be used as a functional material for preparing a uniform graphene electrode film, and the prepared electrode film also has excellent electromagnetic shielding performance and can be applied to various environments.
Example 1
(1) Dissolving or dispersing a proper amount of L-ascorbic acid biocatalyst material in deionized water, and carrying out ultrasonic oscillation treatment for 0.5h under the ice bath condition of 0-10 ℃ to obtain 10mg/ml L-ascorbic acid solution A;
(2) adding a proper amount of graphene oxide gel into an L-ascorbic acid solution A according to a ratio of 1:2 (mass ratio of the graphene oxide gel to the L-ascorbic acid), and performing ultrasonic oscillation treatment for 2 hours under an ice bath condition of 5 ℃ to obtain a graphene oxide gel/L-ascorbic acid dispersion solution B;
(3) at room temperature, magnetically stirring the graphene oxide gel/L-ascorbic acid B at a high speed of 2000 rpm for 10 minutes, and magnetically stirring the mixed solution at a low speed of 300 rpm for 12 hours to obtain a graphene oxide gel/L-ascorbic acid pre-reduction solution C;
(4) dissolving a proper amount of ammonia water (mass ratio of the graphene oxide gel to the ammonia water) in deionized water with the same volume as that of the graphene oxide gel/L-ascorbic acid pre-reduction solution C according to the proportion of 1:10, and magnetically stirring for 5 minutes at room temperature at high speed of 2000-3000 r/min to obtain an ammonia water solution D;
(5) mixing the graphene oxide gel/L-ascorbic acid pre-reduction solution C with an ammonia water solution D according to the volume ratio of 1:1, and then carrying out ultrasonic oscillation treatment for 1h at room temperature to obtain a graphene oxide gel/L-ascorbic acid/ammonia water solution mixed solution E;
(6) placing the graphene oxide gel/L-ascorbic acid/ammonia water solution mixed solution E in a 5L pressure cooker, and controlling the amount of the mixed solution E to be 60% of the capacity of the pressure cooker; then closing the upper pot cover of the pressure cooker, closing the air valve, setting the constant temperature time, and reacting for 5 hours at high temperature and high pressure;
(7) after the reaction is finished, the pressure cooker is powered off and naturally cooled; finally, washing for 5-10 times by using deionized water or ethanol to finally obtain a product, namely a reduced graphene oxide material F1 in an autoclave; the total weight of the reduced graphene oxide material in the pressure cooker of example 1 was 5.778g, and the specific surface area was 1274m 2/g.
The pressure cooker reduced graphene oxide material prepared in example 1 was further subjected to a dispersion test and a conductivity test, the test methods were as follows:
firstly, selecting a proper amount of reduced graphene oxide material, carrying out ultrasonic oscillation treatment for 2 hours, and observing whether a precipitate exists or not; and left for 7 days to observe whether or not they were layered. Then spraying the graphene electrode film on quartz glass in a spraying mode to prepare a graphene electrode film, and testing the conductivity of the graphene electrode film by using a four-probe tester;
further, the electromagnetic shielding performance of the electrode film can be tested.
The experimental result shows that the reduced graphene oxide conductive ink prepared in the embodiment 1 has no obvious layering after standing for 7 days and has excellent water dispersibility; the graphene electrode film prepared by the spraying method has high conductivity (213.3S/cm) and good shielding efficiency (40.3 dB).
Example 2
(1) Dissolving or dispersing a proper amount of glucose biocatalyst material in deionized water, and carrying out ultrasonic oscillation treatment for 1h under the ice bath condition of 0-10 ℃ to obtain a 10mg/ml glucose solution A;
(2) adding a proper amount of graphene oxide gel into the glucose solution A according to the ratio of 1:2 (the mass ratio of the graphene oxide gel to the glucose), and carrying out ultrasonic vibration treatment for 2 hours under the ice bath condition of 5 ℃ to obtain a graphene oxide gel/glucose dispersion solution B;
(3) at room temperature, magnetically stirring the graphene oxide gel/glucose B at a high speed of 2000 rpm for 10 minutes, and magnetically stirring the mixed solution at a low speed of 300 rpm for 12 hours to obtain a graphene oxide gel/glucose pre-reduction solution C;
(4) dissolving a proper amount of ammonia water (mass ratio of the graphene oxide gel to the ammonia water) in deionized water with the same volume as that of the graphene oxide gel/glucose pre-reduction solution C according to the proportion of 1:10, and magnetically stirring for 5 minutes at room temperature and high speed of 2000-3000 r/min to obtain an ammonia water solution D;
(5) mixing the graphene oxide gel/glucose reduction solution C with an ammonia water solution D according to the volume ratio of 1:1, and carrying out ultrasonic oscillation treatment for 1h at room temperature to obtain a glucose/ammonia water solution mixed solution E;
(6) placing the graphene oxide gel/glucose/ammonia water solution mixed solution E in a 5L pressure cooker, and controlling the amount of the mixed solution E to be 60% of the capacity of the pressure cooker; then closing the upper pot cover of the pressure cooker, closing the air valve, setting the constant temperature time, and reacting for 5 hours at high temperature and high pressure;
(7) after the reaction is finished, the pressure cooker is powered off and naturally cooled; finally, washing for 5-10 times by using deionized water or ethanol to finally obtain a product, namely a reduced graphene oxide material F2 in an autoclave;
the total weight of the reduced graphene oxide material in the pressure cooker of example 2 was 5.153g, and the specific surface area thereof was 1383m 2/g.
Further, the experimental results show that the reduced graphene oxide conductive ink prepared in example 2 has no obvious layering after standing for 7 days, and has excellent water dispersibility; the graphene electrode film prepared by the spraying method has high conductivity (197.5S/cm) and good shielding efficiency (39.2 dB).
Example 3
(1) Dissolving or dispersing a proper amount of L-ascorbic acid and glucose biocatalyst material (the mass ratio is 1:1) in deionized water, and carrying out ultrasonic vibration treatment for 0.5h under the ice bath condition of 0-10 ℃ to obtain 10mg/ml L-ascorbic acid/glucose mixed solution A;
(2) adding a proper amount of graphene oxide gel into an L-ascorbic acid/glucose mixed solution A according to a ratio of 1:2 (mass ratio of graphene oxide gel to L-ascorbic acid/glucose), and performing ultrasonic oscillation treatment for 2 hours under the ice bath condition of 5 ℃ to obtain a graphene oxide gel/L-ascorbic acid/glucose dispersed solution B;
(3) stirring the graphene oxide gel/L-ascorbic acid/glucose B at a high speed of 2000 revolutions per minute for 10 minutes at room temperature, and then stirring the mixed solution at a low speed of 300 revolutions per minute for 12 hours to obtain a graphene oxide gel/L-ascorbic acid/glucose pre-reduction solution C;
(4) dissolving a proper amount of ammonia water (mass ratio of the graphene oxide gel to the ammonia water) in deionized water with the same volume as that of the graphene oxide gel/L-ascorbic acid/glucose pre-reduction solution C according to the proportion of 1:10, and magnetically stirring for 5 minutes at room temperature at high speed of 2000-3000 r/min to obtain an ammonia water solution D;
(5) mixing the graphene oxide gel/L-ascorbic acid/glucose pre-reduction solution C with an ammonia water solution D according to the volume ratio of 1:1, and then carrying out ultrasonic oscillation treatment for 1h at room temperature to obtain a graphene oxide gel/L-ascorbic acid/glucose/ammonia water solution mixed solution E;
(6) placing the graphene oxide gel/L-ascorbic acid/glucose/ammonia water solution mixed solution E in a 5L pressure cooker, and controlling the amount of the mixed solution E to be 60% of the capacity of the pressure cooker; then closing the upper pot cover of the pressure cooker, closing the air valve, setting the constant temperature time, and reacting for 5 hours at high temperature and high pressure;
(7) after the reaction is finished, the pressure cooker is powered off and naturally cooled; finally, washing for 5-10 times by using deionized water or ethanol to finally obtain a product, namely a reduced graphene oxide material F3 in an autoclave;
the total weight of the reduced graphene oxide material in the pressure cooker of example 3 was 5.426g, and the specific surface area was 1422m 2/g.
Further, the experimental results show that the reduced graphene oxide conductive ink prepared in example 3 has no obvious delamination after standing for 7 days, and has excellent water dispersibility; the graphene electrode film prepared by the spraying method has high conductivity (235.3S/cm) and good shielding efficiency (40.1 dB).
The invention provides an electromagnetic shielding application, and an electronic component is manufactured by adopting the reduced graphene oxide material and has excellent electromagnetic shielding performance.
In conclusion, the method has the advantages of cheap and easily-obtained raw materials, simple and quick operation steps, high yield and easy industrial large-scale production; meanwhile, the invention is safe and pollution-free in the preparation process;
the pressure cooker graphene material prepared by the method has good water dispersibility, can be used for preparing conductive ink and preparing uniform graphene electrode films, and the prepared electrode films also have excellent electromagnetic shielding performance and can be applied to various environments. The target material is prepared in large batch, and the preparation method has the advantages of simplicity, high yield, low cost, easiness in batch production and the like.
While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention. Are also considered to be within the scope of the invention.
Claims (10)
1. A method for preparing graphene at high pressure and large scale is characterized by comprising the following steps:
the method comprises the following steps: taking a biocatalyst material, dissolving or dispersing the biocatalyst material, then carrying out ultrasonic oscillation treatment,
obtaining a biocatalyst solution;
step two: adding the graphene oxide gel into the biocatalyst solution, and performing ultrasonic oscillation treatment to obtain a dispersion solution mixed by the graphene oxide gel and the biocatalyst solution; performing magnetic stirring pre-reduction on the dispersion solution to obtain a pre-reduction solution mixed by graphene oxide gel and a biocatalyst solution;
step three: dissolving a reducing material, and then performing ultrasonic oscillation treatment to obtain a reducing solution;
step four: mixing the pre-reduction solution and the reducing solution, and then carrying out ultrasonic oscillation treatment to obtain a mixed solution;
step five: and (3) placing the mixed solution into a pressure cooker for cooking, carrying out secondary reduction, and repeatedly cleaning to obtain the reduced graphene oxide material.
2. The high-pressure mass production method of graphene according to claim 1, wherein the biocatalyst material comprises one or more of L-ascorbic acid, L-glutathione, tea polyphenols, glucose, fructose, sucrose, chitosan, gallic acid, yeast, amino acids, and plant extracts containing ketones.
3. The high-pressure mass production method of graphene according to claim 1, wherein the reducing material comprises one or more of ammonium thiocyanate, lithium aluminum hydride, urea, ammonia water, sodium borohydride, sodium hydroxide, potassium hydroxide, aluminum powder, zinc powder, sodium citrate, and iodine hydrogen acid.
4. The high-pressure mass production method of graphene according to claim 1, wherein the mass ratio of the biocatalyst solution to the graphene oxide gel in the pre-reduction solution is 2:1 to 10: 1.
5. The high-pressure mass production method of graphene according to claim 1, wherein the temperature of the magnetic stirring pre-reduction in the second step is normal temperature, and the time is 8 to 24 hours.
6. The high-pressure mass production method of graphene according to claim 1, wherein in the fourth step, the mass ratio of the graphene oxide gel in the pre-reduction solution to the reducing material in the reducing solution is 1:10 to 1: 30.
7. The high-pressure mass production method of graphene according to claim 1, wherein the second reduction in the fifth step is a high-temperature high-pressure reaction in an autoclave, and the constant pressure is maintained for 0.5 to 5 hours.
8. A reduced graphene oxide material, wherein the graphene prepared by the method according to any one of claims 1 to 7 is used.
9. The reduced graphene oxide material of claim 8, wherein the graphene comprises a six-membered carbon ring, wherein the six-membered carbon ring is doped with one or more heteroatoms, and wherein hydrophilic groups are introduced onto carbon atoms in the six-membered carbon ring.
10. Use of a reduced graphene oxide material according to claim 8 or 9 for the manufacture of electronic components for electromagnetic shielding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010414044.4A CN113023712A (en) | 2020-05-15 | 2020-05-15 | High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010414044.4A CN113023712A (en) | 2020-05-15 | 2020-05-15 | High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113023712A true CN113023712A (en) | 2021-06-25 |
Family
ID=76458621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010414044.4A Withdrawn CN113023712A (en) | 2020-05-15 | 2020-05-15 | High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113023712A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536010A (en) * | 2021-12-17 | 2022-12-30 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
-
2020
- 2020-05-15 CN CN202010414044.4A patent/CN113023712A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536010A (en) * | 2021-12-17 | 2022-12-30 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111199835B (en) | Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure | |
| CN109545576B (en) | Preparation method of nickel-cobalt-phosphorus-carbon-nickel hydroxide ternary composite electrode material | |
| CN103787328A (en) | Modified grapheme preparation method | |
| CN101527353A (en) | Lithium ion battery anode composite material and manufacturing method thereof | |
| CN114597341B (en) | Modified pre-lithiated silica material, preparation method and application thereof, and lithium ion battery | |
| CN110429284B (en) | High-capacity and high-rate flexible zinc ion battery and application thereof | |
| CN114583128B (en) | Controllable preparation method of surface highly conductive carbon fluoride | |
| CN103253648A (en) | Preparation method of carbon nanotube by growing on foamed nickel substrate | |
| CN105366664A (en) | Production method for sulfur-doped graphene | |
| Liu et al. | Magnetic-field-assisted preparation of one-dimensional (1-D) wire-like NiO/Co3O4 composite for improved specific capacitance and cycle ability | |
| CN110112458A (en) | A kind of halloysite nanotubes modified polyurethane solid electrolyte, preparation method and its battery | |
| CN111129579A (en) | Sulfide solid electrolyte material, preparation method thereof and solid battery | |
| US20200194782A1 (en) | Double layer-coated nano-silicon negative electrode material, a method for preparing the same and use thereof | |
| CN114122357A (en) | Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof | |
| CN115347140A (en) | Surface-modified composite zinc-based negative electrode, preparation method and battery | |
| CN113023712A (en) | High-pressure mass preparation method of graphene and application of graphene in electromagnetic shielding | |
| CN107601468A (en) | A kind of preparation method of graphene film | |
| CN110993904A (en) | Preparation method of nitrogen-doped antimony-carbon composite material and application of nitrogen-doped antimony-carbon composite material to sodium ion battery electrode | |
| CN113223869B (en) | Three-dimensional porous nanoflower-like NiS 2 Preparation and application of/carbon cloth composite material | |
| CN114700490A (en) | Preparation method of nickel-coated graphite composite particles and application of nickel-coated graphite composite particles in electromagnetic shielding field | |
| CN101101973A (en) | Conductive polymer for dye-sensitized nano crystal solar battery and its making method | |
| Sun et al. | One-piece adhesive-free molding polyvinylidene fluoride@ Ag nanofiber membrane for efficient oxygen reduction reaction in microbial fuel cells | |
| CN109509879A (en) | Clad anode material, preparation method and lithium ion battery altogether | |
| CN116995200A (en) | Multi-element doped porous silicon core-shell composite material and preparation method and application thereof | |
| CN102760861B (en) | Boron-substituted graphene oxide electrode and preparation method thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210625 |