CN110104634B - Three-dimensional graphene and preparation method and application thereof - Google Patents

Three-dimensional graphene and preparation method and application thereof Download PDF

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CN110104634B
CN110104634B CN201910413587.1A CN201910413587A CN110104634B CN 110104634 B CN110104634 B CN 110104634B CN 201910413587 A CN201910413587 A CN 201910413587A CN 110104634 B CN110104634 B CN 110104634B
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dimensional graphene
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pyrolysis
reaction furnace
microwave reaction
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CN110104634A (en
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康守国
李金来
史俊斌
张小诗
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Inner Mongolia Xinminhui Nanotechnology Co ltd
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Xinao Graphene Technology Co ltd
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides three-dimensional graphene and a preparation method and application thereof. The method for preparing the three-dimensional graphene comprises the following steps: pyrolyzing raw material coal in a microwave reaction furnace to obtain pyrolytic semicoke; mixing the pyrolysis semicoke and an activating agent to obtain a mixed material; and activating the mixed material in a microwave reaction furnace to obtain the three-dimensional graphene. Therefore, the obtained three-dimensional graphene has the advantages of developed pore space, large specific surface area, controllable pore size distribution and the like, and can be applied to a super capacitor; in addition, the preparation method has the advantages of small pollution, low energy consumption, long process time, easy control, low preparation cost and easy industrial production.

Description

Three-dimensional graphene and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to three-dimensional graphene and a preparation method and application thereof.
Background
The three-dimensional graphene has good mechanical strength, specific surface area, porous structure and other properties, and based on the properties, the three-dimensional graphene material has good application prospects in the aspects of energy storage batteries, super capacitors, solar batteries, displays, biological detection, fuel batteries and the like. However, the preparation method of the three-dimensional graphene still has many defects, for example, when the three-dimensional graphene is prepared by a resistance furnace heating method, the defects of long heating time, poor operating conditions, high labor intensity, serious environmental pollution and the like exist.
Therefore, research on a method for preparing three-dimensional graphene is awaited.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a method for preparing three-dimensional graphene, which has the advantages of low pollution, low energy consumption, short process time, easy control, and low preparation cost, or the prepared three-dimensional graphene has a large specific surface area and excellent performance.
In one aspect of the present invention, the present invention provides a method of preparing three-dimensional graphene. According to an embodiment of the present invention, the method of preparing three-dimensional graphene includes: pyrolyzing raw material coal in a microwave reaction furnace to obtain pyrolytic semicoke; mixing the pyrolysis semicoke and an activating agent so as to obtain a mixed material; and activating the mixed material in the microwave reaction furnace to obtain the three-dimensional graphene. Thus, by the pyrolysis treatment in the microwave oven, volatile components such as hydrogen, methane, carbon monoxide, carbon dioxide, tar, and the like in the raw material coal can be removed; the number of the semicoke micropores is increased in the pyrolysis process, which is beneficial to the full mixing of the pyrolysis semicoke and the activating agent; the pyrolysis semicoke shrinks while losing weight in the pyrolysis process to form cracks, which is beneficial to the full mixing of the pyrolysis semicoke and the activating agent; compared with the common pyrolysis method, the pyrolysis is carried out in the microwave reaction furnace, so that the raw material coal is heated more uniformly and pyrolyzed more fully, and the pyrolysis reaction rate is improved; in addition, in the activation process, the microwave directly acts on the pyrolysis semicoke, the heating is carried out by the internal friction of the pyrolysis semicoke, compared with the method that the pyrolysis semicoke is placed in a container absorbing microwave materials, the microwave acts on the container to heat the container, and then the pyrolysis semicoke is indirectly heated through heat conduction, the heating method adopting the microwave reaction furnace has higher efficiency and higher heat utilization rate; in addition, the obtained three-dimensional graphene has the advantages of developed pores, large specific surface area, controllable pore size distribution and the like, and can be applied to a super capacitor; in addition, the preparation method has the advantages of small pollution, low energy consumption, long process time, easy control, low preparation cost and easy industrial production.
According to an embodiment of the invention, the pyrolysis treatment satisfies at least one of the following conditions: the temperature of the pyrolysis treatment is 500-900 ℃; the pyrolysis treatment time is 0.1-3 hours; the frequency of the microwave reaction furnace is 915 MHz-2450 MHz.
According to the embodiment of the invention, the fixed carbon content of the raw material coal is 30-80%.
According to an embodiment of the present invention, the step of obtaining the mixed material comprises: kneading the pyrolysis semicoke and the activating agent to obtain the mixed material.
According to the embodiment of the invention, the kneading temperature of the kneading treatment is 100 to 300 ℃, and the kneading time is 1 to 10 hours.
According to the embodiment of the invention, the mass ratio of the pyrolysis semicoke to the activating agent is 1: 0.1-1: 5.
According to an embodiment of the invention, the activator is selected from KOH, KCl, K2CO3、MgO、MgCl2、NaOH、NaCl、Na2CO3、ZnCl2、NaOH、FeCl3And Fe (NO)3)3At least one of (1).
According to an embodiment of the invention, the activation treatment satisfies at least one of the following conditions: the temperature of the activation treatment is 700-1200 ℃; the activation treatment time is 0.1-3 hours; the frequency of the microwave reaction furnace is 915 MHz-2450 MHz; the atmosphere of the activation treatment is an inert gas.
According to an embodiment of the present invention, the method of preparing the three-dimensional graphene further includes: subjecting the product of the activation treatment to at least one of the following treatment steps: performing amorphous carbon removal treatment; acid washing treatment; and (5) high-temperature purification treatment.
According to the embodiment of the invention, the amorphous carbon removing treatment is carried out by utilizing oxidizing gas at 400-600 ℃, wherein the oxidizing gas is at least one of oxygen, carbon dioxide and air;
optionally, the acid cleaning treatment is performed by washing with at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and oxalic acid at 25-120 ℃.
Optionally, the high-temperature purification treatment is completed in an environment with the absolute pressure of less than 30pa at 1500-2400 ℃.
In another aspect of the present invention, the present invention provides a three-dimensional graphene. According to the embodiment of the invention, the three-dimensional graphene is prepared by the method. Therefore, the three-dimensional graphene has the advantages of developed pores, large specific surface area, controllable pore size distribution and the like, and can be applied to the fields of supercapacitors and the like. As can be understood by those skilled in the art, the three-dimensional graphene has all the features and advantages of the method for preparing the three-dimensional graphene, and thus, redundant description is not repeated herein.
In yet another aspect of the present invention, the present invention provides a method of preparing a three-dimensional graphene-carbon nanotube composite. According to an embodiment of the present invention, the method of preparing a three-dimensional graphene-carbon nanotube composite material includes: mixing the three-dimensional graphene prepared by the method or the three-dimensional graphene with a catalyst so as to obtain a mixed product; and placing the mixed product in a microwave reaction furnace, and introducing a gas carbon source into the microwave reaction furnace so as to grow carbon nanotubes on the surface of the three-dimensional graphene, thereby obtaining the three-dimensional graphene-carbon nanotube composite material. Therefore, the preparation method is simple and easy to operate, low in cost, high in production efficiency and easy for industrial production; in addition, under the microwave heating condition, the catalyst cracks the carbon source into solid carbon, and the solid carbon is deposited on the surface of the three-dimensional graphene to grow into the carbon nano tube (namely the carbon nano tube grows in the microwave reaction furnace through chemical vapor deposition), so that the three-dimensional graphene-carbon nano tube composite material is obtained; further, the three-dimensional graphene-carbon nanotube composite material prepared by the method has a large specific surface area and excellent electrical conductivity (electronic conductivity).
According to the embodiment of the invention, the catalyst is selected from a metal catalyst containing at least one of iron, molybdenum, cobalt and nickel, and optionally, the mass ratio of the three-dimensional graphene to the catalyst is 1: 0.01-1: 2.
According to the embodiment of the invention, the microwave frequency in the microwave reaction oven is 300 MHz-300 GHz, preferably, the microwave frequency in the microwave reaction oven is 865 MHz-965 MHz, or 2400 MHz-2500 MHz; optionally, the temperature for growing the carbon nano tube is 600-1000 ℃ and the time is 0.5-2 hours.
According to an embodiment of the invention, the gaseous carbon source is selected from at least one of methane, ethylene, ethane, acetylene, propane, propylene and natural gas.
According to the embodiment of the invention, after the carbon nano tube is grown, at least one of amorphous carbon removal treatment and acid washing treatment is further included, optionally, the amorphous carbon removal treatment is completed by using oxidizing gas at 400-600 ℃, wherein the oxidizing gas is at least one of oxygen, carbon dioxide and air; optionally, the acid cleaning treatment is performed by washing with at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and oxalic acid at a temperature of 25-95 ℃.
In yet another aspect of the present invention, the present invention provides a three-dimensional graphene-carbon nanotube composite. According to the embodiment of the invention, the three-dimensional graphene-carbon nanotube composite material is prepared by the method for preparing the three-dimensional graphene-carbon nanotube composite material. Therefore, the three-dimensional graphene-carbon nanotube composite material has a large specific surface area and excellent electrical conductivity. As will be understood by those skilled in the art, the three-dimensional graphene-carbon nanotube composite material has all the features and advantages of the method for preparing the three-dimensional graphene-carbon nanotube composite material, and thus, the detailed description thereof is omitted.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing three-dimensional graphene according to an embodiment of the present invention.
Fig. 2 is a schematic flow chart of a method for preparing three-dimensional graphene according to another embodiment of the present invention.
Fig. 3 is an SEM electron micrograph of the three-dimensional graphene prepared in example 1.
Fig. 4 is a schematic flow chart of a method for preparing a three-dimensional graphene-carbon nanotube composite material according to another embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides a method of preparing three-dimensional graphene. According to an embodiment of the present invention, referring to fig. 1, the method of preparing three-dimensional graphene includes:
s100: and carrying out pyrolysis treatment on the raw material coal in a microwave reaction furnace so as to obtain pyrolysis semicoke.
According to the embodiment of the invention, the specific type of the raw material coal is not limited, and the raw material coal can be flexibly selected by a person skilled in the art according to actual needs. In an embodiment of the present invention, the specific type of raw coal includes, but is not limited to, at least one of lignite, bituminous coal, anthracite. Therefore, the raw material coal is wide in source and rich in resource reserves, and the cost for preparing the three-dimensional graphene can be greatly reduced by preparing the three-dimensional graphene from the raw material coal. In some embodiments of the invention, lignite is preferred as raw material coal, which not only has low cost, but also has special coalification degree and structural characteristics, and a primarily formed graphene-like lamellar structure is arranged in the lignite, which is beneficial to improving the yield and efficiency of preparing three-dimensional graphene.
According to the embodiment of the invention, in order to improve the yield and purity of the three-dimensional graphene, the fixed carbon content of the raw material coal is 30% to 80%, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. Therefore, the yield and the purity of the prepared three-dimensional graphene are high; if the fixed carbon content is lower than 30%, impurities in the raw material coal are relatively more, the difficulty of impurity removal in the subsequent process is relatively increased, and the purity and yield of the three-dimensional graphene are relatively reduced; if the fixed carbon content is higher than 80%, the cost for obtaining the raw coal is relatively increased.
According to the embodiment of the invention, in order to fully pyrolyze the raw material coal, the pyrolysis treatment satisfies at least one of the following conditions:
the pyrolysis treatment temperature is 500-900 ℃ (such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃), so that the raw material coal can be fully pyrolyzed to obtain pyrolysis semicoke with developed micropore structure, and the subsequent full mixing with an activating agent is facilitated; if the pyrolysis temperature is lower, the pyrolysis of the raw material coal is relatively insufficient, and the microporous structure of the pyrolysis semicoke is not developed, so that the pyrolysis semicoke is not beneficial to being fully mixed with the activating agent; if the pyrolysis temperature is relatively high, the pyrolysis energy consumption is relatively increased, so that the preparation cost is increased, and the performance of the three-dimensional graphene is not obviously improved.
The pyrolysis treatment time is 0.1-3 hours (such as 0.1 hour, 0.2 hour, 0.5 hour, 1 hour, 2 hours or 3 hours), so that the raw material coal can be fully pyrolyzed to obtain pyrolysis semicoke with a developed microporous structure, and the subsequent full mixing with an activating agent is facilitated; if the pyrolysis time is short, the pyrolysis of the raw material coal is insufficient; if the pyrolysis time is too long, the time is long enough to fully pyrolyze the raw material coal, and the time is long, so that only time waste is caused.
The frequency of the microwave reaction furnace is 915 MHz-2450 MHz, so that the raw material coal can be fully heated to reach the required pyrolysis temperature in a short time, and the problem of agglomeration of powder particles in the raw material coal can be effectively solved.
S200: the pyrolysis semicoke and the activating agent are mixed to obtain a mixed material.
According to the embodiment of the invention, in the subsequent activation treatment, in order to enable the pyrolysis semicoke to react sufficiently and obtain the three-dimensional graphene with high yield, the mass ratio of the pyrolysis semicoke to the activating agent is 1: 0.1-1: 5, such as 1:0.1, 1:1, 1:2, 1:3, 1:4 or 1: 5. Therefore, the pyrolysis semicoke can be ensured to fully react in the activation treatment, and the performance of the three-dimensional graphene is improved; in some embodiments of the invention, the mass ratio of the pyrolysis semicoke to the activating agent is preferably 1: 1-1: 4, and if the amount of the activating agent is relatively low, the pyrolysis semicoke is relatively insufficiently activated, so that the performance of the three-dimensional graphene is reduced; if the dosage of the activating agent is too high, the activating agent can excessively ablate the three-dimensional graphene, and the performance of the three-dimensional graphene is affected.
According to an embodiment of the present invention, in order to increase the activation efficiency of the activation treatment, the activator is selected from KOH, KCl, K2CO3、MgO、MgCl2、NaOH、NaCl、Na2CO3、ZnCl2、NaOH、FeCl3And Fe (NO)3)3At least one of (1). Therefore, the material source is wide, the cost is low, the activation effect is good, and the three-dimensional graphene with excellent performance can be obtained.
In order to further improve the efficiency of the pyrolysis of the semicoke according to an embodiment of the present invention, referring to fig. 2, the step of obtaining a mixed material includes 210: the pyrolysis semicoke and the activating agent are kneaded to obtain a mixed material. Thus, the pyrolysis semicoke and the activator can be sufficiently mixed by the kneading treatment, so that the activator is supported on the surface and in the micropores of the pyrolysis semicoke, thereby improving the yield of the three-dimensional graphene.
According to the embodiment of the present invention, in order to sufficiently support the activator on the pyrolysis semicoke, the kneading temperature of the kneading treatment is 100 to 300 ℃ (such as 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃) and the kneading time is 1 to 10 hours (1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours). Therefore, the activating agent can be effectively loaded on the pyrolysis semicoke, and the conversion rate of the activating treatment is further improved; if the temperature of the kneading treatment is lower than 100 ℃, the mixing of the pyrolysis semicoke and the activator is relatively insufficient; if the temperature is higher than 300 ℃, the volatilization of the activator is severe and the energy consumption is increased.
S300: and activating the mixed material in a microwave reaction furnace to obtain the three-dimensional graphene. In the process, a graphite structure in the pyrolytic semicoke is utilized, and the three-dimensional porous graphene with large specific surface area, developed pores and controllable pore size distribution is obtained through intercalation stripping of an activating agent.
According to the embodiment of the invention, in order to obtain the three-dimensional graphene with better performance, the activation treatment meets at least one of the following conditions:
the temperature of the activation treatment is 700-1200 ℃ (such as 700 ℃, 800 ℃, 900 ℃, 1100 ℃ or 1200 ℃), so that the activator and the pyrolysis semicoke can be fully activated, and the three-dimensional graphene with excellent activation performance is obtained; if the temperature of the activation treatment is too low, the activation effect is poor, and the product purity is low; if the temperature of the activation treatment is too high, the energy consumption is too high, and the performance of the three-dimensional graphene is not obviously improved;
the activation treatment time is 0.1-3 hours (such as 0.1 hour, 0.2 hour, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours), so that the full activation of the activating agent and the pyrolysis semicoke can be ensured;
the frequency of the microwave reaction furnace is 915 MHz-2450 MHz, so that the temperature required by activation treatment can be reached in a short time, the activity and uniformity of the activation reaction are improved, and the three-dimensional graphene with excellent performance and high yield can be obtained.
The atmosphere of the activation treatment is inert gas, so that oxygen is isolated to prevent the reaction of oxygen and materials at a higher activation temperature, and the yield of the three-dimensional graphene is reduced.
According to an embodiment of the present invention, the method of preparing three-dimensional graphene further includes: subjecting the activated product to at least one of the following treatment steps: performing amorphous carbon removal treatment; acid washing treatment; and (5) high-temperature purification treatment. Therefore, the three-dimensional graphene obtained in the step 300 is purified to obtain high-purity three-dimensional graphene, specifically: most of metal impurities in the three-dimensional graphene can be removed through acid washing treatment, the metal impurities which are remained in the graphene and are difficult to remove are removed through high-temperature purification treatment, and the impure carbon in the graphene is removed through amorphous carbon removal treatment. In addition, the three-dimensional graphene with different purities can be prepared by the person skilled in the art according to different post-processing steps.
According to the embodiment of the present invention, the three post-processing steps are not strictly limited in sequence, and those skilled in the art can flexibly select the steps according to actual situations. In some embodiments of the present invention, the acid washing treatment is generally set before the high temperature purification treatment according to the purpose of the acid washing treatment and the high temperature purification treatment described above. Therefore, most of metal impurities are removed, and then the residual metal impurities which cannot be removed by acid washing treatment are removed, so that the metal impurities can be removed more effectively and more effectively in an energy-saving manner.
According to the embodiment of the invention, the amorphous carbon removing treatment is performed by using an oxidizing gas at 400-600 ℃ (such as 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃), wherein the oxidizing gas is at least one selected from oxygen, carbon dioxide and air, so that the residual impure carbon in the three-dimensional graphene can be effectively removed.
The specific steps of the step of removing the indefinite carbon are not limited, and those skilled in the art can flexibly select the step according to the actual needs. In some embodiments of the present invention, in order to remove the impure carbon as much as possible, the step of performing the amorphous carbon removing treatment is: a) adding the product obtained in the step S300 into a vertical boiling bed microwave reaction furnace; b) the temperature in the furnace reaches 400-600 ℃, and at least one of oxygen, carbon dioxide and air is introduced; c) and reacting for 0.5-2 h to obtain the graphene material containing a small amount of amorphous carbon.
According to an embodiment of the present invention, the acid cleaning process is performed by washing with at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and oxalic acid at 25 to 120 ℃ (e.g., 25 ℃, 50 ℃, 75 ℃, 100 ℃, or 120 ℃) to effectively remove metal impurities. Thus, impurities such as iron, potassium, and silicon in the graphene obtained in step 300 can be removed.
According to the embodiment of the present invention, the specific steps of the acid washing treatment are not limited, and those skilled in the art can flexibly select the steps according to actual requirements. In some embodiments of the present invention, in order to remove the metal impurities as much as possible, the specific steps of the acid washing treatment are: a) adding three-dimensional graphene containing metal impurities into an acid washing container; b) adding at least one acid of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and oxalic acid into a container; c) the temperature in the container reaches 25-120 ℃; d) stirring at 100-300 rpm; e) and (3) pickling for 2-15 h, so that the three-dimensional graphene containing a small amount of metal impurities can be prepared.
According to the embodiment of the invention, the high-temperature purification treatment is completed in an environment with the absolute pressure of less than 30pa at 1500-2400 ℃ (1500 ℃, 1600 ℃, 1800 ℃, 2000 ℃, 2200 ℃ or 2400 ℃). Therefore, metal impurities which are difficult to remove by acid washing can be effectively removed, side reactions of the three-dimensional graphene at high temperature are prevented in an inert environment, and the yield of the three-dimensional graphene is ensured; if the high-temperature purification temperature is lower, the purity of the obtained three-dimensional graphene is lower; if the temperature of the high-temperature purification is too high, the three-dimensional graphene is graphitized, and the specific surface area of the three-dimensional graphene is further reduced.
According to the embodiment of the present invention, the specific steps of the high temperature purification treatment are not limited, and those skilled in the art can flexibly select the steps according to actual requirements. In some embodiments of the present invention, in order to remove metal impurities as much as possible, the specific steps of the high-temperature purification process are: a) adding three-dimensional graphene containing a small amount of amorphous carbon and a small amount of metal impurities into a high-temperature purification furnace; b) the temperature in the furnace reaches reaction 1500-2400 ℃, and argon or nitrogen is introduced as protective atmosphere; c) vacuumizing, wherein the absolute pressure is lower than 30 pa; d) and reacting for 0.5-6 h, thus obtaining the three-dimensional graphene with remarkably improved performance.
According to the embodiment of the present invention, volatile components such as hydrogen, methane, carbon monoxide, carbon dioxide, tar, and the like in the raw material coal can be removed through pyrolysis treatment in the microwave oven; the number of the semicoke micropores is increased in the pyrolysis process, which is beneficial to the full mixing of the pyrolysis semicoke and the activating agent; the pyrolysis semicoke shrinks while losing weight in the pyrolysis process to form cracks, which is beneficial to the full mixing of the pyrolysis semicoke and the activating agent; compared with the common pyrolysis method, the pyrolysis is carried out in the microwave reaction furnace, so that the raw material coal is heated more uniformly and pyrolyzed more fully, and the pyrolysis reaction rate is improved; in addition, in the activation process, the microwave directly acts on the pyrolysis semicoke, the heating is carried out by the internal friction of the pyrolysis semicoke, compared with the method that the pyrolysis semicoke is placed in a container absorbing microwave materials, the microwave acts on the container to heat the container, and then the pyrolysis semicoke is indirectly heated through heat conduction, the heating method adopting the microwave reaction furnace has higher efficiency and higher heat utilization rate; in addition, the obtained three-dimensional graphene has the advantages of developed pores, large specific surface area, controllable pore size distribution and the like, and can be applied to a super capacitor; in addition, the preparation method has the advantages of small pollution, low energy consumption, long process time, easy control, low preparation cost and easy industrial production.
According to the embodiment of the invention, microwave heating has the advantages of selective and instantaneous heating, and the interaction of microwaves and substances realizes sufficient contact at a molecular level. Compared with the traditional reaction furnace:
1. microwave heating is volume heating of a substance in an electromagnetic field caused by medium loss per se, stirring on a molecular level can be realized, heating is uniform, and the temperature gradient is small. The traditional heating method adopts conduction and convection modes, heating is carried out from the outside to the inside, and the effect of microwave heating cannot be achieved;
2. the microwave is in a totally closed state, permeates into the object at the light speed, and is instantly converted into heat, so that the heat loss in the long-time heating process is saved. When materials are heated in the prior art, a lot of heat can be emitted to the environment in order to avoid overlarge temperature gradient and long heating time;
3. the microwave heating can solve the problem of powder particle agglomeration by the high-frequency reciprocating motion of internal molecules to generate 'internal friction heat'. Traditional heating methods may cause the powder particles to form agglomerates, affecting the powder quality.
Therefore, pyrolysis treatment and activation treatment are carried out through the microwave reaction furnace, sufficient pyrolysis can be carried out on raw material coal in a short time, and the pyrolysis semicoke is sufficiently and quickly activated to obtain the three-position graphene.
In another aspect of the present invention, the present invention provides a three-dimensional graphene. According to the embodiment of the invention, the three-dimensional graphene is prepared by the method. Therefore, the three-dimensional graphene has the advantages of developed pores, large specific surface area, controllable pore size distribution and the like, and can be applied to the fields of supercapacitors and the like. As can be understood by those skilled in the art, the three-dimensional graphene has all the features and advantages of the method for preparing the three-dimensional graphene, and thus, redundant description is not repeated herein.
In yet another aspect of the present invention, the present invention provides a method of preparing a three-dimensional graphene-carbon nanotube composite (which may be referred to herein simply as a composite). According to an embodiment of the present invention, referring to fig. 4, the method of preparing a three-dimensional graphene-carbon nanotube composite material includes:
t100: mixing the three-dimensional graphene prepared by the method or the three-dimensional graphene with a catalyst so as to obtain a mixed product;
according to an embodiment of the invention, the catalyst is selected from metal catalysts comprising at least one of iron, molybdenum, cobalt, nickel, magnesium, aluminium, such as Co/Mo/Al2O3A catalyst. Therefore, the catalyst can effectively catalyze the cracking of the carbon source in the subsequent steps and promote the growth of the carbon nano tube.
According to the embodiment of the invention, in order to obtain the three-dimensional graphene-carbon nanotube composite material with excellent performance, the mass ratio of the three-dimensional graphene to the catalyst is 1: 0.01-1: 2 (such as 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1: 2). Therefore, in the obtained product, the three-dimensional graphene and the carbon nano tube have a proper proportion, so that the specific surface area of the composite material can be effectively improved (or the specific surface area of the three-dimensional graphene is reserved), and the electric conductivity of the composite material can be greatly improved; if the content of the catalyst is low, the content of the grown carbon nano tube is low, and the conductivity of the composite material cannot be improved well relatively; if the content of the catalyst is relatively high, the content of the carbon nanotubes growing on the surface of the three-dimensional graphene is relatively high, the specific surface area of the composite material is relatively reduced, and the finally obtained composite material contains more metal impurities, so that the purity of the composite material is reduced, or the difficulty and cost of subsequent impurity removal are increased.
According to the embodiment of the invention, if the raw material coal contains the metal catalyst and no post-treatment steps such as amorphous carbon removal, acid washing and high-temperature purification are performed in the preparation process of the three-dimensional graphene, the amount of the catalyst can be reduced appropriately by those skilled in the art, so that the cost can be saved.
T200: and placing the mixed product in a microwave reaction furnace, and introducing a gas carbon source into the microwave reaction furnace so as to grow carbon nanotubes on the surface of the three-dimensional graphene, thereby obtaining the three-dimensional graphene-carbon nanotube composite material. Therefore, the microwave heating is rapid and uniform, and the rapid and stable growth of the carbon nano tube can be controlled.
According to the embodiment of the invention, the microwave frequency in the microwave reaction oven is 300 MHz-300 GHz, and in some embodiments of the invention, the microwave frequency in the microwave reaction oven is 865 MHz-965 MHz (such as 915MHz), or 2400 MHz-2500 MHz (such as 2450 MHz). Thus, the carbon nanotubes can be grown rapidly and efficiently in the above frequency range.
According to the embodiment of the present invention, in order to obtain a three-dimensional graphene-carbon nanotube composite material having excellent performance, the temperature at which the carbon nanotubes are grown is 600 to 1000 ℃ (for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃) and the time is 0.5 to 2 hours (for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours). Therefore, in the temperature range, a gas carbon source grows carbon nanotubes on the surface of the three-dimensional graphene through chemical vapor deposition under the action of a catalyst, so that a composite material with excellent specific surface area, conductivity and other properties is obtained, and in addition, a person skilled in the art can select different temperature sections according to the types of different carbon sources; if the temperature is lower than 600 ℃, the cracking of the gas carbon source is insufficient, and the efficiency of growing the carbon nano tube is relatively reduced; if the temperature is higher than 1000 ℃, the catalyst loses activity and even sintering occurs.
According to an embodiment of the invention, the gaseous carbon source is selected from at least one of methane, ethylene, ethane, acetylene, propane, propylene and natural gas. Therefore, the cracking can be efficiently carried out under the conditions of microwave and the temperature, and the growth of the carbon nano tube is further facilitated; moreover, the material has wide sources and low cost, and can further reduce the cost for producing the composite material.
According to some embodiments of the present invention, the step of growing carbon nanotubes is described in detail as follows: a) adding the mixed product obtained in the step T100 into a vertical boiling bed microwave reaction furnace; b) the temperature in the microwave reaction furnace reaches 600-1000 ℃, and then a gas phase carbon source is introduced; c) and (3) reacting for 0.5-2 h to obtain the graphene-carbon nanotube composite material.
According to the embodiment of the invention, the preparation method is simple and easy to operate, has low cost and high production efficiency, and is easy for industrial production; in addition, under the microwave heating condition, the catalyst cracks the carbon source to obtain the carbon nanotube (namely the carbon nanotube grows in a microwave reaction furnace through chemical vapor deposition), and then the three-dimensional graphene-carbon nanotube composite material is obtained; furthermore, the three-dimensional graphene-carbon nanotube composite material prepared by the method has a large specific surface area and excellent conductivity (electronic conductivity), and has a good application prospect in the fields of gas adsorption, electrochemical energy storage, adsorption separation, catalysis and the like.
According to an embodiment of the present invention, in order to improve the purity of the composite material, at least one of a degerming treatment and an acid washing treatment is further included after the carbon nanotubes are grown. Therefore, impurities generated in the production process and impurities brought in by raw materials can be removed through the impurity removal step of the amorphous carbon removal treatment and/or the acid washing treatment, and the purity and the performance of the composite material are improved.
According to an embodiment of the present invention, the decarburizing treatment is performed at 400 to 600 ℃ (such as 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃) by using an oxidizing gas, wherein the oxidizing gas is at least one selected from oxygen, carbon dioxide and air. Therefore, the method can effectively remove the residual impure carbon in the composite material and improve the purity and the performance of the composite material. In some embodiments of the present invention, the concentration of the oxidizing gas may be adjusted by charging a certain proportion of nitrogen gas into the oxidizing gas.
The specific steps of the step of removing the indefinite carbon are not limited, and those skilled in the art can flexibly select the step according to the actual needs. In some embodiments of the present invention, in order to remove the impure carbon as much as possible, the step of performing the amorphous carbon removing treatment is: a) adding the composite material obtained in the step T200 into a vertical boiling bed microwave reaction furnace; b) the temperature in the furnace reaches 400-600 ℃, and at least one of oxygen, carbon dioxide and air is introduced; c) and reacting for 0.5-2 h to obtain the three-dimensional graphene-carbon nanotube composite material containing a small amount of amorphous carbon.
According to an embodiment of the present invention, if the step of preparing the three-dimensional graphene is performed with the deamidation carbon treatment, a person skilled in the art may not perform the deamidation carbon treatment, and naturally, a person skilled in the art may select not to perform the deamidation carbon treatment when preparing the three-dimensional graphene, and may perform the deamidation carbon treatment after growing the carbon nanotubes.
According to an embodiment of the present invention, the acid washing process is performed by washing with at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and oxalic acid at a temperature of 25 to 95 ℃ (e.g., 25 ℃, 40 ℃, 55 ℃, 70 ℃, 80 ℃, or 95 ℃). Thereby, the metal impurities remaining in the raw material coal, the activator, and the catalyst can be removed.
According to the embodiment of the present invention, the specific steps of the acid washing treatment are not limited, and those skilled in the art can flexibly select the steps according to actual requirements. In some embodiments of the present invention, in order to remove the metal impurities as much as possible, the specific steps of the acid washing treatment are: a) adding a composite material containing metal impurities into an acid washing container; b) adding at least one acid of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and oxalic acid into a container; c) the temperature in the container reaches 25-95 ℃; d) stirring at 100-300 rpm; e) and (3) pickling for 2-15 h, thus obtaining the three-dimensional graphene-carbon nanotube composite material containing a small amount of metal impurities.
According to the embodiment of the invention, in order to simplify the operation steps and save the process flow, a person skilled in the art may choose not to perform the acid washing treatment when preparing the three-dimensional graphene, but to perform the acid washing treatment after growing the carbon nanotubes, and simultaneously remove the metal impurities remaining in the raw material coal, the activating agent and the catalyst.
In yet another aspect of the present invention, the present invention provides a three-dimensional graphene-carbon nanotube composite. According to the embodiment of the invention, the three-dimensional graphene-carbon nanotube composite material is prepared by the method for preparing the three-dimensional graphene-carbon nanotube composite material. Therefore, the three-dimensional graphene-carbon nanotube composite material has a large specific surface area and excellent conductivity, and has a good application prospect in the fields of gas adsorption, electrochemical energy storage, adsorption separation, catalysis and the like. As will be understood by those skilled in the art, the three-dimensional graphene-carbon nanotube composite material has all the features and advantages of the method for preparing the three-dimensional graphene-carbon nanotube composite material, and thus, the detailed description thereof is omitted.
Example 1
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 600 ℃ for 120 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and an activating agent K2CO3Mixing according to the mass ratio of 1:3, placing the mixture into a kneader for kneading treatment at the kneading temperature of 200 ℃ for 2h, placing the kneaded product into a microwave reaction furnace, and activating treatment at the temperature of 900 ℃ for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz, so as to obtain a three-dimensional graphene crude product; introducing air into the obtained product at 450 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 2050m2The electric conductivity is 5000S/m, the purity is 99.5%, and a Scanning Electron Microscope (SEM) image of the three-dimensional graphene refers to FIG. 3.
Example 2
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 500 ℃ for 60 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and K2CO3Mixing according to the mass ratio of 1:4, placing the mixture into a kneader to be kneaded at the kneading temperature of 250 ℃ for 1.5h, placing the kneaded product into a microwave reaction furnace to be activated at the temperature of 950 DEG C120min, wherein the frequency of the microwave reaction furnace is 2450MHz, and a three-dimensional graphene crude product is obtained; introducing air into the obtained product at 450 ℃, reacting for 60min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with mixed acid of hydrochloric acid and hydrofluoric acid, pickling for 4 hours at 80 ℃, stirring at the speed of 200 rpm, and removing metal impurities to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 2550m2(ii) a conductivity of 3000S/m and a purity of 99.3%. Since the high-temperature purification process is not performed in this example, the specific surface area of the obtained three-dimensional graphene is large, but the purity is lower than that in other examples.
Example 3
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 650 ℃ for 180 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and K2CO3Mixing according to the mass ratio of 1:4, placing the mixture into a kneader for kneading treatment at the kneading temperature of 200 ℃ for 3h, placing the kneaded product into a microwave reaction furnace, and activating treatment at the temperature of 850 ℃ for 180min, wherein the frequency of the microwave reaction furnace is 2450MHz, so as to obtain three-dimensional graphene; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid washing at 90 ℃ for 8h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid washing treatment into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 2130m2The conductivity is 5500S/m, and the purity is 99.9%.
Example 4
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 900 ℃ for 120 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and K2CO3Mixing according to the mass ratio of 1:3, placing the mixture into a kneader for kneading treatment, wherein the kneading temperature is 200 ℃, the kneading time is 2h, and placing the kneaded productActivating for 120min at 900 ℃ in a microwave reaction furnace, wherein the frequency of the microwave reaction furnace is 2450MHz, and obtaining a three-dimensional graphene crude product; introducing air into the obtained product at 450 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1700 ℃ for 2h to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 2200m2(ii) a conductivity of 5000S/m and a purity of 99.7%.
Example 5
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 900 ℃ for 60 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and K2CO3Mixing according to the mass ratio of 1:4, placing the mixture into a kneader for kneading treatment at the kneading temperature of 250 ℃ for 1.5h, placing the kneaded product into a microwave reaction furnace, and activating at 950 ℃ for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz, so as to obtain a three-dimensional graphene crude product; introducing air into the obtained product at 450 ℃, reacting for 60min, and removing most of the amorphous carbon; and then mixing the mixture subjected to amorphous carbon removal treatment with mixed acid of hydrochloric acid and hydrofluoric acid, carrying out acid cleaning for 4 hours at 80 ℃, stirring at the speed of 200 r/min to remove most of metal impurities, adding the product subjected to acid cleaning treatment into a high-temperature purification furnace, and purifying for 30min at 2300 ℃ to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 320m2(g), the conductivity was 5050S/m, and the purity was 99.9%.
Example 6
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 650 ℃ for 180 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and K2CO3Mixing according to the mass ratio of 1:4, kneading the mixture in a kneader at 200 ℃ for 3h, and placing the kneaded product in a microwave reaction ovenActivating at 600 ℃ for 180min, wherein the frequency of a microwave reaction furnace is 2450MHz, and obtaining a three-dimensional graphene crude product; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid washing at 90 ℃ for 8h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid washing treatment into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 1200m2The electric conductivity is 3200S/m, and the purity is 99.8 percent.
Example 7
Putting coal (with fixed carbon content of 60%) into a microwave reaction furnace, pyrolyzing at 700 deg.C for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and mixing the pyrolysis semicoke with K2CO3Mixing according to the mass ratio of 1:3, placing the mixture into a kneader for kneading treatment at the kneading temperature of 200 ℃ for 2h, placing the kneaded product into a microwave reaction furnace, and activating at 1250 ℃ for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz, so as to obtain a three-dimensional graphene crude product; introducing air into the obtained product at 450 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 2100m2(ii)/g, the conductivity was 5200S/m, and the purity was 99.8%.
Example 8
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 600 ℃ for 120 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and an activating agent K2CO3Mixing according to the mass ratio of 1:0.8, placing the mixture into a kneader for kneading treatment, kneading at 200 ℃ for 2h, placing the kneaded product into a microwave reaction furnace, and activating at 900 ℃ for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz, and a three-dimensional graphene crude product is obtained; introducing air into the obtained product at 450 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 1300m2(ii) a conductivity of 3000S/m and a purity of 99.8%.
Example 9
Putting raw material coal (with fixed carbon content of 60%) into a microwave reaction furnace, carrying out pyrolysis treatment at 600 ℃ for 120 minutes, wherein the frequency of the microwave reaction furnace is 2450MHz to obtain pyrolysis semicoke, and then mixing the obtained pyrolysis semicoke and an activating agent K2CO3Mixing according to the mass ratio of 1:5, placing the mixture into a kneader for kneading treatment at the kneading temperature of 200 ℃ for 2h, placing the kneaded product into a microwave reaction furnace, and activating treatment at the temperature of 900 ℃ for 120min, wherein the frequency of the microwave reaction furnace is 2450MHz, so as to obtain a three-dimensional graphene crude product; introducing air into the obtained product at 450 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 1950m2The conductivity was 2100S/m and the purity was 99.8%.
Comparative example 1
Putting raw material coal (with fixed carbon content of 60%) into a common atmosphere furnace, carrying out pyrolysis treatment at 600 ℃ for 120 minutes to obtain pyrolysis semicoke, and then carrying out pyrolysis semicoke and an activating agent K2CO3Mixing according to the mass ratio of 1:3, placing the mixture into a kneader for kneading treatment at the kneading temperature of 200 ℃ for 2h, placing the kneaded product into a common atmosphere furnace, and activating treatment at 900 ℃ for 120min to obtain a three-dimensional graphene crude product; subjecting the obtained product to 450 deg.CIntroducing air, reacting for 90min, and removing most of the amorphous carbon; and then mixing the product subjected to the amorphous carbon removal treatment with hydrochloric acid, carrying out acid cleaning at 90 ℃ for 4h at a stirring speed of 200 r/min to remove most of metal impurities, adding the product subjected to the acid cleaning into a high-temperature purification furnace, and purifying at 1900 ℃ for 30min to obtain the three-dimensional graphene. The specific surface area of the three-dimensional graphene is 1200m2The conductivity was 2000S/m and the purity was 99.8%.
From examples 1 to 3, it can be seen that the specific surface areas of the prepared three-dimensional graphene are all 2000m2More than 5000S/m of conductivity; from comparison of examples 2 to 5, the specific surface area of the three-dimensional graphene gradually decreases with the increase of the high-temperature purification temperature; by comparing the embodiment 3, the embodiment 6 and the embodiment 7, it can be known that the activation treatment temperature is too low, which results in poor activation efficiency and seriously affects the specific surface area and the conductivity of the prepared three-dimensional graphene, the activation treatment temperature is too high, the specific surface area and the conductivity of the prepared three-dimensional graphene are not obviously improved, the energy consumption is high, and the cost is increased; as can be seen from examples 1-2 and examples 8-9, in the mixture ratio of the pyrolysis semicoke and the activating agent, if the amount of the activating agent is low, the activation treatment is insufficient, and the specific surface area and the conductivity of the prepared three-dimensional graphene are seriously affected, and if the amount of the activating agent is high, the three-dimensional graphene is excessively ablated, and the performance of the three-dimensional graphene is affected; as can be seen from comparison of examples 1 to 9 with comparative example 1, the three-dimensional graphene prepared by the microwave pyrolysis treatment and the microwave activation treatment has a large specific surface area and electrical conductivity.
Example 10
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 60 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent NaOH according to the mass ratio of 1:1, and carrying out activation treatment for 120 minutes at 700 ℃ in the microwave reaction furnace to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Fe-based catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 0.1; then using methane as carbon source, feeding the obtained mixed product into microwave reaction furnace for conversionGrowing carbon nanotubes by chemical vapor deposition (at 900 ℃); introducing air into the obtained product at 400 ℃, reacting for 60min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid, pickling for 4 hours at 90 ℃, stirring at the speed of 200 rpm, and removing metal impurities to obtain the three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 1200m2Per g, a conductivity of 7500S/m, an ash content of 1.5% (i.e. a purity of 98.5%).
Example 11
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 60 minutes at 650 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent KOH according to the mass ratio of 1:2, and carrying out activation treatment for 120 minutes at 800 ℃ in the microwave reaction furnace to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Fe/Mg catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 1; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 500 ℃, reacting for 60min, and removing most of the amorphous carbon; and then mixing the obtained product with mixed acid of hydrochloric acid and hydrofluoric acid, pickling for 4 hours at 80 ℃, stirring at the speed of 200 rpm, and removing metal impurities to obtain the three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 1700m2Per g, a conductivity of 7500S/m, an ash content of 0.9% (i.e., a purity of 99.1%).
Example 12
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1:2(ii) a Then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2100m2Per g, conductivity 9600S/m, ash content 0.5% (purity 99.5%).
Example 13
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 1; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2200m2(ii)/g, conductivity 9500S/m, ash content 0.5% (purity 99.5%).
Example 14
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; the obtained three-dimensional graphiteMixing the alkene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 0.5; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2250m2The conductivity was 8900S/m, and the ash content was 0.4% (purity 99.6%).
Example 15
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 0.2; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2350m2(ii)/g, conductivity 6200S/m, ash content 0.4% (purity 99.6%).
Example 16
Putting coal (with fixed carbon content of 60%) into a microwave reaction furnace, performing microwave pyrolysis treatment at 600 ℃ for 120 minutes to obtain pyrolysis semicoke, and mixing the obtained pyrolysis semicoke with an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the proportionMixing the materials in a mass ratio of 1:4, and activating at 900 ℃ for 180min to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 0.1; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2380m2(ii)/g, conductivity 5200S/m, ash content 0.3% (purity 99.7%).
Example 17
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 0.01; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (with the temperature of 900 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2500m2The conductivity was 4500S/m, the ash content was 0.3% (purity 99.7%).
Example 18
Putting coal (fixed carbon content is 60%) into microwave reaction oven, and performing microwave pyrolysis treatment at 600 deg.C for 120minObtaining pyrolytic semicoke, mixing the obtained pyrolytic semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to a mass ratio of 1:4, and activating at 900 ℃ for 180min to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 2; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (the temperature is 500 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. Measuring the specific surface area of the three-dimensional graphene-carbon nanotube composite material to be 2400m2The conductivity was 3500S/m, the ash content was 1% (purity 99%).
Example 19
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 2; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (at the temperature of 800 ℃) to grow a carbon nano tube; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is measured to be 2300m2(ii)/g, conductivity 6500S/m, ash content 0.5% (purity 99.5%).
Example 20
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 2; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (the temperature is 1000 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2350m2The conductivity is 8600S/m, and the ash content is 0.6% (the purity is 99.4%).
Example 21
Putting coal (with the fixed carbon content of 60%) into a microwave reaction furnace, carrying out microwave pyrolysis treatment for 120 minutes at 600 ℃ to obtain pyrolysis semicoke, mixing the obtained pyrolysis semicoke and an activating agent (comprising three parts of NaOH and one part of ferric chloride) according to the mass ratio of 1:4, and carrying out activation treatment for 180 minutes at 900 ℃ to obtain three-dimensional graphene; mixing the obtained three-dimensional graphene with a Co catalyst to obtain a mixed product, wherein the mixing mass ratio of the three-dimensional graphene to the catalyst is 1: 2; then, using methane as a carbon source, and feeding the obtained mixed product into a microwave reaction furnace to perform chemical vapor deposition (the temperature is 1100 ℃) to grow carbon nanotubes; introducing air into the obtained product at 400 ℃, reacting for 90min, and removing most of the amorphous carbon; and then mixing the obtained product with hydrochloric acid and nitric acid, pickling for 8 hours at 90 ℃, stirring at the speed of 200 r/min, and removing metal impurities to obtain the high-purity three-dimensional graphene-carbon nanotube composite material. The specific surface area of the three-dimensional graphene-carbon nanotube composite material is 2420m2Per g, conductivity 6500S/m, ash content 0.7% (purity 99.3%).
As can be seen from examples 10 to 17 and the test data thereof, as the mass ratio of the three-dimensional graphene to the catalyst increases (or as the amount of the catalyst decreases), the specific surface area of the obtained three-dimensional graphene-carbon nanotube composite material gradually increases, and the conductivity gradually decreases, which indicates that the amount of the carbon nanotubes growing on the surface of the three-dimensional graphene gradually decreases as the amount of the catalyst decreases. According to the embodiments 18 to 21 and the test data thereof, when the carbon source is methane, the carbon nanotube can effectively grow within the range of 600 to 1000 ℃, and the three-dimensional graphene-carbon nanotube composite material with better conductivity and specific surface area is obtained; when the temperature is higher than 1000 ℃, the catalyst begins to lose activity, the generation of the carbon nano tube is influenced, and further the conductivity of the three-dimensional graphene-carbon nano tube composite material begins to be reduced.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (9)

1. A method for preparing three-dimensional graphene, comprising:
pyrolyzing raw material coal in a microwave reaction furnace to obtain pyrolytic semicoke, wherein the temperature of the pyrolysis treatment is 500-900 ℃;
mixing the pyrolysis semicoke and an activating agent to obtain a mixed material, wherein the mass ratio of the pyrolysis semicoke to the activating agent is 1: 0.1-1: 5, and the activating agent is selected from KOH, KCl and K2CO3、MgO、MgCl2、NaOH、NaCl、Na2CO3、ZnCl2、NaOH、FeCl3And Fe (NO)3)3At least one of;
activating the mixed material in the microwave reaction furnace at 700-1200 ℃,
and performing high-temperature purification treatment on the product of the activation treatment to obtain the three-dimensional graphene, wherein the high-temperature purification treatment is completed in an environment with an absolute pressure lower than 30Pa at 1500-2400 ℃.
2. The method of claim 1, wherein the pyrolysis process satisfies at least one of the following conditions:
the pyrolysis treatment time is 0.1-3 hours;
the frequency of the microwave reaction furnace is 915 MHz-2450 MHz.
3. The method of claim 1, wherein the feed coal has a fixed carbon content of 30% to 80%.
4. The method of claim 1, wherein the step of obtaining the mixed material comprises:
kneading the pyrolysis semicoke and the activating agent to obtain the mixed material.
5. The method according to claim 4, wherein the kneading temperature of the kneading treatment is 100 to 300 ℃ and the kneading time is 1 to 10 hours.
6. The method according to claim 1, wherein the activation treatment satisfies at least one of the following conditions:
the activation treatment time is 0.1-3 hours;
the frequency of the microwave reaction furnace is 915 MHz-2450 MHz;
the atmosphere of the activation treatment is an inert gas.
7. The method according to any one of claims 1 to 6, further comprising subjecting the product of the activation treatment to at least one of the following treatment steps:
performing amorphous carbon removal treatment;
and (5) acid pickling treatment.
8. The method according to claim 7, wherein the step of performing the decarburizing treatment is performed by using an oxidizing gas at 400 to 600 ℃, wherein the oxidizing gas is at least one selected from the group consisting of oxygen, carbon dioxide and air.
9. The method according to claim 8, wherein the acid washing treatment is performed by washing with at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and oxalic acid at 25 to 120 ℃.
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