CN113860291A - Method for in-situ synthesis of self-supporting three-dimensional graphene foam and composite material thereof - Google Patents
Method for in-situ synthesis of self-supporting three-dimensional graphene foam and composite material thereof Download PDFInfo
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- CN113860291A CN113860291A CN202110980482.1A CN202110980482A CN113860291A CN 113860291 A CN113860291 A CN 113860291A CN 202110980482 A CN202110980482 A CN 202110980482A CN 113860291 A CN113860291 A CN 113860291A
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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
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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
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- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
Abstract
The invention relates to a method for synthesizing self-supporting three-dimensional graphene foam in situ, which comprises the following steps: determining a solid carbon source, and selecting an adaptive solvent according to different types of the used solid carbon source; mixing one or two of nickel metal powder and copper metal powder and a solid carbon source, placing the mixture in a container, and adding the solvent into the mixed powder to prepare precursor suspension; removing the solvent in the precursor suspension to obtain composite precursor powder, and drying and grinding the composite precursor powder; pressing and forming to obtain a prefabricated block body; under a protective atmosphere, carrying out induction heating by using an alternating current coil, and cooling to obtain a three-dimensional graphene metal composite material; and removing the metal of the three-dimensional graphene metal composite material by using corrosive liquid, and then purifying and drying to obtain the self-supporting three-dimensional graphene foam. The invention also provides a method for synthesizing the self-supporting three-dimensional graphene composite material in situ.
Description
Technical Field
The invention belongs to the field of advanced carbon nano energy storage materials, and particularly relates to a method for in-situ synthesis of self-supporting three-dimensional graphene foam and a composite material thereof by using induction heating based on a metal powder template method.
Background
The rapid development of mobile interconnection technology and the popularity of intelligent heat tide make electronic devices increasingly colorful, and an energy storage device is of great importance as a core component. However, the energy density and power density of the current energy storage device are limited, and in order to further improve the performance of the current energy storage device, the development of a novel energy storage material is urgent.
Graphene (GN) is a polymer made of sp carbon atoms2The two-dimensional carbon nanomaterial which is composed of hybrid orbitals and is in a hexagonal honeycomb lattice has a honeycomb-type layered structure, sigma bonds and other carbon atoms are connected into a six-membered ring, and pz orbitals, which are perpendicular to the plane of the layer, of each carbon atom can form large pi bonds which penetrate through all layers of the multi-atom carbon nanomaterial, so that the two-dimensional carbon nanomaterial has excellent conductivity. Single layer graphene is the highest strength and thinnest material currently known. Due to the excellent conductivity and mechanical properties, graphene is considered to be an ideal material for preparing high-performance energy storage devices.
However, due to the van der waals force and pi-pi acting force, the two-dimensional graphene sheet layers are easy to agglomerate and stack, the effective specific surface area is greatly reduced, and the performance is greatly reduced. And a three-dimensional structure is constructed under the condition of keeping the intrinsic perfect characteristic of the two-dimensional graphene, and the three-dimensional communicated structures which are communicated with each other are beneficial to conducting electrons and uniform loading of active materials to form a composite material, so that the utilization rate of the specific surface area is greatly improved. Therefore, the construction of the graphene three-dimensional network structure becomes the current research focus. At present, the preparation methods of the three-dimensional graphene and the composite material thereof mainly comprise a chemical vapor deposition method, a template method and the like. However, the three-dimensional graphene prepared by the method also has some disadvantages, such as uncontrollable pore structure, complex preparation process and the like. The exploration of a controllable, effective and efficient preparation method of high-quality self-supporting three-dimensional graphene foam with high specific surface area, conductivity, strength and structural stability and a composite material thereof is still a challenge for the current graphene research.
Disclosure of Invention
The invention aims to provide a method for efficiently and controllably preparing self-supporting three-dimensional graphene foam or composite material thereof with controllable pore and network structures. The technical scheme is as follows:
a method of in situ synthesis of a self-supporting three-dimensional graphene foam, comprising the process of:
1) determining a solid carbon source, and selecting an adaptive solvent according to different types of the used solid carbon source.
2) Mixing one or two of nickel metal powder and copper metal powder and a solid carbon source according to the mass ratio of 10 (0.1-5) and placing the mixture into a container, and adding the solvent into the mixed powder to prepare precursor suspension;
3) removing the solvent in the precursor suspension to obtain composite precursor powder, and drying and grinding the composite precursor powder;
4) pressing and molding the composite precursor powder prepared in the step 3) to obtain a prefabricated block;
5) and under a protective atmosphere, carrying out induction heating by using an alternating current coil, and cooling to obtain the three-dimensional graphene metal composite material.
6) And removing the metal of the three-dimensional graphene metal composite material by using corrosive liquid, and then purifying and drying to obtain the self-supporting three-dimensional graphene foam.
Further, in the step 1), when a water-soluble carbon source is used, deionized water or a 1:1 ethanol aqueous solution is used as a solvent; when a carbon source which is easily soluble in an organic solvent is used, chloroform or absolute ethanol is used as the solvent.
In addition, the invention also provides a method for in-situ synthesis of the self-supporting three-dimensional graphene composite material, which is characterized in that after the precursor suspension is prepared in the step 2), one or more of metal salt, a nitrogen source, a reinforcement and a surfactant are selected to prepare an additive dispersion liquid, and the additive dispersion liquid is added into the precursor suspension; and 6) obtaining the self-supporting three-dimensional graphene composite material.
Furthermore, the selected reinforcement is a multi-wall carbon nano tube or a single-wall carbon nano tube.
Furthermore, the selected nitrogen source is urea or thiourea.
Further, the selected surfactant is pluronic.
Compared with the prior art, the invention has the beneficial effects that:
1) the process flow is simple and quick: based on an induction heating process, the three-dimensional graphene is constructed in situ by using metal powder as a template and a catalyst, the operation is simple and easy to implement, the process flow is simple, the method is suitable for industrial batch production, and the synthesis time is short (below 40 s).
2) Controllable preparation of high-quality three-dimensional graphene: based on the catalytic action of the metal template and the ultrahigh-temperature heating and rapid cooling process, the problem of easy agglomeration of the metal template is solved, the preparation difficulty of graphene is reduced, and the obtained graphene foam composite material is high in crystallization degree and few in defects. Meanwhile, the appearance can be controlled by regulating and controlling the cold pressing pressure, the metal powder particle size and the heating frequency and time. By adding different precursors and additives, different types of three-dimensional graphene foam composite materials can be obtained, so that the structure, the form and the performance of the three-dimensional graphene foam composite materials can be regulated and controlled according to actual application.
Drawings
FIG. 1 is an SEM image of a composite precursor powder prepared according to an embodiment of the present invention
FIG. 2 is a Raman spectrum of the self-supporting three-dimensional graphene foam prepared in the embodiment of the invention
Detailed Description
First, the technical means of the present invention will be described. The invention takes metal powder (nickel powder, copper powder, iron powder, copper-nickel alloy and the like) as a catalytic matrix and a metal template, takes organic matters (sucrose, citric acid, PMMA and the like) as a solid carbon source, modifies a precursor by additives (metal salts such as cobalt nitrate, ferric chloride, copper nitrate and the like, nitrogen sources such as urea, thiourea and the like, reinforcements such as multi-walled carbon nanotubes, single-walled carbon nanotubes and the like), and quickly synthesizes the self-supporting three-dimensional graphene foam and the composite material thereof in situ by means of an induction heating technology. The morphology can be controlled by regulating and controlling the cold pressing pressure, the metal powder particle size and the heating frequency and time. By adding different precursors and additives, different types of three-dimensional graphene foam composite materials can be obtained, so that the structure, the form and the performance of the three-dimensional graphene foam composite materials can be regulated and controlled according to actual application. The method is characterized by comprising the following steps:
1) depending on the type of solid carbon source used, an appropriate solvent is selected. When a water-soluble carbon source (sucrose, glucose, citric acid, etc.) is used, deionized water or a 1:1 ethanol aqueous solution is used as a solvent; when a carbon source (PMMA, etc.) which is easily soluble in an organic solvent is used, chloroform or absolute ethanol may be used as the solvent.
2) Mixing metal powder with the particle size of 1-50 mu m and a carbon source (sucrose and citric acid) according to the mass ratio of 10 (0.1-5), placing the mixture into a beaker with a proper volume, adding a quantitative solvent into the mixed powder according to the proportion of about 40 mL/g, and mechanically stirring the mixed liquid in the beaker by using an electric stirrer at the rotating speed of 280 plus 350rpm to obtain a precursor suspension;
3) (optional in the step), one or more of metal salt (cobalt nitrate, ferric chloride, copper nitrate and the like), nitrogen source (urea, thiourea and the like), reinforcement (multi-walled carbon nanotube, single-walled carbon nanotube and the like) and surfactant (pluronic F127 and the like) are mixed according to a certain proportion and placed in a beaker with a proper volume, quantitative deionized water is added, ultrasonic or stirring is carried out to obtain an additive dispersion liquid, and then the additive dispersion liquid is placed in a precursor suspension which is mechanically stirred according to a certain proportion;
4) removing solvent from the suspension by heating and evaporating, rotary evaporator or freeze drying to obtain composite precursor powder, further drying in vacuum oven (pressure of 1.8-2.2mmHg) at 50-100 deg.C, and grinding;
5) pressing and molding the composite precursor powder by using a cold-pressing grinding tool with a certain size at a certain pressure for a certain time to obtain a prefabricated block;
6) placing the prefabricated block body in a quartz tube, and under the condition of low pressure or normal pressure and under the protection of argon-hydrogen mixed gas with a certain proportion, using alternating current coils (the frequency can be set to include low frequency (0.3-1kHZ), intermediate frequency (1-20kHZ), superaudio frequency (20-50kHZ), power frequency (50kHZ), high frequency (50-100kHZ) and ultrahigh frequency (100-500 kHZ); the power is 10-50 kW; heating for 1-40s), and then rapidly cooling to room temperature to obtain the three-dimensional graphene metal composite material.
7) And removing the metal of the three-dimensional graphene metal composite material by using a corrosive liquid with a certain concentration, and then purifying and drying to obtain the self-supporting three-dimensional graphene foam and the composite material thereof.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example one
A beaker (500 mL in volume) was placed on a constant-temperature heating table (closed state), 3g of nickel powder (particle size: 10 μm) and 0.2g of sucrose were weighed and placed therein, 120mL of deionized water was added thereto, and the precursor suspension was continuously mechanically stirred at a rotation speed of 320rpm using an electric stirrer. And starting a constant-temperature heating table (the heating temperature is 80 ℃), heating and evaporating the solution to dryness, transferring the beaker to a vacuum oven (the pressure is 2.0mmHg) for drying for 24 hours after the solution is evaporated to dryness, taking out the composite precursor powder, and grinding the composite precursor powder by using a mortar and pestle. And (3) placing the composite precursor powder into a cold pressing die, pressing and molding the powder at the pressure of about 2500MPa, and maintaining the pressure for 2min to obtain a prefabricated block. And (3) placing the prefabricated block in a quartz tube, carrying out induction heating by using a rate alternating current coil (with the frequency of 40kHZ and the power of 40kW, and the heating time of 10s) under the protection of argon under the normal pressure condition, and then rapidly cooling to room temperature to obtain the three-dimensional graphene metal composite material. And removing the metal of the three-dimensional graphene metal composite material by using 1M FeCl3 corrosive liquid, and purifying and drying the metal by CPD to obtain the self-supporting three-dimensional graphene foam and the composite material thereof.
Example two
A beaker (500 mL in volume) was placed on a constant temperature heating table (closed state), 3g of copper powder (particle size: 10 μm) and 0.1g of glucose were weighed and placed therein, 120mL of deionized water was added thereto, and the precursor suspension was mechanically stirred continuously at a rotation speed of 320rpm using an electric stirrer. Taking a beaker (the volume is 100mL), weighing 30mg of the few-wall carbon nanotube and 30mg of the pluronic F127, placing the carbon nanotube and the pluronic F127 in the beaker, adding 60mL of deionized water, and carrying out ultrasonic treatment for 30min at the power of 120W by using a probe type ultrasonic crusher to obtain a carbon nanotube dispersion liquid. Subsequently, the obtained carbon nanotube dispersion liquid is added to the suspension of the precursor which is being mechanically stirred. And (3) starting a constant-temperature heating table (heating temperature is 110 ℃), heating and evaporating the solution to dryness, transferring the beaker to a vacuum oven (pressure is 2.0mmHg) for drying for 24 hours after evaporation to dryness, taking out the composite precursor powder, and grinding the composite precursor powder by using a mortar and pestle. And (3) placing the composite precursor powder into a cold pressing die, pressing and molding the powder at the pressure of about 1120MPa, and maintaining the pressure for 3min to obtain a prefabricated block. And (3) placing the prefabricated block in a quartz tube, carrying out induction heating by using an alternating current coil (with the frequency of 30kHZ and the power of 20kW and the heating time of 15s) under the condition of normal pressure and under the protection of argon, and then rapidly cooling to room temperature to obtain the three-dimensional graphene metal composite material. And removing the metal of the three-dimensional graphene metal composite material by using 1M FeCl3 corrosive liquid, and purifying and drying the metal by CPD to obtain the self-supporting carbon nanotube/three-dimensional graphene foam composite material.
EXAMPLE III
3g of nickel powder (particle size: 1 μm), 0.6g of glucose, 0.2g of cobalt nitrate and 0.6g of urea were weighed into a plastic beaker (capacity: 500mL), 120mL of deionized water was added, and the precursor suspension was mechanically stirred continuously at a rotation speed of 320rpm using an electric stirrer. The precursor suspension was poured into liquid nitrogen to freeze and freeze-dry. After the freeze-drying was completed, the resulting powder was transferred to a vacuum oven (pressure 2.0mmHg) to be dried for 24 hours, and the composite precursor powder was taken out and ground using a mortar and pestle. And (3) placing the composite precursor powder into a cold pressing die, pressing and molding the powder at the pressure of about 1120MPa, and maintaining the pressure for 3min to obtain a prefabricated block. And (3) placing the prefabricated block in a quartz tube, carrying out induction heating by using an alternating current coil (with the frequency of 20kHZ and the power of 30kW and the heating time of 20s) under the condition of normal pressure and under the protection of argon, and then rapidly cooling to room temperature to obtain the three-dimensional graphene metal composite material. And removing the metal of the three-dimensional graphene metal composite material by using 1M FeCl3 corrosive liquid, and purifying and drying the metal by CPD to obtain the self-supporting carbon nanotube/three-dimensional graphene foam composite material.
Example four
A beaker (500 mL in volume) was placed on a constant temperature heating stage (closed state) in a fume hood, 3g of copper powder (particle size: 10 μm) and 0.1g of PMMA were weighed and placed therein, 120mL of chloroform was added, and the precursor suspension was mechanically stirred continuously at a rotation speed of 320rpm using an electric stirrer. 0.2g of ferric nitrate, 30mg of a small-wall carbon nanotube and 30mg of pluronic F127 were weighed in a beaker (capacity 100mL), 60mL of deionized water was added, and the mixture was subjected to ultrasonic treatment using a probe-type ultrasonic pulverizer at a power of 120W for 30min to obtain a carbon nanotube dispersion. Subsequently, the obtained carbon nanotube dispersion liquid is added to the suspension of the precursor which is being mechanically stirred. And (3) starting a constant-temperature heating table (heating temperature is 110 ℃), heating and evaporating the solution to dryness, transferring the beaker to a vacuum oven (pressure is 2.0mmHg) for drying for 24 hours after evaporation to dryness, taking out the composite precursor powder, and grinding the composite precursor powder by using a mortar and pestle. And (3) placing the composite precursor powder into a cold pressing die, pressing and molding the powder at the pressure of 892MPa, and maintaining the pressure for 6min to obtain a prefabricated block. And (3) placing the prefabricated block in a quartz tube, carrying out induction heating by using an alternating current coil (with the frequency of 60kHZ and the power of 20kW, and the heating time of 15s) under the atmosphere of argon and hydrogen under the normal pressure condition, and then rapidly cooling to room temperature to obtain the three-dimensional graphene metal composite material. And removing the metal of the three-dimensional graphene metal composite material by using 1M FeCl3 corrosive liquid, and purifying and drying the metal by CPD to obtain the self-supporting carbon nanotube/three-dimensional graphene foam composite material.
Claims (8)
1. A method for synthesizing self-supporting three-dimensional graphene foam in situ is characterized by comprising the following steps:
1) determining a solid carbon source, and selecting an adaptive solvent according to different types of the used solid carbon source.
2) Mixing one or two of nickel metal powder and copper metal powder and a solid carbon source according to the mass ratio of 10 (0.1-5) and placing the mixture into a container, and adding the solvent into the mixed powder to prepare precursor suspension;
3) removing the solvent in the precursor suspension to obtain composite precursor powder, and drying and grinding the composite precursor powder;
4) pressing and molding the composite precursor powder prepared in the step 3) to obtain a prefabricated block;
5) under a protective atmosphere, carrying out induction heating by using an alternating current coil, and cooling to obtain a three-dimensional graphene metal composite material;
6) and removing the metal of the three-dimensional graphene metal composite material by using corrosive liquid, and then purifying and drying to obtain the self-supporting three-dimensional graphene foam.
2. The method for in-situ synthesis of the self-supporting three-dimensional graphene foam according to claim 1, wherein in the step 1), when a water-soluble carbon source is used, deionized water or a 1:1 ethanol aqueous solution is used as a solvent; when a carbon source which is easily soluble in an organic solvent is used, chloroform or absolute ethanol is used as the solvent.
3. The method for in situ synthesis of self-supporting three-dimensional graphene foam according to claim 1, wherein the heating frequency is 20-60 kHZ, the power is 20-50kW, and the heating time is not more than 40 s.
4. A method for in-situ synthesis of a self-supporting three-dimensional graphene composite material is characterized by comprising the following steps:
1) determining a solid carbon source, and selecting an adaptive solvent according to different types of the used solid carbon source.
2) Mixing one or two of nickel metal powder and copper metal powder and a solid carbon source according to the mass ratio of 10 (0.1-5) and placing the mixture into a container, and adding the solvent into the mixed powder to prepare precursor suspension;
3) selecting one or more of metal salt, nitrogen source, reinforcer and surfactant to obtain additive dispersion, and adding the additive dispersion into the precursor suspension
4) Removing the solvent in the precursor suspension to obtain composite precursor powder, and drying and grinding the composite precursor powder;
5) pressing and molding the composite precursor powder prepared in the step 4) to obtain a prefabricated block;
6) under a protective atmosphere, carrying out induction heating by using an alternating current coil, and cooling to obtain a three-dimensional graphene metal composite material;
7) and removing the metal of the three-dimensional graphene metal composite material by using corrosive liquid, and then purifying and drying to obtain the self-supporting three-dimensional graphene composite material.
5. The method of in situ synthesis of self-supporting three-dimensional graphene composite material according to claim 4, wherein the reinforcement selected is multi-walled carbon nanotube or single-walled carbon nanotube.
6. The method for in-situ synthesis of the self-supporting three-dimensional graphene composite material according to claim 4, wherein the selected nitrogen source is urea or thiourea.
7. The method for in situ synthesis of self-supporting three-dimensional graphene composite material according to claim 4, wherein the selected surfactant is pluronic.
8. The method for in-situ synthesis of the self-supporting three-dimensional graphene composite material according to claim 4, wherein in the step 1), when a water-soluble carbon source is used, deionized water or a 1:1 ethanol aqueous solution is used as a solvent; when a carbon source which is easily soluble in an organic solvent is used, chloroform or absolute ethanol is used as the solvent.
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Cited By (1)
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| CN116003134A (en) * | 2022-12-09 | 2023-04-25 | 中航装甲科技有限公司 | Boron carbide-based composite material and preparation method and application thereof |
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| CN116003134A (en) * | 2022-12-09 | 2023-04-25 | 中航装甲科技有限公司 | Boron carbide-based composite material and preparation method and application thereof |
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