CN112077329A - Preparation method of carbon-based-metal composite material - Google Patents
Preparation method of carbon-based-metal composite material Download PDFInfo
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- CN112077329A CN112077329A CN201910511795.5A CN201910511795A CN112077329A CN 112077329 A CN112077329 A CN 112077329A CN 201910511795 A CN201910511795 A CN 201910511795A CN 112077329 A CN112077329 A CN 112077329A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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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
- C01B32/194—After-treatment
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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
- C01B32/20—Graphite
- C01B32/21—After-treatment
Abstract
The invention discloses a method for preparing a carbon-based-metal composite material, which comprises the following steps: (1) mixing carbon-based fluoride and halide metal salt, heating and washing the mixture in vacuum or protective atmosphere, and drying the mixture in vacuum or protective atmosphere to obtain carbon-based-metal fluoride; (2) mixing the carbon-based-metal fluoride with a reducing agent, wherein the reducing agent is potassium, magnesium, lithium naphthalene-tetrahydrofuran or sodium naphthalene-tetrahydrofuran. When the reducing agent is potassium or magnesium, heating and cooling the reducing agent under a vacuum condition or a protective atmosphere, dropwise adding methanol into the reduction product until no bubbles emerge, and then filtering, washing and vacuum drying the product to obtain the carbon-based-metal composite material; when the reducing agent is naphthalene lithium-tetrahydrofuran or naphthalene sodium-tetrahydrofuran, stirring at room temperature under the protection of argon atmosphere, dropwise adding methanol into the reaction liquid until no bubbles emerge, and then filtering, washing and vacuum drying to obtain the carbon-based-metal composite material; the method can realize uniform compounding of carbon and metal.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a carbon-based-metal composite material.
Background
The carbon material has excellent mechanical property, electrical property and chemical stability, and has wide application in the aspects of energy storage, catalysis, electromagnetic shielding and the like. In order to further enrich and improve the performance of the carbon material, the carbon material is taken as a base material to carry out doping and compounding, and the method becomes a hot spot of the current application research. Among them, the use of carbon material as carrier to load metal material is an important application aspect.
The current composite technology of carbon material and metal material mainly comprises the processes of electroplating, chemical plating, coprecipitation and the like. In the processes, because the carbon material has high chemical inertness, the carbon material is often required to be pretreated and the surface of the carbon material is modified to improve the wettability of the metal on the surface of the carbon material, and the conventional technical process comprises the steps of carrying out strong oxidation treatment on the carbon material to improve the hydrophilicity, and then carrying out further sensitization and activation according to experimental requirements to improve the adhesion and the adhesion uniformity of the metal on the carbon material, but the process is difficult to obtain a uniform carbon/metal material composite material. And because the wettability of the metal and the carbon material is poor, a metal core or island is often formed on the surface of the carbon material in the process of forming the metal on the surface of the carbon material, and then the metal core or island is taken as a nucleation point, the reaction time and the reaction metal amount are controlled, so that the metal is covered on the surface of the carbon material, and a metal composite layer on the surface is often thicker when the metal is required to completely cover the carbon material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a carbon-based-metal composite material, which not only solves the problem of non-wetting of metal and carbon, but also realizes uniform compounding of carbon and metal.
The invention is realized by the following technical scheme:
a method of preparing a carbon-based-metal composite, comprising the steps of:
(1) mixing 1-1.5 parts of carbon-based fluoride and 2-6 parts of halide metal salt in parts by weight, heating to 280-500 ℃ in vacuum or protective atmosphere, keeping for 6-120 h, naturally cooling to 20-25 ℃, washing the obtained reactant with a cleaning agent, and drying at 60-100 ℃ in vacuum or protective atmosphere for 12-48 h to obtain the carbon-based-metal fluoride; the halide metal salt is chloride metal salt, bromide metal salt or iodide metal salt, and the cleaning agent is ethanol or tetrahydrofuran;
(2) mixing the carbon-based-metal fluoride with a reducing agent, wherein the reducing agent is at least one of potassium, magnesium, naphthalene lithium-tetrahydrofuran or naphthalene sodium-tetrahydrofuran: when the reducing agent is potassium or magnesium, 1-1.5 parts by weight of the carbon-based-metal fluoride and 3-6 parts by weight of the metal simple substance reducing agent are heated to 300-600 ℃ under a vacuum condition or a protective atmosphere, are kept for 12-120 h, are naturally cooled to 20-25 ℃, are dropwise added with methanol until no bubbles emerge, and are subjected to filtration, water washing and vacuum drying at 60-100 ℃ for 12-48 h to obtain the carbon-based-metal composite material; when the reducing agent is naphthalene lithium-tetrahydrofuran or naphthalene sodium-tetrahydrofuran, according to the weight fraction, 1 part of carbon-based-metal fluoride is obtained, 5-7 parts of metal simple substance reducing agent in the naphthalene lithium-tetrahydrofuran or the naphthalene sodium-tetrahydrofuran is obtained, the mixture is stirred at room temperature for 48-168 hours under the protection of argon atmosphere, methanol is dropwise added into the reaction liquid until no bubbles emerge, and then the reaction liquid is filtered, washed with water and dried in vacuum at 60-100 ℃ for 12-48 hours to obtain a carbon-based-metal composite material;
in the above technical scheme, the carbon-based fluoride is at least one of graphite fluoride, graphite fluoride micro-sheets, carbon fluoride black, carbon fluoride nanotubes and graphene fluoride.
In the above technical scheme, the heating process is performed in a reaction kettle, and the reaction kettle is made of stainless steel or quartz.
In the above technical scheme, the halide metal salt is at least one of ferric chloride, cobalt chloride, nickel chloride, bismuth chloride, platinum chloride, tantalum chloride, ruthenium chloride, copper bromide and copper iodide.
In the above technical scheme, the protective atmosphere is argon, and the absolute vacuum degree under the vacuum condition is 10-5Pa～104Pa。
In the above technical scheme, the preparation method of the naphthalene lithium-tetrahydrofuran comprises the following steps: adding lithium to anhydrous tetrahydrofuran dissolved with naphthalene under an argon atmosphere, wherein the molar mass ratio of the lithium to the naphthalene is 3: and 1, stirring for 4-24 h to obtain the naphthalene lithium-tetrahydrofuran.
In the above technical scheme, the preparation method of the sodium naphthalene-tetrahydrofuran comprises the following steps: adding sodium into anhydrous tetrahydrofuran dissolved with naphthalene under an argon atmosphere, wherein the molar mass ratio of the sodium to the naphthalene is 3: and 1, stirring for 4-24 hours to obtain the sodium naphthalene-tetrahydrofuran.
In the technical scheme, in the heating process in the step (1), the heating rate is 1-5 ℃/min;
in the technical scheme, in the heating process in the step (2), the heating rate is 1-3 ℃/min.
In the above technical solution, in the step (1), the mass ratio of the carbon-based fluoride to the halide metal salt is 1:3, and in the step (2), the mass ratio of the carbon-based metal fluoride to the reducing agent is 1: 3.
The invention has the beneficial effects that:
at present, most of the metal-carbon-based composite materials are prepared by electroplating, chemical plating, coprecipitation, evaporation and the like, and are limited by poor wettability of metal and carbon-based materials. The metal covering layer formed by adopting the process has the dimension of nanometer.
The invention aims at the problem that the wettability of a metal material and a carbon-based material is poor, and the uniform metal layer is difficult to cover on the surface of the carbon-based material. The invention takes a carbon fluoride-based material as an original material, and forms uniform and stable metal fluoride on the surface of the carbon-based material through a fluorine-replacing chlorine reaction.
The metal is associated with the carbon-based material by fluorine. Fluorine and carbon are linked by a C-F bond. The metal (X) is in the form of C-F-X in the presence of the carbon-based material. And reducing the fluoride on the surface of the carbon-based material into metal through metal steam reduction, so that a uniform metal covering layer is formed on the surface of the carbon-based material.
Compared with the prior metal-carbon material compounding process, the invention takes the fluorine in the atomic distribution state on the surface of the carbon-based material as the nucleation point to anchor the metal atoms in the form of fluoride, and the metal covering layer with atomic scale can be obtained after reduction, so as to obtain the metal-carbon-based composite material with atomic scale.
Drawings
FIG. 1 is a schematic view of a preparation process of example 1 of the present invention;
fig. 2 is a schematic diagram of the distribution of fe-graphene elements in example 1 of the present invention;
FIG. 3 is a high transmission electron micrograph of Fe-graphene according to example 1 of the present invention;
fig. 4 is an iron-graphene energy spectrum of example 1 of the present invention;
FIG. 5 is a high power transmission electron micrograph of an iron-carbon nanotube according to example 2 of the present invention;
FIG. 6 is an energy spectrum of Fe-C nanotubes in example 2 of the present invention.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Purity and manufacturer of the drugs of the examples
Examples the model and manufacturer of the apparatus
Examples 1 to 12
(1) Grinding and mixing a carbon-based fluoride and a halide metal salt, putting the mixture into a reaction kettle, vacuumizing, sealing, putting the reaction kettle into a box-type furnace, heating to 280-500 ℃, keeping the heating rate at 5 ℃/min for 6-120 h, cooling to 20-25 ℃ along with the furnace, opening the reaction kettle, washing the unreacted halide metal salt by using a cleaning agent, and drying the washed reactant for 12-48 h at the temperature of 60-100 ℃ in vacuum to obtain the carbon-based-metal fluoride; the carbon-based fluoride is at least one of graphite fluoride, graphite fluoride micro-sheets, carbon black fluoride, carbon fluoride nanotubes and graphene fluoride; the halide metal salt is chloride, bromide and iodide metal salt; the cleaning agent is ethanol or tetrahydrofuran;
(2) mixing the carbon-based-metal fluoride with a reducing agent, wherein the reducing agent is at least one of potassium, magnesium, lithium naphthalene-tetrahydrofuran or sodium naphthalene-tetrahydrofuran. When the reducing agent is potassium or magnesium, mixing the reducing agent and the carbon-based-metal fluoride, putting the mixture into a reaction kettle, vacuumizing, sealing, placing the reaction kettle into a box-type furnace, heating to 300-600 ℃, keeping the heating rate at 3 ℃/min for 12-120 h, cooling to 20-25 ℃ along with the furnace, opening the reaction kettle, dropwise adding methanol into a reduction product until no bubbles emerge, filtering, washing with water, and vacuum-drying at 60-100 ℃ for 12-48 h to obtain the carbon-based-metal composite material; when the reducing agent is naphthalene lithium-tetrahydrofuran or naphthalene sodium-tetrahydrofuran, mixing the reducing agent with the carbon-based-metal fluoride, pouring the mixture into a reaction kettle, sealing, stirring at room temperature for 48-168 hours under the protection of argon atmosphere, dropwise adding methanol into the reaction liquid until no bubbles emerge, and then filtering, washing with water, and drying in vacuum at 60-100 ℃ for 12-48 hours to obtain a carbon-based-metal composite material;
wherein, the reactants and the mass thereof in the preparation process of the carbon-based-metal composite material are shown in the table 1; the reaction conditions in the preparation process of the carbon-based-metal composite material are shown in Table 2
TABLE 1
TABLE 2
And (4) analyzing results: fig. 2 is a schematic diagram of the distribution of the iron-graphene element in example 1, and it can be observed that iron is uniformly distributed on the surface of graphene without significant aggregation. The iron-graphene surface of example 1 was observed by high power transmission electron microscopy (fig. 3), and no iron nanoparticle formation was observed. In combination with the elemental composition analysis energy spectrum (fig. 4), the distribution characterization and the microstructure characterization, it can be concluded that uniform iron is formed on the graphene surface by the above process.
FIG. 5 is a high-power transmission electron microscope image of the Fe-C nanotube of example 2, wherein the surface and the internal components of the carbon tube are uniform, and no nanoparticles are observed. Fig. 6 is an energy spectrum of elemental composition analysis of the iron-carbon nanotube, and the energy spectrum analysis shows that the carbon tube sample treated by the above process contains 2.83% of iron by atomic ratio, and it can be inferred that the iron formed on the carbon tube by the above process is uniformly distributed.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a carbon-based-metal composite material is characterized by comprising the following steps:
step 1, mixing 1-1.5 parts of carbon-based fluoride and 2-6 parts of halide metal salt by weight, heating to 280-500 ℃ in vacuum or protective atmosphere, keeping for 6-120 h, naturally cooling to 20-25 ℃, washing the obtained reactant with a cleaning agent, and drying at 60-100 ℃ in vacuum or protective atmosphere for 12-48 h to obtain the carbon-based-metal fluoride; the halide metal salt is chloride metal salt, bromide metal salt or iodide metal salt, and the cleaning agent is ethanol or tetrahydrofuran;
step 2 mixing the carbon-based-metal fluoride with a reducing agent,
when the reducing agent is potassium or magnesium, 1-1.5 parts by weight of the carbon-based-metal fluoride and 3-6 parts by weight of the metal simple substance reducing agent are heated to 300-600 ℃ under a vacuum condition or a protective atmosphere, are kept for 12-120 h, are naturally cooled to 20-25 ℃, are dropwise added with methanol until no bubbles emerge, and are subjected to filtration, water washing and vacuum drying at 60-100 ℃ for 12-48 h to obtain the carbon-based-metal composite material;
when the reducing agent is naphthalene lithium-tetrahydrofuran or naphthalene sodium-tetrahydrofuran, according to the weight percentage, 1 part of carbon-based-metal fluoride is obtained, 5-7 parts of metal simple substance reducing agent in the naphthalene lithium-tetrahydrofuran or the naphthalene sodium-tetrahydrofuran is obtained, the mixture is stirred at room temperature for 48-168 hours under the protection of argon atmosphere, methanol is dropwise added into the reaction liquid until no bubbles emerge, and then the reaction liquid is filtered, washed with water and dried in vacuum at 60-100 ℃ for 12-48 hours to obtain the carbon-based-metal composite material.
2. The preparation method according to claim 1, wherein the carbon-based fluoride is at least one of graphite fluoride, graphite fluoride micro-sheets, carbon black fluoride, carbon fluoride nanotubes and graphene fluoride.
3. The preparation method according to claim 1, wherein the heating process is carried out in a reaction kettle made of stainless steel or quartz.
4. The method according to claim 1, wherein the halide metal salt is at least one of ferric chloride, cobalt chloride, nickel chloride, bismuth chloride, platinum chloride, tantalum chloride, ruthenium chloride, copper bromide, and copper iodide.
5. The method according to claim 1, wherein the protective atmosphere is argon, and the vacuum condition has an absolute vacuum degree of 10-5Pa～104Pa。
6. The method according to claim 1, wherein the lithium naphthalene-tetrahydrofuran is prepared by: adding lithium to anhydrous tetrahydrofuran dissolved with naphthalene under an argon atmosphere, wherein the molar mass ratio of the lithium to the naphthalene is 3: and 1, stirring for 4-24 h to obtain the naphthalene lithium-tetrahydrofuran.
7. The method according to claim 1, wherein the sodium naphthalenide-tetrahydrofuran is prepared by: adding sodium into anhydrous tetrahydrofuran dissolved with naphthalene under an argon atmosphere, wherein the molar mass ratio of the sodium to the naphthalene is 3: and 1, stirring for 4-24 hours to obtain the sodium naphthalene-tetrahydrofuran.
8. The preparation method according to claim 1, wherein the heating rate in the step 1 is 1-5 ℃/min.
9. The preparation method according to claim 1, wherein the heating rate in the step 2 is 1-3 ℃/min.
10. The method according to claim 1, wherein the mass ratio of the carbon-based fluoride to the halide metal salt in step 1 is 1:3, and the mass ratio of the carbon-based-metal fluoride to the reducing agent in step 2 is 1: 3.
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