CN110835423B - Graphene-based composite filler and preparation method thereof - Google Patents
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Abstract
The invention discloses a graphene-based composite filler and a preparation method thereof, and belongs to the technical field of new materials and application thereof. The composite filler comprises graphene powder with a hollow cavity and a functional material filled in the cavity; the filled functional material is phase change material, magnetic material, catalytic material or active substance. The method takes transition metal salt as a template, and utilizes a chemical vapor deposition process to catalytically grow graphene on the surface of the metal salt (reduced to metal) under the conditions of proper temperature and atmosphere. And removing the substrate from the obtained graphene powder by using acid to form graphene powder with a hollow cavity, and filling the graphene powder with a functional material to obtain the composite filler. The graphene prepared by the invention has high crystallization quality and excellent heat conduction and electric conductivity, and can be used as a filler to be applied in various fields after being filled with a functional material.
Description
Technical Field
The invention relates to the technical field of new materials and application thereof, in particular to a graphene-based composite filler and a preparation method thereof.
Background
Researches show that the graphene has excellent electric and heat conducting properties, and the electron mobility of the graphene can reach 200000cm2V-1s-1Can realize the highest current transmission density at room temperature, and the heat conductivity coefficient reaches 5300W m-1K-1Much higher than carbon nanotubes and diamond. In addition, the graphene is a honeycomb-shaped perfect lattice formed by a single layer of carbon atoms, and has high structural stability and chemical stability. Therefore, the graphene has great application potential in the fields of heat conduction, electric conduction, electromagnetic shielding and the likeForce.
The electric and heat conducting composite material has wide application. The graphene is applied to heat-conducting and electric-conducting composite materials, mainly in a powder form and is used as an electric-conducting and heat-conducting filler. The ideal heat-conducting and electric-conducting filler needs to have the following two characteristics: 1. the material has excellent heat conduction and electric conduction performance. Generally, the higher the crystalline quality of the material, the better the thermal and electrical conductivity. Particularly, the graphene conducts heat for phonons (lattice vibration), and the influence of the crystallization quality on the heat conduction performance is more obvious; 2. the composite material is easy to be uniformly and stably dispersed in a matrix, so that a heat-conducting and electric-conducting network passage is better constructed in the composite material. Currently, graphene powder is mainly classified into two main types, one is eigen-state graphene, and the other is (reduced) graphene oxide. For intrinsic graphene, the carbon-oxygen ratio and the crystal quality are high, so that the thermal conductivity and the electric conductivity are high, but due to the inertia of the graphite surface, the exfoliation is difficult, the preparation difficulty of large-size single-layer or few-layer intrinsic graphene is high, and at present, no technology can realize the macro preparation of the large-size single-layer or few-layer intrinsic graphene. Meanwhile, due to the surface inertia and the two-dimensional lamellar structure of the intrinsic graphene, the intrinsic graphene is extremely easy to curl and agglomerate, good dispersion is difficult to obtain in a polymer, and the use performance of the composite material, such as hardness and strength, is greatly influenced while the addition amount of the graphene is limited; for (reduced) graphene oxide, due to the large number of functional groups on the surface, good dispersion of graphene oxide in many polymer matrices can be achieved. However, since the preparation process of graphene oxide generally involves dangerous chemicals such as potassium permanganate and concentrated sulfuric acid, the preparation process is complex, chemical impurities and products are difficult to mix and separate, and the difficulty in removing the impurities is high. Meanwhile, due to the existence of a large number of defects such as surface functional groups, even if the subsequent complex reduction process is carried out, the heat conduction and the electric conductivity of the alloy are still not ideal. Especially, the thermal conductivity is two to three orders of magnitude lower than that of the intrinsic graphene due to the damaged crystal lattice.
As described above, the application of two types of graphene powder as heat and electricity conductive filler has respective problems that are difficult to overcome. Therefore, the development of the graphene powder with the advantages of high quality and easy dispersion is of great significance.
Disclosure of Invention
The invention aims to provide a graphene-based composite filler and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a graphene-based composite filler comprises graphene powder with a hollow cavity and a functional material filled in the hollow cavity; the particle size range of the graphene powder is 5nm-300 mu m.
The graphene powder is in a spherical, tetrahedral, octahedral, polyhedral or rod-shaped form; the filled functional material is a phase change material, a magnetic material, a catalytic material or an active substance.
The phase-change material is one or more of paraffin, fatty acid derivative and polyhydric alcohol.
The graphene powder has high crystallization quality, and a Raman spectrum shows that a graphene characteristic peak is obvious and has no defect peak (D peak); the graphene powder has excellent heat conduction and electric conductivity. The graphene powder prepared by the invention has a regular geometric shape (especially a spherical shape) microscopically, and the agglomeration of conventional two-dimensional lamellar graphene can be avoided, so that the graphene powder can be better dispersed in a matrix, and the preparation of a composite material is facilitated.
The preparation method of the graphene-based composite filler comprises the following steps:
(1) heating the reaction furnace cavity to a set temperature under the protective atmosphere of carrier gas;
(2) adding a required amount of transition metal salt as a matrix into a constant-temperature area of a cavity of the reaction furnace, and keeping the temperature for 0-10 min;
(3) introducing a mixed atmosphere of carbon source gas, reducing gas and carrier gas into the cavity of the reaction furnace, wherein the high-melting-point metal salt is subjected to a reduction reaction in the mixed atmosphere, and graphene is catalytically grown on the surface of the reduced metal salt; the flow ratio of the carbon source gas, the reducing gas and the carrier gas in the mixed atmosphere is 1: (0.5-80): (0-100); the reaction time is 1min-60 min;
(4) taking out the prepared reaction product under the protective atmosphere of carrier gas to obtain graphene powder growing on the substrate;
(5) etching off the metal substrate by using corresponding acid to obtain graphene powder with a hollow cavity structure;
(6) and (3) filling a functional material into the hollow cavity of the obtained graphene powder to obtain the graphene-based composite filler.
In the step (2), the transition metal salt is one or more of nickel chloride, nickel acetate, nickel sulfate, nickel nitrate, copper chloride, copper sulfate, ferric chloride and cobalt chloride.
In the step (1), the set temperature is 800-1200 ℃, and the reduction reaction in the step (3) is performed at the set temperature.
The carbon source gas is one or more of methane, ethane, ethylene and acetylene, the reducing gas is one or two of hydrogen and ammonia, and the carrier gas is one or more of argon, nitrogen and helium.
In the method, the particle size and the shape of the prepared graphene powder can be regulated and controlled by selecting different metal salt matrixes and/or regulating and controlling growth parameters such as temperature, reaction atmosphere and the like in the reduction reaction.
In the step (5), the metal substrate is etched by using corresponding acid liquor, and the metal salt can be recovered by evaporating the reacted etching acid liquor; the corresponding acid liquor used for etching can be recovered through a water-containing gas washing cylinder additionally arranged at the tail gas end of the chemical vapor deposition reaction device, and the whole production process only consumes a certain amount of electric energy and reaction gas.
The design mechanism of the invention is as follows:
the method comprises the steps of taking a transition metal salt as a substrate template, and catalytically growing graphene on the surface of the metal salt (reduced to metal) by utilizing a chemical vapor deposition process under the conditions of proper temperature and atmosphere. And removing the substrate from the obtained graphene powder by using corresponding acid to form a graphene hollow cavity structure. By regulating and controlling reaction parameters, the particle size, the shape and the like of the graphene powder can be regulated and controlled. The metal salt and the corresponding etching acid liquid can be recycled, and the whole production process only consumes a certain amount of electric energy and reaction gas. The invention has simple process, low production cost and easy amplification and mass production. The prepared graphene filler can be directly filled with a phase-change material or filled in a cavity of the graphene filler to prepare a composite filler applied to preparation of a high-performance heat-conducting composite material.
The graphene powder prepared by the invention can completely remove a metal substrate to form a hollow structure with few tiny micropores on the surface. The existence of a few surface micropores is beneficial to the subsequent addition of functional materials into the graphene hollow cavity to form the core-shell structure composite filler with multiple excellent performances. The high-quality graphene outer shell layer has excellent electric conduction and heat conduction performances, and provides an ideal temperature-resistant, oxidation-resistant and corrosion-resistant protective layer for the functional material in the cavity.
The invention has the following advantages:
the hollow graphene powder with the regular form prepared by the process overcomes the problems that the common graphene material has large diameter-thickness ratio and is easy to agglomerate and difficult to disperse in a composite material matrix as a nano filler. Meanwhile, the prepared hollow graphene powder has high crystallization quality and excellent heat conduction and electric conductivity. The metal salt substrate and the corresponding etching acid liquid can be recycled, and the whole production process only consumes a certain amount of electric energy and reaction gas. The invention has simple process, easy amplification and low production cost.
1. The method takes transition metal salt as a substrate template to catalyze and grow the graphene. By regulating the type and the growth parameters of the metal salt, the form and the particle size of the prepared graphene can be regulated, so that different application requirements can be met.
2. The graphene powder prepared by the invention has a hollow cavity structure, and can be directly used as a filler according to different application requirements; functional materials can be filled in the cavity of the composite material, so that the composite material with corresponding functions can be prepared, and if the phase-change material is filled in the cavity, the composite filler with heat conduction capability and phase-change heat storage capability can be obtained.
3. The graphene powder prepared by the invention has a regular geometric shape (especially a spherical shape) microscopically, can avoid the agglomeration of conventional two-dimensional lamellar graphene, obtains better dispersion in a matrix, and is beneficial to the preparation of a composite material.
4. The high-melting-point metal salt (reduced into corresponding metal) used in the invention can be recovered after being etched by using corresponding acid liquor, and the corresponding acid liquor can be recovered by a water-containing gas washing cylinder additionally arranged at the tail gas end of the chemical vapor deposition reaction device, so that the whole production process only consumes a certain amount of electric energy and reaction gas.
5. All reactants and reaction liquid except inert carrier gas can be recycled, harmful waste gas and waste liquid are not generated in the whole process, and the preparation method is low-carbon and environment-friendly.
6. Due to the high reaction temperature and the catalytic activity of the transition metal matrix, the graphene prepared by the method has the crystallization quality which is comparable to that of the mechanically exfoliated eigenstate graphene. The Raman spectrum shows that the characteristic peak of the graphene is obvious and has no defect peak (D peak). Therefore, the conductive and heat-conducting performance is excellent.
7. The invention has simple process, easy amplification and low production cost. The prepared graphene has high crystallization quality, so that the heat conduction performance and the electric conduction performance are excellent. The graphene powder can be directly filled with a phase-change material or filled in a cavity of the graphene powder to prepare a composite filler applied to preparation of a high-performance heat-conducting composite material.
Drawings
Fig. 1 is a nickel-containing graphene polyhedron.
Fig. 2 is a graphene cavity polyhedron.
Fig. 3 is a raman spectrum of graphene on a nickel substrate.
Fig. 4 is a raman spectrum of graphene with the nickel substrate removed.
Fig. 5 is a raman spectrum (on a nickel substrate) of graphene grown with recycled nickel chloride.
Fig. 6 is a graphene dispersion.
Fig. 7 is a graphene microsphere prepared in example 2.
Fig. 8 is spherical graphene fine particles prepared in example 3.
Fig. 9 is graphene particles prepared in example 4.
Fig. 10 shows graphene particles in example 5.
Fig. 11 shows graphene particles in example 6.
Fig. 12 shows graphene particles in example 7.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings and examples.
Example 1:
heating the cavity of the reaction furnace to 900 ℃ under the nitrogen protection atmosphere, adding 50g of nickel chloride into the constant-temperature area of the cavity of the reaction furnace, and keeping the temperature for 2 min; introducing a mixed gas of methane and hydrogen, wherein the flow ratio of the methane to the hydrogen in the mixed gas is 1: and 50, reacting for 3min, and catalytically growing graphene on the surface of the reduced nickel chloride substrate. Taking out the prepared reactant under the nitrogen protection atmosphere. The obtained product was in the form of polyhedron (see FIG. 1), and the average particle size was 6 μm. Putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving heat for 30min at 80 ℃, completely removing nickel in the graphene polyhedron, filtering, cleaning and drying the graphene powder to obtain hollow graphene particles with few tiny micropores on the surface, wherein the structure is shown in figure 2. From the raman spectrum of the obtained sample (fig. 3 is a raman spectrum on a nickel substrate, and fig. 4 is a raman spectrum of the sample without the nickel substrate), it can be seen that the graphene prepared by the method has high crystalline quality due to the high reaction temperature and the catalytic activity of the metal matrix. The Raman spectrum shows that the characteristic peak of the graphene is obvious and has no defect peak (D peak). And heating and evaporating the etching liquid with the graphene powder filtered out, recovering to obtain nickel chloride, and growing graphene again by using the nickel chloride, wherein the shape of the obtained graphene under the same growth parameters is consistent with that of the graphene shown in the figures 1 and 2. Fig. 5 is a raman spectrum of a graphene powder sample grown by using recovered nickel chloride on a nickel substrate, and it can be seen from the graph that the sample grown by using the recovered nickel substrate has excellent crystallization quality, an obvious characteristic peak and no obvious defect peak. The tail gas end of the chemical vapor deposition reaction furnace is connected with a gas washing bottle filled with water, so that hydrogen chloride gas obtained by reducing nickel chloride with hydrogen can be collected to obtain hydrochloric acid, and the hydrochloric acid is recycled for etching and removing the metal substrate of a subsequent sample. Fig. 6 shows the dispersion of the prepared graphene hollow powder in water, and it can be seen from the photo that due to the high crystallization quality and the inert surface, the graphene will settle under the action of its own gravity (density greater than water) after standing for 24 hours. And lightly shaking the container to ensure that the graphene can be uniformly dispersed in water.
In the embodiments described later, the shape of the hollow graphene after the metal substrate is etched is consistent with that before the metal substrate is etched, and the raman spectroscopy, the recovery and the dispersibility verification are consistent with those in embodiment 1, and are not described again.
Example 2:
heating the cavity of the reaction furnace to 900 ℃ under the argon protection atmosphere, adding 50g of nickel chloride into the constant-temperature area of the cavity of the reaction furnace, and preserving heat for 2 min; and introducing a mixed gas of methane, hydrogen and argon, wherein the volume flow ratio of methane to hydrogen to argon in the mixed gas is 1: 10: and 80, reacting for 5min, and catalytically growing graphene on the surface of the reduced nickel chloride substrate. And taking out the prepared reactant under the argon protective atmosphere. The resulting product was spherical (see FIG. 7) and had an average particle size of 3 μm. And (3) putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving the heat for 30min at the temperature of 80 ℃, completely removing nickel in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the graphene microsphere with the hollow cavity.
Example 3:
heating the cavity of the reaction furnace to 1000 ℃ under the argon protection atmosphere, adding 50g of copper sulfate into the constant-temperature area of the cavity of the reaction furnace, and preserving heat for 2 min; and introducing a mixed gas of methane, hydrogen and argon, wherein the volume flow ratio of methane to hydrogen to argon in the mixed gas is 1: 30: and (3) performing reaction for 20min for 100, and performing catalytic growth of graphene on the surface of the reduced copper sulfate substrate. And taking out the prepared reactant under the argon protective atmosphere. The obtained product was spherical (see FIG. 8) and had an average particle size of 1 μm. And putting the prepared reactant into a 2mol/L sulfuric acid aqueous solution (etching solution), preserving the heat at 80 ℃ for 60min, completely removing copper in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the graphene particles with the hollow cavities.
Example 4:
heating the cavity of the reaction furnace to 1000 ℃ under the argon protection atmosphere, adding 50g of cobalt chloride into the constant-temperature area of the cavity of the reaction furnace, and preserving heat for 1 min; and introducing a mixed gas of methane, hydrogen and argon, wherein the volume flow ratio of methane to hydrogen to argon in the mixed gas is 1: 40: and 120, reacting for 15min, and catalytically growing graphene on the surface of the reduced copper sulfate substrate. And taking out the prepared reactant under the argon protective atmosphere. The product obtained was in the form of spheroidal particles (see FIG. 9) with an average particle size of 0.5. mu.m. And (3) putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving the temperature at 80 ℃ for 60min, completely removing copper in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the hollow graphene particle with the hollow cavity.
Example 5:
heating the cavity of the reaction furnace to 900 ℃ under the argon protection atmosphere, adding 50g of nickel chloride into the constant-temperature area of the cavity of the reaction furnace, and preserving heat for 2 min; and introducing mixed gas of ethylene, hydrogen and argon, wherein the volume flow ratio of methane to hydrogen to argon in the mixed gas is 1: 20: and 60, reacting for 10min, and catalytically growing graphene on the surface of the reduced nickel chloride substrate. And taking out the prepared reactant under the argon protective atmosphere. The obtained product is polyhedral particle (as shown in FIG. 10), and has an average particle diameter of 300 nm. And putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving the heat at 80 ℃ for 30min, completely removing nickel in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the graphene particles with the hollow cavities.
Example 6:
heating the cavity of the reaction furnace to 800 ℃ under the argon protection atmosphere, adding 50g of nickel chloride into the constant-temperature area of the cavity of the reaction furnace, and keeping the temperature for 2 min; and introducing a mixed gas of acetylene, hydrogen and argon, wherein the volume flow ratio of methane to hydrogen to argon in the mixed gas is 1: 80: and 60, reacting for 2min, and catalytically growing graphene on the surface of the reduced nickel chloride substrate. And taking out the prepared reactant under the argon protective atmosphere. The obtained product is nearly spherical particles (as shown in FIG. 11), and the average particle diameter is 100 nm. And putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving the heat at 80 ℃ for 30min, completely removing nickel in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the graphene particles with the hollow cavities.
Example 7:
heating the cavity of the reaction furnace to 1100 ℃ under the nitrogen protection atmosphere, adding 50g of nickel chloride into the constant-temperature area of the cavity of the reaction furnace, and keeping the temperature for 2 min; introducing a mixed gas of methane, hydrogen and nitrogen, wherein the volume flow ratio of the methane to the hydrogen to the nitrogen in the mixed gas is 1: 5: and 60, reacting for 18min, and catalytically growing graphene on the surface of the reduced nickel chloride substrate. And taking out the prepared reactant under the argon protective atmosphere. The obtained product was polyhedral particles (see FIG. 12), and had an average particle diameter of 10 μm. And putting the prepared reactant into 3mol/L hydrochloric acid aqueous solution (etching solution), preserving the heat at 80 ℃ for 30min, completely removing nickel in the graphene polyhedron, and filtering, cleaning and drying the graphene powder to obtain the graphene particles with the hollow cavities.
Example 8:
functional materials are filled in the hollow cavity of the graphene powder prepared in the embodiments 1 to 7, the filled functional materials are phase-change materials (the phase-change materials are paraffin, fatty acid derivatives or polyhydric alcohol), magnetic materials, catalytic materials or active substances, and the like, so that a composite filler with a corresponding function can be obtained.
In conclusion, the graphene powder disclosed by the invention is controllable in shape and particle size, high in crystallization quality, excellent in electric conduction and heat conduction performance, simple in preparation method and process, recyclable and reusable in most of raw materials, and low in preparation cost. The prepared graphene powder is in a relatively regular geometric shape such as a monodisperse polyhedron and the like, and overcomes the defects of easy agglomeration and difficult dispersion of the traditional graphene powder as a filler. And filling corresponding functional materials in the hollow cavity of the graphene powder, so as to obtain the graphene-based composite filler with corresponding functions.
The above-mentioned embodiments are provided only for illustrative purposes and should not be construed as limiting the scope of the present invention, and any method that can be substituted or modified equivalently according to the technical solution and the inventive concept thereof should be included in the scope of the present invention.
Claims (7)
1. A composite filler based on graphene is characterized in that: the composite filler comprises graphene powder with a hollow cavity and a functional material filled in the hollow cavity; the particle size range of the graphene powder is 5nm-300 mu m;
the graphene powder is in a spherical, polyhedral or rod-shaped form; the filled functional material is a phase change material, a magnetic material, a catalytic material or an active substance;
the Raman spectrum of the graphene powder shows that the characteristic peak of graphene is obvious and no defect peak appears;
the preparation method of the graphene-based composite filler comprises the following steps:
(1) heating the reaction furnace cavity to a set temperature under the protective atmosphere of carrier gas;
(2) adding a required amount of transition metal salt as a matrix into a constant-temperature area of a cavity of the reaction furnace, and keeping the temperature for 0-10 min;
(3) introducing a mixed atmosphere of carbon source gas, reducing gas and carrier gas into the reaction furnace cavity, wherein the transition group metal salt is subjected to a reduction reaction in the mixed atmosphere, and graphene is catalytically grown on the surface of the reduced transition group metal salt; the flow ratio of the carbon source gas, the reducing gas and the carrier gas in the mixed atmosphere is 1: (0.5-80): (0-100); the reaction time is 1min-60 min;
(4) taking out the prepared reaction product under the protective atmosphere of carrier gas to obtain graphene powder growing on the substrate;
(5) etching off the metal substrate by using corresponding acid to obtain graphene powder with a hollow cavity structure;
(6) and (3) filling a functional material into the hollow cavity of the obtained graphene powder to obtain the graphene-based composite filler.
2. The graphene-based composite filler according to claim 1, wherein: the phase-change material is one or more of paraffin, fatty acid derivative and polyhydric alcohol.
3. The graphene-based composite filler according to claim 1, wherein: in the step (2), the transition metal salt is one or more of nickel chloride, nickel acetate, nickel sulfate, nickel nitrate, copper chloride, copper sulfate, ferric chloride and cobalt chloride.
4. The graphene-based composite filler according to claim 1, wherein: in the step (1), the set temperature is 800-1200 ℃, and the reduction reaction in the step (3) is carried out at the set temperature.
5. The graphene-based composite filler according to claim 1, wherein: the carbon source gas is one or more of methane, ethane, ethylene and acetylene, the reducing gas is one or two of hydrogen and ammonia, and the carrier gas is one or more of argon, nitrogen and helium.
6. The graphene-based composite filler according to claim 1, wherein: in the method, the particle size and the shape of the prepared graphene powder can be regulated and controlled by selecting different metal salt matrixes and/or regulating and controlling the temperature and the reaction atmosphere growth parameters in the reduction reaction.
7. The graphene-based composite filler according to claim 1, wherein: in the step (5), the metal substrate is etched by using corresponding acid liquor, and the metal salt can be recovered by evaporating the reacted etching acid liquor; the corresponding acid liquor used for etching can be recovered through a water-containing gas washing cylinder additionally arranged at the tail gas end of the chemical vapor deposition reaction device, and the whole production process only consumes a certain amount of electric energy and reaction gas.
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