CN114150497B - Graphene-carbon nanofiber composite material and preparation method thereof - Google Patents
Graphene-carbon nanofiber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-carbon nanofiber composite materialThe preparation method comprises growing graphene on the surface of carbon nanofiber, wherein sp is used between the graphene and the carbon nanofiber 2 And C is connected. Firstly, forming carbon defects on the carbon nanofibers, and then, directly growing graphene on the carbon defects, so that the graphene epitaxially grows on the carbon nanofibers. The invention is based on the principle of thermal chemical vapor deposition, the size and the density of graphene on the surface of the carbon nanofiber can be controlled by controlling the growth condition, and the graphene is uniformly distributed on the surface of the carbon nanofiber. The preparation method is simple, no metal catalyst or plasma assistance is needed, the raw material sources are wide, and the obtained graphene-carbon nanofiber composite material has excellent conductivity and mechanical properties.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a graphene-carbon nanofiber composite material and a preparation method thereof.
Background
The carbon nanofiber has the excellent performances of high strength, high modulus, low density, low radiation absorption, corrosion resistance, electric conduction, heat conduction and the like, and has wide application in the fields of aerospace, automobile manufacturing, national defense, military industry and the like. Graphene is a kind of carbon atom in sp 2 The two-dimensional carbon nanomaterial formed by hybridization has excellent mechanical, electrical and thermal properties. The mechanical property, the electric conduction and the heat conduction of the carbon fiber can be enhanced by compounding the graphene and the carbon nanofiber, and the composite material with more excellent performance is obtained.
In recent years, many methods for preparing graphene and carbon nanofiber composites have been developed. The most common method is the physical mixing method. For example, the dispersed graphene solution and the carbon nanofibers are mixed, so that the graphene is adsorbed on the surface of the carbon fibers. Composite materials obtained using this method tend to be poor in both uniformity and stability, affecting many properties of the composite materials. The other is to connect graphene and carbon nanofibers through chemical bonds. Such as amide bonds formed at the interface of graphene and carbon nanofibers by chemical reaction. Compared with physical mixing, the chemically bonded graphene and the carbon nanofiber have stronger interaction force, so that the overall performance of the product is improved. However, the preparation process of the current method is complex, uniform compounding of graphene and carbon nanofibers is difficult to uniformly control, and the bonding effect between the obtained graphene and carbon nanofibers is still weak.
Therefore, a method capable of uniformly and stably compounding graphene and carbon nanofibers and hopefully realizing mass preparation is very important for promoting application of the nano carbon materials.
Disclosure of Invention
In order to overcome the problems, the inventor has conducted intensive research to develop a graphene-carbon nanofiber composite and a preparation method thereof. Based on a thermal chemical vapor deposition method, firstly, the structure of the carbon nanofiber is destroyed, uneven carbon defects are formed on the surface of the carbon nanofiber, and the activity of the carbon defects is high. Then reacts with carbon source gas at high temperature, and the carbon defect is used as a nucleation center for graphene growth, so that graphene grows epitaxially on the carbon nanofiber. Sp is used between graphene and carbon nano fiber in the obtained composite material 2 And the carbon is connected, so that the graphene is uniformly and stably on the surface of the carbon nanofiber. The composite material has excellent conductivity, simple preparation method, no need of metal catalyst or plasma assistance, wide raw material source and low cost, and can realize mass preparation, thereby completing the invention.
An aspect of the present invention is to provide a graphene-carbon nanofiber composite in which graphene is grown on a surface of a carbon nanofiber with sp between the graphene and the carbon nanofiber 2 And C is connected.
The carbon nanofiber is a one-dimensional carbon nanomaterial, and is preferably selected from one or more of carbon nanotubes, biomass-derived carbon fibers and polymer-derived carbon fibers.
Another aspect of the present invention provides a method for preparing a graphene-carbon nanofiber composite, the method comprising the steps of:
step 1, forming carbon defects on carbon nanofibers;
and 2, growing graphene on the carbon defects.
Step 1, the forming of carbon defects on the carbon nanofibers includes:
step 1.1, placing carbon nanofibers or precursors of the carbon nanofibers in an oxygen-free environment, and heating;
and 1.2, introducing a reaction gas and a first inert gas, and preserving heat.
In step 1.1, the temperature is raised to 400 to 1200 ℃, preferably 500 to 1100 ℃.
In the step 1.2, the reaction gas is selected from one or more of hydrocarbon, alcohol, aldehyde and reducing gas, and the reducing gas is selected from one or more of water, carbon dioxide, carbon monoxide, ammonia and hydrogen; and/or
The flow ratio of the reaction gas to the first inert gas is 1: (1 to 10), preferably 1: (1-9).
Step 2, growing graphene on the carbon defects comprises: heating, introducing hydrogen, carbon source gas and second inert gas, and preserving heat.
In step 2, the temperature is raised to 800 to 1800 ℃, preferably 900 to 1500 ℃.
The flow ratio of the hydrogen gas, the carbon source gas and the second inert gas is 1: (1-5): (1-10).
In yet another aspect, the present invention provides a graphene-carbon nanofiber composite prepared according to the method of the second aspect of the present invention.
The invention has the beneficial effects that:
(1) In the graphene-carbon nanofiber composite material provided by the invention, sp is arranged between the interface of graphene and carbon nanofiber 2 The carbon is connected, the bonding effect is strong, and the graphene is uniformly distributed on the carbon nanofiber;
(2) The preparation method is based on a thermal chemical vapor deposition method, firstly, carbon defects are formed on the surface of the carbon nanofiber, the activity of the carbon defects is high, and the activity of non-defects is low, so that graphene grows along the carbon nanofiber epitaxy at the carbon defects, and no metal catalyst or plasma assistance is needed in the whole preparation process;
(3) The composite material obtained by the invention has high product quality, controllable graphene growth size on the surface of the carbon nanofiber and uniform density, and the obtained composite material has excellent conductive performance and mechanical property;
(4) The preparation method provided by the invention is simple, wide in raw material sources, low in cost and capable of large-scale preparation.
Drawings
Fig. 1 shows a schematic structural diagram of a graphene-carbon nanofiber composite according to a preferred embodiment of the present invention;
fig. 2 shows a TEM image of the graphene-carbon nanotube composite material prepared in example 1 of the present invention;
fig. 3 shows a TEM image of the graphene-carbon nanotube composite material prepared in example 2 of the present invention;
fig. 4 shows SEM images and TEM images of graphene-carbon nanofiber composite materials prepared in example 3 of the present invention;
fig. 5 shows the stress-strain curve test results and the conductivity test results obtained in the experimental example of the present invention.
Reference numerals illustrate:
1-carbon nanofibers;
2-graphene.
Detailed Description
The invention is described in further detail below with reference to the drawings and the preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the present invention, there is provided a graphene-carbon nanofiber composite material in which graphene is grown on the surface of carbon nanofibers, the graphene and the carbon nanofibers passing through sp 2 And C is connected.
According to the invention, graphene grows epitaxially on the outer wall of the carbon nanofiber, and the grown graphene is uniformly distributed on the carbon nanofiber.
According to the invention, as shown in fig. 1, a structural schematic diagram of a graphene-carbon nanofiber composite material, 1-carbon nanofiber and 2-graphene is shown, wherein the graphene-carbon nanofiber composite material is obtained by directly growing graphene on carbon defects on the surface of carbon nanofiber, and the graphene passes through sp 2 Carbon is attached to the surface of the carbon nanofibers, as can be seen from side and top views.
According to the invention, the composite material is obtained based on the chemical vapor deposition principle, and the size and the density of the graphene on the surface of the carbon nanofiber can be controlled by controlling the growth conditions, so that the graphene on the surface of the carbon nanofiber has controllable growth size and uniform density.
According to the invention, the carbon nanofiber refers to a one-dimensional carbon nanomaterial, and the carbon nanofiber comprises a carbon nanotube, a biomass-derived carbon fiber, a macromolecule-derived carbon fiber and the like.
According to the present invention, the carbon nanotube is one or more of a multiwall carbon nanotube, a single-wall carbon nanotube and a carbon nanotube sponge, preferably a multiwall carbon nanotube or a carbon nanotube sponge, and the diameter of the carbon nanotube is not particularly limited, preferably 20 to 30nm.
According to the present invention, the carbon nanotube sponge is self-made, preferably, the carbon nanotube sponge is prepared by the following method:
dissolving a catalyst ferrocene in liquid carbon source 1, 2-dichlorobenzene to obtain a precursor solution;
injecting the precursor solution into a tube furnace in a preheating zone, vaporizing, and taking the vaporized precursor into a tube furnace reaction zone by using a mixed gas of argon and hydrogen to react;
preserving heat for a certain time, naturally cooling, and obtaining the carbon nanotube sponge on the wall of the quartz tube.
According to a preferred embodiment of the invention, 0.1 to 35g of ferrocene is dissolved based on 10 to 400ml of 1, 2-dichlorobenzene.
According to a preferred embodiment of the invention, the precursor solution is fed at a rate of 0.02 to 0.2ml/min, preferably 0.03ml/min.
According to a preferred embodiment of the invention, the preheating zone temperature is 220-280 ℃, preferably 250 ℃, and the reaction zone temperature is 820-900 ℃, preferably 860 ℃;
the flow ratio of argon to hydrogen is 1: (4-6), preferably 1:5.
according to a preferred embodiment of the invention, the incubation time is 30 to 240 minutes.
According to a preferred embodiment of the present invention, the graphene-carbon nanofiber composite has excellent electrical conductivity and mechanical properties, and the electrical conductivity of the graphene-carbon nanofiber composite is 3 times or more, preferably 4 to 7 times, that of the carbon nanofiber in which graphene is not grown.
According to a preferred embodiment of the present invention, when the carbon nanofibers are carbon nanotube sponges, the resulting graphene-carbon nanofiber composite has an electrical conductivity higher than 8.0X10 2 S/m, preferably higher than 1.0X10 3 S/m, more preferably 1.2 to 3X 10 3 S/m。
According to a preferred embodiment of the present invention, the graphene-grown carbon nanofibers have excellent mechanical properties, for example, the stress of the graphene-carbon nanofibers can be more than 10 times that of the non-grown carbon nanofibers under the same strain.
According to the present invention, there is provided a method for preparing a graphene-carbon nanofiber composite, the method comprising the steps of:
step 1, forming carbon defects on carbon nanofibers;
step 2, growing graphene on the carbon defects;
and 3, cooling in an inert gas atmosphere to obtain the graphene-carbon nanofiber composite material.
According to the present invention, in step 1, the forming carbon defects on the outer wall of the carbon nanofiber includes:
step 1.1, placing carbon nanofibers or precursors of the carbon nanofibers in an oxygen-free environment, and heating;
and 1.2, introducing a reaction gas and a first inert gas, and preserving heat.
According to the invention, in step 1.1, the precursor of the carbon nanofiber is a precursor of a biomass-derived carbon fiber or a precursor of a polymer-derived carbon fiber,
preferably, the precursor of the carbon nanofiber is bacterial cellulose or polymer fiber.
According to a preferred embodiment of the present invention, the bacterial cellulose is commercially available, such as commercial bacterial cellulose from Hainan food Co.
According to the invention, in step 1.1, the oxygen-free atmosphere is a nitrogen or rare gas atmosphere, preferably a nitrogen, argon or helium atmosphere.
According to the invention, in step 1.1, the temperature is raised to 400 to 1200 ℃, preferably 500 to 1100 ℃, more preferably 600 to 1000 ℃.
According to a preferred embodiment of the invention, in step 1.1,
when the carbon nano-fiber selects the carbon nano-tube, the temperature is raised to 800-1000 ℃, such as 900 ℃;
when the carbon nanofibers are selected from biomass-derived carbon fibers, the temperature is raised to 600-800 ℃, e.g., 700 ℃.
According to the present invention, in step 1.1, there is no particular limitation on the temperature rising rate during the temperature rising, preferably the temperature rising rate is 1 to 20 ℃/min, more preferably the temperature rising rate is 2 to 10 ℃/min.
According to the invention, in step 1.2, a reaction gas and a first inert gas are introduced for heat preservation, so that carbon defects are generated on the outer wall of the carbon nanofiber.
According to the invention, in step 1.2, the reaction gas is one or more of hydrocarbon, alcohol, aldehyde or reducing gas.
The hydrocarbon is selected from one or more of methane, acetylene, ethylene and the like, the alcohol is methanol and/or ethanol, the aldehyde is formaldehyde and/or acetaldehyde, and the reducing gas is selected from one or more of water, carbon monoxide, carbon dioxide, ammonia and hydrogen.
According to a preferred embodiment of the invention, in step 1.2, the reaction gas is hydrogen, acetylene or ammonia.
According to the invention, in step 1.2, the first inert gas is argon, nitrogen or helium.
According to the invention, in step 1.2, the flow ratio of the introduced reaction gas to the first inert gas is 1: (1 to 10), preferably 1: (1-9).
According to a preferred embodiment of the present invention, in step 1.2, the flow rate of the reaction gas is 10 to 50ml/min, and the flow rate of the first inert gas is 50 to 200ml/min.
According to the invention, the incubation time is from 1 to 60 minutes, preferably from 10 to 50 minutes, more preferably from 20 to 30 minutes.
In the invention, the heat preservation time is too short, which can lead to insufficient carbon defects on the surface of the carbon nanofiber, so that graphene cannot be grown, the heat preservation time is too long, which is unfavorable for wasting reaction raw materials, reducing efficiency and being unfavorable for saving energy.
In the present invention, in step 1, when carbon defects are formed using a precursor of carbon nanofibers as a raw material, the precursor of carbon nanofibers is carbonized at a high temperature to form carbon nanofibers, and carbon defects are simultaneously generated on the surfaces of the formed carbon nanofibers.
According to the present invention, in step 1, carbon defects are generated on the surface of the carbon nanofibers, and the generated carbon defects refer to non-graphitized carbon sites with local unevenness.
In the invention, the carbon nano-fiber is placed in the reaction gas for treatment at high temperature, and the original structure of the carbon nano-fiber is destroyed by controlling the flow rate of the reaction gas, the temperature, the time and other conditions, so that uneven carbon defects are formed on the surface of the carbon nano-fiber. The formed carbon defects have a plurality of suspension bonds with higher activity, and compared with other flat areas, the formed carbon defects have higher chemical activity at high temperature and can react with a carbon source preferentially to grow graphene as a nucleation center. Because the defect activity is high and the peripheral non-defect activity is low, the graphene grows perpendicular to the outer wall of the carbon nanofiber.
According to the invention, based on the thermal chemical vapor deposition principle, a carbon source is added, the temperature and the gas flow are controlled, and graphene is directly grown on carbon defects without adding a metal catalyst or plasma assistance.
According to the present invention, in step 2, epitaxially growing graphene on the carbon defects includes: heating, introducing hydrogen, carbon source gas and second inert gas, and preserving heat.
In the invention, in the step 2, the hydrogen can inhibit the generation of amorphous carbon products and promote the growth of graphene.
In the invention, the temperature after the temperature rise in the step 2 is higher than the temperature after the temperature rise in the step 1.
According to the invention, after the end of the heat-preservation in step 2, step 1, the temperature is continuously raised to 800-1800 ℃, preferably to 1000-1800 ℃, more preferably to 1000-1500 ℃, for example 1000 ℃.
According to the invention, the structure of the grown graphene can be ensured at the temperature.
According to the invention, in step 2, the temperature increase rate is 1 to 20℃per minute, preferably 2 to 10℃per minute.
According to the present invention, in step 2, the type of the carbon source gas is not particularly limited, and may be a carbon source gas commonly used in the art, preferably, the carbon source gas is a low molecular organic substance selected from one or more of methanol, ethanol, methane, ethane, ethylene, acetylene, etc., and for example, the carbon source gas is methane.
In the invention, the carbon source gas is cracked at high temperature, and can nucleate at the defect position on the surface of the carbon nanofiber preferentially to form a local graphitized area, and then graphene is further epitaxially grown.
According to the invention, in step 2, the second inert gas is argon or helium, preferably argon.
According to the present invention, in step 2, the flow ratio of the hydrogen gas, the carbon source gas and the second inert gas is 1: (1-5): (1 to 10), preferably 1: (1-4): (1-8).
In the invention, the flow ratio of the hydrogen to the carbon source gas has a great influence on the graphitization degree and the growth speed of the product. When the flow rates of the hydrogen gas and the carbon source gas are relatively low, the graphene grows faster on the surface of the carbon nanofiber, but the graphitization degree is lower. When the flow rate is higher, the graphene grows at a slower speed on the surface of the carbon nanofiber, but the graphitization degree is higher. The flow ratio of the hydrogen to the carbon source gas can ensure proper growth speed and graphitization degree of graphene on the carbon nanofiber in a proper range so as to obtain the graphene-carbon nanofiber composite material with excellent performance.
According to the present invention, in step 2, the holding time is not particularly limited, and the desired graphene size and density may be obtained. The growth time is prolonged, the density and the size of the obtained graphene are obviously increased, and the heat preservation time is preferably 30-600 min, preferably 60-200 min, and more preferably 120-180 min.
In the invention, in the step 2, the heat preservation time is too short, and the graphene growth time is too short, which may cause incomplete graphene growth. The heat preservation time is too long, so that the waste of reaction raw materials is caused, the efficiency is reduced, and the energy conservation is not facilitated.
According to the invention, in the step 3, after the heat preservation is finished, the graphene-carbon nanofiber composite material is obtained by naturally cooling in an inert gas atmosphere such as under the protection of nitrogen atmosphere. In the composite material, graphene grows on the surface of carbon nanofiber and vertically grows outside the carbon nanofiber, and sp is relied between the graphene and the carbon nanofiber 2 And C is connected.
In the invention, under the conditions of high temperature and hydrogen, the carbon source gas is cracked, nucleation is carried out on the carbon defects with high activity, a local graphitization area is formed, and graphene is epitaxially grown, and the grown graphene is uniformly distributed on the carbon nanofibers.
According to a preferred embodiment of the present invention, when the carbon nanofibers are carbon nanotube sponges, the resulting graphene-carbon nanofiber composite has an electrical conductivity higher than 8.0X10 2 S/m, preferably higher than 1.0X10 3 S/m, more preferably (1.2 to 3). Times.10 3 S/m。
According to the invention, based on a chemical vapor deposition method, carbon defects are formed on the surface of one-dimensional carbon nanofiber, and two-dimensional graphene is directly grown on the carbon defects, so that a metal catalyst is not needed, and the graphene-carbon nanofiber composite material is obtained. Dependence on sp between graphene and carbon nanofibers 2 The carbon is connected, so that the graphene and the carbon nanofiber are combined stably, the mechanical property, the electric conduction and heat conduction properties of the carbon nanofiber are enhanced, and the obtained composite material has excellent comprehensive properties.
At sp 2 The graphene and the carbon nanofiber connected by carbon enable the structure of the composite material to be more uniform and stable, the combination effect between the graphene and the carbon nanofiber is stronger, and the preparation method can realize mass preparation and has important significance for promoting the application of the nano carbon material.
The preparation method of the graphene-carbon nanofiber composite material provided by the invention has the advantages of simple equipment, low production cost, no need of a metal catalyst, high product quality, controllable graphene growth size, uniform density and strong product repeatability, and can be used for large-scale preparation.
Examples
Example 1
The carbon nanotubes used were commercial multiwall carbon nanotubes purchased from Nanjing Xianfeng nanomaterial technologies, inc., model: XFM21, diameter 20-30 nm.
Placing the carbon nano tube in a tube furnace, heating to 900 ℃ at a speed of 10 ℃/min under argon atmosphere, then introducing mixed gas of 50ml/min of ammonia gas and 50ml/min of argon gas, and preserving heat for 20min to generate carbon defects on the outer wall of the carbon nano tube;
heating to 1000 ℃ at a speed of 10 ℃/min under argon atmosphere, introducing 80ml/min of methane, 20ml/min of hydrogen and 100ml/min of argon, and preserving heat for 1h;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nano tube composite material, wherein the graphene-carbon nano fiber-1 is marked.
And (3) performing transmission electron microscopy on the obtained graphene-carbon nanotube composite material, wherein a TEM image is shown in fig. 2. As can be seen from fig. 2 (a), graphene is uniformly distributed on the surface of the carbon nanotube. As can be seen from the lattice fringe distribution at the interface of graphene and carbon nanotubes in FIG. 2 (b), the interface of the two is in sp 2 And (3) carbon connection, wherein graphene is epitaxially grown on the outer wall of the carbon nanotube.
Example 2
This example used the same starting materials and synthesis as example 1, except that: heating to 1000 ℃ at a speed of 10 ℃/min under argon atmosphere, introducing 80ml/min of methane, 20ml/min of hydrogen and 100ml/min of argon, and preserving heat for 3 hours to obtain the graphene-carbon nano tube composite material, wherein the graphene-carbon nano fiber-2 is marked.
Transmission electron microscopy was performed on the graphene-carbon nanofiber-2 obtained in example 2, and the obtained TEM image was shown in fig. 3. As can be seen from fig. 3, graphene uniformly grows on the carbon nanotubes, and compared with the graphene-carbon nanofiber-1 of example 1, the size and density of graphene are significantly increased after the growth time is prolonged.
Example 3
Commercial bacterial cellulose available from Hainan food Co., ltd.
Placing bacterial cellulose in a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under argon atmosphere, then introducing mixed gas of hydrogen gas with the concentration of 20ml/min and argon gas with the concentration of 180ml/min into the tube furnace, and preserving heat for 30min, so that carbon defects are generated on the surface of the bacterial cellulose while carbonizing the bacterial cellulose;
continuously heating to 1000 ℃ at a speed of 10 ℃/min under argon atmosphere, then introducing 60ml/min of methane, 20ml/min of hydrogen and 120ml/min of argon, and preserving heat for 2h;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nanofiber composite material, wherein the graphene-carbon nanofiber composite material is marked as graphene-carbon nanofiber-3.
And carrying out scanning electron microscope and transmission electron microscope tests on the obtained graphene-carbon nanofiber composite material, wherein the obtained test results are shown in fig. 4. Fig. 4 (a) and (b) are SEM images and TEM images, respectively, and it can be seen from fig. 4 that graphene is uniformly distributed on the surface of carbon nanofibers, and the carbon nanofibers are connected to each other in a three-dimensional network structure.
Example 4
And (3) adopting a synthesized carbon nano tube sponge.
The preparation process of the carbon nanotube sponge comprises the following steps: the catalyst ferrocene was dissolved in liquid carbon source 1, 2-dichlorobenzene to give a precursor solution at a concentration of 0.06 g/ml. The precursor solution was injected into a tube furnace at a rate of 0.03ml/min in a preheating zone (250 ℃ C.) and vaporized from Ar/H 2 Mixed carrier gas (Ar: H) 2 =1:5) bringing the vaporized precursor into a tube furnace reaction zone (860 ℃) for reaction. Keeping the temperature constant and growing for 60min, naturally cooling, and then obtaining carbon nanotube sponge on the wall of the quartz tube;
placing the carbon nano tube sponge into a tube furnace, heating to 730 ℃ at a speed of 20 ℃/min under an argon atmosphere, then introducing mixed gas of 20ml/min of acetylene and 180ml/min of argon, and preserving heat for 20min to generate carbon defects on the outer wall of the carbon nano tube;
heating to 1000 ℃ at a speed of 10 ℃/min under argon atmosphere, introducing 60ml/min of methane, 20ml/min of hydrogen and 120ml/min of argon, and preserving heat for 3h;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nanotube sponge composite material, wherein the graphene-carbon nanofiber-4 is marked.
Comparative example
Comparative example 1
Commercial bacterial cellulose available from Hainan food Co., ltd.
And (3) placing the bacterial cellulose in a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min under the argon atmosphere, and preserving heat for 2 hours to obtain the carbon nanofiber, wherein the carbon nanofiber is marked as carbon nanofiber-3.
Comparative example 2
And (3) adopting a synthesized carbon nano tube sponge.
The preparation process of the carbon nanotube sponge comprises the following steps: the catalyst ferrocene was dissolved in liquid carbon source 1, 2-dichlorobenzene to give a precursor solution at a concentration of 0.06 g/ml. The precursor solution was injected into a tube furnace at a rate of 0.03ml/min in a preheating zone (250 ℃ C.) and vaporized from Ar/H 2 Mixed carrier gas (Ar: H) 2 =1:5) bringing the vaporized precursor into a tube furnace reaction zone (860 ℃) for reaction. And keeping the temperature constant and growing for a certain time, naturally cooling, and then obtaining the carbon nanotube sponge on the wall of the quartz tube, wherein the carbon nanotube sponge is marked as carbon nanofiber-4.
Experimental example
The mechanical properties of the carbon nanotube sponge after graphene growth can be significantly improved, in particular the strength, stress and elasticity. The graphene-carbon nanotube sponge composite material obtained in example 4 and the carbon nanotube sponge obtained in comparative example 2 were subjected to stress strain test, and the test results are shown in fig. 5 (a).
As can be seen from fig. 5 (a), the stress of graphene-carbon nanofiber-4 after graphene growth is significantly improved under the same degree of strain. The stress of the graphene-carbon nanofiber-4 can reach more than 1.0MPa, for example, when the strain is 70%, the stress of the graphene-carbon nanofiber-4 is more than 10 times that of the carbon nanofiber-4.
Conductivity tests were performed on the graphene-carbon nanofiber composite material obtained in examples 3 to 4, the carbon nanofiber-3 obtained in comparative example 1, the carbon nanofiber-4 obtained in comparative example 2, and commercial carbon cloth (Shanghusen electric Co., ltd. HCP 330P) at room temperature using a KDY-1 four-probe resistivity/sheet resistance tester (Kunlun technologies Co., ltd.) using a four-probe method, and each sample was tested five times and averaged, and the test results were shown in FIG. 5 (b).
As can be seen from FIG. 5 (b), the conductivities of the carbon nanofiber-3 and the carbon nanofiber-4 were 3.03X10, respectively 2 S/m and 4.56X10 2 S/m, and the conductivities of the graphene-carbon nanofiber composites obtained in examples 3 and 4 were 1.244×10, respectively 3 S/m and 2.821X 10 3 S/m is far higher than the carbon nanofiber-3 and the carbon nanofiber-4 which do not grow graphene, 4-7 times of the carbon nanofiber which do not grow graphene, and the conductivity is obviously better than that of commercial carbon cloth by 5.51 multiplied by 10 2 S/m。
The invention has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and scope of the present invention, which all fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (2)
1. A preparation method of a graphene-carbon nanofiber composite material is characterized in that graphene grows on the surface of carbon nanofibers, and sp is used between the graphene and the carbon nanofibers 2 Carbon connection, wherein the carbon nano fiber is a carbon nano tube, the carbon nano tube is a carbon nano tube sponge,
the method comprises the following steps:
step 1, forming carbon defects on carbon nanofibers, wherein the carbon nanofibers are carbon nanotubes, and the carbon nanotubes are 20-30 nm;
the forming of carbon defects on the carbon nanofibers includes:
step 1.1, placing carbon nanofibers in an oxygen-free environment, and heating to 600-1000 ℃;
step 1.2, introducing reaction gas and first inert gas, preserving heat for 10-50 min, wherein the reaction gas is hydrogen, the first inert gas is argon, nitrogen or helium, and the flow ratio of the reaction gas to the first inert gas is 1: (1-9);
step 2, growing graphene on the carbon defects, including: heating to 1000-1500 ℃, wherein the heating rate is 2-10 ℃/min, introducing hydrogen, carbon source gas and second inert gas, preserving heat for 120-180 min, and the flow ratio of the hydrogen, the carbon source gas and the second inert gas is 1: (1-4): (1-8), wherein the carbon source gas is methane.
2. The method according to claim 1, wherein in step 1.2, the incubation time is 20 to 30 minutes.
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| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
| CN109468711A (en) * | 2018-09-28 | 2019-03-15 | 北京化工大学 | Carbon nanotube-graphene composite fibre and its preparation method and application |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
| CN109468711A (en) * | 2018-09-28 | 2019-03-15 | 北京化工大学 | Carbon nanotube-graphene composite fibre and its preparation method and application |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
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