CN114150497A - 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 material and a preparation method thereof, wherein graphene grows on the surface of carbon nanofiber, and sp is formed between the graphene and the carbon nanofiber2Carbon attachment. 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 method is based on the principle of thermal chemical vapor deposition, the size and the density of the graphene on the surface of the carbon nanofiber can be controlled by controlling the growth conditions, and the graphene is uniformly distributed on the surface of the carbon nanofiber. The preparation method is simple, does not need metal catalysts or plasma assistance, has wide raw material sources, 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 nano fiber has the advantages of high strength, high modulus, low density, low radiation absorption, corrosion resistance, electric conduction, heat conduction and the like, and can be widely applied to the fields of aerospace, automobile manufacturing, national defense, military industry and the like. Graphene is a carbon atom sp2The two-dimensional carbon nanomaterial formed by hybridization has excellent mechanical, electrical and thermal properties. Compounding graphene with carbon nanofibersThe mechanical property and the electric and heat conducting properties of the carbon fiber are enhanced, and the composite material with more excellent performance is obtained.
Many methods of preparing graphene and carbon nanofiber composites have been developed in recent years. The most common method is physical mixing. For example, the dispersed graphene solution is mixed with carbon nanofibers, so that graphene is adsorbed on the surface of carbon fibers. Composites obtained using this method tend to be poor in both uniformity and stability, affecting many properties of the composite. Another method is to connect the graphene and the carbon nanofibers by chemical bonds. Such as amide bond formation at the interface of graphene and carbon nanofibers via chemical reaction. Compared with physical mixing, the chemically bonded graphene and the carbon nanofiber have stronger interaction force, and the overall performance of the obtained product is improved. However, the current method has a complex preparation process, uniform compounding of graphene and carbon nanofibers is difficult to control uniformly, and the bonding effect between the obtained graphene and carbon nanofibers is still weak.
Therefore, the development of a method which can uniformly and stably compound graphene and carbon nanofibers and is expected to realize mass preparation is very important for promoting the application of the carbon nanofiber.
Disclosure of Invention
In order to overcome the above problems, the present inventors have conducted intensive studies to develop a graphene-carbon nanofiber composite material and a method for preparing the same. Based on a thermal chemical vapor deposition method, the structure of the carbon nanofiber is firstly destroyed, uneven carbon defects are formed on the surface of the carbon nanofiber, and the activity of the carbon defects is high. And then reacting with a carbon source gas at high temperature, wherein the carbon defects serve as nucleation centers for graphene growth, so that the graphene epitaxially grows on the carbon nanofibers. Sp is formed between graphene and carbon nano fiber in the obtained composite material2And carbon connection is carried out, so that the graphene is uniform and stable on the surface of the carbon nanofiber. The obtained composite material has excellent conductivity, the preparation method is simple, metal catalysts or plasma assistance is not needed, the raw material source is wide, the cost is low, and mass preparation can be realized, so that the invention is completed.
An object of the present invention is to provide a graphene-carbon nanofiber composite material, in which graphene is grown on a surface of a carbon nanofiber, and sp is formed between the graphene and the carbon nanofiber2Carbon attachment.
The carbon nano-fiber is a one-dimensional carbon nano-material, and is preferably selected from one or more of carbon nano-tube, biomass derived carbon fiber and macromolecule derived carbon fiber.
Another aspect of the present invention provides a method for preparing a graphene-carbon nanofiber composite, the method comprising the steps of:
and 2, growing graphene on the carbon defects.
step 1.1, placing the carbon nanofiber or the precursor of the carbon nanofiber in an oxygen-free environment, and heating;
and step 1.2, introducing reaction gas and first inert gas, and preserving heat.
In step 1.1, the temperature is raised to 400-1200 ℃, preferably to 500-1100 ℃.
In the step 1.2, the reaction gas is selected from one or more of hydrocarbons, alcohols, aldehydes and reducing gas, and the reducing gas is selected from one or more of water, carbon dioxide, carbon monoxide, ammonia gas 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: and (4) heating, introducing hydrogen, carbon source gas and second inert gas, and preserving heat.
In step 2, the temperature is raised to 800-1800 ℃, preferably 900-1500 ℃.
The flow ratio of the hydrogen gas, the carbon source gas and the second inert gas is 1: (1-5): (1-10).
In a further aspect of the present invention, there is provided a graphene-carbon nanofiber composite prepared according to the method of the second aspect of the present invention.
The invention has the following beneficial effects:
(1) in the graphene-carbon nanofiber composite material provided by the invention, sp is arranged between the graphene and the carbon nanofiber interface2Carbon connection, strong bonding effect and uniform distribution of graphene on the carbon nanofibers;
(2) the method is based on a thermochemical 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-defect positions is low, so that graphene grows along the carbon nanofiber at the carbon defects in an epitaxial manner, and a metal catalyst or plasma assistance is not required to be added in the whole preparation process;
(3) the composite material product obtained by the invention has high quality, the growth size of the graphene on the surface of the carbon nanofiber is controllable, the density is uniform, and the obtained composite material has excellent conductivity and mechanical property;
(4) the preparation method provided by the invention is simple, wide in raw material source, low in cost and capable of realizing large-scale preparation.
Drawings
Fig. 1 shows a schematic structural view 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 prepared in example 1 of the present invention;
fig. 3 shows a TEM image of the graphene-carbon nanotube composite prepared in example 2 of the present invention;
fig. 4 shows an SEM image and a TEM image of the graphene-carbon nanofiber composite 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.
The reference numbers illustrate:
1-carbon nanofibers;
2-graphene.
Detailed Description
The invention is explained in more detail below with reference to the drawings and 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 a surface of a carbon nanofiber, and the graphene and the carbon nanofiber pass through sp2Carbon attachment.
According to the invention, graphene is epitaxially grown on the outer wall of the carbon nanofiber, and the grown graphene is uniformly distributed on the carbon nanofiber.
According to the present invention, as shown in fig. 1, a schematic structural diagram of a graphene-carbon nanofiber composite, 1-carbon nanofiber, 2-graphene, is provided, wherein the graphene-carbon nanofiber composite is obtained by directly growing graphene on carbon defects on the surface of carbon nanofiber, and the graphene is obtained by sp (sp)2The carbon is attached to the surface of the carbon nanofibers as seen in the side and top views.
According to the invention, the composite material is obtained based on the chemical vapor deposition principle, the size and the density of the graphene on the surface of the carbon nanofiber can be controlled by controlling the growth conditions, namely the growth size of the graphene on the surface of the carbon nanofiber is controllable, and the graphene is uniform in 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 polymer-derived carbon fiber and the like.
According to the invention, the carbon nanotube is one or more of a multi-wall carbon nanotube, a single-wall carbon nanotube and a carbon nanotube sponge, preferably the multi-wall carbon nanotube or the carbon nanotube sponge, and the diameter of the carbon nanotube is not particularly limited, preferably 20-30 nm.
According to the present invention, the carbon nanotube sponge is self-made, and preferably, the carbon nanotube sponge is prepared by the following method:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a precursor solution;
injecting the precursor solution into a tubular furnace in a preheating zone and vaporizing, and introducing the vaporized precursor into a reaction zone of the tubular furnace by using a mixed gas of argon and hydrogen to react;
preserving the heat for a certain time, and naturally cooling to obtain the carbon nano tube sponge on the wall of the quartz tube.
According to a preferred embodiment of the present 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 feed rate of the precursor solution is between 0.02 and 0.2ml/min, preferably 0.03 ml/min.
According to the preferred embodiment of the invention, the temperature of the preheating zone is 220-280 ℃, preferably 250 ℃, and the temperature of the reaction zone is 820-900 ℃, preferably 860 ℃;
the flow ratio of argon to hydrogen is 1: (4-6), preferably 1: 5.
according to the preferred embodiment of the present invention, the heat-preserving time is 30 to 240 min.
According to a preferred embodiment of the present invention, the graphene-carbon nanofiber composite has excellent conductivity and mechanical properties, and the conductivity of the graphene-carbon nanofiber composite is more than 3 times, preferably 4 to 7 times, that of the carbon nanofiber without graphene growth.
According to a preferred embodiment of the present invention, when the carbon nanofiber is a carbon nanotube sponge, the electrical conductivity of the obtained graphene-carbon nanofiber composite is higher than 8.0 × 102S/m, preferably higher than 1.0X 103S/m, more preferably 1.2 to 3X 103S/m。
According to a preferred embodiment of the present invention, the graphene-grown carbon nanofibers have excellent mechanical properties, for example, the graphene-carbon nanofibers can have a stress 10 times or more that of the non-graphene-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 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 of the carbon defect on the outer wall of the carbon nanofiber comprises:
step 1.1, placing the carbon nanofiber or the precursor of the carbon nanofiber in an oxygen-free environment, and heating;
and step 1.2, introducing reaction gas and first inert gas, and preserving heat.
According to the invention, in step 1.1, the precursor of the carbon nanofiber is a precursor of biomass-derived carbon fiber or a precursor of polymer-derived carbon fiber,
preferably, the precursor of the carbon nanofiber is bacterial cellulose or polymer fiber.
According to a preferred embodiment of the invention, the bacterial cellulose is commercially available, such as commercial bacterial cellulose available from Hainan Yide food Co.
According to the invention, in step 1.1, the oxygen-free atmosphere is a nitrogen or noble gas atmosphere, preferably a nitrogen, argon or helium atmosphere.
According to the invention, in step 1.1, the temperature is raised to 400-1200 ℃, preferably 500-1100 ℃, and more preferably 600-1000 ℃.
According to a preferred embodiment of the present invention, in step 1.1,
when the carbon nano-fiber is selected from the carbon nano-tubes, heating to 800-1000 ℃, for example 900 ℃;
when the biomass-derived carbon fiber is selected as the carbon nanofiber, the temperature is raised to 600-800 ℃, for example, 700 ℃.
According to the invention, in step 1.1, the temperature rise rate is not particularly limited in the temperature rise process, preferably, the temperature rise rate is 1-20 ℃/min, and more preferably, the temperature rise rate is 2-10 ℃/min.
According to the invention, in step 1.2, reaction gas and 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 hydrocarbons, alcohols, aldehydes or reducing gases.
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 gas and hydrogen.
According to a preferred embodiment of the present 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 200 ml/min.
According to the invention, the heat preservation time is 1-60 min, preferably 10-50 min, and more preferably 20-30 min.
In the invention, too short heat preservation time can cause that the surface of the carbon nanofiber does not generate enough carbon defects, so that graphene cannot grow, too long heat preservation time is not beneficial to waste of reaction raw materials, efficiency is reduced, and energy conservation is not facilitated.
In the present invention, when the precursor of the carbon nanofiber is used as a raw material to form the carbon defect in step 1, the precursor of the carbon nanofiber is carbonized at a high temperature to form the carbon nanofiber, and the carbon defect is simultaneously generated on the surface of the formed carbon nanofiber.
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 nanofiber is placed in the reaction gas to be treated at high temperature, and the original structure of the carbon nanofiber is destroyed by controlling the conditions of the flow rate of the reaction gas, the temperature, the time and the like, so that uneven carbon defects are formed on the surface of the carbon nanofiber. The formed carbon defects have a plurality of dangling bonds with higher activity, have higher chemical activity at high temperature compared with other flat areas, and preferentially react with a carbon source to be used as nucleation centers for growing the graphene. Due to the fact that defect activity is high, non-defect activity around the defect is low, and graphene grows perpendicular to the outer wall of the carbon nanofiber.
According to the method, based on the thermal chemical vapor deposition principle, a carbon source is added, the temperature and the gas flow are controlled, and the graphene is directly grown on the carbon defects without adding a metal catalyst or assisting by plasma.
According to the invention, step 2, the epitaxially growing graphene on the carbon defects comprises: and (4) 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 present invention, the temperature after the temperature rise in step 2 is higher than the temperature after the temperature rise in step 1.
According to the invention, in step 2, after the heat preservation in step 1 is finished, the temperature is continuously raised to 800-1800 ℃, preferably 1000-1800 ℃, more preferably 1000-1500 ℃, for example 1000 ℃.
In the invention, the structure of the graphene can be ensured to grow at the temperature.
According to the invention, in the step 2, the heating rate is 1-20 ℃/min, preferably 2-10 ℃/min.
According to the present invention, in step 2, the carbon source gas is not particularly limited, and may be a carbon source gas commonly used in the art, and preferably, the carbon source gas is a low molecular organic compound selected from one or more of methanol, ethanol, methane, ethane, ethylene, acetylene, and the like, and for example, the carbon source gas is methane.
In the invention, the carbon source gas is cracked at high temperature, and the carbon source gas can nucleate at the defects on the surface of the carbon nanofiber preferentially to form a local graphitized region, and then the graphene is further epitaxially grown.
According to the present 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 present invention, the flow rates of hydrogen and carbon source gases have a large influence on the graphitization degree and growth rate of the product. When the flow rates of hydrogen and carbon source gases are relatively low, the growth speed of graphene on the surface of the carbon nanofiber is relatively high, but the graphitization degree is relatively low. When the flow rate is relatively high, the growth speed of graphene on the surface of the carbon nanofiber is relatively slow, but the graphitization degree is relatively high. The flow ratio of the hydrogen to the carbon source gas in a proper range can ensure proper growth speed and graphitization degree of graphene on the carbon nanofiber so as to obtain the graphene-carbon nanofiber composite material with excellent performance.
According to the present invention, in step 2, the incubation time is not particularly limited, and the desired size and density of graphene may be obtained. The growth time is prolonged, the density and the size of the obtained graphene are remarkably increased, and preferably, the heat preservation time is 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 growth of graphene. The heat preservation time is too long, which causes waste of reaction raw materials and reduces efficiency, thus being not beneficial to energy conservation.
According to the invention, in 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 a nitrogen atmosphere. In the composite material, graphene grows on the surface of the carbon nanofiber and is vertically generated outside the carbon nanofiber, and sp is relied between the graphene and the carbon nanofiber2Carbon attachment.
In the invention, under the conditions of high temperature and hydrogen gas, the carbon source gas is cracked to nucleate on the carbon defects with high activity to form a local graphitized region, and graphene is epitaxially grown, and the grown graphene is uniformly distributed on the carbon nano-fiber.
According to a preferred embodiment of the present invention, when the carbon nanofibers are carbon nanotube sponges, the obtained graphene-carbon nanotubes are graphene-carbon nanotubesThe electrical conductivity of the fiber composite material is higher than 8.0 x 102S/m, preferably higher than 1.0X 103S/m, more preferably (1.2 to 3). times.103S/m。
The method is based on a chemical vapor deposition method, the carbon defects are formed on the surface of the one-dimensional carbon nanofiber, the two-dimensional graphene is directly grown on the carbon defects, and the graphene-carbon nanofiber composite material is obtained without a metal catalyst. Depends on sp between graphene and carbon nano-fiber2The carbon is connected, so that the combination of the graphene and the carbon nanofiber is stable, the mechanical property and the electric and heat conducting properties of the carbon nanofiber are enhanced, and the obtained composite material has excellent comprehensive properties.
In sp2The structure of the composite material is more uniform and stable due to the carbon-connected graphene and the carbon nanofiber, the bonding 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, strong product repeatability and capability of large-scale preparation.
Examples
Example 1
The carbon nanotubes adopted are commercial multi-walled carbon nanotubes purchased from Nanjing Xiancheng nanomaterial science and technology Limited, type: XFM21, the diameter is 20-30 nm.
Placing a carbon nano tube in a tube furnace, heating to 900 ℃ at the speed of 10 ℃/min under the argon atmosphere, then introducing mixed gas of 50ml/min ammonia gas and 50ml/min argon gas, and preserving heat for 20min to generate carbon defects on the outer wall of the carbon nano tube;
heating to 1000 ℃ at the speed of 10 ℃/min under the argon atmosphere, introducing 80ml/min methane, 20ml/min hydrogen and 100ml/min argon, and preserving heat for 1 h;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nanotube composite material which is marked as graphene-carbon nanofiber-1.
The obtained graphene-carbon nanotube composite material was tested by transmission electron microscopy, and the obtained 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 distribution of the lattice fringes at the interface between graphene and carbon nanotubes in FIG. 2(b), the interface between the two is sp2And carbon is connected, and graphene is epitaxially grown on the outer wall of the carbon nanotube.
Example 2
This example uses the same raw materials and synthesis method as example 1, except that: heating to 1000 ℃ at the speed of 10 ℃/min under the argon atmosphere, introducing 80ml/min methane, 20ml/min hydrogen and 100ml/min argon, and preserving heat for 3 hours to obtain the graphene-carbon nanotube composite material which is marked as graphene-carbon nanofiber-2.
The graphene-carbon nanofiber-2 obtained in example 2 was subjected to a transmission electron microscope test, and the obtained TEM image is shown in fig. 3. As can be seen from fig. 3, graphene is uniformly grown on the carbon nanotube, and as can be seen by comparing 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 from Hainan foods GmbH was used.
Placing the bacterial cellulose in a tubular furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under the argon atmosphere, then introducing a hydrogen gas of 20ml/min and an argon gas mixture of 180ml/min into the tubular furnace, preserving the heat for 30min, and generating carbon defects on the surface of the bacterial cellulose while carbonizing the bacterial cellulose;
under the argon atmosphere, continuously heating to 1000 ℃ at the speed of 10 ℃/min, introducing 60ml/min methane, 20ml/min hydrogen and 120ml/min argon, and preserving heat for 2 hours;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nanofiber composite material which is marked as graphene-carbon nanofiber-3.
Scanning electron microscope and transmission electron microscope tests are performed on the obtained graphene-carbon nanofiber composite material, and the obtained test results are shown in fig. 4. Fig. 4(a) and (b) are SEM and TEM images, respectively, and it can be seen from fig. 4 that graphene is uniformly distributed on the surface of the carbon nanofibers and the carbon nanofibers are connected to each other in a three-dimensional network structure.
Example 4
A synthetic carbon nanotube sponge was used.
The preparation process of the carbon nanotube sponge comprises the following steps: the catalyst ferrocene is dissolved in a liquid carbon source 1, 2-dichlorobenzene to obtain a precursor solution with the concentration of 0.06 g/ml. The precursor solution was injected into the tube furnace in a preheating zone (250 ℃) at a rate of 0.03ml/min and vaporized from Ar/H2Mixed carrier gas (Ar: H)21:5) the vaporized precursor is carried into a tube furnace reaction zone (860 ℃) to react. Keeping the temperature constant for growth for 60min, and naturally cooling to obtain carbon nanotube sponge on the wall of the quartz tube;
placing carbon nanotube sponge in a tube furnace, heating to 730 ℃ at the speed of 20 ℃/min under the argon atmosphere, then introducing 20ml/min acetylene and 180ml/min argon mixed gas, and preserving heat for 20min to generate carbon defects on the outer wall of the carbon nanotube;
heating to 1000 ℃ at the speed of 10 ℃/min under the argon atmosphere, introducing 60ml/min methane, 20ml/min hydrogen and 120ml/min argon, and preserving heat for 3 hours;
and cooling to room temperature under the protection of argon to obtain the graphene-carbon nanotube sponge composite material which is marked as graphene-carbon nanofiber-4.
Comparative example
Comparative example 1
Commercial bacterial cellulose from Hainan foods GmbH was used.
Placing the bacterial cellulose in a tube furnace, heating to 1000 ℃ at the heating rate of 10 ℃/min under the argon atmosphere, and preserving the temperature for 2h to obtain the carbon nanofiber, wherein the label of the carbon nanofiber is carbon nanofiber-3.
Comparative example 2
A synthetic carbon nanotube sponge was used.
The preparation process of the carbon nanotube sponge comprises the following steps: the catalyst ferrocene is dissolved in a liquid carbon source 1, 2-dichlorobenzene to obtain a precursor solution with the concentration of 0.06 g/ml. In a preheating zoneInjecting the precursor solution into a tube furnace at the speed of 0.03ml/min at the temperature of 250 ℃ and vaporizing the precursor solution by Ar/H2Mixed carrier gas (Ar: H)21:5) the vaporized precursor is carried into a tube furnace reaction zone (860 ℃) to react. Keeping the temperature constant and growing for a certain time, naturally cooling to obtain carbon nanotube sponge on the wall of the quartz tube, and marking the carbon nanotube sponge as carbon nanofiber-4.
Examples of the experiments
The mechanical properties of the carbon nanotube sponge after graphene growth can be remarkably improved, particularly the strength, stress and elasticity. The graphene-carbon nanotube sponge composite obtained in example 4 and the carbon nanotube sponge obtained in comparative example 2 were subjected to a stress-strain test, and the test results are shown in fig. 5 (a).
As can be seen from fig. 5(a), the stress of the graphene-carbon nanofiber-4 after graphene growth is significantly increased 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.
The graphene-carbon nanofiber composites 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 a commercial carbon cloth (shanghai hesen electric limited 330 HCP330P) were subjected to conductivity tests at room temperature using a KDY-1 type four-probe resistivity/sheet resistance tester (queenson technologies ltd., guangzhou) by a four-probe method, respectively, five times for each sample and averaged, and the test results were shown in fig. 5 (b).
As can be seen from FIG. 5(b), the electrical conductivities of the carbon nanofiber-3 and the carbon nanofiber-4 were 3.03X 10, respectively2S/m and 4.56X 102S/m, and the electrical conductivity of the graphene-carbon nanofiber composites obtained in examples 3 and 4 was 1.244X 103S/m and 2.821X 103S/m is far higher than that of carbon nanofiber-3 and carbon nanofiber-4 of non-grown graphene, is 4-7 times of that of the carbon nanofiber of the non-grown graphene, and is obviously superior to that of a commercial carbon cloth in conductivity of 5.51 multiplied by 102S/m。
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A graphene-carbon nanofiber composite material, wherein graphene grows on the surface of a carbon nanofiber, and sp is formed between the graphene and the carbon nanofiber2Carbon attachment.
2. The composite material according to claim 1, wherein the carbon nanofibers are one-dimensional carbon nanomaterials, preferably selected from one or more of carbon nanotubes, biomass-derived carbon fibers, and polymer-derived carbon fibers.
3. A preparation method of a graphene-carbon nanofiber composite material is characterized by comprising the following steps:
step 1, forming carbon defects on carbon nanofibers;
and 2, growing graphene on the carbon defects.
4. The method of claim 3, wherein step 1, the forming carbon defects on the carbon nanofibers comprises:
step 1.1, placing the carbon nanofiber or the precursor of the carbon nanofiber in an oxygen-free environment, and heating;
and step 1.2, introducing reaction gas and first inert gas, and preserving heat.
5. The method according to claim 4, wherein in step 1.1, the temperature is raised to 400-1200 ℃, preferably to 500-1100 ℃.
6. The method according to claim 4, wherein in step 1.2, the reaction gas is selected from one or more of hydrocarbons, alcohols, aldehydes and reducing gases, and the reducing gases are selected from one or more of water, carbon dioxide, carbon monoxide, ammonia gas and hydrogen gas; and/or
The flow ratio of the reaction gas to the first inert gas is 1: (1 to 10), preferably 1: (1-9).
7. The method of claim 3, wherein step 2, growing graphene on the carbon defects comprises: and (4) heating, introducing hydrogen, carbon source gas and second inert gas, and preserving heat.
8. The method according to claim 7, wherein the temperature is raised to 800 to 1800 ℃, preferably 900 to 1500 ℃ in step 2.
9. The method of claim 7 or 8, wherein the flow ratio of the hydrogen gas, the carbon source gas, and the second inert gas is 1: (1-5): (1-10).
10. Graphene-carbon nanofiber composite material prepared according to the method of one of claims 3 to 9.
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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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| 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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