CN107938323B - Graphene carbon fiber, preparation method and application thereof - Google Patents
Graphene carbon fiber, preparation method and application thereof Download PDFInfo
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- CN107938323B CN107938323B CN201810004622.XA CN201810004622A CN107938323B CN 107938323 B CN107938323 B CN 107938323B CN 201810004622 A CN201810004622 A CN 201810004622A CN 107938323 B CN107938323 B CN 107938323B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- D06M2101/40—Fibres of carbon
Abstract
The invention provides graphene carbon fibers, a preparation method and application thereof, and belongs to the technical field of graphene and carbon fiber composite materials. The preparation method of the graphene carbon fiber comprises the following steps: and adding carbon fibers into the alloy complexing liquid, and soaking for 15-30 min to obtain a carbon fiber wet material. And drying the wet carbon fiber material to obtain a dry carbon fiber material containing the active assistant. And heating the carbon fiber dry material to 600-900 ℃ in an inert gas atmosphere, introducing multi-carbon cracking gas, and carrying out CVD reaction for 0.5-2 h under the catalytic cracking action of the active auxiliary agent. The preparation method enables graphene to grow in a carbon fiber interlayer in an in-situ deposition manner, improves the interlayer structure, and obtains the graphene carbon fiber which has good electrical conductivity and thermal conductivity and can be used as a novel electrical and thermal conductive composite material for application.
Description
Technical Field
The invention relates to the technical field of carbon fiber composite materials, in particular to graphene carbon fibers, and a preparation method and application thereof.
Background
Carbon Fiber (CF) is a new fiber material of high-strength and high-modulus fiber with carbon content above 95%. It is made up by stacking organic fibres of flake graphite microcrystals along the axial direction of fibre, and making carbonization and graphitization treatment so as to obtain the invented microcrystal graphite material. The carbon fiber is flexible outside and rigid inside, has lighter weight than metal aluminum, higher strength than steel, corrosion resistance and high modulus, and is an important material in national defense, military industry and civil use. It not only has the intrinsic characteristic of carbon material, but also has the soft workability of textile fiber, and is a new generation of reinforced fiber.
The structure of carbon fibers consists of two-dimensionally ordered crystals and pores, wherein the content, size and distribution of the pores have a greater influence on the properties of the carbon fibers. The pores are distributed mainly between the fiber bundles and at the interface between the layers. The higher the void content, the larger the void size, which reduces the area of the interlayer interface in the laminate, and is prone to failure along the layers when the material is stressed, which is why the interlayer shear strength is relatively sensitive to voids. In addition, the pore is a stress concentration area, the bearing capacity is weak, and when the stress is applied, the pore is expanded to form a long crack, so that the crack is damaged.
Due to the fact that a plurality of macropore defects are left between layers of the carbon fiber, electron cloud distribution is uneven, electron transmission is hindered, and the electrical conductivity and the thermal conductivity of the material are poor.
Disclosure of Invention
The invention aims to provide a preparation method of graphene carbon fibers, which is characterized in that multi-carbon pyrolysis gas is cracked and deposited at a lower temperature under the catalytic action of an alloy active auxiliary agent, so that graphene is finally grown and compounded in situ between carbon fiber layers, and the interlayer structure of the fibers is improved.
The invention also aims to provide the graphene carbon fiber prepared by the preparation method, which has good electrical conductivity and thermal conductivity.
The third purpose of the invention is to provide an application of graphene carbon fiber as a conductive and heat-conducting material, which can be used for preparing products such as carbon paper, carbon felt and the like in the fields of infrared electric heating, electric dust removal, environmental protection, electromagnetic shielding and the like.
The invention is realized by adopting the following technical scheme:
a preparation method of graphene carbon fibers comprises the following steps:
(1) adding carbon fibers into the alloy complexing liquid, and soaking for 15-30 min to obtain a carbon fiber wet material;
(2) drying the wet carbon fiber material to obtain a dry carbon fiber material containing the active assistant;
(3) and heating the carbon fiber dry material to 600-900 ℃ in an inert gas atmosphere, introducing multi-carbon cracking gas, and finishing the CVD reaction for 0.5-2 h under the catalytic cracking action of the active auxiliary agent.
Further, in a preferred embodiment of the present invention, the preparation method of the alloy complex liquid comprises: adding the copper-chromium alloy auxiliary agent into water, stirring for 10-15 min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 4-8 h at the temperature of 80-90 ℃.
Further, in a preferred embodiment of the present invention, the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 1 to 2.
Further, in a preferred embodiment of the present invention, in the step (1), the mass ratio of the carbon fibers to the alloy complex liquid is 1: 8 to 10.
Further, in a preferred embodiment of the present invention, in the step (2), the drying is performed at a temperature of 120 to 160 ℃ for 4 to 6 hours.
Further, in a preferred embodiment of the present invention, in the step (3), the multi-carbon pyrolysis gas is at least one selected from methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, ethylene, propylene, n-butene and isobutene.
Further, in a preferred embodiment of the present invention, the step (3) further comprises the step of monitoring the volume percentage of hydrogen in the tail gas of the fluidized bed reactor.
Further, in a preferred embodiment of the present invention, after the step (3), the step of stopping the introduction of the multi-carbon pyrolysis gas, stopping heating, cooling to 20-30 ℃, stopping the introduction of the inert gas, and removing the obtained graphene carbon fiber is further included.
The graphene carbon fiber prepared by the preparation method of the graphene carbon fiber.
The graphene carbon fiber is applied as an electric conduction material and a heat conduction material.
The preparation method of the graphene carbon fiber provided by the preferred embodiment of the invention has the beneficial effects that: adding carbon fibers into the alloy complexing liquid, and soaking for 15-30 min to obtain a carbon fiber wet material, so that the alloy complexing liquid can fully enter an interlayer structure of the carbon fibers or pores of the carbon fibers. And drying the wet carbon fiber material to obtain a dry carbon fiber material, removing water in the wet carbon fiber material, and facilitating subsequent reaction by the residual alloy active auxiliary agent. Heating the carbon fiber dry material to 600-900 ℃ in an inert gas atmosphere, introducing multi-carbon cracking gas, carrying out catalytic cracking by using an active additive, and carrying out a CVD reaction for 0.5-2 h. Under the inert gas atmosphere, the dry carbon fiber material is prevented from contacting oxygen in the air, the carbon fiber is prevented from burning after subsequent heating, after the carbon fiber is heated to 600-900 ℃, the multi-carbon pyrolysis gas is introduced for CVD reaction for 0.5-2 h, the multi-carbon pyrolysis gas is introduced at high temperature, due to the catalytic action of the alloy active auxiliary agent, the multi-carbon pyrolysis gas is subjected to cracking deposition reaction at relatively low temperature, finally, in-situ growth is carried out in the carbon fiber interlayer structure and pores to generate graphene, the interlayer structure is improved, and the obtained graphene carbon fiber has good electrical conductivity and thermal conductivity.
The graphene carbon fiber provided by the invention has the beneficial effects that: the graphene carbon fiber is prepared by the preparation method, the interlayer structure of the carbon fiber and the pores of the carbon fiber are modified by the mesoporous graphene, so that the electron cloud distribution is more uniform, the electron transfer efficiency of the interlayer structure of the carbon fiber is increased, and the electrical conductivity and the thermal conductivity of the graphene carbon fiber are improved.
The application of the graphene carbon fiber provided by the invention has the beneficial effects that: the carbon paper can be used as a conductive material and a heat conductive material, can be used for preparing products such as carbon paper, carbon felt and the like in the fields of infrared electric heating, electric dust removal, environmental protection, electromagnetic shielding and the like, meets the requirements of customers, and has good commercial value.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without creative efforts, and the protection scope of the present invention also belongs to the protection scope of the present invention.
Fig. 1 is a process flow diagram of a preparation method of graphene carbon fibers provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphene carbon fiber, the preparation method thereof, and the application thereof according to the embodiments of the present invention are specifically described below.
Fig. 1 is a process flow diagram of a preparation method of graphene carbon fibers provided by the present invention. Referring to fig. 1, a method for preparing graphene carbon fiber includes the following steps:
(1) preparing an alloy complexing solution: adding the copper-chromium alloy auxiliary agent into water, stirring for 10-15 min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 4-8 h at the temperature of 80-90 ℃. The copper-chromium alloy auxiliary agent is added into water, so that the water and the copper-chromium alloy auxiliary agent are uniformly mixed, the concentration of the copper-chromium alloy auxiliary agent is reduced, the violent reaction between the copper-chromium alloy auxiliary agent and the iron-nickel alloy auxiliary agent when the iron-nickel alloy auxiliary agent is added is avoided, the iron-nickel alloy auxiliary agent is added, the copper-chromium alloy auxiliary agent and the iron-nickel alloy auxiliary agent react at a certain temperature to generate an alloy complex liquid, and the alloy complex liquid is used as a subsequent reaction catalyst.
Preferably, the mass ratio of the copper-chromium alloy auxiliary agent to the water is 1: 30-50, obtaining an alloy complex liquid with a proper concentration, wherein the alloy complex liquid can well enter an interlayer structure of the carbon fibers and pores of the carbon fibers. In the invention, water is deionized water, so that impurities in the water are prevented from influencing the catalytic effect of the alloy complexing liquid.
In the invention, the copper-chromium alloy auxiliary agent, the deionized water and the iron-nickel alloy auxiliary agent are stirred in the stirring reaction kettle for reaction, so that the equipment requirement is not high, and the production cost is low.
Preferably, the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 1 to 2. The alloy complex liquid obtained in the proportion has a good catalytic effect, so that the deposition effect of graphene on carbon fibers is better.
(2) And adding carbon fiber into the alloy complexing liquid, and soaking for 15-30 min to obtain a carbon fiber wet material.
In the dipping process, the alloy complex liquid enters the interlayer structure and the pores of the carbon fibers, so that in the subsequent reaction, the alloy active auxiliary agent is used as a catalyst, the multi-carbon pyrolysis gas is subjected to pyrolysis deposition in the interlayer structure and the pores of the carbon fibers, the in-situ generation of graphene is realized, and the graphene carbon fibers with excellent electrical conductivity and thermal conductivity can be obtained.
Meanwhile, the impregnation process is carried out in a stirring reaction kettle, and the impregnation process can also be carried out in other volumetric containers. The carbon fiber is directly added into the alloy complexing liquid in the stirring reaction kettle, but in the process of adding the carbon fiber, the stirring is stopped, and natural impregnation is carried out, so that the impregnation effect is improved.
In the invention, the carbon fiber is chopped carbon fiber, and the length of the chopped carbon fiber is 1-100 mm.
Preferably, the mass ratio of the carbon fibers to the alloy complex liquid is 1: 8 to 10. The interlayer structure and the pores of the carbon fibers can be fully immersed in the alloy complexing liquid, and the effect of subsequent reaction is improved.
(3) And drying the wet carbon fiber material to obtain a dry carbon fiber material, removing moisture in the wet carbon fiber material, avoiding the influence of the moisture on the cracking reaction, and facilitating the subsequent reaction.
In the invention, the drying is carried out for 4-6 h at the temperature of 120-160 ℃. The temperature avoids the combustion of the carbon fiber and the inactivation of the active auxiliary agent, and avoids the waste caused by overlong drying time, so that the drying effect of the wet carbon fiber material is better.
Preferably, the wet carbon fiber material is uniformly coiled and placed in an electric heating oven for drying. The drying effect of the wet carbon fiber material is better, and the drying time is shortened.
(4) And heating the carbon fiber dry material to 600-900 ℃ in an inert gas atmosphere, introducing multi-carbon cracking gas, and carrying out CVD reaction for 0.5-2 h through catalytic cracking of the active auxiliary agent. Under the inert gas atmosphere, the dry carbon fiber material is prevented from contacting oxygen in the air, the carbon fiber is prevented from burning after subsequent heating, the multi-carbon pyrolysis gas is introduced at high temperature, the multi-carbon pyrolysis gas is subjected to pyrolysis reaction at relatively low temperature due to the catalytic action of the alloy active auxiliary agent, graphene is generated by in-situ deposition in the carbon fiber interlayer structure and pores, the interlayer structure is improved, and the obtained graphene carbon fiber has good electrical conductivity and thermal conductivity.
In detail, the carbon fiber dry material is placed in a fluidized bed reactor, and inert gas is introduced into the fluidized bed reactor; and introducing inert gas, and discharging air in the fluidized bed reactor to avoid the carbon fiber from being burnt after subsequent heating.
According to the invention, the carbon fiber dry material is uniformly filled and compacted and is placed in the fluidized bed reactor, so that the carbon fiber dry material can uniformly contact with the multi-carbon pyrolysis gas subsequently, and the graphene is uniformly deposited in an interlayer structure of the carbon fiber and pores of the carbon fiber.
Preferably, before the inert gas is introduced, the method further comprises the step of detecting the airtightness of the fluidized bed reactor, so as to avoid gas leakage. In the invention, the inert gas is nitrogen or argon, which can not react with the carbon fiber, thereby avoiding the structural change of the carbon fiber.
And continuously introducing inert gas into the fluidized bed reactor, heating the fluidized bed reactor to 600-900 ℃, and introducing multi-carbon pyrolysis gas for reaction for 0.5-2 h. The method comprises the steps of introducing multi-carbon pyrolysis gas at high temperature, wherein carbon fibers and an alloy active additive obtained after an alloy complex liquid is dried are contained in a carbon fiber dry material, firstly, the alloy active additive permeates into a carbon fiber interlayer structure and pores of the carbon fibers under the action of impregnation, and then the multi-carbon pyrolysis gas is catalyzed by the alloy active additive, so that the multi-carbon pyrolysis gas is subjected to cracking deposition reaction at relatively low temperature to generate graphene, mesoporous graphene growth is completed on a carbon fiber carrier, the electron transmission efficiency is increased through the mesoporous graphene, the interlayer structure is improved, and the electrical conductivity and the thermal conductivity of the graphene carbon fibers are improved.
The heating mode may be an electric heating mode or other heating modes as long as the fluidized bed reactor can be heated.
In the invention, the multi-carbon cracking gas is at least one selected from methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, ethylene, propylene, n-butene and isobutene. . When the multi-carbon cracking gas is methane, the temperature in the fluidized bed reactor is 800-900 ℃, the reaction time is 1-2 hours, the temperature is high, the reaction time is long, the generated graphene carbon fiber is of a single structure, and the electrical conductivity and the thermal conductivity of the graphene carbon fiber are good.
When the multi-carbon pyrolysis gas is ethylene, the temperature in the fluidized bed reactor is 700-800 ℃, and the reaction time is 1-1.2 h; when the multi-carbon cracking gas is a mixture of propylene or liquefied petroleum gas such as propane and butane, the temperature in the fluidized bed reactor is 600-700 ℃, the reaction time is 0.5-0.7 h, and the graphene carbon fibers generated by the two are mainly of a multi-structure.
In the invention, the volume ratio of the multi-carbon pyrolysis gas to the inert gas is as follows: 0.1-10: 1, introducing a large amount of multi-carbon pyrolysis gas at the beginning of reaction, and after reacting for a period of time, reducing the amount of the activated assistant and depositing a part of graphene in the interlayer structure of the carbon fibers and the pores of the carbon fibers, so that the required amount of the multi-carbon pyrolysis gas is reduced, and the introducing amount of the multi-carbon pyrolysis gas is reduced.
The method comprises the following steps of (1) monitoring the volume percentage of hydrogen in tail gas of a fluidized bed reactor, wherein the volume percentage of hydrogen in the tail gas of the fluidized bed reactor is 40-50%, when the volume percentage of hydrogen in the tail gas of the fluidized bed reactor is 15-20%, reducing the introduction amount of the multi-carbon pyrolysis gas, so that the volume ratio of the multi-carbon pyrolysis gas to inert gas is 5: 1.
in the present invention, the fluidized bed reactor is a vertical fluidized reactor, and a horizontal reactor, a fixed reactor, or other reaction devices may be used. And the cracking reaction gas can also be continuously added into the fluidized bed reactor by adopting a sectional preheating process.
(5) Stopping introducing the multi-carbon pyrolysis gas, stopping heating the fluidized bed reactor, stopping introducing the inert gas after the fluidized bed reactor is cooled to 20-30 ℃, removing the obtained graphene carbon fiber, and detecting and packaging the graphene carbon fiber. And when the percentage content of hydrogen in the tail gas is less than 5%, stopping introducing the multi-carbon pyrolysis gas, stopping heating the fluidized bed reactor, stopping introducing the inert gas when the fluidized bed reactor is cooled to the room temperature, and removing the obtained graphene carbon fiber. The introduction of the multi-carbon cracking gas is stopped firstly, the introduction of the inert gas is kept in the cooling process, and the condition that air is mixed in the fluidized bed reactor after the cracking reaction is stopped is prevented, so that the graphene carbon fibers are protected and prevented from being combusted.
The preparation method provided by the invention adopts the process technology which uses common chemical equipment, and does not adopt other special equipment except the conventional requirements of high temperature, corrosion resistance, explosion resistance and the like, thereby having lower production cost.
According to the graphene carbon fiber prepared by the preparation method of the graphene carbon fiber composite material, the interlayer structure of the carbon fiber and the pores of the carbon fiber are modified through the mesoporous graphene, so that the electron cloud distribution is more uniform, the electron transfer efficiency of the interlayer structure of the carbon fiber is increased, and the electrical conductivity and the thermal conductivity of the graphene carbon fiber are improved.
The graphene carbon fiber can be used as a conductive material and a heat-conducting material to prepare products such as carbon paper, carbon felt and the like in the fields of infrared electric heating, electric dust removal, environmental protection, electromagnetic shielding and the like.
Example 1
A preparation method of graphene carbon fibers comprises the following steps:
(1) and adding carbon fiber into the alloy complexing liquid, and soaking for 30min to obtain a carbon fiber wet material.
(2) And drying the wet carbon fiber material to obtain a dry carbon fiber material.
(3) And heating the carbon fiber dry material to 600 ℃ in an inert gas atmosphere, and introducing multi-carbon pyrolysis gas for reaction for 0.5 h.
Example 2
A preparation method of graphene carbon fibers comprises the following steps:
(1) preparing an alloy complexing solution: adding the copper-chromium alloy auxiliary agent into a stirring reaction kettle filled with deionized water, stirring for 10min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 4h at 90 ℃ to obtain an alloy complex solution, wherein the mass ratio of the copper-chromium alloy auxiliary agent to water is 1: 30, the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 1.
(2) stopping stirring of the stirring reaction kettle, adding chopped carbon fibers into the alloy complexing liquid, and soaking for 15min to obtain a carbon fiber wet material, wherein the mass ratio of the chopped carbon fibers to the alloy complexing liquid is 1: 8.
(3) and uniformly loading the wet carbon fiber material into a tray, placing the tray in an electric heating oven, and drying the tray for 4 hours at the temperature of 160 ℃ to obtain the dry carbon fiber material.
(4) And uniformly compacting the carbon fiber dry material, placing the carbon fiber dry material in a fluidized bed reactor, and introducing inert gas. And (2) continuously introducing inert gas into the fluidized bed reactor, heating the fluidized bed reactor to 600 ℃, and introducing mixed gas (liquefied petroleum gas) of methane, ethane, ethylene, propane, propylene, n-butane, isobutane, n-butene and isobutene for reaction for 0.5 h.
(5) Stopping introducing the multi-carbon pyrolysis gas, stopping heating the fluidized bed reactor, stopping introducing the inert gas after the fluidized bed reactor is cooled to 20 ℃, removing the obtained graphene carbon fiber, and detecting and packaging the graphene carbon fiber.
Example 3
A preparation method of graphene carbon fibers comprises the following steps:
(1) preparing an alloy complexing solution: adding the copper-chromium alloy auxiliary agent into a stirring reaction kettle filled with deionized water, stirring for 15min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 8h at the temperature of 80 ℃ to obtain an alloy complex solution, wherein the mass ratio of the copper-chromium alloy auxiliary agent to water is 1: 50, the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 2.
(2) stopping stirring of the stirring reaction kettle, adding chopped carbon fibers into the alloy complexing liquid, and soaking for 30min to obtain a carbon fiber wet material, wherein the mass ratio of the chopped carbon fibers to the alloy complexing liquid is 1: 10.
(3) and uniformly loading the wet carbon fiber material into a tray, placing the tray in an electric heating oven, and drying for 6 hours at the temperature of 120 ℃ to obtain a dry carbon fiber material.
(4) And uniformly compacting the carbon fiber dry material, placing the carbon fiber dry material in a fluidized bed reactor, introducing inert gas, continuously introducing the inert gas into the fluidized bed reactor, heating the fluidized bed reactor to 900 ℃, and introducing mixed gas (natural gas) of methane, ethane, propane, n-butane and isobutane to react for 2 hours.
(5) Stopping introducing the multi-carbon pyrolysis gas, stopping heating the fluidized bed reactor, stopping introducing the inert gas after the fluidized bed reactor is cooled to 30 ℃, removing the obtained graphene carbon fiber, and detecting and packaging the graphene carbon fiber.
Example 4
A preparation method of graphene carbon fibers comprises the following steps:
(1) preparing an alloy complexing solution: adding the copper-chromium alloy auxiliary agent into a stirring reaction kettle filled with deionized water, stirring for 12min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 5h at 85 ℃ to obtain an alloy complex solution, wherein the mass ratio of the copper-chromium alloy auxiliary agent to water is 1: 40, the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 1.2.
(2) stopping stirring of the stirring reaction kettle, adding the chopped carbon fibers into the alloy complexing liquid, and soaking for 20min to obtain a carbon fiber wet material, wherein the mass ratio of the chopped carbon fibers to the alloy complexing liquid is 1: 9.
(3) and uniformly loading the wet carbon fiber material into a tray, placing the tray in an electric heating oven, and drying the tray for 5 hours at the temperature of 150 ℃ to obtain the dry carbon fiber material.
(4) And uniformly compacting the carbon fiber dry material, placing the carbon fiber dry material in a fluidized bed reactor, introducing inert gas, continuously introducing the inert gas into the fluidized bed reactor, heating the fluidized bed reactor to 800 ℃, and introducing ethylene for reacting for 1.2 hours.
(5) Stopping introducing the multi-carbon pyrolysis gas, stopping heating the fluidized bed reactor, stopping introducing the inert gas after the fluidized bed reactor is cooled to 25 ℃, removing the obtained graphene carbon fiber, and detecting and packaging the graphene carbon fiber.
Experimental example 1
The graphene carbon fibers obtained in examples 1 to 4 and the carbon fibers on the market were examined for electrical conductivity and thermal conductivity to obtain table 1,
TABLE 1 comparison of conductivity and thermal conductivity
| Conducting property (omega/□) | Heat-conducting property (w/m. k) | |
| Example 1 | 1 | 2.2 |
| Example 2 | 1.2 | 2 |
| Example 3 | 1.1 | 2.1 |
| Example 4 | 0.9 | 1.9 |
| Carbon fiber on the market | >10 | 0.5 |
As can be seen from table 1, the graphene carbon fiber prepared by the method of the present invention has excellent electrical and thermal conductivity and excellent properties.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. A preparation method of graphene carbon fibers is characterized by comprising the following steps:
(1) adding carbon fibers into the alloy complexing liquid, and soaking for 15-30 min to obtain a carbon fiber wet material; the preparation method of the alloy complexing liquid comprises the following steps: adding the copper-chromium alloy auxiliary agent into water, stirring for 10-15 min, adding the iron-nickel alloy auxiliary agent, and continuously stirring and reacting for 4-8 h at the temperature of 80-90 ℃; wherein the mass ratio of the carbon fibers to the alloy complexing liquid is 1: 8-10; the mass ratio of the copper-chromium alloy auxiliary agent to the iron-nickel alloy auxiliary agent is 1: 1-2;
(2) drying the wet carbon fiber material to obtain a dry carbon fiber material containing an active additive;
(3) heating the carbon fiber dry material to 600-900 ℃ in an inert gas atmosphere, introducing multi-carbon cracking gas, and carrying out CVD reaction for 0.5-2 h through catalytic cracking of an active auxiliary agent to obtain graphene carbon fiber; wherein the multi-carbon cracking gas is at least one selected from methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, ethylene, propylene, n-butene and isobutene.
2. The preparation method according to claim 1, wherein in the step (2), the drying is carried out at a temperature of 120 to 160 ℃ for 4 to 6 hours.
3. The method of claim 1, wherein step (3) further comprises the step of monitoring the volume percent hydrogen in the tail gas of the fluidized bed reactor.
4. The preparation method according to claim 1, further comprising, after the step (3), stopping the introduction of the polycarbon pyrolysis gas, stopping the heating, cooling to 20-30 ℃, stopping the introduction of the inert gas, and removing the obtained graphene carbon fiber.
5. The graphene carbon fiber prepared by the preparation method of the graphene carbon fiber according to any one of claims 1 to 4.
6. Use of the graphene carbon fiber of claim 5 as an electrically and thermally conductive material.
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| CN110258106B (en) * | 2019-07-19 | 2021-07-09 | 中南林业科技大学 | Preparation method of sandwich type flexible electromagnetic shielding material based on carbon fiber fabric, metal nickel nanoparticles and graphene |
| CN114014659B (en) * | 2021-11-05 | 2022-12-13 | 新疆农六师碳素有限公司 | Novel high-end carbon product material for aluminum and preparation method thereof |
| CN115491784A (en) * | 2022-08-24 | 2022-12-20 | 凯盛石墨碳材料有限公司 | Preparation method of graphene/carbon fiber/polypropylene fiber with excellent conductivity |
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