CN112680957A - Reinforcing method of graphene fiber non-woven fabric and continuous preparation method of high-performance graphene non-woven fabric - Google Patents
Reinforcing method of graphene fiber non-woven fabric and continuous preparation method of high-performance graphene non-woven fabric Download PDFInfo
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Abstract
The invention discloses a method for enhancing graphene fiber non-woven fabric, which comprises the following steps: and immersing the graphene fiber non-woven fabric or the graphene oxide fiber non-woven fabric into a reinforcing medium, taking out and drying after proper impregnation, and then sequentially carrying out carbonization and graphitization treatment on the composite non-woven fabric to finally obtain the reinforced non-woven fabric. The invention also discloses a continuous preparation method of the high-performance graphene non-woven fabric, and the method is combined with a blowing and spraying method to realize continuous preparation and continuous reinforcement of the non-woven fabric. The method disclosed by the invention is simple in process, efficient and environment-friendly, and is a novel method for preparing the carbon-carbon composite material.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a method for reinforcing a graphene fiber non-woven fabric and a method for continuously preparing a high-performance graphene non-woven fabric.
Technical Field
In 2004, professor a.k.geom, university of manchester, uk, successfully prepared graphene by using a mechanical exfoliation method and hung on a miniature gold frame, and the conclusion that a perfect two-dimensional crystal structure cannot stably exist at a non-absolute zero degree is overcome. In other words, the graphene in a free state can exist stably at room temperature; under the same conditions, any other known material is oxidized or decomposed and becomes unstable even at a thickness 10 times its monolayer thickness. Structurally, Graphene (Graphene) is an sp2 hybridized monolayer carbon atom crystal which is tightly packed into a two-dimensional honeycomb lattice structure, carbon atoms in the layer are connected in a covalent bond mode and have ultrahigh strength (120GPa), so that the carbon-based material with a specific structure is constructed by taking the Graphene as a source material, and the design, controllability and macroscopic preparation of the carbon-based functional material nanostructure are gradually attracted by global scientists.
The graphite oxide non-woven fabric has the characteristics of high electric conductivity, high thermal conductivity, high porosity, multiple functions and the like, and has attracted wide attention since the beginning of one report. The graphene fiber non-woven fabric is mainly formed by directly jet spinning through airflow-assisted spinning or suction filtration through short fibers, the fibers are deposited on a substrate layer by layer in the solidification process, and the non-woven fabric prepared by the two methods has a serious separation phenomenon in the vertical plane direction, so that the comprehensive performance of the graphene fiber non-woven fabric is influenced, particularly the conductivity in the vertical direction is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for reinforcing a graphene fiber non-woven fabric, which changes the separation of fiber layers into connection by adding the combination of a carbonizable precursor reinforcing fiber, particularly the combination of upper and lower layers of fibers, and effectively constructs a stress, phonon and electron transmission network, thereby improving the comprehensive performance of the fibers, particularly the mechanical property, heat conduction and electric conduction performance of the non-woven fabric, and enabling the graphene fiber non-woven fabric to be applied to the fields of heat management, adsorption, filtration, battery electrodes and the like.
The method at least comprises the following steps:
(1) immersing a graphene fiber non-woven fabric with a carbon-oxygen ratio greater than 1 into a reinforcing medium, so that the reinforcing medium is loaded on the surfaces of graphene fibers in the non-woven fabric; the strengthening electrolyte is a melt of the carbonizable precursor or a dispersion of the carbonizable precursor;
(2) transferring the graphene fiber non-woven fabric loaded with the reinforced medium into a high-temperature furnace, and heating to the carbonization temperature of the reinforced medium for carbonization treatment;
(3) and after carbonization treatment, heating to a graphitization temperature for graphitization treatment, thereby obtaining the reinforced graphene fiber non-woven fabric.
In the art, graphene is generally referred to as a graphene material, and includes graphene oxide, reduced graphene oxide, and graphene which is reduced more thoroughly, in step 1, the graphene fiber non-woven fabric with a carbon-to-oxygen ratio greater than 1 may be graphene oxide fiber non-woven fabric, chemically reduced graphene oxide fiber non-woven fabric, graphene oxide fiber non-woven fabric which is reduced by high temperature heat at 1000 ℃, or graphene fiber non-woven fabric which is graphitized at high temperature at 3000 ℃. These nonwovens can be obtained by air-assisted spinning or suction filtration methods.
The invention also relates to a continuous preparation method of the high-strength graphene film, which effectively changes the viscoelasticity of the graphene oxide aqueous solution by adding a proper amount of sodium polyacrylate solution, so that the graphene oxide aqueous solution has viscoelasticity similar to polymerization, and can show ultrahigh tensile property, thereby meeting the condition of realizing airflow-assisted spinning, increasing the spinning speed of the graphene oxide solution from 5 m/min to 500 m/min, collecting fibers by using a substrate soaked with a coagulating bath, and rapidly preparing the graphene oxide/sodium polyacrylate non-woven fabric. And based on the reinforcing method, the high-strength graphene film is introduced into a reinforcing medium through a guide roller to realize continuous loading, and after the loading, the high-strength graphene film is collected through a collecting roller and subjected to two-step heat treatment to obtain the high-strength graphene film. Specifically, the method comprises the following steps:
(1) carrying out airflow-assisted spinning by taking a mixed solution of graphene oxide/sodium polyacrylate as a precursor, collecting graphene oxide/sodium polyacrylate gel fibers by using a reelable substrate, and drying to obtain a graphene oxide/sodium polyacrylate non-woven fabric separated from the substrate; then introducing the separated graphene oxide/sodium polyacrylate non-woven fabric into a reinforcing medium to load the reinforcing medium; and then collected via a collection roller.
In the mixed solution of the graphene oxide and the sodium polyacrylate, the mass fraction of the graphene oxide is 0.2-1.5%, the mass of the sodium polyacrylate accounts for 25-50% of the total mass of the graphene oxide and the sodium polyacrylate, and the weight average molecular weight of the sodium polyacrylate is 100-3500 ten thousand.
The substrate is soaked with a solidification liquid, and the solidification liquid is selected from poor graphene oxide solvents. The strengthening electrolyte is a melt of the carbonizable precursor or a dispersion of the carbonizable precursor;
(2) transferring the graphene fiber non-woven fabric loaded with the reinforced medium into a high-temperature furnace, and heating to the carbonization temperature of the reinforced medium for carbonization treatment;
(3) and after carbonization treatment, heating to a graphitization temperature for graphitization treatment, thereby obtaining the reinforced graphene fiber non-woven fabric.
Further, the poor solvent is selected from ethanol, isopropanol, ethyl acetate, etc., and a mixed solution thereof.
Further, the fiber forming linear velocity of the airflow-assisted spinning is 100-1000 m/min.
Further, the substrate that can be rolled up is PP, PE, PTFE, nylon or the like.
In both of the above aspects of the present application, carbonizable precursors include, but are not limited to:
1) carbonizable nanomaterials, such as graphene oxide, graphene, carbon nanotubes, carbon quantum dots, and the like;
2) carbonizable polymers such as polyacrylonitrile, polyimide, phenol resin, and the like;
3) all natural carbonizable polymeric materials, such as lignin, cellulose, chitosan, and the like;
4) all carbonizable small molecules such as mesophase pitch, glucose, and the like.
In certain preferred embodiments, the carbonizable precursor has a melting temperature below 1000 ℃. The lower melting temperature is beneficial to the precursor capable of being carbonized to enter a molten state as early as possible, and the performance of the material is improved.
In some preferable embodiments, the carbonization temperature in step 2 is 400-2000 ℃, and the graphitization temperature in step 3 is 2800 ℃ or higher.
In the application, the temperature rise time before carbonization is more than 20min, and constant temperature rise or non-constant temperature rise can be adopted.
In some more preferable embodiments, the carbonization time is 30min or more, and the graphitization time is 30min or more.
In some more preferred embodiments, in order to increase the loading amount of the precursor, the carbon-carbon composite material may be repeatedly dip-coated with the graphene fiber non-woven fabric which has been impregnated with the carbonizable precursor or the graphene fiber non-woven fabric which has undergone heat treatment. For example, after repeating the dip-coating step for a plurality of times (drying after each dip-coating, entering the next dip-coating), the carbonization-graphitization treatment step is performed again; or after repeating the steps of dip coating and carbonization for a plurality of times, carrying out graphitization treatment; and repeating the dip coating-carbonization-graphitization treatment steps for multiple times.
In some preferred embodiments, the same nonwoven fabric may be repeatedly dip-coated with different types of carbonizable precursors for loading different precursors. The specific method is the same as above.
The invention also relates to the graphene-carbon composite non-woven fabric obtained by the method, and application of the graphene-carbon composite non-woven fabric as a gas diffusion layer of a fuel cell or other electrochemical electrode materials.
In certain preferred embodiments, the impregnated nonwoven fabric containing the carbonizable precursor is subjected to a 1000 ℃ carbonization treatment and a 3000 ℃ graphitization treatment in this order.
Compared with the prior art, the invention has the following beneficial effects: the mechanical property of the reinforced non-woven fabric reaches more than 2MPa, the heat conducting property reaches 36W/(mK), the in-plane electric conductivity reaches 28000s/m, and the vertical electric conductivity reaches 4500s/m, so that the graphene fiber non-woven fabric can be applied to the fields of heat management, adsorption filtration, battery electrodes, gas diffusion layers of fuel cells and the like.
Drawings
Fig. 1 is a cross section of a pure graphene fiber non-woven fabric, in which fibers in a vertical direction are seriously separated;
FIG. 2 is an electron microscope structure diagram of the surface topography of a graphene fiber non-woven fabric composite material enhanced by mesophase pitch with different contents;
fig. 3 is an electron microscope image of the cross-sectional morphology of the 10 wt.% mesophase pitch-reinforced graphene fiber non-woven fabric carbon-carbon composite, the yellow region being carbonized pitch, and the blue region being graphene fiber.
Fig. 4 shows the percentage of the overall performance of the graphene fiber non-woven fabric composite material enhanced by 10 wt.% mesophase pitch;
fig. 5 shows the percentage of the overall performance of the graphene fiber nonwoven fabric reinforced by 3.3 wt.% phenolic resin;
fig. 6 shows the surface morphology of a graphene fiber nonwoven fabric impregnated with graphene oxide after treatment at 3000 ℃;
fig. 7 shows the surface morphology of the glucose-impregnated graphene fiber nonwoven fabric after the treatment at 000 ℃.
Fig. 8 is a partial continuous production apparatus for high-strength graphene.
Fig. 9 is another apparatus for partially continuously preparing high-strength graphene.
Detailed Description
The invention provides a method for enhancing graphene fiber non-woven fabric, which comprises the following steps:
(1) immersing a graphene fiber non-woven fabric with a carbon-oxygen ratio greater than 1 into a reinforcing medium, so that the reinforcing medium is loaded on the surfaces of graphene fibers in the non-woven fabric; the reinforcing medium in the invention can be a melt of a carbonizable precursor or a dispersion of the carbonizable precursor, and the concentration of the reinforcing medium can be adjusted by a person skilled in the art according to the rule that the infiltration time, the concentration of the medium and the load rate are in direct proportion.
For the reinforcing medium with poor dispersibility, the load rate can be achieved by adopting a multi-infiltration mode.
In the invention, the reinforcing medium is one or more, and a plurality of reinforcing media can be dispersed in the same solvent or form a eutectic body so as to realize synchronous loading. Or the catalyst can be dispersed in different solvents or independently form a melt, and the gradual loading is realized by adopting a multi-infiltration mode. Different reinforcing media can perform different functions or cooperatively perform or even optimize the functions, for example, one reinforcing medium is Polyacrylonitrile (PAN), and the other reinforcing medium is graphene oxide, wherein the graphene oxide can induce carbonization of the Polyacrylonitrile (PAN).
In the invention, an auxiliary agent can be added into the reinforcing medium to induce or promote the melting, carbonization or graphitization of the reinforcing medium.
In the invention, functional additives can be added into the enhancement medium to realize functional modification of the non-woven fabric.
(2) And then transferring the graphene fiber non-woven fabric loaded with the reinforcing medium into a high-temperature furnace, heating to the carbonization temperature of the reinforcing medium, and carrying out carbonization treatment at the carbonization temperature. In the temperature rise process, the reinforcing medium is firstly melted and uniformly spread, and after the temperature reaches the carbonization temperature, the uniformly spread melting medium is carbonized to form solidification connection with the graphene fiber.
(3) And heating to the graphene oxidation temperature for graphitization treatment, thereby obtaining the reinforced graphene fiber non-woven fabric. In this process, the electrical and thermal properties of the graphene and carbonized media are enhanced.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Comparative example 1
Preparing a pure graphene oxide fiber non-woven fabric A by a method (201610568052.8) of filtering the graphene fiber dispersion liquid;
the prepared graphene oxide fiber non-woven fabric is subjected to chemical reduction to obtain a graphene fiber non-woven fabric B, the fiber lap joint structure in the direction perpendicular to the plane is shown in figure 1, and the fibers are seriously separated.
It was found that the strength was 0.2kPa, the elongation at break was 20%, the in-plane conductivity was 3520S/m, the vertical conductivity was 55S/m, and the gas permeation rate was 2600ml mm/(cm)2 hr mmaq)。
Example 1
S1, preparing 20% mass fraction mesophase pitch particle ethanol suspension, and adding 0.1% mass fraction boron carbide serving as a graphitization catalyst into the suspension;
s2, immersing the non-woven fabric A in the comparative example 1 into the ethanol suspension of the mesophase pitch particles, taking out the non-woven fabric A after soaking for a certain time (shown in table 1), naturally drying the non-woven fabric A, then heating to 1000 at a speed of 2 ℃/min for carbonization, keeping the temperature for 1 hour, then heating to 3000 ℃ at a speed of 10 ℃/min for graphitization, and keeping the temperature for 30 minutes to obtain the graphene fiber non-woven fabric carbon-carbon composite materials I-III.
Measuring that the mass of the graphene fiber non-woven fabric carbon-carbon composite material I obtained after soaking for 5 minutes is 31.2mg, and the load rate is 4 wt.%, as shown in fig. 2A; the mass of the obtained graphene fiber non-woven fabric carbon II after being soaked for 10 minutes is 33mg, the load rate is 10 wt.%, and the graph is shown in FIG. 2B; the mass of the graphene fiber non-woven fabric carbon-carbon composite material III obtained after 20 minutes of infiltration is 35mg, and the load rate is 16.7 wt.%, as shown in fig. 2C;
TABLE 1
The 10 wt.% mesophase pitch reinforced graphene fiber non-woven fabric composite material has a vertical fiber lap joint structure as shown in fig. 3, wherein a black area is carbonized mesophase pitch, and a gray area is graphene fiber. It can be seen from the figure that, under the condition of proper loading, the graphene fiber non-woven fabric is partially bonded, and partially maintains a void state, so that the comprehensive performance of the graphene fiber non-woven fabric is enhanced under the condition of keeping the gas permeability basically unchanged (as shown in figure 4).
And (3) using the graphene fiber non-woven fabric composite material prepared in the step (4) as a gas diffusion layer of a fuel cell, wherein the measured equivalent resistance of a loop is 2 ohms, the conductivity is improved by 50% compared with that of commercial carbon fiber paper of Dongli company, and the open-circuit voltage of the graphene fiber non-woven fabric composite material is 1.2 volts and is higher than 0.94 volts of the commercial fuel cell.
TABLE 2
Example 2
S1, preparing pure graphene oxide fiber non-woven fabric by a method (201610568052.8) of suction filtration of graphene fiber dispersion liquid:
s2, sequentially carrying out chemical reduction and thermal high-temperature reduction at 1000 ℃ for one hour on the graphene oxide fiber non-woven fabric to obtain a graphene fiber non-woven fabric;
s3, preparing 1% of phenolic resin solution in mass fraction;
and S4, immersing the obtained graphene fiber non-woven fabric into the phenolic resin solution, taking out the graphene fiber non-woven fabric after 2min, naturally drying the graphene fiber non-woven fabric, heating to 1000 at a speed of 2 ℃/min, carrying out carbonization treatment, keeping the temperature for 1 h, heating to 3000 ℃ at a speed of 10 ℃/min, carrying out graphitization treatment, and keeping the temperature for 30min to obtain the graphene fiber non-woven fabric carbon-carbon composite material, wherein the cross-sectional morphology structure of the graphene fiber non-woven fabric carbon-carbon composite material is shown in.
The measured load factor was 3.3 wt.%, the in-plane conductivity was 23420S/m, the vertical conductivity was 1800S/m, and the gas permeability was 2340ml mm/(cm)2hr mmaq), tensile strength of 3.3 MPa.
Example 3
S1, preparing pure graphene oxide fiber non-woven fabric by a method (201610568052.8) of suction filtration of graphene fiber dispersion liquid:
s2, chemically reducing the graphene oxide fiber non-woven fabric by hydriodic acid/trifluoroacetic acid (volume ratio is 1:3) to obtain a reduced graphene oxide fiber non-woven fabric;
s3, preparing a 0.5% graphene oxide aqueous solution by mass fraction:
and S4, immersing the obtained reduced graphene oxide fiber non-woven fabric into the graphene oxide aqueous solution, taking out the reduced graphene oxide fiber non-woven fabric after 30 minutes, naturally drying the reduced graphene oxide fiber non-woven fabric, heating to 1000 at a speed of 2 ℃/min for carbonization, preserving heat for 1 hour, heating to 3000 ℃ at a speed of 10 ℃/min for graphitization, and preserving heat for 30 minutes to obtain the graphene fiber non-woven fabric carbon-carbon composite material, wherein the surface morphology structure of the graphene fiber non-woven fabric carbon-carbon composite material is shown in FIG. 6.
The measured load factor was 5.8 wt.%, the in-plane conductivity 25630s/m and the vertical conductivity 1760 s-m, gas permeability of 2190ml mm/(cm)2hr mmaq), tensile strength of 4.1 MPa.
Example 4
As shown in fig. 8, a continuous preparation system of a high strength non-woven fabric comprises a substrate 101, six guide rolls 102, a separation roll 103, a coagulation liquid coating device 104, an air flow auxiliary spinning device 105; and a reinforcing medium dip coating device 106 and a take-up roll 107.
In this example, the substrate is a PTFE membrane.
In this embodiment, the solidification liquid coating apparatus 104 is a container containing a solidification liquid in which two guide rollers for guiding the substrate are located, and the solidification liquid is ethanol.
In this embodiment, the enhancement medium dip coating apparatus 106 is a vessel containing enhancement medium that is a 50% mass fraction aqueous glucose solution:
in this embodiment, the airflow-assisted spinning device 105 performs airflow-assisted spinning on the ultrahigh-tensile solution by using a coaxial needle, the types of the inner needle and the outer needle are 18G and 15G, respectively, the fiber-forming linear velocity of the airflow-assisted spinning is 350 m/min, and the spinning solution is prepared by the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 3.0 wt% and a sodium polyacrylate (with the weight-average molecular weight of 100 ten thousand) aqueous solution with the concentration of 1 wt%.
(2) And (2) uniformly mixing the graphene oxide aqueous solution and the sodium polyacrylate aqueous solution according to the mass ratio of 1:1 to obtain a graphene oxide/sodium polyacrylate ultrahigh-tensile solution, wherein the fracture tensile ratio of the fluid is 1350%.
The substrate 101 rotates counterclockwise under the traction of the three guide rollers, firstly passes through the coating area of the coagulating liquid coating device 104 to obtain a PTFE film soaked with ethanol, then enters the spraying area of the airflow auxiliary spinning device 105, collects sprayed gel fibers and forms non-woven fabrics, and then passes through the stripping roller 103 to strip the graphene film on the surface and then enters the circulation again.
The nonwoven fabric peeled by the peeling roller is drawn into the reinforcing medium dip-coating device 106 by the guide roller 102, and is collected by the wind-up roller 107 after being loaded with the reinforcing medium.
And heating the rolled non-woven fabric to 1000 at a speed of 2 ℃/min for carbonization treatment, preserving heat for 1 hour, heating to 3000 ℃ at a speed of 10 ℃/min for graphitization treatment, and preserving heat for 30 minutes to obtain the graphene fiber non-woven fabric carbon-carbon composite material, wherein the surface structure of the graphene fiber non-woven fabric carbon-carbon composite material is shown in figure 7.
The measured load factor was 7.6 wt.%, the in-plane conductivity was 27860s/m, the vertical conductivity was 2330s/m, and the gas permeability was 1990ml mm/(cm)2hr mmaq), tensile strength of 3.6 MPa.
Example 5
As shown in fig. 9, a continuous preparation system of high strength non-woven fabric comprises a base 101, 5 guide rolls 102, a separation roll 103, a coagulating liquid coating device 104, an air flow auxiliary spinning device 105; and a reinforcing medium dip coating device 106 and a take-up roll 107.
In this example, the substrate is a PTFE membrane.
In the present embodiment, the solidification liquid coating apparatus 104 is a conventional spray coating apparatus, and sprays the solidification liquid, which is isopropanol, onto the substrate 101.
In this embodiment, the reinforcing medium dip coating apparatus 106 is a vessel containing the reinforcing medium, which is phenolic resin.
In this embodiment, the airflow-assisted spinning device 105 performs airflow-assisted spinning on the ultrahigh-tensile solution by using a coaxial needle, the types of the inner needle and the outer needle are 25G and 18G, respectively, the fiber-forming linear velocity of the airflow-assisted spinning is 350 m/min, and the spinning solution is prepared by the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 2 wt% and a sodium polyacrylate (with the weight-average molecular weight of 3500 ten thousand) aqueous solution with the concentration of 2 wt%.
(2) And uniformly mixing the graphene oxide aqueous solution and the sodium polyacrylate aqueous solution according to the mass ratio of 1:1 to obtain the graphene oxide/sodium polyacrylate ultrahigh-tensile solution. The elongation at break of this fluid was 1350%.
The substrate 101 rotates counterclockwise under the traction of 2 guide rollers, passes through the coating area of the coagulating liquid coating device 104 to obtain a PTFE film soaked with isopropanol, then enters the spraying area of the air flow auxiliary spinning device 105, collects sprayed gel fibers to form a non-woven fabric, passes through the stripping roller 103 to strip a graphene film on the surface, and then enters the circulation again.
The nonwoven fabric peeled by the peeling roller is drawn into the reinforcing medium dip-coating device 106 by the guide roller 102, and is collected by the wind-up roller 107 after being loaded with the reinforcing medium.
And heating the rolled non-woven fabric to 1000 at a speed of 2 ℃/min for carbonization treatment, preserving heat for 1 hour, heating to 3000 ℃ at a speed of 10 ℃/min for graphitization treatment, and preserving heat for 30 minutes to obtain the graphene fiber non-woven fabric carbon-carbon composite material.
The measured load factor was 7.6 wt.%, the in-plane conductivity was 27860s/m, the vertical conductivity was 2330s/m, and the gas permeability was 1990ml mm/(cm)2hr mmaq), tensile strength of 3.6 MPa.
Claims (17)
1. A method for reinforcing a graphene fiber non-woven fabric is characterized by at least comprising the following steps:
(1) immersing a graphene fiber non-woven fabric with a carbon-oxygen ratio greater than 1 into a reinforcing medium, so that the reinforcing medium is loaded on the surfaces of graphene fibers in the non-woven fabric; the strengthening electrolyte is a melt of the carbonizable precursor or a dispersion of the carbonizable precursor;
(2) transferring the graphene fiber non-woven fabric loaded with the reinforced medium into a high-temperature furnace, and heating to the carbonization temperature of the reinforced medium for carbonization treatment;
(3) and after carbonization treatment, heating to a graphitization temperature for graphitization treatment, thereby obtaining the reinforced graphene fiber non-woven fabric.
2. The reinforcing method according to claim 1, wherein the graphene fiber non-woven fabric with the carbon-oxygen ratio of more than 1 is a graphene oxide fiber non-woven fabric, a chemically reduced graphene oxide fiber non-woven fabric, a graphene oxide fiber non-woven fabric subjected to high-temperature thermal reduction at 1000 ℃, or a graphene fiber non-woven fabric subjected to high-temperature graphitization at 3000 ℃.
3. The reinforcing method according to claim 1, wherein the graphene fiber non-woven fabric with the carbon-oxygen ratio of more than 1 is obtained by air flow assisted spinning continuous preparation or suction filtration.
4. The reinforcement method according to claim 1, wherein the carbonizable precursor includes, but is not limited to: carbonizable nanomaterials, such as graphene oxide, graphene, carbon nanotubes, carbon quantum dots, and the like; carbonizable polymers such as polyacrylonitrile, polyimide, phenol resin, and the like; all natural carbonizable polymeric materials, such as lignin, cellulose, chitosan, and the like; all carbonizable small molecules such as mesophase pitch, glucose, and the like.
5. The reinforcement method according to claim 1, characterized in that the melting temperature of the carbonizable precursor is below 1000 ℃.
6. The reinforcing method according to claim 1, wherein the carbonization temperature in step 2 is 400 to 2000 ℃, and the graphitization temperature in step 3 is 2800 ℃ or higher.
7. The strengthening method according to claim 1, wherein the temperature rise process before carbonization is constant temperature rise or non-constant temperature rise, and the temperature rise time is more than 20 min.
8. The reinforcing method according to claim 1, wherein the carbonization treatment time is 30min or more, and the graphitization treatment time is 30min or more.
9. The reinforcement method according to claim 1, wherein the carbon-carbon composite material of the graphene fiber nonwoven fabric impregnated with the carbonizable precursor or the graphene fiber nonwoven fabric subjected to the heat treatment is subjected to repeated dip coating.
10. The method of claim 1, wherein the dip coating of different types of carbonizable precursors is repeated for a plurality of times on the same nonwoven.
11. The graphene carbon-carbon composite non-woven fabric reinforced by the method of claim 1.
12. Use of the graphene-carbon composite nonwoven fabric according to claim 11 as a gas diffusion layer for fuel cells or other electrochemical electrode materials.
13. Use according to claim 7, characterized in that the impregnated nonwoven fabric containing the carbonisable precursor is subjected to a carbonization treatment at 1000 ℃ and a graphitization treatment at 3000 ℃ in this order.
14. A continuous preparation method of high-performance graphene non-woven fabric is characterized by comprising the following steps:
(1) carrying out airflow-assisted spinning by taking a mixed solution of graphene oxide/sodium polyacrylate as a precursor, collecting graphene oxide/sodium polyacrylate gel fibers by using a reelable substrate, and drying to obtain a graphene oxide/sodium polyacrylate non-woven fabric separated from the substrate; then introducing the separated graphene oxide/sodium polyacrylate non-woven fabric into a reinforcing medium to load the reinforcing medium; then collecting the mixture by a collecting roller;
in the mixed solution of the graphene oxide and the sodium polyacrylate, the mass fraction of the graphene oxide is 0.2-1.5%, the mass of the sodium polyacrylate accounts for 25-50% of the total mass of the graphene oxide and the sodium polyacrylate, and the weight average molecular weight of the sodium polyacrylate is 100-3500 ten thousand;
the substrate is soaked with a solidification liquid, and the solidification liquid is selected from poor graphene oxide solvents;
the strengthening electrolyte is a melt of the carbonizable precursor or a dispersion of the carbonizable precursor;
(2) transferring the graphene fiber non-woven fabric loaded with the reinforced medium into a high-temperature furnace, and heating to the carbonization temperature of the reinforced medium for carbonization treatment;
(3) and after carbonization treatment, heating to a graphitization temperature for graphitization treatment, thereby obtaining the reinforced graphene fiber non-woven fabric.
15. The method for preparing a compound according to claim 14, wherein the poor solvent is selected from the group consisting of ethanol, isopropanol, ethyl acetate, and the like, and a mixed solution thereof.
16. The method as claimed in claim 14, wherein the fiber forming linear velocity of the air-assisted spinning is 100-1000 m/min.
17. The method of claim 14 wherein the substrate is PP, PE, PTFE or nylon.
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