Preparation method and application of nitrogen-doped graphene carbon material

Abstract

The invention discloses a preparation method and application of a nitrogen-doped graphene carbon material, and the method comprises the following steps: preparing graphene powder, urea and zirconium oxide grinding balls, adding ethanol for mixing, and after mixing, carrying out centrifugal separation and vacuum drying to obtain pre-doped graphene powder; introducing Ar and H2 for high-temperature annealing, introducing NH3 and Ar mixed gas after annealing is completed, and supplementing pyridine nitrogen; the base cloth material is divided according to the porosity, the adding amount of a pore forming agent is obtained, the content of other components of the binding agent is obtained according to the adding amount of the pore forming agent, and the binding agent is prepared; preparing an olefinic carbon mother solution, and adding a binding agent into the olefinic carbon mother solution to prepare an olefinic carbon mixed solution; the binding agent is prepared, and the olefinic carbon solution is added, so that the binding strength of the base cloth with different porosities and the olefinic carbon solution is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the field of preparation of graphene carbon materials, and more specifically, to a method for preparing and applying a nitrogen-doped graphene carbon material. Background Art

[0002] In the field of materials science, with the continuous growth of the demand for high-performance materials, how to improve the comprehensive performance of materials has become a research hotspot; for systems involving the composite of graphene carbon materials and base fabrics, there are many problems with traditional coating technologies; the bonding strength between traditional coatings and base fabrics with different porosities is insufficient, and peeling is likely to occur, which greatly limits the service life and application range of the materials. In scenarios such as electromagnetic shielding, catalytic carriers, and flexible sensing, the stability of the coating is crucial, and the peeling problem seriously affects the performance of the materials in these fields; it is difficult for existing technologies to effectively enhance the bonding force between the coating and the substrate while reducing the interfacial contact resistance and improving the conductivity of the composite material; in addition, the regulation of the pore structure of the material has always been a difficult problem, and there is a lack of effective means to precisely control the pore structure, resulting in the inability of the material to achieve efficient adaptation and performance optimization in different application scenarios. Therefore, it is of great practical significance to develop a preparation method that can effectively solve the above problems.

[0003] In response to the problems in the related art, no effective solution has been proposed yet. Summary of the Invention

[0004] In response to the problems in the related art, the present invention proposes a method for preparing and applying a nitrogen-doped graphene carbon material to overcome the above technical problems existing in the related art.

[0005] To this end, the specific technical solution adopted by the present invention is as follows: A method for preparing a nitrogen-doped graphene carbon material, the method comprising the following steps: S1. Prepare graphene powder, urea, zirconia grinding balls, and add ethanol for mixing. After mixing is completed, perform centrifugal separation and vacuum drying to obtain pre-doped graphene powder; S2. Pass Ar and H 2 Perform high-temperature annealing, and after annealing is completed, pass NH 3 Ar mixed gas to supplement pyridine nitrogen; S3. Divide the base fabric material according to the porosity, obtain the addition amount of the pore-forming agent, and obtain the contents of other components of the binder according to the addition amount of the pore-forming agent, and prepare the binder; S4. Prepare a graphene carbon mother liquor, and add the binder to the graphene carbon solution to prepare a graphene carbon mixed solution.

[0006] As a preferred embodiment, the preparation of the pre-doped graphene powder includes the following steps: preparing graphene powder, urea, zirconia grinding balls, adding ethanol for mixing, and performing centrifugal separation and vacuum drying after mixing is completed. S11. Mix the graphene powder, urea, and zirconia grinding balls, and add ethanol as a dispersion medium. During ball milling, mechanical force induces the interlayer peeling of graphene, exposing edge defect sites. Urea decomposes to produce NH 3 , which reacts with -COOH and -OH groups at the edge of graphene to form pyridine nitrogen.

[0007] S12. After mixing is completed, perform centrifugal separation, wash with ethanol 3 times to remove unreacted urea, and vacuum dry at 60 °C for 12 hours to obtain the pre-doped graphene powder.

[0008] As a preferred embodiment, the high-temperature annealing is carried out by introducing Ar and H 2 , and after the annealing is completed, NH 3 , Ar mixed gas is introduced to supplement pyridine nitrogen, including the following steps: S21. Introduce 95% Ar and 5% H 2 , set the flow rate to 50 mL / min, the temperature to 800 °C, the time to 2 hours, and the heating rate to 5 °C / min. S22. Perform plasma treatment, introduce NH 3 , Ar mixed gas, and the ratio of NH 3 to Ar is 1:4. Set the power to 100 W and the treatment time to 10 minutes to supplement pyridine nitrogen.

[0009] Through plasma post-treatment, pyridine nitrogen can be supplemented on the surface of graphene, thereby achieving the effect of improving the uniformity of nitrogen doping.

[0010] As a preferred embodiment, the preparation of the binder includes the following steps: dividing the base fabric material according to the porosity, obtaining the addition amount of the pore-forming agent, obtaining the contents of other components of the binder according to the addition amount of the pore-forming agent. S31. Set the porosity division standard, divide 20% - 40% as low porosity, divide 41% - 60% as medium porosity, and divide 61% - 85% as high porosity. S32. Establish a linear model between porosity and the amount of pore-forming agent. The specific formula is: P = λ×(k 1 ×B + k 2 ×C + b); where P is the porosity, B is the mass percentage of the binder in the graphene-carbon solution, C is the mass percentage of the pore-forming agent in the binder, k 1 , k 2are the coefficients of the influence of the binder and the pore-forming agent on the porosity, b is the constant term, representing the basic porosity when both B and C are zero, λ is the substrate modification coefficient, and the substrate modification coefficient is obtained by fitting experimental data; Among them, the pore-forming agent is sodium bicarbonate; S33. Obtain the addition ranges of the pore-forming agent at low porosity, medium porosity, and high porosity according to the model, and combine the obtained addition ranges of the pore-forming agent with the process constraint conditions to determine the addition ranges of other components of the binder; S34. Prepare polyurethane, carbon nanotubes, amino silane, glutaraldehyde, ethanol-water mixture, and the pore-forming agent is sodium bicarbonate according to the obtained proportion ranges, and prepare the binder.

[0011] As a preferred embodiment, the specific steps of obtaining the addition ranges of the pore-forming agent at low porosity, medium porosity, and high porosity according to the model, and obtaining the addition ranges of other components of the binder are as follows: S331. The addition range of the pore-forming agent at low porosity is 6% - 8%, the addition range of the pore-forming agent at medium porosity is 8% - 12%, and the addition range of the pore-forming agent at high porosity is 12% - 14%; S332. According to the addition range of the pore-forming agent at low porosity, the ranges of other additives including polyurethane, carbon nanotubes, amino silane, glutaraldehyde, and ethanol-water mixture are 50% - 54%, 1% - 2%, 1.5% - 2%, 0.8% - 1%, and 30% - 40% respectively; according to the addition range of the pore-forming agent at medium porosity, the ranges of other additives including polyurethane, carbon nanotubes, amino silane, glutaraldehyde, and ethanol-water mixture are 48% - 52%, 1.5% - 2%, 1.5% - 2%, 0.8% - 1%, and 36% - 45% respectively; according to the addition range of the pore-forming agent at high porosity, the ranges of other additives including polyurethane, carbon nanotubes, amino silane, glutaraldehyde, and ethanol-water mixture are 42% - 50%, 1.5% - 2%, 1.2% - 2%, 0.8% - 1%, and 43% - 50% respectively; S333. The ethanol-water mixture is a mixture of ethanol and water, and the component ratio of ethanol to water is 6:4.

[0012] As a preferred embodiment, the steps of preparing polyurethane, carbon nanotubes, amino silane, glutaraldehyde, ethanol-water mixture, and the pore-forming agent is sodium bicarbonate according to the obtained proportion ranges, and preparing the binder include the following steps: S341. Prepare ethanol and deionized water, mix ethanol and deionized water according to a volume ratio of 6:4 to obtain an ethanol-water mixture, then add PU to part of the ethanol-water mixture, heat it in a water bath at 60 °C, set the magnetic stirring parameter to 500 rpm, stir for 30 minutes until completely dissolved, then add amino silane and glutaraldehyde in sequence, and set the stirring parameter to 400 rpm and stir for 10 minutes; When dissolving polyurethane, the temperature ≤ 65 °C to prevent the performance of the binder from failing due to the degradation of polyurethane dissolution.

[0013] S342. Slowly sprinkle in carbon nanotube powder and synchronously perform ultrasonic treatment for 20 minutes, set the parameters to 40 kHz and 200 W. After the treatment is completed, cool the system temperature to below 40 °C, add sodium bicarbonate powder, set the stirring parameter to 200 rpm and stir for 10 minutes, and finally set the vacuum degree to -0.1 MPa for vacuum degassing, and the degassing time is 15 minutes.

[0014] As a preferred embodiment, the preparation of the carbon-based mother liquor and the addition of the binder to the carbon-based solution to prepare a carbon-based mixture include the following steps: S41. Prepare carbon-based powder, ethanol-water mixture, dispersant, and binder according to the amount; S42. Take the ethanol-water mixture, add the carbon-based powder and the dispersant to the ethanol-water mixture, stir magnetically for 30 minutes, set the stirring parameter to 200 rpm, then perform ultrasonic dispersion, set the parameter to 40 kHz and ultrasonic for 60 minutes, and control the temperature with an ice bath to make the temperature less than 30 °C; S43. Add the binder to the carbon-based dispersion, set the magnetic stirring parameter to increase gradually from 200 rpm to 1000 rpm, and stir for 30 minutes at the same time; after stirring is completed, perform ultrasonic treatment for 5 minutes, set the parameter to 40 kHz and 100 W, and finally perform vacuum degassing for 10 minutes, set the parameter to -0.1 MPa.

[0015] As a preferred embodiment, the preparation of the carbon-based powder, ethanol-water mixture, dispersant, and binder according to the amount includes the following steps: S411. The proportion range of each raw material is carbon-based powder, 3% - 8%, binder, 6% - 14%, dispersant, 0.1% - 0.5%, ethanol-water mixture 77% - 90%; where the dispersant is SDBS.

[0016] An application of a nitrogen-doped graphene carbon material, which uses the preparation method of a nitrogen-doped graphene carbon material described in any one of the above, includes the following steps: S1. Prepare polyester fiber and pure cotton base cloth, soak the cloth in a mixture of deionized water and ethanol and perform ultrasonic treatment for 30 min to wash away impurities and stains, and then dry it in a vacuum oven at 50 °C for 30 min; S2. Immerse the polyester fiber and the pure cotton base fabric in the solution of graphene carbide with binders of different concentrations for 20 minutes in sequence, and then dry them in a vacuum oven at 50 °C for 30 minutes; S3. Go through 3 dipping cycles to obtain the polyester fiber and the pure cotton base fabric with completed infiltration.

[0017] The beneficial effects of the present invention are as follows: 1. By preparing the binder and adding it into the solution of graphene carbide, the present invention can effectively improve the bonding strength between base fabrics with different porosities and the solution of graphene carbide. The polyurethane in the binder serves as a flexible bonding phase, which can not only penetrate the pores of the base fabric to form mechanical anchoring, but also construct a three-dimensional conductive network with graphene carbide powder through molecular chain entanglement, significantly enhancing the interfacial bonding force and anti-peeling performance. The carbon nanotubes serve as a reinforcing phase in the binder, forming a bridging effect with graphene carbide powder, further reducing the interfacial contact resistance, increasing the conductivity of the composite material. At the same time, the amino silane can also greatly enhance the covalent bonding strength between the coating and the substrate through siloxane bonds, solving the problem of easy shedding of traditional coatings. The pore-forming agent endows the material with an adjustable pore structure through precise addition ratio and process control, and forms a synergistic enhancement effect with the binder and the solution of graphene carbide.

[0018] 2. By dividing the porosities of different base fabrics into low porosity, medium porosity, and high porosity, and establishing the relationship between different porosities and the addition amount of the pore-forming agent, the present invention can regulate the proportion range of the pore-forming agent in the binder, and can also obtain an accurate range of the pore-forming agent. In addition, by determining the proportion range of the pore-forming agent, the determination of the proportion ranges of other components can be quickly realized, achieving the high-efficiency adaptation and performance optimization of flexible materials in scenarios such as electromagnetic shielding, catalytic carriers, and flexible sensing. Description of the Drawings

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0020] Figure 1 It is a preparation flow chart of a nitrogen-doped graphene carbon material according to an embodiment of the present invention.

[0021] Figure 2 It is a schematic diagram of the infiltration process of the solution of graphene carbide according to an embodiment of the present invention.

[0022] Figure 3 It is a schematic diagram after the pure cotton fabric and the polyester fiber are infiltrated according to an embodiment of the present invention.

[0023] Figure 4It is the curve graph of the electrical shielding effectiveness of the first test and the test after being placed for dozens of days in the embodiments of the present invention.

[0024] In the figure: A, pure cotton fabric; B, polyester fiber; C, curve of the electrical shielding effectiveness of the first test; D, curve of the electrical shielding effectiveness of the test after being placed for dozens of days. Specific embodiments

[0025] To further illustrate each embodiment, the present invention provides accompanying drawings. These drawings are part of the disclosure of the present invention. They are mainly used to illustrate the embodiments and can be combined with the relevant descriptions in the specification to explain the operating principles of the embodiments. With reference to these contents, those of ordinary skill in the art should be able to understand other possible embodiments and the advantages of the present invention. The components in the figures are not drawn to scale, and similar component symbols are usually used to represent similar components.

[0026] According to an embodiment of the present invention, a preparation method and application of a nitrogen-doped graphene carbon material are provided.

[0027] Now, the present invention will be further described in conjunction with the accompanying drawings and specific embodiments. As Figures 1 - 3 shown, a preparation method of a nitrogen-doped graphene carbon material according to an embodiment of the present invention includes the following steps: S1. Prepare graphene powder, urea, zirconia grinding balls, and add ethanol for mixing. After mixing is completed, perform centrifugal separation and vacuum drying to obtain pre-doped graphene powder; Further, S11. Mix graphene powder, urea, and zirconia grinding balls, and add ethanol as a dispersion medium; S12. After mixing is completed, perform centrifugal separation, wash with ethanol 3 times to remove unreacted urea, and vacuum dry at 60 °C for 12 hours to obtain pre-doped graphene powder; S2. Pass in Ar and H 2 for high-temperature annealing. After annealing is completed, pass in a mixed gas of NH 3 and Ar to supplement pyridine nitrogen; Further, passing in Ar and H 2 for high-temperature annealing and passing in a mixed gas of NH 3 and Ar to supplement pyridine nitrogen includes the following steps: S21. Pass in 95% Ar and 5% H 2 , set the flow rate to 50 mL / min, the temperature to 800 °C, the time to 2 hours, and the heating rate to 5 °C / min; S22. Perform plasma treatment, pass in a mixed gas of NH 3 and Ar, the ratio of NH 3 to Ar is 1:4, set the power to 100 W, and the treatment time to 10 minutes to supplement pyridine nitrogen.

[0028] S3. Divide the base fabric materials according to the porosity, obtain the addition amount of the pore-forming agent, obtain the contents of other components of the binder according to the addition amount of the pore-forming agent, and prepare the binder. Further, dividing the base fabric materials according to the porosity, obtaining the addition amount of the pore-forming agent, obtaining the contents of other components of the binder according to the addition amount of the pore-forming agent, and preparing the binder includes the following steps: S31. Set the porosity division standard, divide 20% - 40% as low porosity, divide 41% - 60% as medium porosity, and divide 61% - 85% as high porosity. S32. Establish a linear model between the porosity and the amount of pore-forming agent. The specific formula is: P = λ×(k 1 ×B + k 2 ×C + b); where P is the porosity, B is the mass percentage of the binder in the carbon-ene solution, C is the mass percentage of the pore-forming agent in the binder, k 1 , k 2 are the coefficients of the influence of the binder and the pore-forming agent on the porosity respectively, b is the constant term, representing the basic porosity when both B and C are zero, λ is the base fabric correction coefficient, and the base fabric correction coefficient is obtained by fitting experimental data. Among them, the pore-forming agent is sodium bicarbonate. It should be noted that the formula is established based on the data in Table 1, Table 2, Table 3, Table 4, and Table 5 below: Experimental Table 1 of Kevlar Fiber Fireproof and Flame Retardant Fabric

[0029] Experimental Table 2 of Glass Fiber Fireproof and Flame Retardant Fabric

[0030] Experimental Table 3 of Nylon

[0031] Experimental Table 4 of Polyester Fiber

[0032] Experimental Table 5 of Cotton

[0033] It should be noted that the initial base fabric porosity in Table 1, Table 2, Table 3, Table 4, and Table 5 is the base fabric porosity measured before the experiment, and the measured porosity is the porosity that can be generated under this proportion of pore-forming agent. S33. Obtain the addition ranges of the pore-forming agent at low porosity, medium porosity, and high porosity according to the model, and combine the obtained addition ranges of the pore-forming agent with the process constraint conditions to determine the addition ranges of other components of the binder; The specific steps for obtaining the addition ranges of the pore-forming agent at low porosity, medium porosity, and high porosity according to the model and combining the obtained addition ranges of the pore-forming agent with the process constraint conditions to determine the addition ranges of other components of the binder are as follows: S331. The obtained addition ranges of the pore-forming agent at low porosity are 6% - 8%, at medium porosity are 8% - 12%, and at high porosity are 12% - 14%; It should be noted that the constraint conditions include the total amount conservation constraint and the functional constraint. Among them, the total amount conservation constraint is: polyurethane + carbon nanotubes + aminosilane + glutaraldehyde + ethanol-water = 100% - pore-forming agent%. The functional constraint is that polyurethane ≥ 42% to ensure the peel strength, the range of carbon nanotubes does not exceed 1.0% - 2.5%, and the ethanol-water mixture accounts for the remaining amount ± 3% to regulate the solution viscosity so that the solution viscosity is between 800 - 1500 cP; S332. According to the addition range of the pore-forming agent at low porosity, the ranges of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are respectively: 50% - 54%, 1% - 2%, 1.5% - 2%, 0.8% - 1%, 30% - 40%; According to the addition range of the pore-forming agent at medium porosity, the ranges of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are respectively: 48% - 52%, 1.5% - 2%, 1.5% - 2%, 0.8% - 1%, 36% - 45%; According to the addition range of the pore-forming agent at high porosity, the ranges of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are respectively: 42% - 50%, 1.5% - 2%, 1.2% - 2%, 0.8% - 1%, 43% - 50%; S333. The ethanol-water mixture is a mixture of ethanol and water, and the component ratio of ethanol to water is 6:4; It should be noted that dynamically adjusting the contents of other components according to the proportion range of the pore-forming agent can balance the pore structure, mechanical strength, and functional properties of the material through the synergistic effect, and ensure the stability of key properties while increasing the porosity; S34. Prepare polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, ethanol-water mixture, and the pore-forming agent sodium bicarbonate according to the obtained proportion ranges, and carry out the preparation of the binder; Prepare polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, ethanol-water mixture, and pore-forming agent sodium bicarbonate according to the obtained proportion range, and carry out the preparation of the binder, including the following steps: Further, in S341, prepare ethanol and deionized water, mix ethanol and deionized water according to a volume ratio of 6:4 to obtain an ethanol-water mixture, then add PU to part of the ethanol-water mixture, heat it in a water bath at 60 °C, set the magnetic stirring parameter to 500 rpm, stir for 30 minutes until completely dissolved, then add aminosilane and glutaraldehyde in sequence, and set the stirring parameter to 400 rpm and stir for 10 minutes; When dissolving polyurethane, the temperature ≤ 65 °C to prevent the performance of the binder from failing due to the degradation of polyurethane during dissolution. In S342, slowly sprinkle in carbon nanotube powder and simultaneously perform ultrasonic treatment for 20 minutes, set the parameters to 40 kHz and 200 W. After the treatment is completed, cool the system temperature to below 40 °C, add sodium bicarbonate powder, set the stirring parameter to 200 rpm and stir for 10 minutes, and finally set the vacuum degree to -0.1 MPa for vacuum degassing, and the degassing time is 15 minutes.

[0034] In S4, prepare an ene-carbon mother liquor and add the binder to the ene-carbon solution to prepare an ene-carbon mixture.

[0035] Further, the preparation of the ene-carbon mother liquor and adding the binder to the ene-carbon solution to prepare the ene-carbon mixture includes the following steps: In S41, prepare ene-carbon powder, ethanol-water mixture, dispersant, and binder according to the amount; In S42, take the ethanol-water mixture, add the ene-carbon powder and the dispersant to the ethanol-water mixture, stir magnetically for 30 minutes, set the stirring parameter to 200 rpm, then perform ultrasonic dispersion, set the parameter to 40 kHz and ultrasonic for 60 minutes, and simultaneously control the temperature with an ice bath to make the temperature less than 30 °C; In S43, add the binder to the ene-carbon dispersion, set the magnetic stirring parameter to accelerate gradient from 200 rpm to 1000 rpm, and stir for 30 minutes at the same time; after stirring is completed, perform ultrasonic treatment for 5 minutes, set the parameters to 40 kHz and 100 W, and finally perform vacuum degassing for 10 minutes, set the parameter to -0.1 MPa.

[0036] Further, the preparation of ene-carbon powder, ethanol-water mixture, dispersant, and binder according to the amount includes the following steps: In S411, the proportion range of each raw material is: ene-carbon powder, 3% - 8%, binder, 6% - 14%, dispersant, 0.1% - 0.5%, ethanol-water mixture 77% - 90%; the dispersant is SDBS.

[0037] It should be noted that the optimal proportion of the binder is obtained through experiments, and the experimental data are shown in the following Tables 6, 7, and 8: Experimental Table 6 of the low-porosity base fabric

[0038] Experimental Table 7 of the medium-porosity base fabric

[0039] Experimental Table 8 of the high-porosity base fabric

[0040] From the experimental data in Tables 6, 7, and 8, it can be concluded that the optimal proportion of the binder is 6% - 14%.

[0041] An application of a nitrogen-doped graphene carbon material, which adopts the preparation method of a nitrogen-doped graphene carbon material in any one of the above, and includes the following steps: S1. Prepare polyester fibers and pure cotton base fabrics, soak the fabrics in a mixture of deionized water and ethanol for 30 min by ultrasonic treatment to wash away impurities and stains, and then dry them in a vacuum oven at 50 °C for 30 min; S2. Dip the polyester fibers and pure cotton base fabrics in the graphene carbon solution with binders of different concentrations for 20 min in sequence, and then dry them in a vacuum oven at 50 °C for 30 min; S3. Experience 3 dipping cycles to obtain the polyester fibers and pure cotton base fabrics with complete infiltration.

[0042] It should be noted that the experimental data after the infiltration of polyester fibers and pure cotton fabrics are shown in the following Table 9: Experimental Data Table 9 after Infiltration

[0043] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing nitrogen-doped graphene carbon material, characterized in that: The method comprises the following steps: S1, preparing graphene powder, urea, and zirconium oxide grinding balls, adding ethanol to mix, and after mixing, centrifuging and vacuum drying to obtain pre-doped graphene powder; S2, introducing Ar and H2 for high temperature annealing, after the annealing is completed, introducing NH3 and Ar mixed gas, supplementing pyridine nitrogen; S3, dividing the base fabric material according to the porosity, and obtaining the amount of the pore-forming agent added, obtaining the content of other components of the binder according to the amount of the pore-forming agent added, and preparing the binder; S4, preparing an olefin-carbon mother solution, and adding a binder into the olefin-carbon solution to prepare an olefin-carbon mixed solution.

2. The method for preparing a nitrogen-doped graphene carbon material according to claim 1, characterized in that: The preparation of graphene powder, urea, and zirconium oxide grinding balls, and the addition of ethanol for mixing, and the centrifugal separation and vacuum drying after the mixing are completed to obtain the pre-doped graphene powder comprises the following steps: S11, mixing graphene powder, urea, and zirconium oxide grinding balls, and adding ethanol as a dispersion medium; S12. After the mixing is completed, centrifugal separation is performed, and unreacted urea is removed by washing with ethanol for 3 times, and vacuum drying is performed at 60° C. for 12 hours to obtain pre-doped graphene powder.

3. The method for preparing a nitrogen-doped graphene carbon material according to claim 1, characterized in that: The step of introducing Ar and H2 for high temperature annealing, introducing NH3 and Ar mixed gas after the annealing is completed, and supplementing pyridine nitrogen comprises the following steps: S21, introduce 95% Ar and 5% H2, set the flow rate to 50 mL / min, the temperature to 800°C, the time to 2 hours, and the heating rate to 5°C / min; S22. Plasma treatment was performed by introducing a mixed gas of NH3 and Ar, wherein the ratio of NH3 to Ar was 1:4, the power was set to 100 W, the treatment time was 10 minutes, and pyridine nitrogen was supplemented.

4. The method for preparing a nitrogen-doped graphene carbon material according to claim 1, characterized in that: The base fabric material is divided according to the porosity, and the amount of the pore-forming agent added is obtained, and the content of other components of the binder is obtained according to the amount of the pore-forming agent added, and the preparation of the binder includes the following steps: S31. Set a porosity classification standard, classify 20% to 40% as low porosity, classify 41% to 60% as medium porosity, and classify 61% to 85% as high porosity; S32. Establish a linear model of porosity and pore-forming dosage. The specific formula is: P = λ × (k1 × B + k2 × C + b); Wherein, P is the porosity, B is the mass percentage of the binder in the olefinic carbon solution, C is the mass percentage of the pore former in the binder, k1 and k2 are the coefficients of the binder and pore former on the porosity, respectively, b is a constant term, representing the basic porosity when B and C are both zero, λ is the base fabric correction coefficient, and the base fabric correction coefficient is obtained by fitting the experimental data; Wherein, the pore-forming agent is sodium bicarbonate; S33, obtaining the addition range of the pore former under low porosity, medium porosity and high porosity according to the model, and determining the addition range of other components of the binder by combining the obtained addition range of the pore former with the process constraints; S34, preparing polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, ethanol-water mixture, and sodium bicarbonate as a pore-forming agent according to the obtained ratio range, and preparing a binder.

5. The method for preparing a nitrogen-doped graphene carbon material according to claim 4, characterized in that: The specific steps of obtaining the addition range of the pore former under low porosity, medium porosity and high porosity according to the model and obtaining the addition range of other components of the binder are as follows: S331, the addition range of the pore former under low porosity is 6% to 8%, the addition range of the pore former under medium porosity is 8% to 12%, and the addition range of the pore former under high porosity is 12% to 14%; S332. According to the addition range of the pore-forming agent at low porosity, the ranges of the components of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are: 50%-54%, 1%-2%, 1.5%-2%, 0.8%-1%, and 30%-40%; according to the addition range of the pore-forming agent at medium porosity, the ranges of the components of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are: 48%-52%, 1.5%-2%, 1.5%-2%, 0.8%-1%, and 36%-45%; according to the addition range of the pore-forming agent at high porosity, the ranges of the components of other additives including polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, and ethanol-water mixture are: 42%-50%, 1.5%-2%, 1.2%-2%, 0.8%-1%, and 43%-50%; S333, the ethanol-water mixture is a mixture of ethanol and water, and the composition ratio of ethanol to water is 6:

4.

6. The method for preparing a nitrogen-doped graphene carbon material according to claim 4, characterized in that: The steps of preparing polyurethane, carbon nanotubes, aminosilane, glutaraldehyde, ethanol-water mixture, and sodium bicarbonate as the pore-forming agent according to the obtained ratio range and preparing the binder include the following steps: S341, prepare ethanol and deionized water, and mix the ethanol and deionized water in a volume ratio of 6:4 to obtain an ethanol-water mixture, then add PU to part of the ethanol-water mixture, heat it in a 60°C water bath, set the magnetic stirring parameter to 500 rpm, stir for 30 minutes until it is completely dissolved, then add aminosilane and glutaraldehyde in sequence, set the stirring parameter to 400 rpm and stir for 10 minutes; S342. Slowly sprinkle carbon nanotube powder and perform ultrasonic treatment for 20 minutes. Set the parameters to 40 kHz, 200 W. After the treatment, reduce the system temperature to below 40°C, add sodium bicarbonate powder, set the stirring parameters to 200 rpm and stir for 10 minutes. Finally, set the vacuum degree to -0.1 MPa for vacuum degassing, and the degassing time is 15 minutes.

7. The method for preparing a nitrogen-doped graphene carbon material according to claim 6, characterized in that: The step of preparing an olefin-carbon mother solution and adding a binder to the olefin-carbon solution to prepare an olefin-carbon mixed solution comprises the following steps: S41, preparing carbonene powder, ethanol-water mixture, dispersant, and binder according to the amount; S42, taking an ethanol-water mixture, and adding the olefinic carbon powder and the dispersant to the ethanol-water mixture, magnetically stirring for 30 minutes, and setting the stirring parameter to 200 rpm, and then performing ultrasonic dispersion, setting the parameter to 40 kHz ultrasound for 60 minutes, and at the same time controlling the temperature with an ice bath to make the temperature less than 30°C; S43. Add the binder to the olefinic carbon dispersion, set the magnetic stirring parameters to accelerate from 200 rpm to 1000 rpm, and stir for 30 minutes; after stirring, ultrasonicate for 5 minutes, set the parameters to 40 kHz, 100 W, and finally perform vacuum degassing for 10 minutes, setting the parameters to -0.1 MPa.

8. The method for preparing nitrogen-doped graphene carbon material according to claim 7, characterized in that: The step of preparing the carbon olefin powder, the ethanol-water mixture, the dispersant, and the binder in the appropriate amounts comprises the following steps: S411. The proportions of the raw materials are as follows: olefinic carbon powder, 3% to 8%, binder, 6% to 14%, dispersant, 0.1% to 0.5%, and ethanol-water mixture, 77% to 90%; wherein the dispersant is SDBS.

9. An application of a nitrogen-doped graphene carbon material, wherein the application adopts the method for preparing a nitrogen-doped graphene carbon material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Prepare polyester fiber and pure cotton base fabric, soak the fabric in a mixture of deionized water and ethanol for 30 minutes, wash away impurities and stains, and then dry them in a vacuum oven at 50°C for 30 minutes; S2, the polyester fiber and the pure cotton base fabric were sequentially dipped into the olefin carbon solution with different concentrations of the binder for 20 min, and then dried in a vacuum oven at 50°C for 30 min; S3. After three dipping cycles, the impregnated polyester fiber and pure cotton base fabric are obtained.

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