CN110165229B - Graphene composite carbon fiber paper and preparation method and application thereof - Google Patents
Graphene composite carbon fiber paper and preparation method and application thereof Download PDFInfo
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- CN110165229B CN110165229B CN201910451169.1A CN201910451169A CN110165229B CN 110165229 B CN110165229 B CN 110165229B CN 201910451169 A CN201910451169 A CN 201910451169A CN 110165229 B CN110165229 B CN 110165229B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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Abstract
The invention relates to a preparation method of graphene composite carbon fiber paper, which comprises the following steps: plating a layer of metal on the surface of the carbon fiber by chemical plating to generate a carbon fiber/metal compound; growing graphene on the carbon fiber/metal composite by vapor deposition to generate graphene modified carbon fiber; and (3) preparing graphene modified carbon fiber paper from the obtained graphene modified carbon fiber by using carbon paper. The invention also relates to graphene composite carbon fiber paper prepared by the method and application thereof. Compared with other similar technologies, the method disclosed by the invention has the advantages that the utilization rate of graphene in carbon fiber paper is highest, and the graphene is dispersed most uniformly.
Description
Technical Field
The invention relates to the field of preparation and application of new materials, in particular to graphene composite carbon fiber paper and a preparation method and application thereof.
Background
The gas diffusion layer is an important component of the proton exchange membrane fuel cell, not only plays a role of supporting the catalyst layer, but also is a diffusion channel of reaction gas and product water, and determines the performance of the fuel cell to a great extent. Due to the special use environment, higher requirements are put on the performance of the gas diffusion layer, and the specific requirements are as follows: 1. the contact resistance is small; 2. has certain mechanical strength, bending resistance and compression resistance; 3. the conveying of gas and the leading-out of water are facilitated; 4. the conductivity is high; 5. the heat transfer speed is high; 6. stronger electrochemical corrosion resistance.
At present, carbon fibers are mainly used as raw materials of the gas diffusion layer, the requirements of the gas diffusion layer are met to a certain extent by virtue of excellent chemical and thermal stability of the carbon fibers, but the mechanical strength, the heat conduction performance and the electrical conductivity of the carbon fibers still cannot meet the increasingly improved performance requirements of the fuel cell.
GrapheneThe material is a honeycomb planar film formed by carbon atoms in an sp2 hybridization mode, is a quasi-two-dimensional material with the thickness of only one atomic layer, is called monoatomic layer graphite, and is a novel nano material which is thin, has the highest strength and has the strongest electric and heat conducting performance and is discovered at present. The theoretical conductivity of the graphene can reach 106S/cm, and the theoretical specific surface area can reach 2630m2The theoretical breaking strength can reach 130Gpa, the thermal conductivity coefficient can reach 5000W/(m.k), and the carbon paper is an ideal carbon paper material.
Chinese patent application No. CN107815926A, entitled "method for preparing high-strength composite carbon paper", discloses that under the action of an external electric field, carbon nanotubes are used as a framework, and high-strength graphene is introduced into the framework, so that the mechanical properties and electrical conductivity of the carbon paper can be greatly improved. However, in the actual preparation process, the graphene dispersion liquid used in the method is not pure graphene, but a surface dispersant and the like are added, under the action of an electric field force, graphene cannot rapidly and uniformly enter a carbon nanotube framework, and the obtained carbon paper has nonuniform graphene, so that the strength is nonuniform.
The chinese patent with publication number CN207558942U discloses that carbon fiber is used as a substrate, doped with carbon nanotubes, and then coated with graphene and PTFE, and the prepared carbon paper has high conductivity, excellent drainage performance and stability. The single-layer graphene with non-uniform graphene existing in the carbon paper in the method cannot improve the high conductivity of the carbon paper by utilizing the high conductivity of the graphene.
Disclosure of Invention
In view of the above, the main purpose of the present invention is to provide graphene composite carbon fiber paper, and a preparation method and an application thereof.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The preparation method of the graphene composite carbon fiber paper provided by the invention comprises the following steps:
the method comprises the following steps: plating a layer of metal on the surface of the carbon fiber by chemical plating to generate a carbon fiber/metal compound;
step two: growing graphene on the carbon fiber/metal composite by vapor deposition to generate graphene modified carbon fiber;
step three: and (3) preparing graphene modified carbon fiber paper from the obtained graphene modified carbon fiber by using carbon paper.
Further, in the first step, the diameter of the carbon fiber is 5-30 μm, and the length of the carbon fiber is 0.5-300 mm.
Further, in the first step, the metal is selected from copper, nickel, chromium, tin or their combination.
Further, in the first step, the thickness of the metal is 0.1-10 μm.
Further, in the first step, the electroplating solution used in the electroless plating comprises a main salt, a reducing agent, a complexing agent, a conductive salt and a buffering agent; the main salt is selected from a chlorinated metal compound or a sulfated metal compound, and the addition amount of the main salt is 0.1g/L-500 g/L; the reducing agent is selected from one of formaldehyde, sodium hypophosphite, sodium borohydride, alkylamine borane or hydrazine, and the addition amount of the reducing agent is 0.1g/L-500 g/L; the complexing agent is one of citrate, tartrate, cyanide or ethylene diamine tetraacetic acid, and the addition amount of the complexing agent is 0.1g/L-500 g/L; the conductive salt is selected from one of sodium hydroxide, potassium hydroxide or sulfuric acid, and the addition amount of the conductive salt is 0.1g/L-500 g/L; the buffer is selected from one of sodium acetate, borax, potassium pyrophosphate or benzotriazole, and the addition amount of the buffer is 0.1g/L-500 g/L.
Further, in the first step, the electroplating solution used in the electroless plating further comprises an accelerator and a surfactant; the accelerator is selected from one of malonic acid, succinic acid, aminoacetic acid, propionic acid or sodium fluoride, and the addition amount of the accelerator is 0.1g/L-500 g/L; the surfactant is selected from one of dodecyl sulfate, dodecyl sulfonate or n-octyl sodium sulfate, and the addition amount of the surfactant is 0.1g/L-500 g/L.
Further, in the first step, the carbon fiber/metal composite is generated by: preparing an electroplating solution, putting the electroplating solution into an electrolytic tank, then putting carbon fibers, adjusting the current density to 0.1-1A, continuously electroplating for 10-20 min, filtering the carbon fibers, taking out the carbon fibers, washing the carbon fibers with deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fibers for 6-12 hours at the temperature of 90-95 ℃ in vacuum to finally obtain the carbon fiber/copper composite.
Further, the method also comprises the step of pretreating the carbon fiber before the step one; the pretreatment of the carbon fiber specifically comprises the following steps:
1) weighing carbon fibers, putting the carbon fibers into acetone, carrying out ultrasonic treatment for 10-12 hours, taking out the carbon fibers, and carrying out vacuum drying at 90-95 ℃ for 12-20 hours;
2) mixing concentrated sulfuric acid and concentrated nitric acid, adding the carbon fiber obtained in the step 1), performing ultrasonic treatment for 5-10 hours, filtering, and washing with deionized water until the pH value of the filtrate is 7;
3) dropwise adding ammonia water into the silver nitrate solution until the solution is clear, putting the carbon fiber obtained in the step 2) into the solution, performing ultrasonic treatment for 2-5 hours, filtering, washing with deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fiber for 5-12 hours at 90 ℃ in vacuum.
Further, in the second step, the precursor gas used for the vapor deposition is at least one selected from methane, ethylene, formaldehyde, acetylene, hydrogen, propylene and propyne.
Further, in the second step, the temperature of the vapor deposition is 1000-3000 ℃, and the time is 1-10 hours.
Further, in the second step, the number of layers of the graphene formed by vapor deposition is 1-10; the thickness of the graphene is 0.335-3.35 nm.
Further, in the second step, the generation of the graphene modified carbon fiber specifically includes: and (3) placing the carbon fiber/copper composite obtained in the step one into a CVD (chemical vapor deposition) deposition chamber, heating to 1200-1300 ℃ in 20-30min through hydrogen-argon mixed gas, keeping the temperature for 20min, stopping inputting, reacting for 30min through precursor gas, evacuating the previous precursor gas through nitrogen, cooling to normal temperature, and taking out a resultant to obtain the carbon fiber/copper/graphene composite, namely the graphene modified carbon fiber.
Further, in the second step, the hydrogen-argon mixed gas consists of 90% (v/v) of argon and 10% (v/v) of hydrogen.
Further, in the third step, a step of manufacturing a graphene modified carbon fiber paper precursor is also included; the pulping additive used in the preparation of the graphene modified carbon fiber paper precursor is at least one selected from polytetrafluoroethylene solution, polyacrylamide solution, polytetrafluoroethylene solution, polyacrylic acid solution, sodium alginate solution, phenolic resin solution or sodium carboxymethylcellulose solution.
Further, in the third step, the graphene modified carbon fiber paper resin is cured, and the thermosetting polymer resin used in the curing is at least one selected from urea resin, melamine-methanol resin, epoxy resin, polyurethane, polyimide, phenolic resin or organic silicon resin.
Further, in the third step, the preparation of the graphene modified carbon fiber paper from the graphene modified carbon fiber specifically comprises: weighing the carbon fiber/copper/graphene compound obtained in the step two, placing the carbon fiber/copper/graphene compound in a pulping additive, stirring for 30min, then carrying out ultrasonic treatment for 30min, and alternately carrying out 5 times to obtain polyacrylamide solution slurry containing the carbon fiber/copper/graphene compound; and then, dipping the precursor into a 300-mesh square filter screen, filtering solid substances in the slurry on the screen to obtain a graphene modified carbon fiber carbon paper precursor, dipping the precursor into a thermosetting polymer resin solution with the concentration of 1-2 wt% for 3 hours, then carrying out hot press molding under the conditions of 160-180 ℃, the pressure of 5-8Mpa and the hot press time of 5-10min, repeatedly repeating the dipping-hot press molding process for 2 times, and then carrying out high-temperature carbonization on the prepared sample at the temperature of 1200-1500 ℃ for 3 hours in an argon atmosphere to finally obtain the graphene modified carbon fiber carbon paper.
According to the graphene composite carbon fiber paper provided by the invention, the graphene composite carbon fiber paper comprises carbon fibers, a metal coating is arranged on the carbon fibers, and a graphene layer is arranged on the metal coating.
Further, the number of graphene layers is a single layer.
Further, the graphene composite carbon fiber paper is prepared by the method.
According to the fuel cell provided by the invention, the fuel cell comprises carbon paper, and the carbon paper is the graphene composite carbon fiber paper.
By means of the technical scheme, the invention at least has the following advantages:
1. compared with other similar technologies, the method disclosed by the invention has the advantages that the utilization rate of graphene in carbon fiber paper is highest, and the graphene is dispersed most uniformly;
2. according to the method, the metal coating and the carbon fiber can be fused through chemical plating, so that graphene can grow on the metal coating, namely the graphene, the carbon fiber and the metal body are fused to form a structural three-layer uniform structure, and further the performances such as mechanics, conductivity or resistivity are improved;
3. according to the method, the graphene grows on the metal surface through CVD, so that the graphene is more uniformly distributed on the surface of the carbon fiber, the high electrical conductivity, the high strength and the high thermal conductivity of the graphene are fully exerted, and the gas entering blockage caused by the graphene inevitably in other methods is avoided;
4. The method improves the conductivity and the heat transfer efficiency of the carbon paper from the aspect of single carbon fiber modification instead of the prior carbon paper phase doping modification.
Drawings
FIG. 1 is a schematic representation of the structure of a carbon fiber according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a carbon fiber metal layer according to an embodiment of the present invention;
fig. 3 is a schematic view of graphene-modified carbon fibers according to an embodiment of the present invention;
fig. 4 is a graph illustrating an influence of graphene modification on a thermal conductivity of carbon paper according to an embodiment of the present invention;
fig. 5 is a graph illustrating the effect of graphene modification on the resistivity of carbon paper according to an embodiment of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Materials, reagents and the like used in the following examples are commercially available.
Example 1
As shown in fig. 1 to fig. 3, the present embodiment provides a preparation method of graphene-modified carbon fiber paper, including the following steps:
step one, chemical plating of carbon fiber
Firstly, pretreating carbon fibers:
1. 30.0g of carbon fiber is weighed and put into 500ml of acetone, and is subjected to ultrasonic treatment (a common ultrasonic instrument with the power of 600W) for 12 hours, and then is taken out and is dried in vacuum at 90 ℃ for 12 hours.
2. Mixing 100ml of concentrated sulfuric acid (the mass fraction of the concentrated sulfuric acid is 98%) with 100ml of concentrated nitric acid (the mass fraction of the concentrated sulfuric acid is 69%), adding the carbon fiber obtained in the first step into the mixture, performing ultrasonic treatment (a common ultrasonic instrument, the power is 600W) for 5 hours, filtering (filtering through a conventional filter funnel), and washing with a large amount of deionized water until the pH value of the filtrate is 7.
3. And (3) dropwise adding ammonia water with the mass fraction of 20% into 5g/L silver nitrate solution until the solution is clear (silver ammonia solution is generated), putting the carbon fiber obtained in the second step into the solution, performing ultrasonic treatment (common ultrasonic instrument, power is 600W) for 2 hours, filtering (filtering through a conventional filter funnel), washing with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fiber for 12 hours at 90 ℃ in vacuum.
And then, chemical copper plating:
preparing 250ml of electroplating solution for electroless copper plating, wherein the electroplating solution contains 30mg/L of formaldehyde, 40g/L of potassium hydroxide, 30g/L of copper sulfate, 20g/L of disodium ethylene diamine tetraacetate, 200g/L of sodium citrate and 10g/L of benzotriazole, putting the electroplating solution into an electrolytic tank, then putting carbon fibers, adjusting the current density to be 0.1-1A, continuously electroplating for 20min, filtering the carbon fibers (through a conventional filter funnel), taking out the carbon fibers, cleaning the carbon fibers with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fibers for 12 hours at 90 ℃ in vacuum to finally obtain the carbon fiber/copper composite.
Step two, carbon fiber/metal CVD deposition
And (2) putting the carbon fiber/copper composite obtained in the step one into a CVD (chemical vapor deposition) deposition chamber, reacting for 30min by using a mixed gas of hydrogen and argon (argon gas 90% (v/v) and hydrogen gas 10% (v/v)), heating to 1200 ℃ for about 20min, keeping the temperature for 20min, stopping the reaction, reacting for 30min by using a mixed gas of methane 60% (v/v), formaldehyde 10% (v/v) and acetylene 30% (v/v), discharging the reaction gas (the previous mixed gas) by using nitrogen, cooling to normal temperature, and taking out a product to obtain the carbon fiber/copper/graphene composite, namely the graphene modified carbon fiber.
Step three, manufacturing graphene modified carbon fiber paper
And (3) weighing 20g of the carbon fiber/copper/graphene compound obtained in the second step, placing the carbon fiber/copper/graphene compound in a polyacrylamide solution with the mass fraction of 0.2%, stirring for 30min, then performing ultrasonic treatment (with the power of 600W) for 30min, and performing ultrasonic treatment and stirring alternately for 5 times to obtain the polyacrylamide solution slurry containing the carbon fiber/copper/graphene compound. And then papermaking (a 300-mesh square filter screen is used for soaking in the slurry, then solid matters in the slurry are filtered on the screen), a graphene modified carbon fiber carbon paper precursor is obtained, the precursor is soaked in a phenolic resin solution with the concentration of 2 wt% for 3 hours, then hot-press forming is carried out under the conditions of 180 ℃, the pressure of 8Mpa and the hot-press time of 5min, the soaking-hot-press forming process is repeated for 2 times, and then the prepared sample is carbonized at the high temperature of 1200 ℃ in an argon atmosphere (100% argon) for 3 hours, so that the graphene modified carbon fiber carbon paper is finally prepared. The graphene composite carbon fiber paper comprises carbon fibers 1, wherein a metal coating 2 is arranged on the carbon fibers 1, and a graphene layer 3 is arranged on the metal coating 2 (see fig. 1-3).
Fig. 4 and 5 are graphs comparing the thermal conductivity and resistivity indexes of the carbon fiber paper modified by graphene with those of the carbon fiber paper without modification (suzhou waltz new material); wherein the test method of the heat conductivity coefficient is a steady-state heat flow meter method, and is referred to GB/T10295-; the resistivity test method is a four-probe method.
As shown in FIG. 4, the thermal conductivity of the carbon fiber paper (product structure is shown in FIG. 1) is 4.4W/m.k, and after modification, the obtained graphene composite carbon fiber paper (product structure is shown in FIG. 3) is 7.2W/m.k, which shows that the thermal conductivity can be increased by modification. As shown in fig. 5, the resistivity of the carbon fiber paper (product structure shown in fig. 1) was 0.008 Ω · cm, and the graphene composite carbon fiber paper (product structure shown in fig. 3) obtained after modification was 0.005 Ω · cm, which indicates that the resistivity can be reduced by the modification.
Example 2
As shown in fig. 1 to fig. 3, the present embodiment provides a preparation method of graphene-modified carbon fiber paper, including the following steps:
step one, chemical plating of carbon fiber
Firstly, pretreating carbon fibers:
1. 30.0g of carbon fiber is weighed, put into 500ml of acetone, ultrasonically treated (a common ultrasonic instrument with the power of 600W) for 10 hours, taken out and vacuum-dried at 90 ℃ for 12 hours.
2. Mixing 100ml of concentrated sulfuric acid (the mass fraction of the concentrated sulfuric acid is 98%) with 100ml of concentrated nitric acid (the mass fraction of the concentrated sulfuric acid is 69%), adding the carbon fiber obtained in the first step into the mixture, performing ultrasonic treatment (a common ultrasonic instrument with the power of 600W) for 10 hours, filtering (filtering through a conventional filter funnel), and washing with a large amount of deionized water until the pH value of the filtrate is 7.
3. And (3) dropwise adding ammonia water with the mass fraction of 20% into 5g/L silver nitrate solution until the solution is clear (silver ammonia solution is generated), putting the carbon fiber obtained in the second step into the solution, carrying out ultrasonic treatment (common ultrasonic instrument, power is 600W) for 5 hours, filtering (filtering through a conventional filter funnel), washing with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fiber for 5 hours at 90 ℃ in vacuum.
And then chemical nickel plating:
preparing 250ml of electroplating solution for electroless copper plating, wherein the electroplating solution contains 20mg/L of acetaldehyde, 40g/L of sodium hydroxide, 30g/L of nickel sulfate, 30g/L of disodium ethylene diamine tetraacetate, 180g/L of sodium citrate and 10g/L of tolyltriazole, putting the electroplating solution into an electrolytic tank, then putting carbon fibers, adjusting the current density to 0.5-1.5A, continuously electroplating for 10min, filtering the carbon fibers (filtering through a conventional filter funnel), taking out the carbon fibers, washing the carbon fibers with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fibers for 6 hours at 90 ℃ in vacuum to finally obtain the carbon fiber/nickel composite.
Step two, carbon fiber/metal CVD deposition
And (2) putting the carbon fiber/nickel composite obtained in the step one into a CVD (chemical vapor deposition) deposition chamber, reacting for 30min by using a mixed gas of hydrogen and argon (argon gas 90% (v/v) and hydrogen gas 10% (v/v)), heating to 2000 ℃ for about 30min, keeping the temperature for 60min, stopping the reaction, reacting for 30min by using a mixed gas of methane 60% (v/v), formaldehyde 10% (v/v) and acetylene 30% (v/v), stopping inputting, evacuating the reaction gas (the previous mixed gas) by using nitrogen, cooling to normal temperature, and taking out a product to obtain the carbon fiber/nickel/graphene composite, namely the graphene modified carbon fiber.
Step three, manufacturing graphene modified carbon fiber paper
And (3) weighing 25g of the carbon fiber/nickel/graphene compound obtained in the second step, placing the carbon fiber/nickel/graphene compound in a polytetrafluoroethylene solution with the mass fraction of 0.1%, stirring for 30min, then performing ultrasonic treatment (with the power of 600W) for 30min, and performing ultrasonic treatment and stirring alternately for 5 times to obtain the polytetrafluoroethylene solution slurry containing the carbon fiber/nickel/graphene compound. And then papermaking (a 300-mesh square filter screen is used for soaking in the slurry, then solid matters in the slurry are filtered on the screen), a graphene modified carbon fiber carbon paper precursor is obtained, the precursor is soaked in 1 wt% of phenolic resin solution for 3 hours, then hot press forming is carried out under the conditions of 160 ℃, the pressure of 5Mpa and the hot press time of 10min, the soaking-hot press forming process is repeated for 2 times, and then the prepared sample is carbonized at 1500 ℃ for 3 hours in an argon atmosphere (100% argon), and finally the graphene modified carbon fiber carbon paper is obtained. The graphene composite carbon fiber paper comprises carbon fibers 1, wherein a metal coating 2 is arranged on the carbon fibers 1, and a graphene layer 3 is arranged on the metal coating 2 (see fig. 1-3).
The graphene composite carbon fiber paper modified by graphene is 8.3W/m.k, which shows that the thermal conductivity coefficient can be increased by modification. After modification, the resistivity of the obtained graphene composite carbon fiber paper is 0.0049 omega cm, which shows that the resistivity can be reduced by modification.
Example 3
As shown in fig. 1 to fig. 3, the present embodiment provides a preparation method of graphene-modified carbon fiber paper, including the following steps:
step one, chemical plating of carbon fiber
Firstly, pretreating carbon fibers:
1. 20.0g of carbon fiber is weighed, put into 500ml of acetone, ultrasonically treated (a common ultrasonic instrument with the power of 600W) for 10 hours, taken out and vacuum-dried at 90 ℃ for 20 hours.
2. Mixing 100ml of concentrated sulfuric acid (the mass fraction of the concentrated sulfuric acid is 98%) with 100ml of concentrated nitric acid (the mass fraction of the concentrated sulfuric acid is 69%), adding the carbon fiber obtained in the first step into the mixture, performing ultrasonic treatment (a common ultrasonic instrument, the power is 600W) for 5 hours, filtering (filtering through a conventional filter funnel), and washing with a large amount of deionized water until the pH value of the filtrate is 7.
3. And (3) dropwise adding ammonia water with the mass fraction of 20% into 5g/L silver nitrate solution until the solution is clear (silver ammonia solution is generated), putting the carbon fiber obtained in the second step into the solution, performing ultrasonic treatment (common ultrasonic instrument, power is 600W) for 2 hours, filtering (filtering through a conventional filter funnel), washing with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fiber for 12 hours at 90 ℃ in vacuum.
And then carrying out chemical copper plating:
preparing 250ml of electroplating solution for electroless copper plating, wherein the electroplating solution contains 20mg/L of formaldehyde, 40g/L of potassium hydroxide, 30g/L of copper sulfate, 20g/L of disodium ethylene diamine tetraacetate, 200g/L of sodium citrate and 10g/L of benzotriazole, putting the electroplating solution into an electrolytic tank, then putting carbon fibers, adjusting the current density to be 0.1-1A, continuously electroplating for 30min, filtering the carbon fibers (through a conventional filter funnel), taking out the carbon fibers, cleaning the carbon fibers with a large amount of deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fibers for 12 hours at 90 ℃ in vacuum to finally obtain the carbon fiber/copper composite.
Step two, carbon fiber/metal CVD deposition
And (2) putting the carbon fiber/copper composite obtained in the step one into a CVD (chemical vapor deposition) deposition chamber, passing a mixed gas of hydrogen and argon (argon gas 90% (v/v) and hydrogen gas 10% (v/v)), heating to 1300 ℃ for about 30min, keeping for 20min, stopping, passing a mixed gas of methane 60% (v/v), formaldehyde 10% (v/v) and acetylene 30% (v/v), reacting for 30min, stopping inputting, exhausting the reaction gas (the previous mixed gas) through nitrogen, cooling to normal temperature, taking out a product, and obtaining the carbon fiber/copper/graphene composite, namely the graphene modified carbon fiber.
Step three, manufacturing graphene modified carbon fiber paper
And (3) weighing 15g of the carbon fiber/copper/graphene compound obtained in the second step, placing the carbon fiber/copper/graphene compound in a polyacrylamide solution with the mass fraction of 0.2%, stirring for 30min, performing ultrasonic treatment (with the power of 600W) for 30min, and performing ultrasonic treatment and stirring alternately for 5 times to obtain the polyacrylamide solution slurry containing the carbon fiber/copper/graphene compound. And then papermaking (a 300-mesh square filter screen is used for dipping in the slurry, then solid matters in the slurry are filtered on the screen), a graphene modified carbon fiber carbon paper precursor is obtained, the precursor is dipped in a phenolic resin solution with the concentration of 2 wt% for 3 hours, then hot-press forming is carried out under the conditions of 180 ℃, the pressure of 10Mpa and the hot-press time of 10min, the dipping-hot-press forming procedure is repeated for 2 times, then the prepared sample is carbonized at the high temperature of 1300 ℃ in an argon atmosphere (100% argon) for 3 hours, and finally the graphene modified carbon fiber carbon paper is prepared. The graphene composite carbon fiber paper comprises carbon fibers 1, wherein a metal coating 2 is arranged on the carbon fibers 1, and a graphene layer 3 is arranged on the metal coating 2 (see fig. 1-3).
The graphene composite carbon fiber paper modified by graphene is 7.5W/m.k, which shows that the thermal conductivity coefficient can be increased by modification. After modification, the resistivity of the obtained graphene composite carbon fiber paper is 0.0052 omega-cm, which shows that the resistivity can be reduced by modification.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (14)
1. A preparation method of graphene composite carbon fiber paper is characterized by comprising the following steps:
the method comprises the following steps: plating a layer of metal on the surface of the carbon fiber by electroplating to generate a carbon fiber/metal compound;
step two: growing graphene on the carbon fiber/metal composite by vapor deposition to generate graphene modified carbon fiber;
step three: utilizing carbon paper to make the obtained graphene modified carbon fiber into graphene modified carbon fiber paper, wherein the making of the graphene modified carbon fiber into graphene modified carbon fiber paper specifically comprises the following steps: weighing the carbon fiber/copper/graphene compound obtained in the step two, placing the carbon fiber/copper/graphene compound in a pulping additive, stirring for 30min, then carrying out ultrasonic treatment for 30min, and alternately carrying out 5 times to obtain polyacrylamide solution slurry containing the carbon fiber/copper/graphene compound; and then, dipping the precursor into a 300-mesh square filter screen, filtering solid substances in the slurry on the screen to obtain a graphene modified carbon fiber carbon paper precursor, dipping the precursor into a thermosetting polymer resin solution with the concentration of 1-2 wt% for 3 hours, then carrying out hot press molding under the conditions of 160-180 ℃, the pressure of 5-8Mpa and the hot press time of 5-10min, repeatedly repeating the dipping-hot press molding process for 2 times, and then carrying out high-temperature carbonization on the prepared sample at the temperature of 1200-1500 ℃ for 3 hours in an argon atmosphere to finally obtain the graphene modified carbon fiber carbon paper.
2. The method according to claim 1, wherein in the first step, the carbon fiber has a diameter of 5 to 30 μm and a length of 0.5 to 300 mm; the metal is selected from copper, nickel, chromium, tin, or combinations thereof; the thickness of the metal is 0.1-10 μm.
3. The method according to claim 1, wherein in the first step, the plating solution used in the plating comprises a main salt, a reducing agent, a complexing agent, a conductive salt and a buffer; the main salt is selected from a chlorinated metal compound or a sulfated metal compound, and the addition amount of the main salt is 0.1g/L-500 g/L; the reducing agent is selected from one of formaldehyde, sodium hypophosphite, sodium borohydride, alkylamine borane or hydrazine, and the addition amount of the reducing agent is 0.1g/L-500 g/L; the complexing agent is one of citrate, tartrate, cyanide or ethylene diamine tetraacetic acid, and the addition amount of the complexing agent is 0.1g/L-500 g/L; the conductive salt is selected from one of sodium hydroxide, potassium hydroxide or sulfuric acid, and the addition amount of the conductive salt is 0.1g/L-500 g/L; the buffer is selected from one of sodium acetate, borax, potassium pyrophosphate or benzotriazole, and the addition amount of the buffer is 0.1g/L-500 g/L.
4. The method according to claim 3, wherein in the first step, the plating solution used in the plating further comprises an accelerator and a surfactant; the accelerator is selected from one of malonic acid, succinic acid, aminoacetic acid, propionic acid or sodium fluoride, and the addition amount of the accelerator is 0.1g/L-500 g/L; the surfactant is selected from one of dodecyl sulfate, dodecyl sulfonate or n-octyl sodium sulfate, and the addition amount of the surfactant is 0.1g/L-500 g/L.
5. The method of claim 1, wherein in step one, the carbon fiber/metal composite is formed by: preparing an electroplating solution, putting the electroplating solution into an electrolytic tank, then putting carbon fibers, adjusting the current density to 0.1-1A, continuously electroplating for 10-20 min, filtering the carbon fibers, then taking out, cleaning with deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fibers for 6-12 hours at 90-95 ℃ in vacuum to finally obtain the carbon fiber/copper composite.
6. The method of claim 1, further comprising, before the first step, a step of pretreating the carbon fiber; the pretreatment of the carbon fiber specifically comprises:
1) weighing carbon fibers, putting the carbon fibers into acetone, carrying out ultrasonic treatment for 10-12 hours, taking out the carbon fibers, and carrying out vacuum drying at 90-95 ℃ for 12-20 hours;
2) mixing concentrated sulfuric acid and concentrated nitric acid, adding the carbon fiber obtained in the step 1), performing ultrasonic treatment for 5-10 hours, filtering, and washing with deionized water until the pH value of the filtrate is 7;
3) dropwise adding ammonia water into the silver nitrate solution until the solution is clear, putting the carbon fiber obtained in the step 2) into the solution, performing ultrasonic treatment for 2-5 hours, filtering, washing with deionized water until the pH value of the filtrate is 7, and then drying the obtained carbon fiber for 5-12 hours at 90 ℃ in vacuum.
7. The method according to claim 1, wherein in the second step, the precursor gas used in the vapor deposition is at least one selected from methane, ethylene, formaldehyde, acetylene, hydrogen, propylene, and propyne; the temperature of the vapor deposition is 1000-3000 ℃, and the time is 1-10 hours; the number of layers of the graphene formed by vapor deposition is 1-10; the thickness of the graphene is 0.335-3.35 nm.
8. The preparation method according to claim 1, wherein in the second step, the generation of the graphene-modified carbon fiber specifically comprises: and (3) placing the carbon fiber/copper composite obtained in the step one into a CVD (chemical vapor deposition) deposition chamber, heating to 1200-1300 ℃ in 20-30min through hydrogen-argon mixed gas, keeping the temperature for 20min, stopping inputting, reacting for 30min through precursor gas, evacuating the previous precursor gas through nitrogen, cooling to normal temperature, and taking out a resultant to obtain the carbon fiber/copper/graphene composite, namely the graphene modified carbon fiber.
9. The method according to claim 8, wherein the hydrogen-argon mixture gas comprises 90% (v/v) of argon and 10% (v/v) of hydrogen.
10. The preparation method according to claim 1, wherein the third step further comprises a step of preparing a graphene-modified carbon fiber paper precursor; the pulping additive used in the preparation of the graphene modified carbon fiber paper precursor is at least one selected from a polytetrafluoroethylene solution, a polyacrylamide solution, a polytetrafluoroethylene solution, a polyacrylic acid solution, a sodium alginate solution, a phenolic resin solution or a sodium carboxymethylcellulose solution.
11. The preparation method of claim 1, further comprising curing the graphene-modified carbon fiber paper resin in step three, wherein the thermosetting polymer resin used in the curing is at least one selected from urea formaldehyde resin, melamine-methanol resin, epoxy resin, polyurethane, polyimide, phenolic resin or silicone resin.
12. The graphene composite carbon fiber paper is characterized by being prepared by the method of any one of claims 1 to 11, and comprising carbon fibers, wherein a metal coating is arranged on the carbon fibers, and a graphene layer is arranged on the metal coating.
13. The graphene composite carbon fiber paper according to claim 12, wherein the number of graphene layers is a single layer.
14. A fuel cell comprising a carbon paper, wherein the carbon paper is the graphene composite carbon fiber paper according to any one of claims 12 to 13.
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| CN111548629B (en) * | 2020-06-28 | 2022-09-06 | 太仓碧奇新材料研发有限公司 | Conductive rubber for 5G communication base station and preparation method thereof |
| CN112609100A (en) * | 2020-11-27 | 2021-04-06 | 西南科技大学 | Foam copper and preparation method and application thereof |
| CN113463246B (en) * | 2021-06-15 | 2022-11-29 | 上海大学绍兴研究院 | Carbon fiber preform, preparation method thereof and densification method of carbon fiber preform |
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