CN110165229A - A kind of compound carbon fiber paper of graphene and its preparation method and application - Google Patents
A kind of compound carbon fiber paper of graphene and its preparation method and application Download PDFInfo
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- CN110165229A CN110165229A CN201910451169.1A CN201910451169A CN110165229A CN 110165229 A CN110165229 A CN 110165229A CN 201910451169 A CN201910451169 A CN 201910451169A CN 110165229 A CN110165229 A CN 110165229A
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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
- H01M4/8647—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
- H01M4/8673—Electrically conductive 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of preparation methods of the compound carbon fiber paper of graphene, comprising the following steps: plates one layer of metal in carbon fiber surface using chemical plating, generates carbon fiber/metal composite；Graphene is grown on carbon fiber/metal composite using vapor deposition, to generate graphene modified carbon fiber；Obtained graphene modified carbon fiber is generated into graphene modified carbon fiber paper using carbon paper production.The invention further relates to the compound carbon fiber papers of graphene and application thereof of above method preparation.Method of the invention is modified to individual carbon fibers, compares with other similar techniques, makes utilization rate highest of the graphene in carbon fiber paper, disperses the most uniform.
Description
Technical field
The present invention relates to new material preparation and application field, in particular to the compound carbon fiber paper of a kind of graphene and its preparation
Methods and applications.
Background technique
Gas diffusion layers are the important components of Proton Exchange Membrane Fuel Cells, not only play the role of supporting Catalytic Layer, but also
It is reaction gas and the diffusion admittance for generating product water, has been largely fixed the performance of fuel cell.Since special makes
With environment, higher requirement is proposed to the performance of gas diffusion layers, specific as follows: 1. contact resistances want small；2. having certain
Mechanical strength, bend resistance and resistance to compression；3. being conducive to the conveying of gas and the export of water；4. conductivity wants high；5. pair hot
Transmission speed is fast；6. stronger electrochemical corrosion resistance.
It is raw material that gas diffusion layers, which mainly use carbon fiber, at present, certain by its more excellent chemistry and thermal stability
The demand of gas diffusion layers is met in degree, but mechanical strength, heating conduction, electric conductivity are not still able to satisfy fuel cell increasingly
The performance requirement of raising.
Graphene be a kind of honeycomb flat film formed by carbon atom with sp2 hybrid form, be one kind only one
The quasi- two-dimensional material of atomic layer level thickness does monoatomic layer graphite so being called, and is that presently found thin, maximum intensity, conduction are led
A kind of strongest novel nano-material of hot property.For graphene Theory Conductivity up to 106S/cm, theoretical specific surface area is reachable
2630m2/ g, theoretical strength, up to 5000W/ (mk), are a kind of ideal carbon paper materials up to 130Gpa, thermal coefficient
Material.
A kind of Chinese patent application " preparation method of high-strength composite carbon paper " of Publication No. CN107815926A is open
Under the action of outer electric field force, using carbon nanotube as skeleton, high strength graphite alkene is introduced in skeleton, can increase substantially carbon paper
Mechanical property and electric conductivity.But in actual fabrication process, the graphene dispersing solution used in this method is not pure graphite
Alkene, but be added to surface dispersant etc., under electric field force effect, graphene can not quickly and evenly enter carbon nanotube bone
In frame, graphene exists uneven in obtained carbon paper, uneven so as to cause intensity.
It is substrate that the China that Authorization Notice No. is CN207558942U, which is disclosed using new patent using carbon fiber, is used in combination
It is carbon nano tube-doped, it is then coated with graphene and PTFE, manufactured carbon paper has high conductivity, excellent drainage performance
And stability.Existing forms and heterogeneous single-layer graphene of the graphene in carbon paper in this method, cannot utilize graphite
Alkene high electric conductivity promotes carbon paper high conductivity.
Summary of the invention
In view of this, the main purpose of the present invention is to provide compound carbon fiber paper of graphene and preparation method thereof and answering
With.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.
A kind of preparation method of the compound carbon fiber paper of graphene proposed according to the present invention, comprising the following steps:
Step 1: one layer of metal is plated in carbon fiber surface using chemical plating, generates carbon fiber/metal composite；
Step 2: growing graphene on carbon fiber/metal composite using vapor deposition, modified to generate graphene
Carbon fiber；
Step 3: obtained graphene modified carbon fiber is generated into graphene modified carbon fiber paper using carbon paper production.
Further, wherein in step 1, the diameter of the carbon fiber is 5-30 μm, length 0.5-300mm.
Further, wherein in step 1, the metal is selected from copper, nickel, chromium, tin or combinations thereof.
Further, wherein in step 1, the metal with a thickness of 0.1-10 μm.
Further, wherein in step 1, electroplate liquid used in the chemical plating include main salt, reducing agent, complexing agent,
Conductive salt and buffer；The main salt is selected from chlorination metallic compound or sulphated metal compound, additional amount 0.1g/L-
500g/L；The reducing agent is selected from one of formaldehyde, sodium hypophosphite, sodium borohydride, alkyl amine borine or hydrazine, additional amount
For 0.1g/L-500g/L；The complexing agent is in citrate, tartrate, cyanide or disodium ethylene diamine tetraacetate
One kind, additional amount 0.1g/L-500g/L；The conductive salt is selected from one of sodium hydroxide, potassium hydroxide or sulfuric acid,
Additional amount is 0.1g/L-500g/L；The buffer is selected from one of sodium acetate, borax, potassium pyrophosphate or phenylpropyl alcohol ribavirin,
Its additional amount is 0.1g/L-500g/L.
Further, wherein in step 1, electroplate liquid used in the chemical plating further includes accelerator and surface-active
Agent；The accelerator is selected from one of malonic acid, succinic acid, amion acetic acid, propionic acid or sodium fluoride, additional amount 0.1g/
L-500g/L；The surfactant in lauryl sulfate, dodecane sulfonate or n-octyl sodium sulphate one
Kind, additional amount 0.1g/L-500g/L.
Further, wherein in step 1, carbon fiber/metal composite generation specifically: electroplate liquid is prepared, by the electricity
Plating solution is put into electrolytic cell, and carbon fiber is subsequently placed into, and current density 0.1-1A, continuous electroplating 10min-20min is adjusted, by carbon fiber
It takes out after dimensional filter, is cleaned with deionized water, until filtrate pH value is 7, then dried 90-95 DEG C of carbon fiber vacuum obtained
6-12 hours, finally obtain carbon fiber/copper complex.
Further, wherein further including carrying out pretreated step to carbon fiber before step 1；It is described to carbon fiber
Pretreatment is carried out to specifically include:
1) carbon fiber is weighed, is put into acetone, 10-12 hours ultrasonic, after taking-up, 90-95 DEG C of vacuum drying 12-20 is small
When；
2) concentrated sulfuric acid is mixed with concentrated nitric acid, the carbon fiber that step 1) is obtained is added thereto, it is 5-10 hours ultrasonic after mistake
Filter, is rinsed with deionized water, until filtrate pH value is 7；
3) ammonium hydroxide is added dropwise into silver nitrate solution, until solution is clarified, the carbon fiber investment that step 2) is obtained wherein, surpasses
Sound filters after 2-5 hours, is cleaned with deionized water, until filtrate pH value is 7, then dries 90 DEG C of carbon fiber vacuum obtained
5-12 hours.
Further, wherein in step 2, precursor gas used in the vapor deposition be selected from methane, ethylene, formaldehyde,
At least one of acetylene, hydrogen, propylene or propine.
Further, wherein in step 2, the temperature of the vapor deposition is 1000-3000 DEG C, and the time is 1-10 hours.
Further, wherein in step 2, the number of plies for the graphene that the vapor deposition is formed is 1-10 layers；The graphite
Alkene with a thickness of 0.335-3.35nm.
Further, wherein in step 2, the generation of graphene modified carbon fiber is specifically included: the carbon that step 1 is obtained
Fiber/copper complex is put into CVD deposition room, and by hydrogen-argon-mixed, then 20-30min is heated to 1200-1300 DEG C, is protected
Stop after holding 20min, then by precursor gas, stop input after reacting 30min, by nitrogen by precursor gas before
Body emptying, and it is cooled to room temperature, product is taken out, carbon fiber/copper/graphene complex, i.e. graphene modified carbon fiber are obtained.
Further, described hydrogen-argon-mixed by argon gas 90% (v/v) and hydrogen 10% (v/v) group wherein in step 2
At.
Further, wherein in step 3, further include the steps that making graphene modified carbon fiber paper presoma；Make stone
Slurrying additive used is selected from polytetrafluoroethylsolution solution, polyacrylamide solution, gathers when black alkene modified carbon fiber paper presoma
In tetrafluoroethene solution, polyacrylic acid solution, sodium alginate soln, phenol resin solution or carboxymethylcellulose sodium solution extremely
Few one kind.
Further, further include graphene modified carbon fiber paper resin solidification wherein in step 3, when solidification heat used
Curable type macromolecule resin is selected from Lauxite, melamine-methanol resin, epoxy resin, polyurethane, polyimides, phenolic aldehyde tree
At least one of rouge or organic siliconresin.
Further, wherein in step 3, graphene modified carbon fiber generates the production tool of graphene modified carbon fiber paper
Body includes: the carbon fiber/copper/graphene complex for weighing step 2 and obtaining, and is placed in slurrying additive, stirs 30min, then
Ultrasonic 30min, alternately 5 times are obtained containing carbon fiber/copper/graphene complex polyacrylamide solution slurry；Then
It with the square filter screen of 300 mesh, is immersed in in spreading mass, the solid matter filtering in slurry is then obtained into graphite online
It is small to be immersed in the thermosetting macromolecule resin solution of 1-2wt% concentration 3 by alkene modified carbon fiber carbon paper presoma for this presoma
When, then at 160-180 DEG C, pressure 5-8Mpa, hot pressing time is hot-forming under conditions of being 5-10min, is iteratively repeated leaching
Stain-hot forming process 2 times then carries out sample obtained 1200-1500 DEG C of high temperature cabonization 3 hours in argon atmosphere,
Finally obtained graphene modified carbon fiber carbon paper.
The compound carbon fiber paper of a kind of graphene proposed according to the present invention, the compound carbon fiber paper of graphene includes carbon fiber
Dimension, the carbon fiber are equipped with the coat of metal, and the coat of metal is equipped with graphene layer.
Further, wherein the number of plies of the graphene layer is single layer.
Further, wherein the compound carbon fiber paper of the graphene is prepared by the above method.
A kind of fuel cell proposed according to the present invention, the fuel cell include carbon paper, and the carbon paper is above-mentioned stone
The black compound carbon fiber paper of alkene.
By above-mentioned technical proposal, the present invention is at least had the advantage that
1. method of the invention is modified to individual carbon fibers, is compared with other similar techniques, make graphene in carbon fiber paper
In utilization rate highest, disperse it is the most uniform；
2. method of the invention can guarantee that the coat of metal and carbon fiber blend by chemical plating, enable graphene
It is enough to be grown on the coat of metal, that is, realize that graphene, carbon fiber & metallic object blend, form the body phase three in structure
Layer homogeneous texture, and then performance such as mechanics is brought, the promotion of conductivity either resistivity etc.；
3. method of the invention grows graphene in metal surface by CVD, makes graphene in carbon fiber surface EDS maps
More evenly, the high conductivity, high intensity and high-termal conductivity of graphene are given full play to, and avoid and occur in other methods,
The inevitably barrier that graphene enters gas；
4. method of the invention, the angle modified from individual carbon fibers, rather than carbon paper before is bulk phase-doped modified, changes
It has been apt to the conductivity and heat transfer efficiency of carbon paper.
Detailed description of the invention
Fig. 1 is the carbon fiber structural schematic diagram of the embodiment of the present invention；
Fig. 2 is the structural schematic diagram of metal cladding on the carbon fiber of the embodiment of the present invention；
Fig. 3 is the graphene modified carbon fiber schematic diagram of the embodiment of the present invention；
Fig. 4 is the modified influence diagram to carbon paper thermal coefficient of graphene described in the embodiment of the present invention；
Fig. 5 is the modified influence diagram to carbon paper resistivity of graphene described in the embodiment of the present invention.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The materials, reagents and the like used in the following examples is commercially available.
Embodiment 1
As shown in Figure 1-Figure 3, a kind of preparation method of graphene modified carbon fiber paper is present embodiments provided, including following
Step:
Step 1, carbon fiber chemical plating
Carbon fiber is pre-processed first:
1. weighing 30.0g carbon fiber, it is put into 500ml acetone, ultrasonic (ordinary ultrasonic instrument, power 600W) 12 hours,
After taking-up, 90 DEG C vacuum drying 12 hours.
2. by the 100ml concentrated sulfuric acid (concentrated sulfuric acid mass fraction be 98%) and 100ml concentrated nitric acid, (concentrated sulfuric acid mass fraction is
69%) it mixes, the carbon fiber that the first step is obtained is added thereto, and ultrasonic (ordinary ultrasonic instrument, power 600W) is filtered after 5 hours
(being filtered by conventional filtration funnel) is rinsed with a large amount of deionized waters, until filtrate pH value is 7.
3. the ammonium hydroxide that mass fraction is 20% is added dropwise into the silver nitrate solution of 5g/L, until solution clarification (generates silver-colored ammonia
Solution), wherein, ultrasonic (ordinary ultrasonic instrument, power 600W) filters (logical the carbon fiber investment that second step is obtained after 2 hours
Cross the filtering of conventional filtration funnel), it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum that will then obtain
90 DEG C dry 12 hours.
Next electroless copper:
It is formulated for the electroplate liquid 250ml of electroless copper, wherein containing formaldehyde 30mg/L, potassium hydroxide 40g/L, copper sulphate
30g/L, disodium ethylene diamine tetraacetate 20g/L, sodium citrate 200g/L, phenylpropyl alcohol ribavirin 10g/L put the electroplate liquid into electrolysis
In slot, it is subsequently placed into carbon fiber, current density 0.1-1A, continuous electroplating 20min is adjusted, carbon fiber filter (is passed through into conventional mistake
The filtering of filter funnel) it takes out afterwards, it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum 90 that will then obtain
DEG C drying 12 hours, finally obtain carbon fiber/copper complex.
Step 2, carbon fiber/metallic CVD deposition
Carbon fiber/copper complex that step 1 is obtained, is put into CVD deposition room, passes through hydrogen-argon-mixed (argon gas 90%
(v/v), hydrogen 10% (v/v)), then 20min or so is heated to 1200 DEG C, stops after keeping 20min, then passes through methane
60% (v/v), formaldehyde 10% (v/v), the mixed gas of acetylene 30% (v/v) stop input after reacting 30min, pass through nitrogen
Reaction gas (mixed gas before) is emptied, and is cooled to room temperature, product is taken out, it is compound to obtain carbon fiber/copper/graphene
Object, i.e. graphene modified carbon fiber.
Step 3, the production of graphene modified carbon fiber paper
Carbon fiber/copper/graphene complex that 20g step 2 obtains is weighed, the polyacrylamide of mass fraction 0.2% is placed in
In amine aqueous solution, stir 30min, then ultrasound (ordinary ultrasonic instrument, power 600W) 30min, alternately 5 times (ultrasound with stir
Mix alternately), it obtains containing carbon fiber/copper/graphene complex polyacrylamide solution slurry.Then carry out copy paper
(with the square filter screen of 300 mesh, being immersed in then to filter the solid matter in slurry online in spreading mass), obtains stone
This presoma is immersed in the phenol resin solution of 2wt% concentration 3 hours, then by black alkene modified carbon fiber carbon paper presoma
At 180 DEG C, pressure 8Mpa, hot pressing time is hot-forming under conditions of being 5min, is iteratively repeated dipping-hot forming process 2
It is secondary, sample obtained is then subjected to 1200 DEG C of high temperature cabonizations (3 hours) in argon atmosphere (100% argon gas), it is final to be made
Graphene modified carbon fiber carbon paper.The compound carbon fiber paper of graphene includes carbon fiber 1, and the carbon fiber 1 is equipped with metal
Coating 2, the coat of metal 2 are equipped with graphene layer 3 (see Fig. 1-Fig. 3).
Fig. 4, Fig. 5 are respectively carbon fiber paper and non-modified carbon fiber paper (the Suzhou China passed through after graphene is modified
Base new material) thermal coefficient, resistivity index comparison diagram；Wherein, the test method of thermal coefficient is stable state heat-flow meter method, reference
GB/T 10295-2008；The test method of resistivity is four probe method.
As shown in figure 4, the thermal coefficient of carbon fiber paper (product structure such as Fig. 1) is 4.4W/mk, process is modified, institute
The compound carbon fiber paper of graphene (product structure such as Fig. 3) obtained is 7.2W/mk, this illustrates that modification can increase thermal coefficient.
As shown in figure 5, the resistivity of carbon fiber paper (product structure such as Fig. 1) is 0.008 Ω cm, process is modified, resulting graphite
The compound carbon fiber paper of alkene (product structure such as Fig. 3) is 0.005 Ω cm, this illustrates that modification can reduce resistivity.
Embodiment 2
As shown in Figure 1-Figure 3, a kind of preparation method of graphene modified carbon fiber paper is present embodiments provided, including following
Step:
Step 1, carbon fiber chemical plating
Carbon fiber is pre-processed first:
1. weighing 30.0g carbon fiber, it is put into 500ml acetone, ultrasonic (ordinary ultrasonic instrument, power 600W) 10 hours,
After taking-up, 90 DEG C vacuum drying 12 hours.
2. by the 100ml concentrated sulfuric acid (concentrated sulfuric acid mass fraction be 98%) and 100ml concentrated nitric acid, (concentrated sulfuric acid mass fraction is
69%) it mixes, the carbon fiber that the first step is obtained is added thereto, ultrasonic (ordinary ultrasonic instrument, power 600W) mistake after 10 hours
It filters (being filtered by conventional filtration funnel), is rinsed with a large amount of deionized waters, until filtrate pH value is 7.
3. the ammonium hydroxide that mass fraction is 20% is added dropwise into the silver nitrate solution of 5g/L, until solution clarification (generates silver-colored ammonia
Solution), wherein, ultrasonic (ordinary ultrasonic instrument, power 600W) filters (logical the carbon fiber investment that second step is obtained after 5 hours
Cross the filtering of conventional filtration funnel), it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum that will then obtain
90 DEG C dry 5 hours.
Next chemical nickel plating:
It is formulated for the electroplate liquid 250ml of electroless copper, wherein containing acetaldehyde 20mg/L, sodium hydroxide 40g/L, nickel sulfate
30g/L, disodium ethylene diamine tetraacetate 30g/L, sodium citrate 180g/L, phenylpropyl alcohol ribavirin 10g/L put the electroplate liquid into electrolysis
In slot, it is subsequently placed into carbon fiber, adjusts current density 0.5-1.5A, carbon fiber filter (is passed through routine by continuous electroplating 10min
Filter tunnel filtering) it takes out afterwards, it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum that will then obtain
90 DEG C dry 6 hours, finally obtain carbon fiber/nickel composite.
Step 2, carbon fiber/metallic CVD deposition
Carbon fiber/nickel composite that step 1 is obtained, is put into CVD deposition room, passes through hydrogen-argon-mixed (argon gas 90%
(v/v), hydrogen 10% (v/v)), then 30min or so is heated to 2000 DEG C, stops after keeping 60min, then passes through methane
60% (v/v), formaldehyde 10% (v/v), the mixed gas of acetylene 30% (v/v) stop input after reacting 30min, pass through nitrogen
Reaction gas (mixed gas before) is emptied, and is cooled to room temperature, product is taken out, it is compound to obtain carbon fiber/nickel/graphene
Object, i.e. graphene modified carbon fiber.
Step 3, the production of graphene modified carbon fiber paper
Carbon fiber/nickel/graphene complex that 25g step 2 obtains is weighed, the polytetrafluoroethyl-ne of mass fraction 0.1% is placed in
In alkene solution, stir 30min, then ultrasound (ordinary ultrasonic instrument, power 600W) 30min, alternately 5 times (ultrasound with stir
Mix alternately), it obtains containing carbon fiber/nickel/graphene complex polytetrafluoroethylsolution solution slurry.Then carry out copy paper
(with the square filter screen of 300 mesh, being immersed in then to filter the solid matter in slurry online in spreading mass), obtains stone
This presoma is immersed in the phenol resin solution of 1wt% concentration 3 hours, then by black alkene modified carbon fiber carbon paper presoma
At 160 DEG C, pressure 5Mpa, hot pressing time is hot-forming under conditions of being 10min, is iteratively repeated dipping-hot forming process 2
It is secondary, sample obtained is then subjected to 1500 DEG C of high temperature cabonizations (3 hours) in argon atmosphere (100% argon gas), it is final to be made
Graphene modified carbon fiber carbon paper.The compound carbon fiber paper of graphene includes carbon fiber 1, and the carbon fiber 1 is equipped with metal
Coating 2, the coat of metal 2 are equipped with graphene layer 3 (see Fig. 1-Fig. 3).
It is 8.3W/mk by graphene compound carbon fiber paper of the graphene after modified, this illustrates that modification can increase
Thermal coefficient.By modified, the resulting compound carbon fiber paper resistivity of graphene is 0.0049 Ω cm, this illustrates that modification can
To reduce resistivity.
Embodiment 3
As shown in Figure 1-Figure 3, a kind of preparation method of graphene modified carbon fiber paper is present embodiments provided, including following
Step:
Step 1, carbon fiber chemical plating
Carbon fiber is pre-processed first:
1. weighing 20.0g carbon fiber, it is put into 500ml acetone, ultrasonic (ordinary ultrasonic instrument, power 600W) 10 hours,
After taking-up, 90 DEG C vacuum drying 20 hours.
2. by the 100ml concentrated sulfuric acid (concentrated sulfuric acid mass fraction be 98%) and 100ml concentrated nitric acid, (concentrated sulfuric acid mass fraction is
69%) it mixes, the carbon fiber that the first step is obtained is added thereto, and ultrasonic (ordinary ultrasonic instrument, power 600W) is filtered after 5 hours
(being filtered by conventional filtration funnel) is rinsed with a large amount of deionized waters, until filtrate pH value is 7.
3. the ammonium hydroxide that mass fraction is 20% is added dropwise into the silver nitrate solution of 5g/L, until solution clarification (generates silver-colored ammonia
Solution), wherein, ultrasonic (ordinary ultrasonic instrument, power 600W) filters (logical the carbon fiber investment that second step is obtained after 2 hours
Cross the filtering of conventional filtration funnel), it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum that will then obtain
90 DEG C dry 12 hours.
Next electroless copper:
It is formulated for the electroplate liquid 250ml of electroless copper, wherein containing formaldehyde 20mg/L, potassium hydroxide 40g/L, copper sulphate
30g/L, disodium ethylene diamine tetraacetate 20g/L, sodium citrate 200g/L, phenylpropyl alcohol ribavirin 10g/L put the electroplate liquid into electrolysis
In slot, it is subsequently placed into carbon fiber, current density 0.1-1A, continuous electroplating 30min is adjusted, carbon fiber filter (is passed through into conventional mistake
The filtering of filter funnel) it takes out afterwards, it is cleaned with a large amount of deionized waters, until filtrate pH value is 7, the carbon fiber vacuum 90 that will then obtain
DEG C drying 12 hours, finally obtain carbon fiber/copper complex.
Step 2, carbon fiber/metallic CVD deposition
Carbon fiber/copper complex that step 1 is obtained, is put into CVD deposition room, passes through hydrogen-argon-mixed (argon gas 90%
(v/v), hydrogen 10% (v/v)), then 30min or so is heated to 1300 DEG C, stops after keeping 20min, then passes through methane
60% (v/v), formaldehyde 10% (v/v), the mixed gas of acetylene 30% (v/v) stop input after reacting 30min, pass through nitrogen
Reaction gas (mixed gas before) is emptied, and is cooled to room temperature, product is taken out, it is compound to obtain carbon fiber/copper/graphene
Object, i.e. graphene modified carbon fiber.
Step 3, the production of graphene modified carbon fiber paper
Carbon fiber/copper/graphene complex that 15g step 2 obtains is weighed, the polyacrylamide of mass fraction 0.2% is placed in
In amine aqueous solution, stir 30min, then ultrasound (ordinary ultrasonic instrument, power 600W) 30min, alternately 5 times (ultrasound with stir
Mix alternately), it obtains containing carbon fiber/copper/graphene complex polyacrylamide solution slurry.Then carry out copy paper
(with the square filter screen of 300 mesh, being immersed in then to filter the solid matter in slurry online in spreading mass), obtains stone
This presoma is immersed in the phenol resin solution of 2wt% concentration 3 hours, then by black alkene modified carbon fiber carbon paper presoma
At 180 DEG C, pressure 10Mpa, hot pressing time is hot-forming under conditions of being 10min, is iteratively repeated dipping-hot forming process
2 times, sample obtained is then subjected to 1300 DEG C of high temperature cabonizations (3 hours) in argon atmosphere (100% argon gas), it is final to be made
Graphene modified carbon fiber carbon paper.The compound carbon fiber paper of graphene includes carbon fiber 1, and the carbon fiber 1 is equipped with metal
Coating 2, the coat of metal 2 are equipped with graphene layer 3 (see Fig. 1-Fig. 3).
It is 7.5W/mk by graphene compound carbon fiber paper of the graphene after modified, this illustrates that modification can increase
Thermal coefficient.By modified, the resulting compound carbon fiber paper resistivity of graphene is 0.0052 Ω cm, this illustrates that modification can
To reduce resistivity.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of preparation method of the compound carbon fiber paper of graphene, which comprises the following steps:
Step 1: one layer of metal is plated in carbon fiber surface using chemical plating, generates carbon fiber/metal composite；
Step 2: growing graphene on carbon fiber/metal composite using vapor deposition, to generate the modified carbon fiber of graphene
Dimension；
Step 3: obtained graphene modified carbon fiber is generated into graphene modified carbon fiber paper using carbon paper production.
2. preparation method as described in claim 1, which is characterized in that in step 1, the diameter of the carbon fiber is 5-30 μm,
Length is 0.5-300mm；The metal is selected from copper, nickel, chromium, tin or combinations thereof；The metal with a thickness of 0.1-10 μm.
3. preparation method as described in claim 1, which is characterized in that in step 1, electroplate liquid used in the chemical plating
Including main salt, reducing agent, complexing agent, conductive salt and buffer；The main salt is selected from chlorination metallic compound or sulphated metal
Compound, additional amount 0.1g/L-500g/L；The reducing agent is selected from formaldehyde, sodium hypophosphite, sodium borohydride, alkylamine
One of borine or hydrazine, additional amount 0.1g/L-500g/L；The complexing agent is selected from citrate, tartrate, cyaniding
One of object or disodium ethylene diamine tetraacetate, additional amount 0.1g/L-500g/L；The conductive salt be selected from sodium hydroxide,
One of potassium hydroxide or sulfuric acid, additional amount 0.1g/L-500g/L；The buffer is selected from sodium acetate, borax, burnt phosphorus
One of sour potassium or phenylpropyl alcohol ribavirin, additional amount 0.1g/L-500g/L.
4. preparation method as claimed in claim 3, which is characterized in that in step 1, electroplate liquid used in the chemical plating
It further include accelerator and surfactant；The accelerator is in malonic acid, succinic acid, amion acetic acid, propionic acid or sodium fluoride
One kind, additional amount 0.1g/L-500g/L；The surfactant is selected from lauryl sulfate, dodecyl sodium sulfonate
One of salt or n-octyl sodium sulphate, additional amount 0.1g/L-500g/L.
5. preparation method as described in claim 1, which is characterized in that in step 1, carbon fiber/metal composite generation tool
Body are as follows: prepare electroplate liquid, which is put into electrolytic cell, be subsequently placed into carbon fiber, adjust current density 0.1-1A, continuously
10min-20min is electroplated, will take out after carbon fiber filter, cleaned with deionized water, until filtrate pH value is 7, will then obtain
Drying 6-12 hours of 90-95 DEG C of carbon fiber vacuum, finally obtain carbon fiber/copper complex.
6. preparation method as described in claim 1, which is characterized in that further include being located in advance before step 1 to carbon fiber
The step of reason；It is described to carbon fiber carry out pretreatment specifically include:
1) weigh carbon fiber, be put into acetone, it is 10-12 hours ultrasonic, after taking-up, 90-95 DEG C vacuum drying 12-20 hours；
2) concentrated sulfuric acid is mixed with concentrated nitric acid, the carbon fiber that step 1) is obtained is added thereto, and is filtered after 5-10 hours ultrasonic, is used
Deionized water is rinsed, until filtrate pH value is 7；
3) ammonium hydroxide is added dropwise into silver nitrate solution, until solution is clarified, the carbon fiber that step 2) is obtained is put into wherein, ultrasonic 2-
It filters after 5 hours, is cleaned with deionized water, until filtrate pH value is 7, the 90 DEG C of drying 5-12 of carbon fiber vacuum that will then obtain
Hour.
7. preparation method as described in claim 1, which is characterized in that in step 2, presoma used in the vapor deposition
Gas is selected from least one of methane, ethylene, formaldehyde, acetylene, hydrogen, propylene or propine；The temperature of the vapor deposition is
1000-3000 DEG C, the time is 1-10 hours；The number of plies for the graphene that the vapor deposition is formed is 1-10 layers；The graphene
With a thickness of 0.335-3.35nm.
8. preparation method as described in claim 1, which is characterized in that in step 2, the generation of graphene modified carbon fiber has
Body includes: the carbon fiber/copper complex for obtaining step 1, is put into CVD deposition room, by hydrogen-argon-mixed, then 20-
30min is heated to 1200-1300 DEG C, stops after keeping 20min, then passes through precursor gas, stops after reaction 30min defeated
Enter, precursor gas before is emptied by nitrogen, and be cooled to room temperature, take out product, obtain carbon fiber/copper/graphite
Alkene compound, i.e. graphene modified carbon fiber.
9. preparation method as claimed in claim 8, which is characterized in that described hydrogen-argon-mixed by argon gas 90% (v/v) and hydrogen
Gas 10% (v/v) composition.
10. preparation method as described in claim 1, which is characterized in that further include the modified carbon fiber of production graphene in step 3
The step of tieing up paper presoma；It makes slurrying additive used when graphene modified carbon fiber paper presoma and is selected from polytetrafluoroethylene (PTFE)
Solution, polyacrylamide solution, polytetrafluoroethylsolution solution, polyacrylic acid solution, sodium alginate soln, phenol resin solution or carboxylic
At least one of methylcellulose sodium solution.
11. preparation method as described in claim 1, which is characterized in that further include graphene modified carbon fiber paper in step 3
Resin solidification, when solidification thermosetting macromolecule resin used be selected from Lauxite, melamine-methanol resin, epoxy resin,
At least one of polyurethane, polyimides, phenolic resin or organic siliconresin.
12. preparation method as described in claim 1, which is characterized in that in step 3, graphene modified carbon fiber generates graphite
The production of alkene modified carbon fiber paper specifically includes: weighing carbon fiber/copper/graphene complex that step 2 obtains, is placed in slurrying
In additive, 30min is stirred, then ultrasound 30min, alternately 5 times, obtain containing carbon fiber/copper/graphene complex
Polyacrylamide solution slurry；Then with the square filter screens of 300 mesh, it is immersed in in spreading mass, then by the solid in slurry
Substance filtering obtains graphene modified carbon fiber carbon paper presoma, this presoma is immersed in the heat of 1-2wt% concentration online
3 hours in curable type high-molecular resin solution, then at 160-180 DEG C, pressure 5-8Mpa, hot pressing time is the item of 5-10min
It is hot-forming under part, it is iteratively repeated dipping-hot forming process 2 times, then carries out sample obtained in argon atmosphere
1200-1500 DEG C high temperature cabonization 3 hours, final obtained graphene modified carbon fiber carbon paper.
13. a kind of compound carbon fiber paper of graphene, which is characterized in that the compound carbon fiber paper of graphene includes carbon fiber, institute
Carbon fiber is stated equipped with the coat of metal, the coat of metal is equipped with graphene layer.
14. the compound carbon fiber paper of graphene as claimed in claim 13, which is characterized in that the number of plies of the graphene layer is single
Layer.
15. the compound carbon fiber paper of graphene as claimed in claim 13, which is characterized in that the compound carbon fiber paper of graphene
It is to be prepared by the described in any item methods of claim 1-12.
16. a kind of fuel cell, which is characterized in that the fuel cell includes carbon paper, and the carbon paper is appointed for claim 13-15
The compound carbon fiber paper of graphene described in one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334153A (en) * | 2020-04-13 | 2020-06-26 | 绍兴诺鼎卫浴洁具股份有限公司 | Heat-conducting modified polyurethane super-hydrophobic composite coating and preparation method thereof |
| CN111548629A (en) * | 2020-06-28 | 2020-08-18 | 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 |
| CN113463246A (en) * | 2021-06-15 | 2021-10-01 | 上海大学绍兴研究院 | Carbon fiber preform, preparation method thereof and densification method of carbon fiber preform |
| CN114808521A (en) * | 2022-04-20 | 2022-07-29 | 江南大学 | Method for preparing electrode precursor by using copper-plated carbon fiber papermaking |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020175073A1 (en) * | 2000-01-27 | 2002-11-28 | Makoto Nakamura | Porous carbon electrode material, method fro manufacturing the same, and carbon fiber paper |
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| CN102182100A (en) * | 2011-04-12 | 2011-09-14 | 武汉赛洋暖通设备有限公司 | Carbon fiber heating paper and preparation method thereof |
| CN102436934A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite nanometer carbon paper and preparation method thereof |
| CN103144356A (en) * | 2013-03-12 | 2013-06-12 | 南京航空航天大学 | High-conductivity composite carbon fiber and preparation method thereof |
| CN103556543A (en) * | 2013-10-24 | 2014-02-05 | 浙江科技学院 | Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper |
| CN103910532A (en) * | 2013-01-05 | 2014-07-09 | 中国科学院宁波材料技术与工程研究所 | Coating inorganic fiber toughened MAX phase ceramic composite material, preparation method and uses thereof |
| CN105810973A (en) * | 2016-05-18 | 2016-07-27 | 青岛墨金烯碳新材料科技有限公司 | Graphene gas diffusion film of fuel cell and preparation method of graphene gas diffusion film |
| US20160215389A1 (en) * | 2015-01-27 | 2016-07-28 | Purdue Research Foundation | Compositions of matter and methods of producing a carbonized cloth for growth of graphene nano-petals |
| CN105818476A (en) * | 2016-03-21 | 2016-08-03 | 中南大学 | Surface-modification three-dimensional-network-carbon-fiber-reinforced composite material and preparing method |
| CN108467023A (en) * | 2018-05-10 | 2018-08-31 | 哈尔滨理工大学 | A kind of preparation of the graphene/carbon nano-fiber composite material of three-dimensional structure |
| CN108707998A (en) * | 2018-04-11 | 2018-10-26 | 杭州牛墨科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
-
2019
- 2019-05-28 CN CN201910451169.1A patent/CN110165229B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020175073A1 (en) * | 2000-01-27 | 2002-11-28 | Makoto Nakamura | Porous carbon electrode material, method fro manufacturing the same, and carbon fiber paper |
| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| CN102182100A (en) * | 2011-04-12 | 2011-09-14 | 武汉赛洋暖通设备有限公司 | Carbon fiber heating paper and preparation method thereof |
| CN102436934A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite nanometer carbon paper and preparation method thereof |
| CN103910532A (en) * | 2013-01-05 | 2014-07-09 | 中国科学院宁波材料技术与工程研究所 | Coating inorganic fiber toughened MAX phase ceramic composite material, preparation method and uses thereof |
| CN103144356A (en) * | 2013-03-12 | 2013-06-12 | 南京航空航天大学 | High-conductivity composite carbon fiber and preparation method thereof |
| CN103556543A (en) * | 2013-10-24 | 2014-02-05 | 浙江科技学院 | Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper |
| US20160215389A1 (en) * | 2015-01-27 | 2016-07-28 | Purdue Research Foundation | Compositions of matter and methods of producing a carbonized cloth for growth of graphene nano-petals |
| CN105818476A (en) * | 2016-03-21 | 2016-08-03 | 中南大学 | Surface-modification three-dimensional-network-carbon-fiber-reinforced composite material and preparing method |
| CN105810973A (en) * | 2016-05-18 | 2016-07-27 | 青岛墨金烯碳新材料科技有限公司 | Graphene gas diffusion film of fuel cell and preparation method of graphene gas diffusion film |
| CN108707998A (en) * | 2018-04-11 | 2018-10-26 | 杭州牛墨科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
| CN108467023A (en) * | 2018-05-10 | 2018-08-31 | 哈尔滨理工大学 | A kind of preparation of the graphene/carbon nano-fiber composite material of three-dimensional structure |
Non-Patent Citations (4)
| Title |
|---|
| 杨孝寰 等: "《最新科技知识手册》", 30 November 1986 * |
| 薛云飞 等: "《先进金属基复合材料》", 30 April 2019 * |
| 邹文俊: "碳纤维纸基屏蔽材料的制备与性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 郑志军 等: "《机械制造工程训练教程》", 31 July 2015 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334153A (en) * | 2020-04-13 | 2020-06-26 | 绍兴诺鼎卫浴洁具股份有限公司 | Heat-conducting modified polyurethane super-hydrophobic composite coating and preparation method thereof |
| CN111548629A (en) * | 2020-06-28 | 2020-08-18 | 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 |
| CN113463246A (en) * | 2021-06-15 | 2021-10-01 | 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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