CN107946621A - A kind of feature graphene, which is modified, improves Carbon fibe or the corrosion resistant method of carbon fiber composite - Google Patents
A kind of feature graphene, which is modified, improves Carbon fibe or the corrosion resistant method of carbon fiber composite Download PDFInfo
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- CN107946621A CN107946621A CN201710985844.XA CN201710985844A CN107946621A CN 107946621 A CN107946621 A CN 107946621A CN 201710985844 A CN201710985844 A CN 201710985844A CN 107946621 A CN107946621 A CN 107946621A
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
It is modified the invention discloses a kind of feature graphene and improves Carbon fibe or the corrosion resistant method of carbon fiber composite, this method is in Process of Surface Modification is carried out to Carbon fibe or carbon fiber composite using polytetrafluoroethylene (PTFE), binding ability between polytetrafluoroethylene (PTFE) and Carbon fibe or carbon fiber composite can be improved by introducing feature graphene, polytetrafluoroethylene (PTFE) is set to form the more complete and strong hydrophobic anti-corrosion network structure for combining power in Carbon fibe or carbon fibre composite surface, obtain strong hydrophobic, strong corrosion resistant, durability good Carbon fibe or carbon fiber composite；Particularly this method can obtain the hydrophobicity carbon fiber carbon paper for Proton Exchange Membrane Fuel Cells, improve its corrosion resistance and durability for being used under severe rugged environment, and this method is easy to operate, can realize large-scale production.
Description
Technical field
The present invention relates to a kind of feature graphene to be modified Carbon fibe or carbon fiber composite, and in particular to one kind has
The modification Carbon fibe or carbon fiber composite of strong corrosion resistant performance, it is more particularly to a kind of that there is corrosion resistant feature graphene
Strengthen the preparation method of used in proton exchange membrane fuel cell carbon paper, belong to Proton Exchange Membrane Fuel Cells material preparation technology neck
Domain.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of using macromolecule membrane as electrolyte, using Pt/C or Pt-Ru/C as electro-catalysis
Agent, is sent reactant hydrogen gas and oxygen to catalyst layer by the bipolar plates with gas channel, so that by reactant chemical energy
Change into the device of electric energy.Carbon fibe paper (carbon paper) is used as a kind of one-dimensional carbon/carbon composite, is widely used in proton exchange membrane
The gas diffusion layers base material of fuel cell, not only due to it has a uniform thin porous layer structure, good porosity and
Gas permeability, and primary raw material is graphitisable Carbon fibe, has excellent electric conductivity, chemical stability and heat endurance etc.
Feature.
In fact, the working environment of Proton Exchange Membrane Fuel Cells is very harsh, such as the meeting in startup and closing
Produce back voltage, high humility and oxygen-enriched environment of a 1.4V etc..The corrosion of carbon paper can cause micro-structure (hydrophobic performance)
The increase with resistivity is destroyed, and then influences the performance and endurance quality of fuel cell, under such a severe rugged environment, Carbon fibe
Paper must have good chemical stability as gas diffusion layers, not produce corrosion and degraded.Mainly there are two methods to change at present
The corrosion resistance of kind Carbon fibe paper, the first uses high-content polytetrafluoroethylene (PTFE) (PTFE) surface coated treatment, but carbon paper
Surface resistivity with the increase for being added to the order of magnitude of PTFE contents, and then influence the property of Proton Exchange Membrane Fuel Cells
Energy；At the same time in the operating condition, exposed carbon matrix outside, which occurs to corrode, is easy to cause coming off for PTFE.On the other hand, have
People proposes to suppress to corrode using high-pressure pump, although this method can effectively discharge unnecessary product water, grinds
Study carefully and show that still there are serious corrosion phenomenon under this device.
The content of the invention
For it is of the prior art improvement Carbon fibe material corrosion resistance method there are the defects of, mesh of the invention
Be to be to provide a kind of specific performance for utilizing feature graphene (graphene oxide, redox graphene), pass through work(
Energy property graphene improves Carbon fibe or carbon fiber composite is connected with the interface of PTFE (polytetrafluoroethylene (PTFE)), can improve
Binding ability between PTFE and Carbon fibe or carbon fiber composite, obtains more in carbon fiber or carbon fiber composite surface
Completely, the good hydrophobic membrane of associativity, so as to strengthen the corrosion resistance of Carbon fibe or carbon fiber composite, particularly obtains
Modified Activated Carbon fibrous paper can effectively improve the durability of Proton Exchange Membrane Fuel Cells or hydrogen fuel cell electrode and comprehensive
Energy.
In order to realize above-mentioned technical purpose, it is modified the present invention provides a kind of feature graphene and improves Carbon fibe or Carbon fiber
Tie up the corrosion resistant method of composite material, including following three kinds of parallel technical solutions：
Scheme one：Comprise the following steps：
1) Carbon fibe material is placed in macromolecule carbon source maceration extract after impregnating, drying, obtains prepreg；
2) prepreg obtains persursor material by mould compression molding；
3) persursor material carries out charing process and graphitization processing obtains feature graphene Modified Activated Carbon undulation degree
Material；
4) the feature graphene Modified Activated Carbon fibrous material, which is placed in polytetrafluoroethylsolution solution, carries out impregnation, dries
It is dry, sintering, to obtain the final product；
Feature graphene is added with the macromolecule carbon source maceration extract and/or polytetrafluoroethylsolution solution；
Scheme two：Comprise the following steps：
1) after macromolecule carbon source solution being coated in carbon fiber composite surface, drying, then carry out charing process and stone
Blackization processing, obtains feature graphene surface and is modified carbon fiber composite；
2) feature graphene surface modification carbon fiber composite is placed in polytetrafluoroethylsolution solution and carried out at dipping
Reason, is dried, sintering, to obtain the final product；
Feature graphene is added with the macromolecule carbon source solution and/or polytetrafluoroethylsolution solution；
Scheme three：Comprise the following steps：
1) after macromolecule carbon source solution being coated in carbon fiber composite surface, drying, obtains feature graphene table
Face is modified carbon fiber composite；
2) feature graphene surface modification carbon fiber composite is placed in polytetrafluoroethylsolution solution and carried out at dipping
Reason, is dried, sintering, to obtain the final product；
Feature graphene is added with the macromolecule carbon source solution and/or polytetrafluoroethylsolution solution.
Preferable scheme, the Carbon fibe material include Carbon fibe, Carbon fibe paper or other Carbon fibe precast bodies.
Feature stone in preferable scheme, macromolecule carbon source maceration extract or macromolecule carbon source solution or polytetrafluoroethylsolution solution
Black alkene addition mass percent concentration is 0.01%~30%；Preferably 0.01%~15%；More preferably it is 0.1~1.5%.
Preferable scheme, the process of compression molding are：First mould is preheated, prepreg is put into mould, 0.1~
Under 60MPa pressure, 150~250 DEG C, when insulation 0.5~5 is small are risen to the heating rate of 1.0~5.0 DEG C/min.
Preferable scheme, the charing process carry out under protective atmosphere, and carbonization temperature is 800~1500 DEG C.During charing
Between be the conventional time.
Preferable scheme, the graphitization processing carry out under protective atmosphere, and graphitization temperature is 1500~3500 DEG C.
Graphitization time is the conventional time.
Preferable scheme, in the feature graphene Modified Activated Carbon fibrous material load capacity of polytetrafluoroethylene (PTFE) for 0.5~
15wt%.
Preferable scheme, the feature graphene surface are modified the load of carbon fiber composite surface polytetrafluoroethylene (PTFE)
Measure as 0.5~15wt%.
Preferable scheme, in the polytetrafluoroethylsolution solution mass percent concentration of polytetrafluoroethylene (PTFE) for 0.5~
10%.
Preferable scheme, the baking in scheme one in step 4) or in scheme two in step 2) or in scheme three in step 2)
Dry process is：First spontaneously dry at room temperature 1~30 it is small when, then at a temperature of being placed in 70~100 DEG C it is dry 1~10 it is small when.
Preferable scheme, the sintering carry out under protective atmosphere, and sintering temperature is 50~350 DEG C, sintering time 0.5
~3 it is small when.
Preferable scheme, the protective atmosphere are nitrogen and/or inert gas.Inert gas such as argon gas.
Technical scheme is carrying out hydrophobically modified using polytetrafluoroethylene (PTFE) to Carbon fibe or carbon fiber composite
During, it is compound to Carbon fibe or Carbon fibe by introducing feature graphene (graphene oxide or redox graphene etc.)
Material is surface-treated, using feature graphene surface oxygen-containing functional group (C=O etc.) can effectively with water-repelling agent (example
Such as polytetrafluoroethylene (PTFE)) fluorine atom that contains be combined with each other, can be formed in the presence of same unit mass water-repelling agent more complete
Hydrophobic network structure, can improve water-repelling agent (such as polytetrafluoroethylene (PTFE)) in Carbon fibe or carbon fiber composite wettability of the surface
And filming performance, so as to improve water-repelling agent on the surfaces such as Carbon fibe, Carbon fibe paper, Carbon fibe base substrate, carbon fiber composite point
Cloth uniformity and with reference to power, the final corrosion resistance for improving Carbon fibe or carbon fiber composite, hydrophobicity, electric conductivity, power
Learn the comprehensive performances such as performance.
The process for preparation of the graphene containing feature of the present invention and the solution of macromolecule carbon source：(1) first function equipment stone
Black alkene solution：By graphene oxide or redox graphene, mixed with ethanol, acetone, toluene, dimethylbenzene, water equal solvent
Feature graphene mixed liquor；(2) maceration extract or coating liquid are prepared, by feature graphene mixed liquor and macromolecule carbon source (phenol
Urea formaldehyde, pitch etc.) mixed, obtain maceration extract or coating liquid, wherein the mass percent of graphene for 0.01%~
15%, maceration extract or coating liquid are stirred, ultrasonic wave disperse 1~24 it is small when, disperse graphene uniform.
In technical scheme, the concentration of macromolecule carbon source in macromolecule carbon source solution, and in carbon fiber or charcoal
Dipping (coating) amount on fibrous composite etc. is according to feature graphene Modified Activated Carbon fibrous material or feature graphene table
The density that face is modified carbon fiber composite determines that its density of general warranty is in 0.30~0.60g/cm3In the range of, this is
Those skilled in the art are easy to implement.
In technical scheme, the drying course in scheme one, scheme two or scheme three in step 1) is first natural
Air-dry, transfer in baking oven, the freeze-day with constant temperature at room temperature~150 DEG C.
In technical scheme, macromolecule carbon source solution can be used to carry out two to molding Carbon fibe material
Secondary dipping.
Technical scheme, is made with preparing the method for the feature graphene Modified Activated Carbon fibrous paper with strong corrosion resistant
Carry out being specifically exemplified by illustrating for preferred solution, comprise the following steps that：
(1) prepreg is prepared：
The carbon yield of carbon source is calculated according to thermogravimetric (TG) collection of illustrative plates in the macromolecule carbon such as phenolic resin, pitch source, according to work(
The final densities of energy property graphene Modified Activated Carbon fibrous paper calculate the pickup of macromolecule carbon source, and according to result of calculation, preparation contains
The maceration extract of feature graphene and macromolecule carbon source, wherein feature graphene mass percent concentration for 0.1%~
1.5%, by maceration extract under 45KHz frequencies ultrasound 1~24 it is small when, standby function graphene be completely dissolved it is scattered, for impregnating
Carbon fibe paper, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain prepreg；
(2) compression molding prepares persursor material
Die forming process and mould pressing process system are：When mold temperature is up to 50~130 DEG C, prepreg is put into
Wherein and set pressure and temperature, under 0.5~10MPa pressure, mold temperature with the speed of 2.5~3.5 DEG C/min by 50~
130 DEG C rise to 150~250 DEG C and keep the temperature 0.5~5 it is small when, obtain persursor material；
(3) charing, graphitization heat treatment
Graphene Modified Activated Carbon fibrous paper is made by charing, graphitization technique in persursor material；Charing and graphite chemical industry
Skill is existing common process, and such as preferable carbonization temperature is 800~1500 DEG C, and preferable graphitization temperature is 2000~3500
DEG C, protection gas is made with inert gases such as nitrogen or argon gas；
(4) polytetrafluoroethylene (PTFE) (PTFE) coating hydrophobic treatment
Prepare the PTFE solution that mass percent concentration is 5~10% and Carbon fibe is modified to ready feature graphene
Paper carries out dipping hydrophobic treatment；Such as feature graphene Modified Activated Carbon fibrous paper is immersed in prepared PTFE solution, keeps 30
~60 second time, and to carrying out weight weighing before and after feature graphene Modified Activated Carbon fibrous material hydrophobic treatment, is controlled with this
The upper carrying capacity of PTFE is 5~10%, be dried at room temperature for 24 it is small when after, it is small to be put into 70~100 DEG C of baking oven dry 6~10
When, then it is sintered in tube furnace, temperature is 260~350 DEG C；It is lazy with nitrogen or argon gas etc. when soaking time 1~3 is small
Property gas does protection gas.
Compared with the prior art, the advantageous effects that technical solution of the present invention is brought：
The corrosion resistant feature graphene of the present invention is modified in the preparation process of Carbon fibe or carbon fiber composite, by
In introducing feature graphene (graphene oxide, redox graphene) on Carbon fibe or carbon fiber composite surface, its
The functional group that surface is enriched with higher specific surface area and surface, has many carboxyls and hydroxyl, in macromolecule carbon in corner
The compatibility of resin (such as phenolic resin) and carbon fiber surface can be improved in the dipping process of source, is answered in Carbon fibe or Carbon fibe
In the preforming curing of condensation material and heat treatment process, feature graphene can crosslink with matrix resin and produce chemistry
Bond is closed, and bridge beam action is played on fiber and basal body interface, facilitates the combination that two-phase is good；Feature graphene thermal at the same time
Graphite platelet structure is formed after processing has big surface area, can increase the contact between matrix and fiber, conduct the road of electronics
Footpath increases, so as to improve the electric conductivity of Carbon fibe or carbon fiber composite.
The corrosion resistant feature graphene of the present invention is modified in the preparation process of Carbon fibe or carbon fiber composite, by
There is high specific surface area and abundant functional group in feature graphene, relatively traditional Carbon Materials after the processing of feature graphene thermal
Can retain more oxygen-containing functional groups (C=O keys), these oxygen-containing functional groups with PTFE solution dipping process with PTFE
There are inductive effect, enhancing Carbon fibe or the combination power of carbon fiber composite and PTFE coatings for the fluorine atom on top layer；Together
When in corner there is many carboxyls and hydroxyl due to feature graphene, feature graphene in dipping process with resin and
Fiber surface has a good compatibility, in subsequent compression molding, curing and heat treatment process, feature graphene and matrix tree
Fat crosslinks and produces chemical bonds so that feature graphene not only can be uniformly dispersed in the inside of carbon paper but also
It can be tightly combined with carbon matrix, therefore more preferable hydrophobic network structure can be formed in the case of carrying capacity on identical PTFE.
The method of the present invention can obtain the two-dimentional feature graphene Modified Activated Carbon fibrous paper of large area, i.e., for proton
The Carbon fibe paper of exchange film fuel battery, its density are about 0.30~0.50g/cm3, thickness be about 0.10~0.50mm, and its
The polytetrafluoroethylene (PTFE) hydrophobic membrane on surface is more complete, and is combined more preferably between carbon fibre material, can improve dredging for carbon paper at the same time
Water-based and corrosion resistance of the carbon paper under Proton Exchange Membrane Fuel Cells severe rugged environment, so as to improve proton exchange membrane combustion
Expect the comprehensive performance of battery.
The method of the present invention can produce good the changing for Proton Exchange Membrane Fuel Cells of comprehensive performance with mass
Property Carbon fibe paper, and this method is not only easy to operate, but also can in amplitude peak ensure the porosity and thoroughly of Carbon fibe paper
In the case of gas, improve the electric conductivity and intensity of Carbon fibe paper.
Brief description of the drawings
【Fig. 1】Strengthen the work of used in proton exchange membrane fuel cell carbon paper corrosion resistance for feature graphene in the present invention
Skill flow chart；
【Fig. 2】It is to be schemed using 1,2,3,4,5,6 Modified Activated Carbon fiber paper plane EIS of the embodiment of the present invention；
【Fig. 3】It is to be schemed using 1,2,3,4,5,6 Modified Activated Carbon fiber paper plane Tafel of the embodiment of the present invention；
【Fig. 4】It is to use 1,2,3,4,5,6 Modified Activated Carbon fiber paper plane corrosion current of the embodiment of the present invention-time diagram；
【Fig. 5】It is to use 1,2,3,4,5,6 Modified Activated Carbon fibrous paper weight change figure of the embodiment of the present invention；
【Fig. 6】It is to use 1,2,3,4,5,6 Modified Activated Carbon fibrous paper surface contact angle variation diagram of the embodiment of the present invention；
【Fig. 7】It is that the feature graphene of non-PTFE processing is modified the XPS comparison diagrams of carbon paper and traditional carbon paper；
【Fig. 8】It is to be schemed using 1 Modified Activated Carbon fiber paper plane SEM of the embodiment of the present invention；
【Fig. 9】It is to be schemed using the plane SEM of 5 Modified Activated Carbon fibrous paper of the embodiment of the present invention；
【Figure 10】For using 1 and 5 Modified Activated Carbon fibrous paper accelerated corrosion 24 of the embodiment of the present invention it is small when front and rear surfaces charcoals, fluorine,
The distribution diagram of element of oxygen；
【Figure 11】It is the feelings using 1 and 5 Modified Activated Carbon fibrous paper accelerated corrosion 24 of present example front and rear thermogravimetric analysis when small
Condition；
【Figure 12】It is using 1 and 5 Modified Activated Carbon fibrous paper accelerated corrosion 24 of present example infrared analysis feelings front and rear when small
Condition；
【Figure 13】It is the analysis using 1 and 5 Modified Activated Carbon fibrous paper accelerated corrosion 24 of present example XPS front and rear when small
Situation.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further details present invention, and the claims in the present invention
Protection domain is not limited by the example.
Embodiment 1
Referring to Fig. 1 and Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 9, Figure 10, Figure 11 and Figure 12.
(1) impregnated phenolic resin
The carbon yield of resin is calculated according to thermogravimetric (TG) collection of illustrative plates of phenolic resin, is calculated by the final densities of Carbon fibe paper
Go out the pickup of maceration extract, according to result of calculation, Carbon fibe paper is impregnated using resin impregnating liquid, shifted after air-drying
Into baking oven, at 75~85 DEG C constant temperature place 1~2.5 it is small when the Carbon fibe paper dried.
(2) it is molded
Mould pressing process system is：When mold temperature is up to 115~125 DEG C, the Carbon fibe paper of drying is put into wherein and set
Constant-pressure and temperature, under 1.5~2.5MPa pressure, mold temperature is risen with the speed of 2.5~3.5 DEG C/min by 115~125 DEG C
When to 180~230 DEG C and insulation 1~2.5 is small.
(3) it is heat-treated
Fuel cell Carbon fibe is made by charing, graphitization technique in the Carbon fibe paper of completion of cure, surfacing
Paper.Its density is 0.35g/cm3, thickness is 0.13mm or so.
(4) PTFE coatings hydrophobic treatment
The upper carrying capacity for controlling PTFE is 5-10%, be dried at room temperature for 24 it is small when after be put into 70-100 DEG C of baking oven it is dry
When 6-10 is small, then it is sintered in tube furnace, temperature is 260-350 DEG C；When soaking time 1-3 is small, with nitrogen or argon gas
Protection gas is done Deng inert gas.
Embodiment 2
Referring to Fig. 1 and Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
(1) feature graphene and resin maceration extract are impregnated
Prepare the solubility difference of the feature graphene and resin dipping mixed liquor, wherein feature graphene of different ratio
For 0.1%, when by mixed liquor, ultrasound 6 is small under 45KHz or so, standby function graphene is dissolved completely in ethanol solution, leaching
Stain Carbon fibe base substrate, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain Carbon fibe paper.
(2) (3) (4) as shown in example 1.
Embodiment 3
Referring to Fig. 1 and Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
(1) feature graphene and resin maceration extract are impregnated
Prepare the solubility difference of the feature graphene and resin dipping mixed liquor, wherein feature graphene of different ratio
For 0.5%, when by mixed liquor, ultrasound 6 is small under 45KHz or so, standby function graphene is dissolved completely in ethanol solution, leaching
Stain Carbon fibe base substrate, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain Carbon fibe paper.
(2) (3) (4) as shown in example 1.
Embodiment 4
Referring to Fig. 1 and Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
(1) feature graphene and resin maceration extract are impregnated
Prepare the solubility difference of the feature graphene and resin dipping mixed liquor, wherein feature graphene of different ratio
For 0.75%, when by mixed liquor, ultrasound 6 is small under 45KHz or so, standby function graphene is dissolved completely in ethanol solution, leaching
Stain Carbon fibe base substrate, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain Carbon fibe paper.
(2) (3) (4) as shown in example 1.
Embodiment 5
Referring to Fig. 1 and Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 8, Fig. 9, Figure 10, Figure 11 and Figure 12.
(1) feature graphene and resin maceration extract are impregnated
The feature graphene and resin maceration extract of different ratio are prepared, the solubility of wherein feature graphene is respectively
1.0%, when by mixed liquor, ultrasound 6 is small under 45KHz or so, standby function graphene is dissolved completely in ethanol solution, dipping
Carbon fibe base substrate, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain Carbon fibe paper.
(2) (3) (4) as shown in example 1.
Embodiment 6
Referring to Fig. 1 and Fig. 7, Figure 13.
(1) feature graphene and resin maceration extract are impregnated
The feature graphene and resin maceration extract of different ratio are prepared, the solubility of wherein feature graphene is respectively
1.5%, when by mixed liquor, ultrasound 6 is small under 45KHz or so, standby function graphene is dissolved completely in ethanol solution, dipping
Carbon fibe base substrate, air-dry after be transferred in baking oven, at 75~85 DEG C constant temperature place a hour obtain Carbon fibe paper.
(2) (3) (4) as shown in example 1.
As can be seen from Figure 2：With increase of the graphene oxide content from zero to 1%, hydrophobicity carbon paper it is corrosion-resistant
Performance improves, and graphene oxide content increases to 1.5% reduction from 1%.It is noted that the Rb of CP-1GO-P reaches
7.66E004 Ω cm2, are that numerical value is highest in all samples, show that CP-1GO-P has best corrosion resistance.
As can be seen from Figure 3：As graphene oxide content from 0 increases to 1%, the corrosion potential of hydrophobicity carbon paper is past
Positive offset, 0.05V is risen to from -0.12；Subsequent graphene oxide content is further added by, and current potential declines on the contrary, from 0.05 to-
0.12V, shows that CP-1GO-P has most positive corrosion potential.With the increase corrosion current density of graphene oxide content
(icorr) first reduce and become larger afterwards, it is 7.16E-008 that corrosion current density is relatively low when GO is 1%, in conclusion 1%GO is modified
Hydrophobicity carbon paper have preferable resistance to corrosion, it is consistent with EIS results.
As can be seen from Figure 4：The current density of CP-1GO-P is 0.256mA-2, shows most stable of protection feature.
As can be seen from Figure 5：With increase of the graphene oxide additive amount from 0 to 1%, before and after the corrosion of hydrophobicity carbon paper
Weight rate reduce, then when graphene oxide content from 1% increase by 1.5%, mass change rise.Mass change
Difference shows that the change of CP-1GO-P is minimum, illustrates during accelerated corrosion is tested, the 1%GO of addition can effectively suppress water
Carbon corrosion reaction between carbon, further hinders the progress of corrosion.
As can be seen from Figure 6：The angle of wetting change of unmodified hydrophobicity carbon paper is more than the modification of any graphene oxide and dredges
Water-based carbon paper, shows after accelerated corrosion is tested, the surface of unmodified carbon paper becomes more hydrophilic.Meanwhile with graphene oxide
The increase angle of wetting that additive amount increases to 0.75% from 0 changes decline, this is probably since addition graphene oxide promotes
The combination power of PTFE and carbon matrix, so as to reduce coming off for PTFE；Increase to 1.5% from 1% then as additive amount, this can
Can be due to excessive graphene oxide occur in dipping process stack and caused by uneven distribution.
As can be seen from Figure 10：The hole diameter on CP-GO-P-COR surfaces is only 200nm；But in T-CP-P-COR
The SEM pictures of 2000 times of amplifications find surface irregularity with respect to T-CP-P, the aperture diameter on surface is 5 to 10 μm, surface
Destroy seriously, may be due to " a hole corrosion " for erosion formation.Collection of illustrative plates, which is swept, from carbon, fluorine, oxygen element face can be seen that CP-GO-
The fluorine of P is not only evenly distributed on above carbon matrix, while also has presence on the carbon fiber of part.
As can be seen from Figure 11：After accelerated corrosion tests, T-CP-P has the PTFE matter of bigger than CP-1GO-P
Amount loss, this is probably since the PTFE on CP-1GO-P surfaces combines closely with charcoal paper matrix, it more difficult to is corroded, therefore aoxidizes stone
The addition of black alkene improves the corrosion resistance of hydrophobicity carbon paper, its result matches with weight change observed result.
As can be seen from Figure 12：Seen in collection of illustrative plates it can be seen that CP-1GO-P is not more produced compared with CP-1GO-P-COR
New peak shape, but CP-1GO-P-COR is located at peak value of the C=O stretching vibration absworption peaks than CP-1GO-P at 1710cm-1
Height, this shows that compared with unmodified hydrophobicity his carbon paper, the hydrophobicity carbon paper surface that graphene oxide is modified has more C=
O functional groups, while the electron cloud of F and the C=O functional group of ptfe surface is combined by inductive effect, therefore add oxygen
Graphite alkene can improve the bond strength of PTFE coatings and charcoal paper matrix.
As can be seen from Figure 13：Figure a finds out that all samples are mainly made of fluorine, oxygen, carbon, element sulphur.T-CP-P's contains
Oxygen amount only has 1.31at%, and the Surface Oxygen constituent content for adding CP-1GO-P after graphene oxide has brought up to 5.03at%, adds
After fast corrosion test, the oxygen content of T-CP-P-COR is 12.52at%, improves 11.21at%；And CP-1GO-P-COR is only carried
High 0.1at%, unmodified hydrophobicity carbon paper test rear surface oxygen with respect to graphene oxide modified hydrophobic carbon paper in accelerated corrosion
Content greatly increases.
Claims (10)
1. a kind of feature graphene, which is modified, improves Carbon fibe or the corrosion resistant method of carbon fiber composite, it is characterised in that：
Scheme one：Comprise the following steps：
1) Carbon fibe material is placed in macromolecule carbon source maceration extract after impregnating, drying, obtains prepreg；
2) prepreg obtains persursor material by mould compression molding；
3) persursor material carries out charing process and graphitization processing obtains feature graphene Modified Activated Carbon fibrous material；
4) the feature graphene Modified Activated Carbon fibrous material, which is placed in polytetrafluoroethylsolution solution, carries out impregnation, dries, and burns
Knot, to obtain the final product；
Feature graphene is added with the macromolecule carbon source maceration extract and/or polytetrafluoroethylsolution solution；
Scheme two：Comprise the following steps：
1) after macromolecule carbon source solution being coated in carbon fiber composite surface, drying, then carry out charing process and graphitization
Processing, obtains feature graphene surface and is modified carbon fiber composite；
2) feature graphene surface modification carbon fiber composite is placed in polytetrafluoroethylsolution solution and carries out impregnation, dried
It is dry, sintering, to obtain the final product；
Feature graphene is added with the macromolecule carbon source solution and/or polytetrafluoroethylsolution solution；
Scheme three：Comprise the following steps：
1) after macromolecule carbon source solution being coated in carbon fiber composite surface, drying, obtains feature graphene surface and changes
Property carbon fiber composite；
2) feature graphene surface modification carbon fiber composite is placed in polytetrafluoroethylsolution solution and carries out impregnation, dried
It is dry, sintering, to obtain the final product；
Feature graphene is added with the macromolecule carbon source solution and/or polytetrafluoroethylsolution solution.
2. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：The Carbon fibe material includes Carbon fibe, Carbon fibe paper or other Carbon fibe precast bodies.
3. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：Feature stone in macromolecule carbon source maceration extract or macromolecule carbon source solution or polytetrafluoroethylsolution solution
The addition mass percent concentration of black alkene is 0.01%~30%.
4. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：The process of compression molding is：First mould is preheated, prepreg is put into mould, 0.1~
Under 60MPa pressure, 150~250 DEG C, when insulation 0.5~5 is small are risen to the heating rate of 1.0~5.0 DEG C/min.
5. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：The charing process carries out under protective atmosphere, and carbonization temperature is 800~1500 DEG C.
6. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：The graphitization processing carries out under protective atmosphere, and graphitization temperature is 1500~3500 DEG C.
7. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：In the feature graphene Modified Activated Carbon fibrous material load capacity of polytetrafluoroethylene (PTFE) for 0.5~
15wt%；The feature graphene surface be modified the load capacity of carbon fiber composite surface polytetrafluoroethylene (PTFE) for 0.5~
15wt%.
8. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：The mass percent concentration of polytetrafluoroethylene (PTFE) is 0.5~10% in the polytetrafluoroethylsolution solution.
9. a kind of feature graphene according to claim 1 is modified raising Carbon fibe or carbon fiber composite is corrosion-resistant
Method, it is characterised in that：Drying in scheme one in step 4) or in scheme two in step 2) or in scheme three in step 2)
Process is：First spontaneously dry at room temperature 1~30 it is small when, then at a temperature of being placed in 70~100 DEG C it is dry 1~10 it is small when.
10. a kind of feature graphene according to claim 1, which is modified, improves Carbon fibe or carbon fiber composite corrosion resistant
The method of erosion, it is characterised in that：The sintering carries out under protective atmosphere, and sintering temperature is 50~350 DEG C, and sintering time is
0.5~3 it is small when.
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