CN115418880A - Impregnating resin material for densifying and modifying carbon fiber paper, high-performance carbon fiber paper and preparation method thereof - Google Patents
Impregnating resin material for densifying and modifying carbon fiber paper, high-performance carbon fiber paper and preparation method thereof Download PDFInfo
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- CN115418880A CN115418880A CN202210956886.1A CN202210956886A CN115418880A CN 115418880 A CN115418880 A CN 115418880A CN 202210956886 A CN202210956886 A CN 202210956886A CN 115418880 A CN115418880 A CN 115418880A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 66
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 172
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 114
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005011 phenolic resin Substances 0.000 claims abstract description 32
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 32
- 239000000805 composite resin Substances 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- 238000000280 densification Methods 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 238000007598 dipping method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 23
- -1 phenolic aldehyde Chemical class 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 5
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000945 filler Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 15
- 238000005087 graphitization Methods 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- 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
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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 invention discloses an impregnating resin material for densifying and modifying carbon fiber paper, which is mainly obtained by in-situ polymerization of surface-modified conductive carbon and phenolic resin; conducting carbon powder is subjected to ultrasonic immersion cleaning by concentrated nitric acid, and then conducting carbon is subjected to surface modification by adopting a silane coupling agent. Also discloses a preparation method of the impregnating resin material, high-performance carbon fiber paper impregnated by the impregnating resin material and a preparation method thereof. The impregnated resin material is carbon/phenolic aldehyde composite resin obtained by in-situ polymerization, has higher carbon residue rate, the carbon particles and the phenolic aldehyde resin in the prepared impregnating solution form uniform and stable dispersion liquid, the phenolic aldehyde resin and the carbon particles are uniformly adhered to the carbon fiber framework of the impregnated carbon fiber paper, and the scanning electron microscope proves that the carbon particles on the carbon paper are uniformly distributed. The carbonized resin carbon and carbon particles are still attached to the surface of the carbon fiber framework and between the carbon fiber framework, so that a good densification effect is realized, and the mechanical property of the carbon paper is favorably improved.
Description
Technical Field
The invention belongs to the technical field of impregnating resin, and particularly relates to an impregnating resin material for densifying and modifying carbon fiber paper and a preparation method thereof, as well as high-performance carbon fiber paper densified and modified by the impregnating resin material and a preparation method thereof.
Background
The proton exchange membrane fuel cell is taken as the hydrogen fuel cell with the most application potential at present, the technical optimization of the base material of the carbon fiber paper of the diffusion layer in the membrane electrode becomes the key for improving the performance of the cell, and the characteristics of the carbon paper, such as air permeability, electric conductivity, corrosion resistance and the like, obviously influence the operation condition of the membrane electrode and even the whole galvanic pile.
At home and abroad, thermosetting polymer resin solutions such as phenolic resin, furfural resin, furan resin and the like are generally adopted to densify carbon fiber paper, and conductive carbon filler is often added to improve the conductivity of the carbon fiber paper, and the carbon fiber paper and the resin are compounded to densify and reinforce the carbon fiber paper. The carbon filler is poor in dispersibility in an aldehyde resin solution, uniform dispersion is difficult to realize, a suspension state for a long time cannot be maintained, the carbon filler can be rapidly settled within a few minutes to cause insufficient impregnation of a carbon paper blank, the carbon filler on a carbon fiber skeleton structure is not uniformly loaded, and finally the problems of unsatisfactory densification effect and non-uniform density of the carbon paper are caused.
For example, patent documents CN 111900417A and CN 107946621A both include a conductive carbon filler introduced by a dipping process, and the process method thereof is roughly as follows: the method comprises the steps of preparing a mixed solution of conductive carbon powder, thermosetting resin and an organic solvent as a carbon paper impregnating material, then placing a carbon fiber paper precursor into the impregnating material for impregnation treatment, and obtaining the carbon paper with high carbon content after curing, carbonization and graphitization.
The technology provided by the patents CN 111900417A and CN 107946621A has the following defects and shortcomings:
(1) The problem of poor dispersibility of the conductive carbon powder in the impregnating compound can not be solved. The original carbon particles have few surface functional groups, cannot be uniformly dispersed in a solution, and are easy to agglomerate, so that the carbon particles are not uniformly distributed on a carbon paper fiber framework or resin carbon and are easy to agglomerate, and the carbon paper has non-uniform density. In addition, local agglomeration of carbon particles also tends to cause a decrease in key permeability properties. The probability of causing a decrease in homogeneity is greater as the filler concentration is increased.
(2) Besides agglomeration, original carbon particles do not have long-acting dispersion stability in an impregnating material, and can generate a remarkable sedimentation phenomenon in a short time, so that the carbon particles are accumulated at the bottom of an impregnating solution, the impregnation efficiency is seriously influenced, the load capacity provided by one-time impregnation process is insufficient, the carbon residue rate after carbonization is low, the carbon paper is often required to be repeatedly impregnated for multiple times, the working procedures are multiplied, and the density, the strength and the like of the carbon paper are not ideal.
Disclosure of Invention
The invention aims to solve the technical problems that the defects and the defects mentioned in the background technology are overcome, and an impregnated resin material for densifying and modifying carbon fiber paper and a preparation method thereof are provided, and high-performance carbon fiber paper densified and modified by the impregnated resin material and a preparation method thereof are provided.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
in a first aspect, the invention provides an impregnating resin material for densifying and modifying carbon fiber paper, which is mainly obtained by in-situ polymerization of surface-modified conductive carbon and phenolic resin; the surface modified conductive carbon is prepared by the following method: conducting carbon powder is subjected to ultrasonic immersion cleaning by concentrated nitric acid, and then surface modification is carried out on the conducting carbon powder by adopting a silane coupling agent.
In the above impregnating resin material, preferably, the surface modified conductive carbon is 3-10wt% of the phenolic resin.
Preferably, the in-situ polymerization is to add conductive carbon powder, phenol, ammonia water, formaldehyde and other materials into a reaction system according to an alkaline environment required by the polymerization of the thermosetting phenolic resin, and then continuously stir for reaction to cure the resin, so as to realize the in-situ polymerization of the surface modified conductive carbon and the phenolic resin.
In a second aspect, the invention provides a preparation method of an impregnating resin material for densifying and modifying carbon fiber paper, which comprises the following steps:
(1) Carrying out ultrasonic immersion cleaning, centrifuging and drying on the conductive carbon powder by using concentrated nitric acid to obtain pretreated conductive carbon powder; the step can increase oxygen-containing groups such as surface hydroxyl, carboxyl and the like, and is favorable for improving the modification effect of the subsequent coupling agent;
(2) Adding the pretreated conductive carbon powder into a silane coupling agent-ethanol solution, heating and stirring, and then centrifuging and drying to obtain surface modified conductive carbon powder; the step realizes the modification of the surface of the carbon;
(3) Mixing the surface modified conductive carbon powder with phenol and ammonia water (adding materials into a reaction system according to an alkaline environment required by thermosetting phenolic resin polymerization), adding a formaldehyde solution while stirring for precondensation (adding a mixed solution in a step-by-step mode is beneficial to controlling the reaction rate, so that the phenolic resin can reach the expected molecular weight, and the whole process is carried out under the stirring action), then raising the temperature, continuously stirring for reaction to solidify the resin (the molecular chain of the phenolic resin is continuously increased at the stage, the viscosity molecular weight is gradually increased, and the viscosity of the reaction system is tested for 5 min/time in the period), rapidly cooling the water to room temperature to terminate the reaction, and carrying out vacuum drying to obtain the impregnating resin material for the densification modification of the high-performance carbon fiber paper.
In the step (1), the conductive carbon powder is any one or more of conductive carbon black, acetylene black, graphite powder, microcrystalline graphite, ketjen black, carbon nano tubes and graphene; the ultrasonic immersion cleaning time is 30-120min.
Preferably, in the step (2), the silane coupling agent is any one or any combination of two of KH550, KH560 and KH570, and the silane coupling agent-ethanol solution contains the silane coupling agent with a concentration of 1-3wt%; the heating and stirring temperature is 25-60 ℃, and the time is 4-6h.
The principle of modifying the conductive carbon by adopting the silane coupling agent is to form the chemical bonding of O-Si-O by utilizing the hydrolysis between the alkoxy group of the silane coupling agent and the hydroxyl group on the surface of the conductive carbon. However, the number of oxygen-containing groups on the untreated carbon surface is too small to facilitate the grafting reaction of the silane coupling agent. Therefore, the invention provides a pre-oxidation method by using concentrated nitric acid, a large number of oxygen-containing groups (hydroxyl and carboxyl) are formed on the surface of the conductive carbon, and the grafting efficiency of a subsequent coupling agent is favorably improved; therefore, the silane coupling agent-ethanol solution is controlled to be at a lower coupling agent concentration of 1-3wt%, and is stirred for 4-6h at 25-60 ℃ to obtain the coupling agent grafted and modified conductive carbon filler.
Preferably, in the step (2), the surface modified conductive carbon is added in an amount of 3-10wt% of the final product phenolic resin. Compared with the simple synthesis of phenolic resin, the difference of the invention is that the pre-addition of the conductive carbon easily causes the sudden increase of the viscosity of the system, causes the gelation phenomenon and causes the synthesis failure. The amount of conductive carbon added to the system is therefore critical and the maximum amount of addition is found to be no more than 10wt% of the phenolic resin yield.
Preferably, in step (3), the amount of ammonia added is 8-12vol.% of the total volume of the reactants; the addition amount of the surface modified conductive carbon powder is 3-10wt% of the yield of the phenolic resin; the formaldehyde solution is 35-37% formalin solution, and the molar ratio of formaldehyde to phenol in the formaldehyde solution is (1.2-1.8) to 1.
Preferably, in the step (3), the specific operation steps of adding the formaldehyde solution while stirring for pre-condensation are as follows: gradually adding formaldehyde solution into the reaction system at a speed of 5-6 min/time, and reacting for 30-40min at 40-60 ℃ under mechanical stirring; the temperature of the stirring reaction is 90-98 ℃, and the time is 30-60min; the resin curing means that the viscosity of the resin reaches 15-20 Pa.s; the vacuum drying temperature is 40-60 deg.C, and the drying time is 6-12h.
In a third aspect, the present invention provides a high-performance carbon fiber paper, which is obtained by impregnating the carbon fiber paper with the impregnated resin material.
In a fourth aspect, the invention provides a preparation method of high-performance carbon fiber paper, which comprises the following steps: and dissolving the impregnated resin material in an organic solvent, stirring to form uniform dispersion, then impregnating the carbon fiber paper precursor, and drying to obtain the high-performance carbon fiber paper.
In the preparation method of the high-performance carbon fiber paper, preferably, the organic solvent is any one or more of DMF, ethylene glycol, isopropanol and n-butanol; the concentration of the conductive carbon/phenolic resin composite resin solution contained in the organic solvent is 6-10wt%; the stirring time is 30-60min; the dipping time is 15-30min; the drying temperature is 60-75 ℃, and the drying time is 1-1.5h.
The technical principle of the invention is as follows: the method comprises the steps of firstly carrying out surface modification on conductive carbon filler powder to realize uniform and stable dispersion in a reaction solution system, and then preparing carbon/phenolic aldehyde composite resin (namely, impregnating resin material) by adopting a method of in-situ polymerization of phenolic resin, wherein the carbon filler in the composite resin is uniformly distributed, and the impregnating material solution prepared from the composite resin has long-acting dispersion stability, can keep the suspension dispersion state of filler particles for a long time, is favorable for impregnation densification of a high-performance carbon fiber paper (carbon paper for short) blank and uniform distribution of the carbon filler, and enhances the compactness and mechanical strength of a carbon fiber framework structure in the carbon paper blank. The carbon paper prepared by the impregnated resin material has obviously increased conductivity, the comprehensive performance of the carbon paper is improved, and the favorable influence on the performance of the fuel cell is expected.
Even if the beneficial effect of the conductive carbon filler on the carbon paper is fully proved at the present stage, a large optimization space still exists in the impregnation compounding process so as to realize effective densification and conductivity improvement of the carbon paper. The main improvement aspects of the invention are as follows:
(1) The carbon filler is modified by adopting the silane coupling agent, so that the dispersing capacity of the carbon filler in the solvent is effectively improved, and the phenomena of agglomeration and sedimentation are reduced. The modification process of the carbon filler is to hydrolyze Si-OR alkoxy groups in silane coupling agent molecules to generate silicon hydroxyl Si-OH, and to perform dehydration condensation with hydroxyl on the surface of carbon particles to form-Si-O-bonds; one end of the silane coupling agent is connected with the hydroxyl on the surface of the carbon inorganic substance through a covalent bond, the lipophilic group on the other end of the silane coupling agent forms a hydrogen bond with organic molecules, and the hydrogen bond is used as a molecular bridge to organically connect the interfaces of the carbon material and the organic solvent, so that the compatibility of the carbon powder in the organic solvent is improved, the dispersing ability is well improved, the suspending ability of conductive particles in the solution is finally improved, the coagulation tendency of the conductive particles is effectively inhibited, the dispersing uniformity and stability of the conductive particles are favorably improved, and the polymer resin and the filler in the impregnating compound are favorably attached to the fiber framework of the carbon paper.
(2) The carbon/phenolic aldehyde composite resin is prepared by an in-situ synthesis process, so that the uniform dispersion of the conductive carbon particles in the resin is realized, and the prepared impregnation liquid has long-acting dispersion stability. The conductive carbon can be uniformly and stably dispersed in a reaction medium through surface modification, and the amino functional groups on the surface of the carbon filler and the like can generate covalent bonds or hydrogen bonds with the phenolic resin by adopting an in-situ polymerization phenolic resin mode to form uniform and integrated composite resin. The mass ratio of the carbon filler to the phenolic resin can be adjusted according to different requirements, and composite resins with different carbon filler contents are prepared, so that the impregnation requirements of different carbon paper densification are met, and the densification effect can be achieved by one-time impregnation, so that repeated impregnation procedures are avoided, the material utilization rate is improved, and the energy consumption is saved.
(3) The carbon/phenolic resin composite resin prepared by the in-situ method has higher carbon residue rate, the dispersibility of carbon particles in the impregnating compound can be greatly improved, and the prepared impregnating solution is used for impregnating and densifying the carbon paper, so that the uniform adhesion on the fiber framework of the carbon paper can be realized, and the uniformity of the carbon paper can be improved. The composite resin is suspended and stabilized in an impregnation liquid prepared from organic solvents such as ethanol, dimethylformamide (DMF) and the like for 24 hours without sedimentation.
(4) After the phenolic resin/carbon composite resin impregnating material prepared by the invention is used for carrying out impregnation densification and carbonization processes on carbon paper, carbon particles are uniformly dispersed in a carbon fiber framework and resin carbon and can be used as a nucleation medium in a subsequent graphitization stage to promote the graphitization process of the resin carbon, so that the graphitization degree of the carbon paper is improved, and the electrical conductivity of the carbon paper is increased.
Compared with the prior art, the invention has the beneficial effects that:
1. the impregnated resin material is carbon/phenolic aldehyde composite resin obtained by in-situ polymerization, has higher carbon residue rate (for example, the carbon residue rate of 10wt% of carbon black/phenolic aldehyde composite resin reaches 65%), and carbonized resin carbon and carbon particles are still attached to the surface of a carbon fiber framework and between the carbon fiber framework, so that a good densification effect is realized, and the mechanical property of carbon paper is favorably improved.
2. The impregnated resin material of the invention forms uniform and stable dispersion liquid with the phenolic resin in the prepared impregnation liquid, the phenolic resin and the carbon particles are uniformly adhered on the carbon fiber framework of the impregnated carbon fiber paper, and the scanning electron microscope proves that the carbon particles on the carbon paper are uniformly distributed.
3. The preparation method of the impregnated resin material is simple in operation method, low in cost and environment-friendly on the whole; the coupling agent is adopted to modify the surface of the conductive carbon filler, lipophilic groups can be introduced on the surface of carbon, the affinity of particles and an organic solvent is coordinated, the solution is favorably maintained in a uniform state, and the prepared impregnated resin material has outstanding dispersion stability and can be suspended stably for more than 24 hours without obvious settlement.
4. According to the high-performance carbon fiber paper, the carbon/phenolic aldehyde composite resin is used as a densification modification impregnated resin material of the carbon fiber paper, and after densification modification, carbonization and graphitization, the density, uniformity, graphitization degree, conductivity, mechanical properties and corrosion resistance of the carbon paper are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a micrograph of a sample of example 1 of the present invention;
fig. 2 is a microscopic image of the carbon paper prepared in comparative example 1.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of densified and modified high-performance carbon fiber paper comprises the following steps:
the first step is as follows: and (3) pretreating, namely ultrasonically soaking and washing the conductive carbon black powder for 30min by adopting concentrated nitric acid, centrifugally separating out the carbon black powder with the surface modified by oxidation, and drying for later use.
The second step is that: surface modification, preparing an ethanol solution containing 2.5wt% of KH550 (. Gamma. -aminopropyltriethoxysilane), adding 1wt% of the above pretreated carbon black fine particles, heating and stirring at 25 ℃ for 4 hours, centrifuging, and drying to obtain modified carbon black.
The third step: mixing materials, namely formaldehyde: phenol is mixed according to a molar ratio of 1.5:1, weighing, wherein the addition amount of ammonia water is 10 vol% of the total volume of reactants, directly blending phenol and ammonia water, and adding conductive carbon black according to 10wt% of the yield of the phenolic resin;
the fourth step: pre-condensing, gradually adding 37% formaldehyde (formalin solution) into the reaction system for 6 min/five times, and reacting for 30min at 60 ℃ under mechanical stirring;
the fifth step: polycondensation, namely increasing the reaction temperature to 95 ℃, continuously stirring and reacting for 45min to solidify the resin, and testing the viscosity of the reaction system for 5 min/time;
and a sixth step: discharging, when the viscosity is detected to reach 15-20 Pa.s, rapidly cooling to room temperature to terminate the reaction, and placing the obtained conductive carbon black/phenolic aldehyde composite resin at 40 ℃ for vacuum drying for 12h to obtain the impregnating resin material for densifying and modifying the high-performance carbon fiber paper. The thermogravimetric test result shows that the carbon residue rate of the impregnated resin material reaches 60 percent;
the seventh step: and (3) dipping, dissolving the prepared dipping resin material (carbon black modified phenolic resin) in DMF (N, N-dimethylformamide) with the concentration of 6wt%, and stirring at a constant speed for 30min to form a uniform dispersion liquid, namely dipping liquid. Immersing the carbon fiber paper precursor for 25min, and drying at 60 ℃ for 1h to obtain a carbon paper blank modified by the carbon black/phenolic aldehyde composite resin.
The finished carbon paper obtained by subsequent carbonization and graphitization treatment has the porosity of 77.5 percent, the average graphitization degree of 91.1 percent, the average surface resistivity of 4.7m omega cm, the average volume resistivity of 11.7m omega cm and the average surface density of 88.3g/m 2 Average air permeability of 2300ml · mm/(cm) 2 hr.mmAq), tensile strength of 45.2MPa, bending strength of 85.5MPa, self-corrosion current density in acidic medium of 1.26 pA.cm -2 。
Example 2:
a preparation method of densified and modified high-performance carbon fiber paper comprises the following steps:
the first step is as follows: pretreating, namely ultrasonically soaking and washing graphite powder for 30min by using concentrated nitric acid, centrifugally separating out graphite powder with the surface modified by oxidation, and drying for later use;
the second step: surface modification, namely firstly preparing 1.5wt% ethanol solution of KH550, adding the graphite powder oxidized by the concentrated nitric acid, heating and stirring at 35 ℃ for 4h, centrifuging and drying to obtain modified graphite powder;
the third step: mixing materials, namely formaldehyde: phenol is added according to a molar ratio of 1.8:1, weighing, wherein the addition amount of ammonia water is 8 vol% of the total volume of reactants, directly blending phenol and ammonia water, and adding graphite powder according to 10wt% of the yield of the phenolic resin;
the fourth step: pre-condensing, gradually dripping 37% formaldehyde into the reaction system for 6 min/time, and reacting for 30min at 60 ℃ under mechanical stirring;
the fifth step: polycondensation, namely increasing the reaction temperature to 92 ℃, continuously stirring and reacting for 60min to solidify the resin, and testing the viscosity of the reaction system for 5 min/time;
and a sixth step: discharging, when the viscosity is detected to reach 15-20 Pa.s, rapidly cooling to room temperature to terminate the reaction, and placing the obtained graphite powder/phenolic aldehyde composite resin at 40 ℃ for vacuum drying for 12h to obtain an impregnation resin material for densification modification of the high-performance carbon fiber paper;
the seventh step: and (3) dipping, dissolving the prepared dipping resin material (graphite powder/phenolic aldehyde composite resin) in ethylene glycol with the concentration set as 10wt%, and uniformly stirring for 30min to form uniform dispersion liquid, namely dipping liquid. And (3) soaking the carbon fiber paper precursor for 30min, and drying at 60-75 ℃ for 1h to obtain the carbon paper blank modified by the graphite powder/phenolic aldehyde composite resin.
The finished carbon paper obtained by subsequent carbonization and graphitization treatment has the porosity of 76.3 percent, the average graphitization degree of 93.4 percent, the average surface resistivity of 4.5m omega cm, the average volume resistivity of 11.6m omega cm and the average surface density of 84.9g/m 2 Average air permeability of 2100 ml. Mm/(cm) 2 Hr. MmAq), tensile strength 38.5MPa, bending strength 85.5MPa, self-corrosion current density in acidic medium1.74pA·cm -2 。
Example 3
A preparation method of densified and modified high-performance carbon fiber paper comprises the following steps:
the first step is as follows: pretreating, ultrasonically soaking and washing the carbon nano tube for 30min by using concentrated nitric acid, centrifugally separating out carbon powder with the surface modified by oxidation, and drying for later use;
the second step: surface modification, namely firstly preparing 3wt% of ethanol solution of a silane coupling agent KH560 (gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane), adding the carbon nano tubes oxidized by the concentrated nitric acid, heating and stirring for 4 hours at 45 ℃, centrifuging and drying to obtain modified carbon nano tubes;
the third step: mixing materials, namely formaldehyde: phenol is mixed according to a molar ratio of 1.2:1, weighing ammonia water, wherein the addition amount of the ammonia water is 12 vol% of the total volume of reactants, directly blending phenol and the ammonia water, and adding the carbon nano tube according to 8wt% of the yield of the phenolic resin;
the fourth step: pre-condensing, gradually dripping 37% formaldehyde into the reaction system for 6 min/time, and reacting for 30min at 40 ℃ under mechanical stirring;
the fifth step: polycondensation, namely increasing the reaction temperature to 95 ℃, continuously stirring and reacting for 60min to solidify the resin, and testing the viscosity of the reaction system for 5 min/time;
and a sixth step: discharging, when the viscosity is detected to reach 15-20 Pa.s, rapidly cooling to room temperature to terminate the reaction, and placing the obtained carbon nano tube/phenolic aldehyde composite resin at 60 ℃ for vacuum drying for 8h to obtain an impregnating resin material for densification modification of high-performance carbon fiber paper;
the seventh step: and (3) dipping, dissolving the prepared dipping resin material (carbon nano tube/phenolic aldehyde composite resin) in isopropanol, setting the concentration to be 10wt%, and uniformly stirring for 30min to form uniform dispersion liquid, namely dipping liquid. And (3) immersing the carbon fiber paper precursor for 2 minutes and drying at 60 ℃ for 1 hour to obtain a carbon nanotube modified carbon paper blank.
The finished carbon paper obtained by subsequent carbonization and graphitization treatment has the porosity of 75.5 percent, the average graphitization degree of 90.4 percent, the average surface resistivity of 5.2m omega cm, the average volume resistivity of 13.8m omega cm and the average surface density of 81.7g/m 2 Average permeability of airThe rate is 2150 ml/mm/(cm) 2 hr.mmAq), tensile strength of 41MPa, bending strength of 76.2MPa, self-corrosion current density in acidic medium of 2.18 pA.cm -2 。
Comparative example 1:
a preparation method of carbon fiber paper comprises the following steps:
the first step is as follows: preparing materials, namely preparing an ethanol solution of 6wt% of thermosetting phenolic resin (not modified), adding conductive carbon black particles (the concentration is 10% of that of the phenolic resin) into the resin solution, uniformly stirring to uniformly disperse the carbon black, and preparing the carbon black into an impregnating compound for later use;
the second step is that: and (3) dipping, namely dipping the carbon felt precursor into a dipping material for 25min, and drying for 1h at the temperature of 60 ℃ to obtain a carbon paper blank.
In the comparative example, the impregnation material is prepared by adopting a physical mixing method, and then the carbon paper is impregnated, microscopic electron microscope images (figure 2) show that the carbon black is unevenly distributed on the resin carbon, obvious segregation and agglomeration among particles exist, while carbon paper blanks prepared by the in-situ synthesis method in the embodiment 1 can observe a very smooth surface (figure 1), and the carbon black is uniformly distributed at each position, so that the in-situ synthesis method can effectively improve the dispersion uniformity of the carbon black.
Comparative example 2:
a preparation method of carbon fiber paper comprises the following steps:
the first step is as follows: mixing materials, namely formaldehyde: phenol is mixed according to a molar ratio of 1.8:1, weighing, wherein the addition amount of ammonia water is 8 vol% of the total volume of reactants, directly blending phenol and ammonia water, and adding graphite powder according to 10wt% of the yield of the phenolic resin;
the second step is that: pre-condensing, gradually dripping 37 percent of formaldehyde into the reaction system for 6 min/time, and reacting for 30min at 60 ℃ under mechanical stirring;
the third step: polycondensation, namely increasing the reaction temperature to 92 ℃, continuously stirring and reacting for 60min to solidify the resin, and testing the viscosity of the reaction system for 5 min/time;
the fourth step: discharging, when the viscosity is detected to reach 15-20 Pa.s, rapidly cooling to room temperature to terminate the reaction, and placing the obtained graphite powder/phenolic aldehyde composite resin at 40 ℃ for vacuum drying for 12h;
the fifth step: and (3) dipping, dissolving the prepared carbon/phenolic aldehyde composite resin in glycol with the concentration set as 10wt%, and uniformly stirring for 30min to form uniform dispersion liquid, namely dipping liquid. Immersing the carbon fiber paper precursor for 30min, and drying at 60-75 ℃ for 1h to obtain the carbon paper blank modified by the carbon filler.
In the comparative example, graphite powder is not modified, an in-situ synthesis route is also adopted, and the average areal density of the finished carbon paper finally prepared is 74g/m 2 The tensile strength is 19.2MPa, the bending strength is 44.8MPa, and the comparison shows that the surface density and the strength are obviously lower than those of the carbon paper obtained by the subsequent treatment of the example 2, which indicates that the unmodified graphite powder can not meet the requirement of the impregnating compound on the stability, the loading capacity on the carbon paper is insufficient, and the compactness and the mechanical property of the carbon paper are reduced.
Claims (10)
1. An impregnating resin material for densifying and modifying carbon fiber paper is characterized in that the impregnating resin material is mainly obtained by in-situ polymerization of surface modified conductive carbon and phenolic resin; the surface modified conductive carbon is prepared by the following method: conducting carbon powder is subjected to ultrasonic immersion cleaning by concentrated nitric acid, and then surface modification is carried out on the conducting carbon powder by adopting a silane coupling agent.
2. The impregnating resin charge of claim 1, wherein said surface modified conductive carbon is 3-10wt% of said phenolic resin.
3. A preparation method of an impregnated resin material for densification modification of carbon fiber paper is characterized by comprising the following steps:
(1) Carrying out ultrasonic immersion cleaning, centrifuging and drying on the conductive carbon powder by using concentrated nitric acid to obtain pretreated conductive carbon powder;
(2) Adding the pretreated conductive carbon powder into a silane coupling agent-ethanol solution, heating and stirring, centrifuging, and drying to obtain surface-modified conductive carbon powder;
(3) Mixing the surface modified conductive carbon powder with phenol and ammonia water, adding formaldehyde solution while stirring for pre-condensation, raising the temperature, continuously stirring for reaction to solidify the resin, rapidly cooling to room temperature by water to terminate the reaction, and drying in vacuum to obtain the impregnating resin material for the densification modification of the high-performance carbon fiber paper.
4. The method for preparing the impregnated resin material for densifying and modifying carbon fiber paper according to claim 3, wherein in the step (1), the conductive carbon powder is any one or more of conductive carbon black, acetylene black, graphite powder, microcrystalline graphite, ketjen black, carbon nanotubes and graphene; the ultrasonic immersion cleaning time is 30-120min.
5. The method for preparing the impregnating resin material for the densification modification of the carbon fiber paper, according to the claim 3, wherein in the step (2), the silane coupling agent is any one or any combination of two of KH550, KH560 and KH570, and the silane coupling agent-ethanol solution contains 1-3wt% of silane coupling agent; the heating and stirring temperature is 25-60 ℃, and the time is 4-6h.
6. The method for preparing the impregnating resin material for densifying and modifying carbon fiber paper according to claim 3, wherein in the step (3), the amount of ammonia added is 8-12vol.% of the total volume of reactants; the addition amount of the surface modified conductive carbon powder is 3-10wt% of the yield of the phenolic resin; the formaldehyde solution is a formalin solution with the mass concentration of 35-37%, and the molar ratio of formaldehyde to phenol contained in the formaldehyde solution is (1.2-1.8) to 1.
7. The preparation method of the impregnating resin material for the densification modification of the carbon fiber paper, which is used for the densification modification of the carbon fiber paper, is characterized in that in the step (3), the specific operation steps of adding formaldehyde solution for precondensation with stirring are as follows: gradually adding formaldehyde solution into the reaction system at a speed of 5-6 min/time, and reacting for 30-40min at 40-60 ℃ under mechanical stirring; the temperature of the stirring reaction is 90-98 ℃, and the time is 30-60min; the resin curing means that the viscosity of the resin reaches 15-20 Pa.s; the vacuum drying temperature is 40-60 deg.C, and the drying time is 6-12h.
8. A high-performance carbon fiber paper, which is obtained by impregnating carbon fiber paper with the impregnated resin material according to any one of claims 1 to 2 or the impregnated resin material prepared by the method for preparing the impregnated resin material for densifying and modifying the carbon fiber paper according to any one of claims 3 to 7.
9. The preparation method of the high-performance carbon fiber paper is characterized by comprising the following steps: dissolving the impregnated resin material of any one of claims 1 to 2 or the impregnated resin material prepared by the preparation method of the impregnated resin material for densifying and modifying the carbon fiber paper of any one of claims 3 to 7 in an organic solvent, stirring to form a uniform dispersion, then immersing in a carbon fiber paper precursor, and drying to obtain the high-performance carbon fiber paper.
10. The method for preparing the high-performance carbon fiber paper according to claim 9, wherein the organic solvent is any one or more of DMF, ethylene glycol, isopropanol and n-butanol; the concentration of the conductive carbon/phenolic resin composite resin solution contained in the organic solvent is 6-10wt%; the stirring time is 30-60min; the dipping time is 15-30min; the drying temperature is 60-75 ℃, and the drying time is 1-1.5h.
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