CN115852733A - Carbon fiber paper for gas diffusion layer of fuel cell and preparation method thereof - Google Patents
Carbon fiber paper for gas diffusion layer of fuel cell and preparation method thereof Download PDFInfo
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- CN115852733A CN115852733A CN202210296343.1A CN202210296343A CN115852733A CN 115852733 A CN115852733 A CN 115852733A CN 202210296343 A CN202210296343 A CN 202210296343A CN 115852733 A CN115852733 A CN 115852733A
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- carbon fiber
- fiber paper
- fuel cell
- diffusion layer
- gas diffusion
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 105
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 105
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 238000009792 diffusion process Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000004132 cross linking Methods 0.000 claims description 33
- 238000003763 carbonization Methods 0.000 claims description 32
- 238000005087 graphitization Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 238000005096 rolling process Methods 0.000 claims description 29
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920002554 vinyl polymer Polymers 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 18
- -1 polypropylene Polymers 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 14
- 239000011302 mesophase pitch Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- MATSKSZAPIUFCB-UHFFFAOYSA-N 2,3-bis(ethenyl)phenol Chemical compound OC1=CC=CC(C=C)=C1C=C MATSKSZAPIUFCB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 18
- 229910002804 graphite Inorganic materials 0.000 description 16
- 239000010439 graphite Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
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Abstract
The invention discloses a carbon fiber paper for a gas diffusion layer of a fuel cell and a preparation method thereof, wherein the raw materials for preparing the carbon fiber paper comprise: the density of the obtained carbon fiber paper can be controlled to be 0.36g/cm 3 The porosity can reach 80%, the bending strength can reach 43MPa, the thickness can be controlled between 100 and 500um, and the surface roughness is controlledAt 6um, the resistivity can reach 4.5m omega cm (in-plane), and the thermal conductivity can reach 22W/mK (25 ℃, in-plane).
Description
Technical Field
The invention relates to the technical field of carbon fiber paper for a gas diffusion layer of a fuel cell, in particular to carbon fiber paper for the gas diffusion layer of the fuel cell and a preparation method thereof.
Background
Carbon fiber paper is applied to a gas diffusion layer for a fuel cell with its uniform porous structure and excellent gas permeability, lower specific resistance and higher mechanical strength, higher chemical stability and heat resistance, and contributes to the development of a fuel cell, particularly a hydrogen fuel cell, which has been rapidly developed in recent years.
Manufacturers of carbon fiber paper for gas diffusion layers of automotive fuel cells, which are superior in performance at the present stage, mainly include foreign companies such as eastern Japan company, SGL company in Germany, and Ballard company in Canada. The main preparation process of the carbon fiber paper comprises the following steps: preparing base paper by a short carbon fiber-paper making method, impregnating resin, pressing and forming, carbonizing at high temperature and graphitizing, and obtaining the carbon fiber paper. The preparation process mainly has the following problems: (1) The carbon fiber is mainly dispersed in water in the preparation process, so that the pollution problem exists; (2) In the process of resin impregnation, in order to improve the impregnation efficiency, solvents such as alcohol and the like are often required to be added to reduce the viscosity of resin glue solution, and the solvents are removed by adopting a drying method after impregnation, so that the pollution problem is also caused, the drying also increases the preparation time, and the production efficiency is reduced; (3) After resin is impregnated, the resin needs to be pressed, cured and formed, and for intermittent preparation, the resin needs to be cured for several hours, so that the energy consumption is high, the time consumption is long, and the efficiency is low; (4) In the high-temperature carbonization and graphitization processes, the carbon residue after carbonization by using the conventional phenolic resin is low, the mechanical property is low, in addition, the carbon fiber paper is not easy to be converted into graphitized carbon, and the prepared carbon fiber paper has low conductivity. The problems of pollution caused by water dispersion, solvent pollution caused by a high-viscosity solubilizer, low efficiency and high energy consumption caused by high-temperature pressing and long pressing time, poor mechanical property and low conductivity caused by low residual carbon content and low graphitization rate and the like are urgently needed to be solved.
In the prior art, carbon fiber paper for a gas diffusion layer of a fuel cell is prepared by other methods, but a large amount of electrolyte is used, and the use of the electrolyte causes a large amount of pollution. However, this production method is liable to volatilization and pollutes the environment, and the prior art has problems of low carbon residue rate, poor heat shrinkage performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the existing material and the preparation method, and provides the carbon fiber paper for the gas diffusion layer of the fuel cell, which has the advantages of uniform pores, excellent air permeability, low resistivity, high mechanical strength, good chemical stability, excellent heat resistance and simple and quick preparation process.
The invention also aims to provide a preparation method of the carbon fiber paper for the gas diffusion layer of the fuel cell, which has a novel resin structure and is quickly cured and formed.
The technical scheme adopted by the invention is as follows:
the carbon fiber paper for the gas diffusion layer of the fuel cell comprises the following raw materials in parts by mass:
carbon fiber 100 parts
10-30 parts of vinyl phenol
10-30 parts of benzaldehyde
0.4 to 1.2 portions of ammonia water
1-3 parts of vinyl auxiliary crosslinking agent
5-10 parts of soluble mesophase pitch
3-5 parts of polypropylene powder.
The soluble mesophase pitch is a mixture composed of a plurality of flat disc-shaped fused ring aromatic hydrocarbons, and the relative molecular mass of the soluble mesophase pitch is 370-2000.
The particle size of the polypropylene powder is 1-3 microns.
The carbon fiber is PAN-grade carbon fiber yarn subjected to vinyl silane surface treatment, the diameter of the PAN-grade carbon fiber yarn is 7-7.5 micrometers, the PAN-grade carbon fiber yarn is cut into 3-5cm in length, and then the PAN-grade carbon fiber yarn becomes a carbon fiber paper preform through the airflow effect and the adhesive bonding effect.
The vinylphenol is one or more of p-vinylphenol, o-vinylphenol, divinyl phenol or trivinylphenol;
the mass concentration of the ammonia water is 10-100%;
the vinyl auxiliary crosslinking agent is a vinyl bond-containing monovinyl low-molecular compound, a divinyl crosslinking agent or a polyvinyl crosslinking agent.
The ammonia water initiates the condensation polymerization reaction of the vinylphenol and the formaldehyde under the action of irradiation crosslinking heat, and plays a role of an initiator.
Wherein the monovinyl low molecular compound includes but is not limited to acrylic acid, hydroxypropyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl methacrylate, methacrylic acid, styrene or diacetone acrylamide; divinyl crosslinkers include, but are not limited to, divinylbenzene, tripropylene glycol dipropylene ether ester, diacrylic acid-1,4-butanediol ester; polyvinyl crosslinkers include, but are not limited to, trivinylbenzene, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate, pentaerythritol tetraacrylate, or pentaerythritol tetraacrylate;
when the vinyl crosslinking agent can play a role in promoting crosslinking, the vinyl crosslinking agent and the vinylphenol can perform a co-crosslinking reaction under the action of energy initiated by irradiation to form an irradiated vinyl crosslinking network. The irradiated vinyl crosslinked network further forms a cross network with the phenolic resin crosslinked network, so that the distance between benzene ring structures in the whole large crosslinked network is shortened, high carbon residue is formed in the high-temperature carbonization and graphitization processes, and the strength of the carbon fiber/carbon material is improved.
The soluble mesophase pitch can form a large amount of residual carbon in the high-temperature carbonization and graphitization processes, the residual carbon can be converted into carbon with a graphite structure, and the resistance of the carbon fiber paper is reduced, so that the conductivity of the carbon fiber paper is improved.
The polypropylene powder can prevent the phenolic resin from excessively shrinking after reaction, and ensure zero shrinkage of a cured product, thereby ensuring the thickness and thickness uniformity of the finally prepared carbon paper.
The invention also aims to provide a method for preparing the carbon fiber paper for the gas diffusion layer of the fuel cell, which has the advantages of high production efficiency, simple operation, high strength, small resistance, good chemical stability, excellent heat resistance, small pollution and low energy consumption, namely high efficiency and low energy consumption.
A method of making carbon fiber paper for a gas diffusion layer of a fuel cell, the method comprising the steps of:
(1) Cutting carbon fibers and spraying resin to form paper: cutting continuous carbon fibers into 3-5cm short carbon fibers, spraying a resin system consisting of vinyl phenol, benzaldehyde, ammonia water, a vinyl crosslinking agent, soluble mesophase pitch and polypropylene powder, wherein the spraying thickness is 100-500um;
(2) Irradiation crosslinking: irradiating by electron beams; in the electron beam irradiation process, the irradiation voltage is 0.1-2MeV, the current is 0.1-10mA, and the irradiation time is 30S-5min;
(3) Rolling and heating for crosslinking: continuously preparing a multi-network cured product by a rolling heating crosslinking process method, and forming the cured product with a certain thickness under the action of rolling heating; rolling for 30-60 min at 160-200 deg.C;
(4) High-temperature carbonization and graphitization: rapidly preparing carbon fiber paper through high-temperature carbonization and graphitization reaction; the temperature in the carbonization process is 400-700 ℃, the heating rate is 50-200 ℃/h, and the carbonization process is vacuumized; the high-temperature carbonization temperature is 900-1500 ℃, the heating rate is 50-200 ℃/h, and the carbonization process is vacuumized; the temperature in the graphitization process is 2000-3200 ℃, the heating rate is 50-200 ℃/h, and nitrogen is filled in the graphitization process for protection.
In the step (1), the cut carbon fibers are directly sprayed and liquid-phase impregnated to form paper, so that the resin is fully contacted with the carbon fibers, and the carbon fibers are impregnated by using a low-viscosity polymer precursor;
the invention does not need to add a diluting solvent, and the preparation process is more environment-friendly and pollution-free.
The whole preparation process does not need to add a metal catalyst, and the final product has high purity after carbonization.
The invention can rapidly crosslink vinyl groups to form a vinyl crosslinking network within five minutes, improves the efficiency and reduces the energy consumption, and is one of the innovation points of the invention.
In addition, the vinyl phenol and formaldehyde with special structures are used for initiating a crosslinking reaction in a chain manner, so that the reaction efficiency is greatly improved.
The thermal initiation of the phenolic condensation reaction by irradiation is another aspect of the present invention.
The rolling heating process in the step (3) is a continuous production process, the rolling can ensure the thickness of the product, namely the thickness uniformity, and meanwhile, the heating can promote the crosslinking reaction, thereby ensuring the complete reaction.
The continuous rolling production of the invention improves the production efficiency and simultaneously ensures the product quality uniformity, which is one of the innovation points of the invention.
The carbon fiber paper (see the carbon fiber paper micro-topography figure in the attached figure 2 in detail) has the following advantages:
(1) Low density and high porosity
The chopped carbon fibers are stacked in the spraying process to form a porous network structure, the carbon fibers are bonded by a resin system, and the resin is carbonized into the porous bonding structure after high-temperature carbonization and graphitization, so that the carbon fiber paper has lower density and higher porosity, and the density of the carbon fiber paper can be controlled to be 0.35-0.45g/cm 3 The porosity can reach 80%.
(2) High strength
According to the invention, through the double-network crosslinking and grafting effects of the vinyl phenolic resin, the vinyl phenolic resin has high crosslinking density, the vinyl phenolic resin is tightly combined with carbon fibers, the intermolecular distance is small, and meanwhile, by adding the soluble mesophase pitch with high carbon residue, the finally carbonized and graphitized material has high mechanical property and high material strength, and is beneficial to operation and subsequent use. The bending strength can reach 43MPa.
(3) Uniform thickness and low surface roughness
The polypropylene powder in the resin formula system can ensure that the shrinkage is zero in the reaction process, and the cured composite material system has uniform thickness and smooth surface by heating and rolling. In the carbonization and graphitization processes, the carbon fiber paper after carbonization and graphitization is further ensured to have uniform thickness and low surface roughness due to the control effect of the graphite paper and the graphite blocks. The thickness of the material can be controlled to be 100-500um, and the surface roughness is controlled to be 6um.
(4) Low resistivity and high thermal conductivity
The resin formula system is added with the soluble mesophase pitch with high carbon residue, so that the carbonized and graphitized carbon fibers have higher carbon residue, the high carbon residue connects the carbon fibers into a network whole, the electrical resistivity is favorably reduced, the heat conductivity coefficient is favorably improved, meanwhile, the carbon residue is converted into a graphite structure in the high-temperature graphitization process, the electrical resistivity can be further reduced, the heat conductivity coefficient is improved, and the carbon fiber paper network whole has lower electrical resistivity and higher heat conductivity coefficient. The resistivity of the carbon fiber paper can reach 4.5m omega cm (in-plane), and the thermal conductivity can reach 22W/mK (25 ℃, in-plane).
(5) Environment-friendly
A small molecular compound system is used in the preparation process, so that the impregnation is easy, the problem that the conventional resin is high in viscosity and difficult to impregnate is solved, and meanwhile, the solvent pollution is avoided in the reaction process, so that the preparation method is very environment-friendly.
(6) High efficiency and low energy consumption
In the preparation process, the heat of the irradiation crosslinking polyethylene is used for initiating the phenolic condensation reaction, the heating and the curing are not needed, the energy consumption is low, in addition, the irradiation crosslinking initiation rate is high, and the vinyl crosslinking can be initiated within 5 minutes. The rolling heating crosslinking process is continuous operation, so that the reaction rate can be increased, and the product quality can be ensured.
The carbon fiber paper obtained by the invention can meet the strict performance requirements of the gas diffusion layer of the fuel cell by virtue of various excellent performances.
Drawings
FIG. 1 is a preparation example of a carbon fiber paper preparation method according to the present invention;
FIG. 2 is an example of a micro-topography of carbon fiber paper prepared by the present invention.
Detailed Description
The present invention is described in further detail below by way of examples. However, the present invention is not limited to the following examples.
Example 1
A preparation method of carbon fiber paper for a gas diffusion layer of a fuel cell comprises the following steps:
(1) Cutting carbon fibers and spraying resin to form paper: continuous carbon fiber is cut into 3 cm's short carbon fiber under the effect of three-roller cutting knife, and the resin system (including vinylphenol 10 parts, benzaldehyde 15 parts, aqueous ammonia 1 part, styrene 1 part, soluble mesophase pitch 5 parts, polypropylene powder 3 parts) mixes the blowout in the spray gun, and carbon fiber and resin system are sprayed on release paper under the effect of air current, and the final mass ratio of spraying liquid and carbon fiber is 35:100, and the thickness is controlled to be 200um.
(2) Irradiation crosslinking: and flatly paving the sprayed and dipped sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the model and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time is 5min.
(3) Rolling and heating for crosslinking: transferring the irradiated sample to a rolling machine, wherein the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High-temperature carbonization and graphitization: the cured product is placed in a graphite mold for fixation and then carbonized and graphitized, the cured product is clamped in the middle of graphite paper with the thickness of 200 microns, then the cured product is placed in a high-temperature furnace for direct carbonization and graphitization reaction under the pressing of a graphite plate with the thickness of 2 cm, the carbonization and graphitization temperature is 400 ℃/3h +600 ℃/3h +700 ℃/2h +1200 ℃/1h +2500 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and nitrogen is filled for protection when the graphitization temperature is 2500 ℃. And cooling to normal temperature by water, taking out, weighing and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.35g/cm 3 The porosity was 82%, and the flexural strength was 41MPa. The thickness is 200um, and the surface roughness is 6.3um. The resistivity of the carbon fiber paper can reach 5.0m omega cm (in-plane), and the thermal conductivity can reach 21W/mK (25 ℃, in-plane).
Example 2
A preparation method of carbon fiber paper for a gas diffusion layer of a fuel cell comprises the following steps:
(1) Cutting carbon fibers and spraying resin to form paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the effect of three-roller cutting knife, the resin system (including 10 parts of vinylphenol, 13 parts of benzaldehyde, 1 part of ammonia water, 1 part of tripropylene glycol dipropylene ether ester, 6 parts of soluble mesophase pitch and 4 parts of polypropylene powder) is mixed and sprayed out in the spray gun, the carbon fiber and the resin system are sprayed on release paper under the effect of air flow, and the final mass ratio of the spraying liquid to the carbon fiber is 35:100, and the thickness is controlled to be 300um.
(2) Irradiation crosslinking: and flatly paving the sprayed and dipped sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the model and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time is 5min.
(3) Rolling and heating for crosslinking: transferring the irradiated sample to a rolling machine, wherein the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High-temperature carbonization and graphitization: the cured product is put into a graphite mold for fixation and then carbonized and graphitized, the cured product is clamped between 200 micron-thick graphite paper, then the cured product is put into a high-temperature furnace for direct carbonization and graphitization reaction under the pressing of a 2 cm-thick graphite plate, the carbonization and graphitization temperature is 400 ℃/3h +600 ℃/3h +700 ℃/3h +1200 ℃/1h +2800 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and nitrogen is filled for protection when the graphite is graphitized at 2800 ℃. And cooling to normal temperature by water, taking out, weighing and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.36g/cm 3 The porosity was 80% and the flexural strength was 42MPa. The thickness is 300um, and the surface roughness is 6.1um. The resistivity of the carbon fiber paper can reach 4.7m omega cm (in-plane), and the thermal conductivity can reach 21.5W/mK (25 ℃, in-plane).
Example 3
A preparation method of carbon fiber paper for a gas diffusion layer of a fuel cell comprises the following steps:
(1) Cutting carbon fibers and spraying resin to form paper: the continuous carbon fiber is cut into 3 cm's short carbon fiber under the effect of three-roller cutting knife, and the resin system (including vinylphenol 10 parts, benzaldehyde 10 parts, aqueous ammonia 1 part, pentaerythritol tetraacrylate 1 part, soluble mesophase pitch 8 parts, polypropylene powder 5 parts) mixes the blowout in the spray gun, and carbon fiber and resin system are sprayed on release paper under the effect of air current, and the final mass ratio of spraying liquid and carbon fiber is 35:100, and the thickness is controlled to be 400um.
(2) Irradiation crosslinking: and flatly paving the sprayed and dipped sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the model and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time is 5min.
(3) Rolling and heating for crosslinking: transferring the irradiated sample to a rolling machine, wherein the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High-temperature carbonization and graphitization: the cured product is put into a graphite mold for fixation and then carbonized and graphitized, the cured product is clamped between 200 micron-thick graphite paper, and then the cured product is put into a high-temperature furnace for direct carbonization and graphitization reaction under the pressing of a 2 cm-thick graphite plate, wherein the carbonization and graphitization temperature is 400 ℃/3h +600 ℃/3h +700 ℃/3h +1200 ℃/1h +3200 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and nitrogen is filled for protection when graphitizing is 3200 ℃. And cooling to normal temperature by water, taking out, weighing and finally preparing the carbon fiber paper.
The density of the carbon fiber paper can be controlled to be 0.36g/cm 3 The porosity can reach 80%. The bending strength can reach 43MPa. The thickness of the material can be controlled to be 400um, and the surface roughness is controlled to be 6um. The resistivity of the carbon fiber paper can reach 4.5m omega cm (in-plane), and the thermal conductivity can reach 22W/mK (25 ℃, in-plane).
Comparative example 1
(1) Cutting carbon fibers and spraying resin to form paper: continuous carbon fiber is cut into 3 cm's short carbon fiber under the effect of three-roller cutting knife, and the resin system (including vinyl phenol 10 parts, benzaldehyde 15 parts, aqueous ammonia 1 part, styrene 1 part) mixes the blowout in the spray gun, and carbon fiber and resin system are sprayed under the effect of air current on release paper, and the final mass ratio of spraying liquid and carbon fiber is 27:100, and the thickness is controlled to be 200um.
(2) Irradiation crosslinking: and flatly paving the sprayed and dipped sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the model and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time is 5min.
(3) Rolling and heating for crosslinking: transferring the irradiated sample to a rolling machine, wherein the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High-temperature carbonization and graphitization: the cured product is put into a graphite mold for fixation and then carbonized and graphitized, the cured product is clamped between 200 micron-thick graphite paper, then the cured product is put into a high-temperature furnace for direct carbonization and graphitization reaction under the pressing of a 2 cm-thick graphite plate, the carbonization and graphitization temperature is 400 ℃/3h +600 ℃/3h +700 ℃/2h +1200 ℃/1h +2500 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and nitrogen is filled for protection when the graphite is graphitized at 2500 ℃. And cooling to normal temperature by water, taking out, weighing and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.36g/cm 3 The porosity was 80% and the flexural strength was 30MPa. The thickness is 190um, and the surface roughness is 20um. The resistivity of the carbon fiber paper can reach 8.0m omega cm (in-plane), and the thermal conductivity can reach 15W/mK (25 ℃, in-plane). As the anti-shrinkage agent polypropylene powder and the high-carbon-residue soluble mesophase pitch are not added, the material has the defects of thickness shrinkage, uneven surface, high roughness, lower strength, higher resistivity and lower heat conductivity coefficient.
Comparative example 2
(1) Cutting carbon fibers and spraying resin to form paper: continuous carbon fiber is cut into 3 cm's short carbon fiber under the effect of three-roller cutting knife, and the resin system (including 10 parts of phenol, 15 parts of benzaldehyde, 1 part of aqueous ammonia, 1 part of hydroxyethyl acrylate) mixes the blowout in the spray gun, and carbon fiber and resin system are sprayed under the effect of air current on release paper, and the final mass ratio of spraying liquid and carbon fiber is 27:100, and the thickness is controlled to be 200um.
(2) Irradiation crosslinking: and flatly paving the sprayed and dipped sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the model and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time is 5min.
Until now, the liquid resin system could not be crosslinked under irradiation condition, the resin could not be cured, the solid material could not be prepared, and the sample preparation failed.
Claims (6)
1. The carbon fiber paper for the gas diffusion layer of the fuel cell is characterized by comprising the following raw materials in parts by weight:
carbon fiber 100 parts
10-30 parts of vinyl phenol
10-30 parts of benzaldehyde
0.4 to 1.2 portions of ammonia water
1-3 parts of vinyl auxiliary crosslinking agent
5-10 parts of soluble mesophase pitch
3-5 parts of polypropylene powder.
2. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the soluble mesophase pitch is a mixture of a plurality of flat disk-like condensed ring aromatic hydrocarbons, and has a relative molecular mass of 370 to 2000.
3. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the particle size of the polypropylene powder is 1 to 3 μm.
4. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the carbon fibers are PAN-grade carbon fiber yarns surface-treated with vinylsilane, having a diameter of 7 to 7.5 μm, cut into a length of 3 to 5cm, and then formed into a carbon fiber paper preform by air flow and adhesive bonding.
5. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the vinylphenol is one or more of p-vinylphenol, o-vinylphenol, divinylphenol, or trivinylphenol; the mass concentration of the ammonia water is 10-100%; the vinyl auxiliary crosslinking agent is a vinyl bond-containing monovinyl low-molecular compound, a divinyl crosslinking agent or a polyvinyl crosslinking agent.
6. The method for producing a carbon fiber paper for a gas diffusion layer of a fuel cell according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) Cutting carbon fibers and spraying resin to form paper: cutting continuous carbon fibers into 3-5cm short carbon fibers, spraying a resin system consisting of vinyl phenol, benzaldehyde, ammonia water, a vinyl crosslinking agent, soluble mesophase pitch and polypropylene powder, wherein the spraying thickness is 100-500um;
(2) Irradiation crosslinking: irradiating by electron beams; in the electron beam irradiation process, the irradiation voltage is 0.1-2MeV, the current is 0.1-10mA, and the irradiation time is 30S-5min;
(3) Rolling and heating for crosslinking: continuously preparing a multi-network cured product by a rolling heating crosslinking process method, and forming the cured product with a certain thickness under the action of rolling heating; rolling for 30-60 min at 160-200 deg.C;
(4) High-temperature carbonization and graphitization: rapidly preparing carbon fiber paper through high-temperature carbonization and graphitization reaction; the temperature in the carbonization process is 400-700 ℃, the heating rate is 50-200 ℃/h, and the carbonization process is vacuumized; the high-temperature carbonization temperature is 900-1500 ℃, the heating rate is 50-200 ℃/h, and the carbonization process is vacuumized; the temperature in the graphitization process is 2000-3200 ℃, the heating rate is 50-200 ℃/h, and nitrogen is filled in the graphitization process for protection.
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| KR20180023830A (en) * | 2016-08-25 | 2018-03-07 | 국일제지 주식회사 | A manufacturing method of carbon paper for fuel cell gas diffusion layers which adds pitch-based carbon fibers and aqueous binders, and carbon paper for the fuel cell gas diffusion layers using the same |
| CN108914681A (en) * | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of carbon fiber paper |
| CN113277868A (en) * | 2021-05-25 | 2021-08-20 | 杭州幄肯新材料科技有限公司 | Light carbon fiber/carbon composite thermal field material and preparation method thereof |
| CN113584940A (en) * | 2021-06-24 | 2021-11-02 | 浙江超探碳纤维科技有限公司 | Preparation method of carbon fiber paper |
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| KR20180023830A (en) * | 2016-08-25 | 2018-03-07 | 국일제지 주식회사 | A manufacturing method of carbon paper for fuel cell gas diffusion layers which adds pitch-based carbon fibers and aqueous binders, and carbon paper for the fuel cell gas diffusion layers using the same |
| CN108914681A (en) * | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of carbon fiber paper |
| CN113277868A (en) * | 2021-05-25 | 2021-08-20 | 杭州幄肯新材料科技有限公司 | Light carbon fiber/carbon composite thermal field material and preparation method thereof |
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