CN117144711A - Carbon fiber base paper for gas diffusion layer of hydrogen energy fuel cell and preparation method thereof - Google Patents
Carbon fiber base paper for gas diffusion layer of hydrogen energy fuel cell and preparation method thereof Download PDFInfo
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- CN117144711A CN117144711A CN202311321342.9A CN202311321342A CN117144711A CN 117144711 A CN117144711 A CN 117144711A CN 202311321342 A CN202311321342 A CN 202311321342A CN 117144711 A CN117144711 A CN 117144711A
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- carbon fiber
- base paper
- fiber base
- diffusion layer
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 211
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 211
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000007789 gas Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 238000009792 diffusion process Methods 0.000 title claims abstract description 49
- 239000000446 fuel Substances 0.000 title claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003063 flame retardant Substances 0.000 claims abstract description 74
- 239000002270 dispersing agent Substances 0.000 claims abstract description 47
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 39
- 239000002562 thickening agent Substances 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 238000005520 cutting process Methods 0.000 claims abstract description 21
- 239000013530 defoamer Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims description 56
- 230000001070 adhesive effect Effects 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000725 suspension Substances 0.000 claims description 24
- 239000000805 composite resin Substances 0.000 claims description 20
- 239000002518 antifoaming agent Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000012796 inorganic flame retardant Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 231100000956 nontoxicity Toxicity 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 230000035699 permeability Effects 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/06—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods
- D21B1/061—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods using cutting devices
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
Abstract
The invention discloses carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell and a preparation method thereof, and relates to the technical field of preparation of carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell, and the carbon fiber base paper comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant; and the parts by weight of the raw materials are as follows: 70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant. According to the invention, by using the arrangement of the chopped carbon fibers and the water-soluble polymer dispersing agent obtained by the high-speed cutting machine, the chopped carbon fibers can be uniformly dispersed in the slurry, so that the effect of higher porosity can be ensured when the carbon fiber base paper is prepared, and the air permeability of the carbon fiber base paper is improved.
Description
Technical Field
The invention relates to the technical field of preparation of carbon fiber base paper of a gas diffusion layer of a hydrogen energy fuel cell, in particular to carbon fiber base paper of a gas diffusion layer of a hydrogen energy fuel cell and a preparation method thereof.
Background
The hydrogen fuel cell gas diffusion layer is an important component of a fuel cell membrane electrode, is positioned between a flow field and a catalyst layer, is an important structure for supporting the catalyst layer and collecting current, provides a plurality of channels for electrode reaction, such as gas, protons, electrons, water and the like, is based on the requirement of the gas diffusion layer, is researched and developed for many years, is a carbon material, in particular a carbon fiber base paper, is light in weight, flat in surface, corrosion-resistant, uniform in pore and high in strength, has adjustable thickness according to the use requirement, is suitable for durable fuel cells, is mature in manufacturing process and stable in performance due to the current use condition, and is the first choice of the material of the gas diffusion layer.
The existing carbon fiber base paper of the gas diffusion layer of the hydrogen energy fuel cell has the following defects:
1. patent document JP2008130416a discloses a method of manufacturing a membrane electrode assembly, but in the above-mentioned publication, when the fuel cell gas diffusion layer is used, a catalyst ink for a cathode of the gas diffusion layer of the cathode is coated on one surface of carbon paper, which easily causes a technical problem of a decrease in gas permeability;
2. patent document KR100801657B1 discloses a fuel cell including a gas diffusion layer of carbon nanotubes or carbon nanofibers, but the above-mentioned publication has a complicated preparation process and is liable to cause environmental pollution during the preparation process;
3. patent document US08409769B2 discloses a gas diffusion layer for a fuel cell, but in the above-mentioned publication, when the gas diffusion layer for a fuel cell is used, the thickness is increased by using microporous layer ink, which easily causes uneven thickness of carbon fiber base paper and a rough surface;
4. patent document CN111180744B discloses a method of forming a gas diffusion layer on carbon paper and carbon paper formed with the gas diffusion layer, but the carbon paper of the gas diffusion layer in the above publication has poor corrosion resistance and flame retardant effect, and is prone to damage during use.
Disclosure of Invention
The invention aims to provide carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell and a preparation method thereof, so as to solve the technical problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
Preferably, the preparation method of the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
Preferably, in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the length of the chopped carbon fibers is 3-7 mm, the diameter is 7-7.5um, and the water-soluble polymer dispersing agent is polyacrylamide dispersing agent;
and placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, thereby obtaining the carbon fiber suspension slurry with the slurry concentration of 0.10-0.25%.
Preferably, the stirrer in the first step adopts a servo motor, the stirring time is kept between 20 and 25 minutes, and the rotating speed of the stirrer is kept between 300 and 350r/min.
Preferably, in the inclined wire wet forming process in the second step, the inclination angle of the wire portion is adjusted within a range of 0 to 30 degrees.
Preferably, the epoxy resin in the third step is bisphenol a epoxy resin;
the thickening agent adopts a hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving the heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
Preferably, the flame-retardant adhesive can fully and uniformly permeate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-pressing solidification temperature in the hot-pressing drying box is 80-120 ℃, the drying time is 20-50 min, and the pressure is 5-15 MPa.
Preferably, in the carbonization process in the fifth step, heating to 1200-1600 ℃ in high-purity nitrogen, and maintaining for 5-10 min;
the graphitization process adopts heating to 2000-3000 ℃ in high-purity argon, and maintaining for 5-20S; and further obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, by using the arrangement of the chopped carbon fibers and the water-soluble polymer dispersing agent obtained by the high-speed cutting machine, the chopped carbon fibers can be uniformly dispersed in the slurry, so that the effect of higher porosity can be ensured when the carbon fiber base paper is prepared, and the air permeability of the carbon fiber base paper is improved;
2. according to the invention, through the arrangement of the flame-retardant adhesive and the vacuum wet suction box, the flame-retardant adhesive can be fully and uniformly permeated into the precursor of the carbon fiber base paper, the preparation process is simple and quick, and the flame-retardant adhesive is pollution-free and environment-friendly;
3. according to the invention, through the arrangement of the hot-pressing drying box, the precursor coated with the carbon fiber base paper can be subjected to scene drying and hot pressing, so that the smoothness of the surface of the carbon fiber/resin composite body can be improved, the compactness of the structure is improved, the contact resistance is reduced, and the conductivity is improved;
4. according to the invention, the flame-retardant adhesive is uniformly permeated into the precursor of the carbon fiber base paper, so that the corrosion resistance and flame retardant effect of the carbon fiber base paper are improved.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific direction, be configured and operated in the specific direction, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "provided," "connected," and the like are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1: referring to fig. 1, an embodiment of the present invention is provided: the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
A preparation method of carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell is characterized by comprising the following steps: the method comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
In some embodiments, in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the chopped carbon fibers have a length of 3mm and a diameter of 7.5um, and the water-soluble polymer dispersant is a polyacrylamide dispersant;
and (3) placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, so as to obtain the carbon fiber suspension slurry with the slurry concentration of 0.10%.
In some embodiments, the stirrer in step one employs a servo motor and the stirring time is maintained at 20min and the rotational speed of the stirrer is maintained at 350r/min.
In some embodiments, the inclined wire wet forming process in step two has a wire portion inclined at an angle of 30 degrees.
In some embodiments, the epoxy resin in step three is bisphenol a type epoxy resin;
the thickening agent adopts hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
In some embodiments, the flame-retardant adhesive can fully and uniformly penetrate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-press curing temperature in the hot-press drying box is 80 ℃, the drying time is 50min, and the pressure is 15MPa.
In some embodiments, the carbonization process in the fifth step is performed by heating to 1200 ℃ in high purity nitrogen for 10min;
the graphitization process adopts heating to 2000 ℃ in high-purity argon, and maintaining for 20S; and further obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
Example 2: referring to fig. 1, an embodiment of the present invention is provided: the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
A preparation method of carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell is characterized by comprising the following steps: the method comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
In some embodiments, in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the chopped carbon fibers have a length of 4mm and a diameter of 7.3um, and the water-soluble polymer dispersant is a polyacrylamide dispersant;
and (3) placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, so as to obtain the carbon fiber suspension slurry with the slurry concentration of 0.15%.
In some embodiments, the stirrer in step one employs a servo motor and the stirring time is maintained at 22min and the rotational speed of the stirrer is maintained at 340r/min.
In some embodiments, the inclined wire wet forming process in step two has an inclination angle of the wire portion of 25 degrees.
In some embodiments, the epoxy resin in step three is bisphenol a type epoxy resin;
the thickening agent adopts hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
In some embodiments, the flame-retardant adhesive can fully and uniformly permeate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-press curing temperature in the hot-press drying box is 90 ℃, the drying time is 40min, and the pressure is 13MPa.
In some embodiments, the carbonization process in the fifth step is performed by heating to 1300 ℃ in high-purity nitrogen for 8min;
the graphitization process adopts heating to 2400 ℃ in high-purity argon, and maintaining for 16S; and further obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
Example 3: referring to fig. 1, an embodiment of the present invention is provided: the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
A preparation method of carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell is characterized by comprising the following steps: the method comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
In some embodiments, in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the chopped carbon fibers have a length of 6mm and a diameter of 7.2um, and the water-soluble polymer dispersant is a polyacrylamide dispersant;
and (3) placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, so as to obtain the carbon fiber suspension slurry with the slurry concentration of 0.20%.
In some embodiments, the stirrer in step one employs a servo motor and the stirring time is maintained at 24 minutes and the rotational speed of the stirrer is maintained at 320r/min.
In some embodiments, the inclined wire wet forming process in step two has a wire portion inclined at 20 degrees.
In some embodiments, the epoxy resin in step three is bisphenol a type epoxy resin;
the thickening agent adopts hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
In some embodiments, the flame-retardant adhesive can fully and uniformly permeate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-press curing temperature in the hot-press drying box is 110 ℃, the drying time is 30min, and the pressure is 8MPa.
In some embodiments, the carbonization process in step five is performed by heating to 1450 ℃ in high purity nitrogen for 7min;
the graphitization process adopts heating to 2700 ℃ in high-purity argon, and maintaining for 10S; and further obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
Example 4: referring to fig. 1, an embodiment of the present invention is provided: the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
A preparation method of carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell is characterized by comprising the following steps: the method comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
In some embodiments, in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the chopped carbon fibers have a length of 7mm and a diameter of 7um, and the water-soluble polymer dispersant is a polyacrylamide dispersant;
and (3) placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, so as to obtain the carbon fiber suspension slurry with the slurry concentration of 0.25%.
In some embodiments, the stirrer in step one employs a servo motor and the stirring time is maintained at 25 minutes and the rotational speed of the stirrer is maintained at 300r/min.
In some embodiments, the inclined wire wet forming process in step two has a wire portion inclined at an angle of 30 degrees.
In some embodiments, the epoxy resin in step three is bisphenol a type epoxy resin;
the thickening agent adopts hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
In some embodiments, the flame-retardant adhesive can fully and uniformly permeate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-press curing temperature in the hot-press drying box is 120 ℃, the drying time is 20min, and the pressure is 5MPa.
In some embodiments, the carbonization process in the fifth step is performed by heating to 1600 ℃ in high purity nitrogen for 5min;
the graphitization process adopts heating to 3000 ℃ in high-purity argon, and maintaining for 5S; thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell
The carbon fiber base paper prepared by the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 has uniform porous structure, excellent air permeability, compact structure and smooth surface, so as to reduce contact resistance, improve conductivity and higher electronic conductivity, have certain mechanical strength, corrosion resistance and flame retardant effect, and the preparation process is simple and quick and is environment-friendly.
The preparation method has the advantages that the chopped carbon fibers and the water-soluble polymer dispersing agent are arranged by using the high-speed cutting machine, so that the chopped carbon fibers can be uniformly dispersed in slurry, the effect of higher porosity can be guaranteed when the carbon fiber base paper is prepared, the air permeability of the chopped carbon fibers is improved, the flame-retardant adhesive can be fully and uniformly permeated into the carbon fiber base paper precursor through the arrangement of the flame-retardant adhesive and the vacuum wet suction box, the preparation process is simple and quick, the flame-retardant adhesive is pollution-free, the environment-friendly use is realized, the carbon fiber base paper precursor can be smeared through the arrangement of the hot-pressing drying box, the scene is dried and hot-pressed, the smoothness of the surface of the carbon fiber/resin composite body can be improved, the structural compactness is improved, the contact resistance is reduced, the electric conductivity is improved, and the corrosion resistance and the flame-retardant effect of the carbon fiber base paper are improved through uniformly permeating the flame-retardant adhesive into the carbon fiber base paper precursor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell, which is characterized in that: the preparation method comprises the following raw materials: carbon fiber, water-soluble polymer dispersant, epoxy resin, thickener, defoamer and flame retardant;
and the parts by weight of the raw materials are as follows:
70-85% of carbon fiber, 1-2% of water-soluble polymer dispersant, 20-30% of epoxy resin, 2-5% of thickener, 1-1.5% of defoamer and 4-8% of flame retardant.
2. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step one: preparation of carbon fiber suspension slurry
Cutting the carbon fiber in a high-speed cutting machine to obtain chopped carbon fiber, then placing the chopped carbon fiber and a water-soluble polymer dispersing agent in a dispersing tank with a stirrer, adding a proper amount of water into the dispersing tank, stirring and mixing to form carbon fiber suspension slurry, and uniformly dispersing the chopped carbon fiber in the slurry by the water-soluble polymer dispersing agent;
step two: preparation of carbon fiber base paper precursor
Dewatering and papermaking the carbon fiber suspension slurry prepared in the first step by using an inclined wire wet forming process, so as to obtain a carbon fiber base paper precursor with a specified water content;
step three: preparation of flame retardant adhesives
Placing epoxy resin, a thickening agent, a defoaming agent, a flame retardant and a proper amount of water into a stirring tank, and mixing and stirring to obtain a flame-retardant adhesive;
step four: preparation of carbon fiber/resin composite
Uniformly coating an adhesive on the surface of a carbon fiber base paper precursor, uniformly sucking the adhesive through a vacuum wet suction box to enable the flame-retardant adhesive to fully and uniformly penetrate into the carbon fiber base paper precursor, and placing the carbon fiber base paper precursor coated with the adhesive into a hot-press drying box for drying and hot-press curing to obtain a carbon fiber/resin composite;
step five: preparation of carbon fiber base paper
And (3) sequentially carbonizing and graphitizing the carbon fiber/resin composite body obtained in the step four, thereby obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
3. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: in the first step, the carbon fibers are cut into chopped carbon fibers by using a high-speed cutting machine, the length of the chopped carbon fibers is 3-7 mm, the diameter of the chopped carbon fibers is 7-7.5 mu m, and the water-soluble polymer dispersing agent is polyacrylamide dispersing agent;
and placing the cut carbon fibers, the water-soluble polymer dispersing agent and a proper amount of water into a dispersing tank with a stirrer for stirring, thereby obtaining the carbon fiber suspension slurry with the slurry concentration of 0.10-0.25%.
4. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: the stirrer in the first step adopts a servo motor, the stirring time is kept between 20 and 25 minutes, and the rotating speed of the stirrer is kept between 300 and 350r/min.
5. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: in the inclined wire wet forming process in the second step, the inclination angle of the wire part is adjusted within the range of 0-30 degrees.
6. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: the epoxy resin in the third step adopts bisphenol A type epoxy resin;
the thickening agent adopts a hydrophobic modified nonionic polyurethane associative thickening agent, and has the effects of improving the heat resistance, wear resistance, heat preservation and ageing resistance of the product;
the defoaming agent is an organic silicon defoaming agent, and has the effects of good water solubility, quick defoaming, no toxicity and environmental protection;
the flame retardant is an inorganic flame retardant sold in the market;
and mixing the materials by a stirring tank to form the flame-retardant adhesive with flame-retardant effect.
7. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: the flame-retardant adhesive can fully and uniformly permeate into the precursor of the carbon fiber base paper by using the vacuum adsorption effect of the vacuum wet suction box in the fourth step, the drying and hot-pressing solidification temperature in the hot-pressing drying box is 80-120 ℃, the drying time is 20-50 min, and the pressure is 5-15 MPa.
8. The method for preparing carbon fiber base paper for a gas diffusion layer of a hydrogen energy fuel cell according to claim 2, wherein the method comprises the following steps: in the carbonization process in the fifth step, heating to 1200-1600 ℃ in high-purity nitrogen, and maintaining for 5-10 min;
the graphitization process adopts heating to 2000-3000 ℃ in high-purity argon, and maintaining for 5-20S; and further obtaining the carbon fiber base paper for the gas diffusion layer of the hydrogen energy fuel cell.
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