CN110129992B - Carbon fiber paper for fuel cell and preparation method thereof - Google Patents
Carbon fiber paper for fuel cell and preparation method thereof Download PDFInfo
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
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- D06C7/00—Heating or cooling textile fabrics
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- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a preparation method of carbon fiber paper for a fuel cell, which comprises the following steps: (1) carrying out graphitization treatment on the carbon fibers; (2) preparing a carbon paper prefabricated part by adopting a dry papermaking method; (3) carbonizing the carbon paper prefabricated part; (4) carrying out chemical vapor deposition on the carbonized carbon paper prefabricated part; (5) and (3) carrying out purification treatment and graphitization treatment on the carbon paper prefabricated part subjected to chemical vapor deposition treatment to finally obtain the carbon fiber paper for the fuel cell. Compared with the conventional wet papermaking technology, the method is more environment-friendly, the process is simpler, the cost is lower, and the requirements of different fluid diffusion can be met.
Description
Technical Field
The invention relates to the technical field of preparation of high-performance carbon fiber paper, in particular to carbon fiber paper for a fuel cell, which meets different fluid diffusion requirements, and a preparation method thereof.
Background
A Proton Exchange Membrane Fuel Cell (PEMFC) is a power generation device that continuously converts chemical energy in fuel and oxidant directly into electrical energy in an electrochemical reaction without combustion. As a new star of the fuel cell in the 21 st century, the proton exchange membrane fuel cell not only has the inherent characteristics of the fuel cell, but also has the advantages of high energy conversion efficiency, no pollution, quick start, long service life of the cell, high specific power, high specific energy and the like because the proton exchange membrane fuel cell takes hydrogen energy as a main power source, and has wide application in the technical fields of energy sources and energy conservation.
The carbon fiber paper is the base body part of the diffusion layer electrode which is the core component of the proton exchange membrane fuel cell, and the quality of the carbon fiber paper is directly related to the performance of the fuel cell. As a diffusion layer matrix of a fuel cell, the pore characteristics (pore diameter, porosity, pore distribution, pore surface characteristics), electrical resistivity, thermal conductivity, mechanical strength, purity, corrosion resistance and the like of carbon paper are required to meet the technical performance requirements of the proton exchange membrane fuel cell. Currently, international carbon fiber paper manufacturers mainly include SGL corporation, Toray corporation, germany corporation, and Ballard corporation, canada. The research on carbon fiber paper in China starts late, and has a large gap with foreign countries. In recent years, there have been many studies and related patents. Through patent and related paper search, the conventional wet papermaking method (also called papermaking method) is usually adopted in the current method for preparing carbon fiber paper, that is, a carbon fiber raw material is adopted, a paper pattern sheet making device is utilized to form a carbon fiber paper sheet, a flat plate dryer is used for drying to obtain carbon fiber base paper (a carbon paper precursor), then the carbon fiber base paper is soaked in a resin solution, and the carbon fiber paper meeting the requirements is prepared through processes of curing, carbonization, graphitization and the like.
However, the most prominent problem of carbon fibers in wet papermaking is dispersion and formation. The carbon fibers are not easily dispersed during beating and are generally first cut to a suitable length by a high-speed cutter. If the fibers are cut too short, they tend to disperse easily and can be used to make paper with good uniformity, but the strength is low. On the contrary, if the fiber is cut too long, the fiber is difficult to disperse, is easy to be flocculated into lumps, and is difficult to make paper with good evenness. Meanwhile, a water-soluble polymer dispersant is required to be added in the dispersing process, so that the carbon fibers are suspended and dispersed uniformly and then are conveyed to papermaking. The addition of the polymer dispersant is too much, the concentration of the carbon fiber slurry is too low, the water filtration is too fast, and the carbon fiber slurry cannot be manufactured on a common fourdrinier papermaking machine and a common cylinder papermaking machine; the polymer dispersant is too little, the fiber is not easy to disperse, the concentration of the slurry is too high, the water filtration is too slow, and the large-scale production is not facilitated. In addition, the wet papermaking technology also has the environmental protection problems of liquid discharge and the like in the production process.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a carbon fiber paper for fuel cells and a method for preparing the same. Compared with the conventional wet papermaking technology, the method is more environment-friendly, the process is simpler, the cost is lower, and the requirements of different fluid diffusion can be met.
The technical scheme of the invention is as follows:
the carbon fiber paper for the fuel cell has the thickness of 0.10-0.30mm and the volume density of 0.30-0.60g/cm3The porosity is 60-90%; the resistivity in the thickness direction is less than or equal to 0.16 omega cm, and the resistivity in the plane direction is less than or equal to 0.01 omega cm; coefficient of thermal conductivity at room temperature: the vertical direction is more than or equal to 1.7W/(mK), and the parallel direction is more than or equal to 21W/(mK); gas permeability less than or equal to 50mmH2O/mm。
A method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) carrying out graphitization treatment on the carbon fibers;
(2) preparing a carbon paper prefabricated part by adopting a dry papermaking method;
(3) carbonizing the carbon paper prefabricated part;
(4) carrying out chemical vapor deposition on the carbonized carbon paper prefabricated part;
(5) and (3) carrying out purification treatment and graphitization treatment on the carbon paper prefabricated part subjected to chemical vapor deposition treatment to finally obtain the carbon fiber paper for the fuel cell.
The graphitization treatment conditions in the step (1) are as follows: graphitizing the carbon fiber at 1800-3000 ℃ under the argon protective atmosphere; and the graphitization degree of the carbon fiber is improved while the photoresist is removed.
The preparation method of the carbon paper prefabricated member in the step (2) comprises the following steps:
cutting the graphitized carbon fiber into carbon fibers with the length of 10-100 mm;
secondly, opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a roller rotating at a high speed to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine by using an airflow fiber conveying machine to further card the carbon fibers, and then forming a non-woven paper sheet by using a web forming process;
thirdly, adopting hot melt adhesive to bond the non-woven paper sheets at the temperature of 100-150 ℃, drying at the temperature of 80-120 ℃, coiling and coiling to obtain the carbon paper prefabricated member.
In the step (2), the rotating speed of the roller is 3000 and 7500 r/min; the airflow fiber conveying machine and the airflow carding machine adopt compressed air as a medium, and the gas flow rate is 5-40 m/s; the net forming process adopts a vibration fiber feeding machine and a vacuum suction sinking net laying machine which are matched for use, and the short carbon fibers are forced to be settled, wherein the vibration frequency is 800-; the thickness of the non-woven paper sheet is 0.01-0.3 mm.
In the third step (2), the hot melt adhesive is one or the mixture of LDPE powder and HDPE powder; uniformly distributed on the non-woven paper sheet by a dusting mode, and bonded at the temperature of 100-150 ℃.
The carbonization process in the step (3) comprises the following steps: adopting phenolic resin or pitch resin to impregnate the single-layer or multi-layer laminated carbon paper prefabricated body, and curing for 2-8 hours at the temperature of 180-220 ℃; then carbonizing at the temperature of 600-1000 ℃ under the protection of nitrogen; the times of the dipping-curing-carbonizing cycle are controlled to be 1 to 5 times according to the performance requirements of the fuel cell.
The chemical vapor deposition process in the step (4) comprises the following steps: and placing the carbonized carbon paper prefabricated part in a chemical vapor deposition furnace, vacuumizing the reaction furnace, starting to heat when the pressure is less than 1000Pa, introducing a mixed gas of propylene and nitrogen when the temperature reaches 900-1150 ℃, introducing a mixed gas of the propylene and the nitrogen, wherein the flow rate of the propylene is 2-3L/min, the flow rate ratio of the propylene to the nitrogen is 1:2, the deposition pressure is 1000Pa, and controlling the final density and porosity of the composite material by controlling the heat preservation time for 10-100 h.
The purification treatment method in the step (5) comprises the following steps: immersing the carbon paper prefabricated part subjected to chemical vapor deposition treatment into a fluorine-containing or chlorine-containing chemical reagent, purifying for 2-30min at the temperature of 20-80 ℃ to eliminate metal and nonmetal elements in the carbon paper, and then graphitizing the carbon paper at the high temperature of 1800-2700 ℃ in the argon protective atmosphere to further improve the performance of the carbon paper.
The chemical agent containing fluorine or chlorine is as follows: one or more of freon, hydrofluoric acid, hypochlorous acid and hydrochloric acid; the mass concentration of the reagent is 0.01-5%.
The beneficial technical effects of the invention are as follows:
(1) compared with the traditional manufacturing method of the carbon fiber paper prefabricated part, the dry method technology is adopted to improve the dispersibility of the short carbon fibers with longer length.
(2) Compared with the traditional manufacturing method of the carbon fiber paper prefabricated part, the dry method technology is adopted to improve the length of the carbon fiber in the carbon fiber paper, and the high-strength carbon paper strength can be obtained more conveniently.
(3) The carbon fibers and pores in the carbon fiber paper preform prepared by the dry method technology are uniformly distributed, so that the obtained carbon fiber paper has uniform performance.
(4) And simultaneously, the impregnation-curing-carbonization and chemical vapor deposition methods are adopted, so that the performance of the carbon fiber paper can be adjusted according to the performance requirements of the fuel cell.
(5) The performance of the carbon fiber paper can be further improved by adopting a chemical purification method and a high-temperature graphitization method.
(6) The carbon fiber paper for the fuel cell, prepared by the invention, has excellent electrical property and heat conductivity, and also has a series of advantages of good strength, high modulus and the like.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1:
a method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) T700-48K and T300-48K carbon fibers with the mass ratio of 3:7 are used as raw materials, and are cut into short fibers with the diameter of 50mm after being graphitized at the temperature of 2400 ℃;
(2) opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a high-speed rotary roller with the rotating speed of 6000 rpm to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine through an airflow fiber conveying machine with the flow speed of 20m/s to further card the carbon fibers, then using vibration with the vibration frequency of 960r/min to match a vacuum lapping machine with the vacuum suction force of 1000Pa to the fiber machine, and forcibly settling the chopped carbon fibers to form a non-woven paper sheet with the thickness of 0.080 mm; and finally, adhering the non-woven paper sheet at 120 ℃ by using LDPE hot melt adhesive, drying at 80 ℃, and coiling to obtain the carbon paper prefabricated member.
(3) Impregnating the 3-layer carbon paper prefabricated part by adopting phenolic resin, curing for 4 hours at 180 ℃, and then carbonizing at 900 ℃ in a nitrogen protective atmosphere; the impregnation-curing-carbonization process was repeated once.
(4) And (3) putting the carbon paper prefabricated part processed in the step (3) into a chemical vapor deposition furnace, vacuumizing the reaction furnace, starting to heat when the pressure is less than 1000Pa, introducing a mixed gas of propylene and nitrogen when the temperature reaches 1050 ℃, wherein the flow rate of the propylene is 7L/min, the flow rate ratio of the propylene to the nitrogen is 1:2, the deposition pressure is 1000Pa, and the chemical vapor deposition lasts for 10 hours.
(5) The carbon paper is purified by hydrochloric acid with the concentration of 0.1% at room temperature for 5min to eliminate metal and nonmetal elements in the carbon paper, and then graphitized at 2700 ℃ for 0.5 h under the protection of argon gas for further improving the performance of the carbon paper.
The performance of the prepared carbon fiber paper is as follows: the thickness is 0.23mm, and the bulk density is 0.42g/cm3Porosity 82%; resistivity in the plane direction was 3.5 m.OMEGA.cm; the tensile strength was 53N/cm.
Example 2:
a method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) T700-12K carbon fibers and T300-12K carbon fibers in a mass ratio of 5:5 are used as raw materials, and are cut into short fibers of 30mm after being graphitized at the temperature of 2500 ℃.
(2) Opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a high-speed rotary roller with the rotation speed of 4000 revolutions per minute to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine through an airflow fiber conveying machine with the flow speed of 15m/s to further card the carbon fibers, then using vibration with the vibration frequency of 1050r/min to match a vacuum lapping machine with the vacuum suction force of 800Pa to the fiber machine, and forcibly settling the chopped carbon fibers to form 0.2mm non-woven paper sheets; and finally, adhering the non-woven paper sheet at 120 ℃ by using LDPE hot melt adhesive, drying at 80 ℃, and coiling to obtain the carbon paper prefabricated member.
(3) The single-layer carbon paper preform is impregnated by phenolic resin, cured at 200 ℃ for 6 hours, carbonized at 900 ℃ in a nitrogen protective atmosphere, and the impregnation-curing-carbonization process is repeated once.
(4) And (3) carrying out chemical vapor deposition on the carbon paper prefabricated member treated in the step (3) for 15 hours at 1050 ℃, 1000Pa pressure, 3L/min propylene flow rate and 1:2 propylene-nitrogen flow rate ratio.
(5) And (2) adopting hydrofluoric acid with the concentration of 0.5% to purify the carbon paper for 15min at room temperature, eliminating metal and nonmetal elements in the carbon paper, and then graphitizing the carbon paper for 1 hour at the high temperature of 2300 ℃ under the protection of argon gas, so that the performance of the carbon paper is further improved.
The performance of the prepared carbon fiber paper is as follows: the thickness is 0.205mm, and the bulk density is 0.44g/cm3Porosity 80%; resistivity in the plane direction was 9.8 m.OMEGA.cm; the tensile strength was 25N/cm.
Example 3:
a method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) T700-24K carbon fiber and T300-24K carbon fiber in a mass ratio of 6:4 are used as raw materials, and are cut into short fibers of 80mm after being graphitized at 2700 ℃.
(2) Opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a high-speed rotary roller with the rotating speed of 5000 r/min to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine through an airflow fiber conveying machine with the flow speed of 30m/s to further card the carbon fibers, then using vibration with the vibration frequency of 1200r/min to match a vacuum lapping machine with the vacuum suction force of 1500Pa to force the chopped carbon fibers to settle to form 0.12mm non-woven paper sheets; and finally, adhering the non-woven paper sheets at 120 ℃ by adopting HDPE hot melt adhesive, drying at 80 ℃, coiling and coiling to obtain the carbon paper prefabricated member.
(3) The 2-layer carbon paper preform was impregnated with phenolic resin and cured at 200 ℃ for 4 hours. And then carbonizing at 900 ℃ in the nitrogen protective atmosphere, and repeating the impregnation-curing-carbonization process once.
(4) And (3) carrying out chemical vapor deposition on the carbon paper prefabricated member treated in the step (3) for 10 hours at the temperature of 1100 ℃, the pressure of 1000Pa, the flow rate of propylene of 4L/min and the flow rate ratio of propylene to nitrogen of 1: 2.
(5) The carbon paper is purified for 10min at room temperature by adopting Freon with the concentration of 1 percent, metal and non-metal elements in the carbon paper are eliminated, and then the carbon paper is graphitized for 1 hour at the high temperature of 2500 ℃ under the protection atmosphere of argon gas, so that the performance of the carbon paper is further improved.
The performance of the prepared carbon fiber paper is as follows: the thickness is 0.25mm, and the bulk density is 0.40g/cm3Porosity 84%; resistivity in the plane direction was 6.3 m.OMEGA.cm; the tensile strength was 35N/cm.
Example 4:
a method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) T700-50K carbon fiber and T300-50K carbon fiber in a mass ratio of 4:6 are used as raw materials, and are cut into short fibers of 50mm after being graphitized for 1 hour at 2300 ℃.
(2) Opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a high-speed rotary roller with the rotating speed of 6500 r/min to disperse the fiber raw materials into a single fiber state, further carding the carbon fibers in the chopped carbon fibers manned airflow carding machine by using an airflow fiber conveying machine with the flowing speed of 35m/s, and then forcibly settling the chopped carbon fibers by using vibration with the vibration frequency of 1200r/min to match a vacuum lapping machine with the vacuum suction force of 1500Pa to form a 0.25mm non-woven paper sheet; and finally, adhering the non-woven paper sheet at 120 ℃ by using LDPE hot melt adhesive, drying at 80 ℃, and coiling to obtain the carbon paper prefabricated member.
(3) The single-layer carbon paper preform was impregnated with phenolic resin and cured at 200 ℃ for 6 hours. Subsequently, carbonization is carried out at 900 ℃ under the protection of nitrogen. The impregnation-curing-carbonization process was repeated twice.
(4) And (3) carrying out chemical vapor deposition on the carbon paper prefabricated member treated in the step (3) for 10 hours at the temperature of 1100 ℃, the pressure of 1000Pa, the flow rate of propylene of 5L/min and the flow rate ratio of propylene to nitrogen of 1: 2.
(5) Adopting 1% hydrochloric acid to purify the carbon paper for 15min at room temperature, and eliminating metal and nonmetal elements in the carbon paper; and then graphitizing the carbon paper at 2500 ℃ for 1 hour under the protection of argon gas, thereby further improving the performance of the carbon paper.
The performance of the prepared carbon fiber paper is as follows: the thickness is 0.25mm, and the bulk density is 0.48g/cm3Porosity 76%; resistivity in the plane direction was 9.5 m.OMEGA.cm; the tensile strength was 42N/cm.
Example 5:
a method for preparing carbon fiber paper for fuel cells, which comprises the following steps:
(1) T700-12K carbon fiber and T300-12K carbon fiber in a mass ratio of 7:3 are used as raw materials, and are cut into short fibers of 40mm after being graphitized for 0.5 hour at 2300 ℃.
(2) Opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a high-speed rotary roller with the rotating speed of 4500 rpm to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine through an airflow fiber conveying machine with the flow speed of 20m/s to further card the carbon fibers, then using vibration with the vibration frequency of 1000r/min to match a vacuum lapping machine with the vacuum suction force of 950Pa to the fiber machine, and forcibly settling the chopped carbon fibers to form 0.10mm non-woven paper sheets; and finally, adhering the non-woven paper sheet at 120 ℃ by using a hot melt adhesive, drying at 80 ℃, and coiling to obtain the carbon paper prefabricated member.
(3) 2 layers of carbon paper preforms were impregnated with phenolic resin and cured at 180 ℃ for 3 hours. Subsequently, carbonization is carried out at 900 ℃ under the protection of nitrogen.
(4) And (3) carrying out chemical vapor deposition on the carbon paper prefabricated member treated in the step (3) for 5 hours at the temperature of 1050 ℃, the pressure of 1000Pa, the flow rate of propylene of 3L/min and the flow rate ratio of propylene to nitrogen of 1: 2.
(5) Adopting 0.5% hydrochloric acid to purify the carbon paper for 10min at room temperature, and eliminating metal and nonmetal elements in the carbon paper; and then, carrying out graphitization treatment on the carbon paper for 1 hour at 2700 ℃ under the argon protection atmosphere, thereby further improving the performance of the carbon paper.
The performance of the prepared carbon fiber paper is as follows: the thickness is 0.20mm, and the bulk density is 0.34g/cm3Porosity 88%; resistivity in the plane direction was 5.8 m.OMEGA.cm; the tensile strength was 18N/cm.
Claims (5)
1. A preparation method of carbon fiber paper for fuel cells is characterized by comprising the following steps:
(1) carrying out graphitization treatment on the carbon fibers; graphitizing the carbon fiber at 1800-3000 ℃ under the argon protective atmosphere; the graphitization degree of the carbon fiber is improved while the photoresist is removed;
(2) preparing a carbon paper prefabricated part by adopting a dry papermaking method;
the preparation method of the carbon paper prefabricated member comprises the following steps:
cutting the graphitized carbon fiber into carbon fibers with the length of 10-100 mm;
secondly, opening the chopped carbon fibers by using a double-roller fiber opener, using air as a dispersion medium, using a roller rotating at a high speed to disperse the fiber raw materials into a single fiber state, then bringing the chopped carbon fibers into an airflow carding machine by using an airflow fiber conveying machine to further card the carbon fibers, and then forming a non-woven paper sheet by using a web forming process; the rotating speed of the roller is 3000 and 7500 r/min; the airflow fiber conveying machine and the airflow carding machine adopt compressed air as a medium, and the gas flow rate is 5-40 m/s; the net forming process adopts a vibration fiber feeding machine and a vacuum suction sinking net laying machine which are matched for use, and the short carbon fibers are forced to be settled, wherein the vibration frequency is 800-;
thirdly, adopting hot melt adhesive to bond the non-woven paper sheets at the temperature of 100-150 ℃, drying at the temperature of 80-120 ℃, coiling and coiling to obtain the carbon paper prefabricated member;
(3) carbonizing the carbon paper prefabricated part; adopting phenolic resin or asphalt resin to impregnate the carbon paper prefabricated part, and curing for 2-8 hours at the temperature of 180-220 ℃; then carbonizing at the temperature of 600-1000 ℃ under the protection of nitrogen; controlling the cycle times of dipping, curing and carbonizing to be 1-5 times according to the performance requirement of the fuel cell;
(4) carrying out chemical vapor deposition on the carbonized carbon paper prefabricated part;
(5) purifying and graphitizing the carbon paper prefabricated part subjected to chemical vapor deposition treatment to finally prepare the carbon fiber paper for the fuel cell; the purification treatment method comprises the following steps: immersing the carbon paper prefabricated part subjected to chemical vapor deposition treatment into a fluorine-containing or chlorine-containing chemical reagent, purifying for 2-30min at the temperature of 20-80 ℃ to eliminate metal and non-metal elements in the carbon paper, and then graphitizing the carbon paper at the temperature of 1800-2700 ℃ in an argon protective atmosphere to further improve the performance of the carbon paper;
the carbon fiber paper for the fuel cell has a thickness of 0.10 to 0.30mm and a bulk density of 0.30 to 0.60g/cm3The porosity is 60-90%; the resistivity in the thickness direction is less than or equal to 0.16 omega cm, and the resistivity in the plane direction is less than or equal to 0.01 omega cm; coefficient of thermal conductivity at room temperature: the vertical direction is more than or equal to 1.7W/(mK), and the parallel direction is more than or equal to 21W/(mK); gas permeability less than or equal to 50mmH2O/mm。
2. The process of claim 1 wherein the thickness of the nonwoven sheet in step (2) is from 0.01 to 0.3 mm.
3. The preparation method of claim 1, wherein the hot melt adhesive in the third step (2) is one or a mixture of LDPE and HDPE powder; uniformly distributed on the non-woven paper sheet by a dusting mode, and bonded at the temperature of 100-150 ℃.
4. The method according to claim 1, wherein the chemical vapor deposition in the step (4) is performed by: and placing the carbonized carbon paper prefabricated part in a chemical vapor deposition furnace, vacuumizing the reaction furnace, starting to heat when the pressure is less than 1000Pa, introducing a mixed gas of propylene and nitrogen when the temperature reaches 900-1150 ℃, introducing a mixed gas of the propylene and the nitrogen, wherein the flow rate of the propylene is 2-3L/min, the flow rate ratio of the propylene to the nitrogen is 1:2, the deposition pressure is 1000Pa, and controlling the final density and porosity of the composite material by controlling the heat preservation time for 10-100 h.
5. The method of claim 1, wherein the fluorine-or chlorine-containing chemical agent is: one or more of freon, hydrofluoric acid, hypochlorous acid and hydrochloric acid; the mass concentration of the chemical agent containing fluorine or chlorine is 0.01-5%.
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| CN112761025B (en) * | 2019-11-04 | 2022-11-11 | 广州汽车集团股份有限公司 | Carbon paper for gas diffusion layer, preparation method thereof and fuel cell |
| CN111900417B (en) * | 2020-07-31 | 2022-03-29 | 齐鲁工业大学 | Preparation method of carbon paper for high-carbon-content fuel cell gas diffusion layer |
| CN113147135B (en) * | 2020-11-18 | 2023-07-28 | 上海嘉资新材料科技有限公司 | Carbon fiber paper, flexible and crimpable carbon paper made of carbon fiber raw paper, and preparation method and system thereof |
| CN113136737B (en) * | 2021-02-23 | 2023-07-28 | 上海嘉资新材料科技有限公司 | Preparation method and equipment of carbon fiber paper blank and ultrathin carbon fiber paper |
| CN113135000A (en) * | 2021-03-08 | 2021-07-20 | 上海嘉资新材料有限公司 | High-flux carbon paper for fuel cell and preparation method thereof |
| CN113258081B (en) * | 2021-06-15 | 2021-11-19 | 长沙理工大学 | Modified electrode for flow battery, preparation method of modified electrode and flow battery |
| CN114256475A (en) * | 2021-12-15 | 2022-03-29 | 上海嘉资新材料科技有限公司 | Substrate layer of fuel cell gas diffusion layer, and preparation method and device thereof |
| CN114597428B (en) * | 2022-03-10 | 2022-11-29 | 湖南金博氢能科技有限公司 | Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell |
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