CN116516719A - Fuel cell carbon paper and preparation method thereof - Google Patents
Fuel cell carbon paper and preparation method thereof Download PDFInfo
- Publication number
- CN116516719A CN116516719A CN202310507777.6A CN202310507777A CN116516719A CN 116516719 A CN116516719 A CN 116516719A CN 202310507777 A CN202310507777 A CN 202310507777A CN 116516719 A CN116516719 A CN 116516719A
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- China
- Prior art keywords
- tencel
- carbon paper
- fiber
- fibers
- fuel cell
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000000446 fuel Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 123
- 229920000433 Lyocell Polymers 0.000 claims abstract description 82
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005011 phenolic resin Substances 0.000 claims abstract description 8
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 206010061592 cardiac fibrillation Diseases 0.000 claims abstract description 6
- 230000002600 fibrillogenic effect Effects 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000012744 reinforcing agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003623 enhancer Substances 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010009 beating Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920001046 Nanocellulose Polymers 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
- D21D1/30—Disc mills
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D5/00—Purification of the pulp suspension by mechanical means; Apparatus therefor
- D21D5/02—Straining or screening the pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
-
- 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
- D21H21/08—Dispersing agents for fibres
-
- 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
-
- 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
- D21H21/18—Reinforcing agents
-
- 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
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
-
- 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
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of fuel cell carbon paper, which specifically comprises the following steps: s1, fibrillation treatment of tencel fibers; s2, mixing and proportioning carbon fibers and tencel fibrillated fibers; s3, preparing a carbon paper precursor; s4, preparing fuel cell carbon paper. According to the preparation method of the carbon paper of the fuel cell, the tencel fibers with small diameters are obtained through fibrillation treatment of the tencel fibers, and the tencel fibrillated fibers are uniformly distributed among the carbon fibers through combination with the carbon fibers, so that the uniform distribution of phenolic resin in the carbon fibers can be controlled, low volume resistivity is obtained, and the conductivity of the carbon paper is improved.
Description
Technical Field
The invention relates to the technical field of battery carbon paper, in particular to fuel battery carbon paper and a preparation method thereof.
Background
Proton exchange membrane fuel cells can utilize hydrogen as a fuel to reduce pollution, and are considered to be the first clean and efficient power generation technology in the 21 st century. The gas diffusion layer plays important roles of water vapor gas mass transfer, current collection, catalytic layer support and electrode structure stabilization in the proton exchange membrane fuel cell. The gas diffusion layer is typically composed of a microporous layer and a substrate layer. Carbon fibers have high conductivity and chemical corrosion resistance, and carbon paper prepared by using the carbon fibers has been widely used as a substrate layer of a gas diffusion layer of a fuel cell.
The patent with publication number of CN111900418A adds a small amount of nanocellulose to improve the dispersibility and mechanical strength of the carbon fiber, and has higher air permeability. However, the nano cellulose has too small diameter or is in a flake shape, is easy to form a film after being dried, cannot form a uniform nano cellulose fiber interweaved network in the carbon fiber, and is not beneficial to the structural control of the phenolic resin in the carbon fiber paper. In the patent with publication number CN103556543A, plant fibers are added to prepare carbon paper base paper, but the diameter of the plant fibers is about 50 mu m, and the diameter of the carbon fibers is usually 7 mu m, and the addition of the plant fibers can seriously affect the conductive network of the carbon fiber main body.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the carbon paper of the fuel cell and the preparation method thereof, which are characterized in that the tencel fiber is fibrillated to obtain the tencel fibrillated fiber with small diameter, and the tencel fibrillated fiber is uniformly distributed among the carbon fibers by being assembled with the carbon fibers, so that the uniform distribution of phenolic resin in the carbon fibers can be controlled, the low volume resistivity is obtained, and the conductivity of the carbon paper is improved.
In order to achieve the technical scheme, the invention provides a preparation method of fuel cell carbon paper, which comprises the following steps:
s1, fibrillation treatment of tencel fibers: preparing 1.7dtex 4mm tencel fiber into a tencel fiber slurry with the concentration of 3%, pulping the tencel fiber slurry to 90 DEG SR by a disc mill, then treating the tencel fiber slurry by a 300-mesh pulp screen, and collecting the fibers passing through the pulp screen to obtain tencel fibrillated fibers;
s2, mixing and proportioning carbon fibers and tencel fibrillated fibers: the components in mass fraction: 50-90% of carbon fiber, 10-50% of tencel fibrillated fiber, and uniformly mixing to obtain a fiber raw material;
s3, preparing a carbon paper precursor: mixing the fiber raw material prepared in the step S2 with a surfactant, a dispersing agent and a reinforcing agent to obtain mixed slurry, making the mixed slurry into a wet paper web, and performing squeezing and drying treatment to obtain a carbon paper precursor;
s4, preparing fuel cell carbon paper: and (3) immersing the carbon paper precursor obtained in the step (S3) in an ethanol solution of phenolic resin, and sequentially performing low-temperature pre-curing, hot pressing, carbonization and graphitization treatment to obtain the fuel cell carbon paper.
Preferably, in the step S1, the maximum diameter of the tencel fibrillated fibers obtained by collecting the fibers through the screen is controlled to be smaller than 2.5 μm.
Preferably, in the step S2, the length of the carbon fiber is controlled to be 1-30mm.
Preferably, the surfactant in the step S3 accounts for 0.1-5% of the mass of the fiber raw material; the dispersant accounts for 0.0001 to 0.5 percent of the mass of the fiber raw material; the reinforcing agent accounts for 1-20% of the mass of the fiber raw material.
Preferably, the surfactant is one or a combination of tween-80, sodium dodecyl benzene sulfonate and ATPMS, the dispersing agent is one or a combination of hydroxyethyl cellulose, sodium carboxymethyl cellulose, anionic polyacrylamide and polyethylene oxide, and the reinforcing agent is one or a combination of polyvinyl alcohol, styrene-acrylic emulsion and styrene-butadiene latex.
Preferably, the surfactant is Tween-80, the dispersing agent is sodium carboxymethyl cellulose, and the reinforcing agent is styrene-acrylic emulsion.
Preferably, the drying temperature in the step S3 is 60-110 ℃, and the quantification of the carbon paper precursor is controlled to be 15-90g/m 2 。
Preferably, the low-temperature pre-curing temperature in the step S4 is 100-140 ℃; the hot pressing temperature is 170-210 ℃; the hot pressing pressure is 3-7MPa; hot pressing for 1h; the carbonization temperature is 1300-2500 ℃.
The invention also provides the fuel cell carbon paper which is prepared by the method.
The preparation method and the device for the carbon paper of the fuel cell have the beneficial effects that: according to the invention, the tencel fibers are subjected to fibrillation treatment, so that the diameters of the tencel fibrillated fibers are mainly concentrated at 0.1-2 mu m, the maximum diameter is smaller than 2.5 mu m, the conductive network of a carbon fiber main body is not affected, and the tencel fibrillated fibers can form a uniform tencel fibrillated fiber interweaving network in the carbon fibers through combination with the carbon fibers, thereby controlling uniform distribution of phenolic resin in the carbon fibers, obtaining lower volume resistivity and improving the conductivity of the carbon paper of the battery.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
FIG. 2 is a cross-sectional profile of a fuel cell carbon paper prepared according to the method of example 1;
FIG. 3 is a profile of a fuel cell carbon paper cut surface prepared according to the method of comparative example 1.
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 obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Firstly, fibrillating the tencel fiber, wherein the preparation method of the tencel fibrillated fiber comprises the following steps:
preparing 1.7dtex 4mm tencel fiber into a tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 75 DEG SR, 80 DEG SR, 85 DEG SR, 90 DEG SR and 95 DEG SR by a disc mill, then treating the tencel fiber slurry by a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. Analyzing the dimension average length of the tencel fibrillated fibers with different beating degrees by using a Morficompact fiber analyzer; analyzing the maximum diameter of the tencel fibrillated fiber by using an electron microscope; and (5) analyzing the pulp screening yield after 300-mesh screening by using a dynamic water filter. The analysis results are shown in table 1:
TABLE 1 fiber Properties of tencel fibers after beating and sieving
The tencel fibrillated fibers mainly play a role of winding on the carbon fibers, and a larger capillary force is obtained by utilizing the lyophilic property and smaller pore diameter of the tencel fibrillated fibers, so that the phenolic resin is controlled to be distributed in the carbon fibers, the carbon fibers are tightly bonded under the action of the resin, and further, a lower volume resistivity is obtained. As can be seen from the data in table 1, as the freeness increases, the average length of the tencel fibrillated fibers decreases, and too small a fiber length will reduce the number of windings of the tencel fibrillated fibers on the carbon fibers. The beaten fiber still has a large number of fiber diameters of tens of micrometers, which weakens the capillary force of tencel fibrillated fiber, influences the conductive network of the carbon fiber main body and reduces the resistivity of the carbon paper. The pulped fibers are thus subjected to a screening process to reduce the fiber diameter. And (3) integrating the fiber length, the pulp screening yield and the maximum diameter of the pulp screened fiber, and selecting to grind the tencel fiber pulp to 90 DEG SR through a disc grinder to obtain the optimal tencel fibrillated fiber.
Example 1
A fuel cell carbon paper prepared by the method comprising:
(1) Preparing tencel fiber with the concentration of 1.7dtex and 4mm into tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 90 DEG SR through a disc mill, then treating the tencel fiber slurry through a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. Controlling the concentration of the fiber raw material slurry to be 0.03%, controlling the mass ratio of the carbon fiber to the tencel fibrillated fiber to be 70:30, sequentially adding 2% of Tween-80, 200% of CMC and 5% of styrene-acrylic emulsion into the fiber slurry, and fully stirring to uniformly disperse the fibers; the dispersed slurry is pumped to an inclined wire former to be formed into a wet paper sheet, and the wet paper sheet is pressed and dried to obtain the paper sheet with the ration of 30g/m 2 Is a carbon paper precursor;
(2) Immersing a carbon paper precursor in an ethanol solution of phenolic resin with the concentration of 20%, extruding the excessive feed liquid by using an extruding roller, putting the immersed and extruded paper sheet into a baking oven with the temperature of 120 ℃ for pre-curing for 1h, and then putting the pre-cured paper sheet into a flat vulcanizing machine for hot press curing for 1h at the temperature of 190 ℃ and the pressure of 5 MPa. And (3) placing the solidified paper sheet into a vacuum tube furnace to carry out carbonization treatment on the carbon paper under the protection of nitrogen, increasing the carbonization temperature to 2000 ℃, keeping the temperature for 2 hours at a heating rate of 30 ℃/min, and obtaining the carbon paper of the fuel cell after the carbonization treatment.
Example 2
A fuel cell carbon paper prepared by the method comprising:
the mass ratio of carbon fiber to tencel fibrillated fiber was controlled to be 90:10, and the rest of the procedure was the same as in example 1.
Example 3
A fuel cell carbon paper prepared by the method comprising:
the mass ratio of carbon fiber to tencel fibrillated fiber was controlled to be 50:50, and the rest of the procedure was the same as in example 1.
Comparative example 1
A fuel cell carbon paper prepared by the method comprising:
controlling the concentration of the fiber raw material slurry to be 0.03%, sequentially adding 2% of Tween-80, 200% of CMC and 5% of styrene-acrylic emulsion into the fiber slurry by adopting 100% of carbon fibers, and fully stirring to uniformly disperse the fibers; the dispersed slurry is pumped to an inclined wire former to be formed into a wet paper sheet, and the wet paper sheet is pressed and dried to obtain the paper sheet with the ration of 30g/m 2 Is a carbon paper precursor; the rest of the procedure is the same as in example 1.
Comparative example 2
A fuel cell carbon paper prepared by the method comprising:
the mass ratio of carbon fiber to tencel fibrillated fiber was controlled to be 30:70, and the rest of the procedure was the same as in example 1.
Comparative example 3
Preparing tencel fiber with the concentration of 1.7dtex and 4mm into tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 75 DEG SR through a disc mill, then treating the tencel fiber slurry through a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. The remaining steps were the same as in example 1.
Comparative example 4
Preparing tencel fiber with the concentration of 1.7dtex and 4mm into tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 80 DEG SR through a disc mill, then treating the tencel fiber slurry through a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. The remaining steps were the same as in example 1.
Comparative example 5
Preparing tencel fiber with the concentration of 1.7dtex and 4mm into tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 85 DEG SR through a disc mill, then treating the tencel fiber slurry through a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. The remaining steps were the same as in example 1.
Comparative example 6
Preparing tencel fiber with the concentration of 1.7dtex and 4mm into tencel fiber slurry with the concentration of 3%, respectively pulping the tencel fiber slurry to the beating degree of 95 DEG SR through a disc mill, then treating the tencel fiber slurry through a 300-mesh pulp screen, and collecting the fiber passing through the pulp screen to obtain the tencel fibrillated fiber. The remaining steps were the same as in example 1.
Substrate Performance test
The substrates prepared in examples 1-3 and comparative examples 1-6 were subjected to performance testing, test items and methods as follows:
1. observing the appearance of the section of the carbon paper, and observing the distribution condition of resin carbon in the section of the carbon paper in the carbon fiber by adopting an electron microscope;
2. the thickness of the carbon paper is measured by L&A No.251 thickness tester of W company is used for testing, and the area of a test sample is 200mm 2 ；
3. The carbon paper resistivity test is carried out by adopting an RH-450 carbon paper vertical resistivity tester of Guangzhou Ruhu instrument limited company, wherein the size of a test sample is 2cm multiplied by 2cm, and the test pressure is 1MPa.
The specific test results are shown in table 2:
table 2 the fuel cell carbon paper performance test parameters of the present invention
As can be seen from table 3 and fig. 1, the carbon paper of the embodiment 2 of the present invention has a thickness of 125 μm, a compact structure of the cut surface, uniform arrangement of resin carbon among the fibers, and low bulk resistivity and good conductivity. As can be seen from Table 3 and FIG. 2, the carbon paper in comparative example 1 has a thickness of 155 μm, a loose structure in the cut surface, less resin carbon is arranged between the fibers, and the carbon paper has a high bulk resistivity and poor conductivity. The data in comparative examples 1-3 and comparative examples 1-2 show that the mass ratio of carbon fiber to tencel fibrillated fiber has a great influence on the final paper bulk resistivity, and that lower bulk resistivities can be obtained when the mass ratio of carbon fiber to tencel fibrillated fiber is 70:30. As can be seen from the data in comparative examples 1 and 3 to 6, the freeness of the tencel fiber slurry during fibrillation has a great influence on the bulk resistivity of the final paper, and when the freeness is 90 ° SR, the maximum diameter is less than 2.5 μm (the diameter of the tencel fibrillated fibers is mainly concentrated in 0.1 to 2 μm), the tencel fibrillated fibers with appropriate diameters can be obtained, and then the conductive network of the carbon fiber body is not affected when the tencel fiber slurry is combined with the carbon fibers, so that lower bulk resistivity can be obtained.
The foregoing is a preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, so that the equivalents and modifications can be made without departing from the spirit of the disclosure.
Claims (9)
1. The fuel cell carbon paper and the preparation method thereof are characterized by comprising the following steps:
s1, fibrillation treatment of tencel fibers: preparing 1.7dtex 4mm tencel fiber into a tencel fiber slurry with the concentration of 3%, pulping the tencel fiber slurry to 90 DEG SR by a disc mill, then treating the tencel fiber slurry by a 300-mesh pulp screen, and collecting the fibers passing through the pulp screen to obtain tencel fibrillated fibers;
s2, mixing and proportioning carbon fibers and tencel fibrillated fibers: the components in mass fraction: 50-90% of carbon fiber, 10-50% of tencel fibrillated fiber, and uniformly mixing to obtain a fiber raw material;
s3, preparing a carbon paper precursor: mixing the fiber raw material prepared in the step S2 with a surfactant, a dispersing agent and a reinforcing agent to obtain mixed slurry, making the mixed slurry into a wet paper web, and performing squeezing and drying treatment to obtain a carbon paper precursor;
s4, preparing fuel cell carbon paper: and (3) immersing the carbon paper precursor obtained in the step (S3) in an ethanol solution of phenolic resin, and sequentially performing low-temperature pre-curing, hot pressing, carbonization and graphitization treatment to obtain the fuel cell carbon paper.
2. The method for producing a carbon paper for a fuel cell according to claim 1, wherein the maximum diameter of the fibrillated fibers of the tencel obtained by collecting the fibers by a screen in step S1 is controlled to be smaller than 2.5 μm.
3. The method for producing carbon paper for fuel cell according to claim 1, wherein the carbon fiber length is controlled to be 1-30mm in step S2.
4. The method for preparing the carbon paper for the fuel cell according to claim 1, wherein the surfactant in the step S3 accounts for 0.1% -5% of the mass of the fiber raw material; the dispersant accounts for 0.0001 to 0.5 percent of the mass of the fiber raw material; the reinforcing agent accounts for 1-20% of the mass of the fiber raw material.
5. The method according to claim 4, wherein the surfactant is one or a combination of tween-80, sodium dodecyl benzene sulfonate and ATPMS, the dispersant is one or a combination of hydroxyethyl cellulose, sodium carboxymethyl cellulose, anionic polyacrylamide and polyethylene oxide, and the reinforcing agent is one or a combination of polyvinyl alcohol, styrene-acrylic emulsion and styrene-butadiene latex.
6. The method for preparing carbon paper for fuel cells according to claim 1 or 4, wherein the surfactant is tween-80, the dispersant is sodium carboxymethyl cellulose, and the enhancer is styrene-acrylic emulsion.
7. The method for preparing carbon paper for fuel cell according to claim 1, wherein the drying temperature in the step S3 is 60-110 ℃, and the basis weight of the carbon paper precursor is controlled to be 15-90g/m 2 。
8. The method for preparing carbon paper for fuel cell according to claim 1, wherein the low temperature pre-curing temperature in the step S4 is 100-140 ℃; the hot pressing temperature is 170-210 ℃; the hot pressing pressure is 3-7MPa; hot pressing for 1h; the carbonization temperature is 1300-2500 ℃.
9. A fuel cell carbon paper prepared by the method of any one of claims 1-8.
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| CN202310507777.6A CN116516719A (en) | 2023-05-08 | 2023-05-08 | Fuel cell carbon paper and preparation method thereof |
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| CN202310507777.6A CN116516719A (en) | 2023-05-08 | 2023-05-08 | Fuel cell carbon paper and preparation method thereof |
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Application publication date: 20230801 |