CN117497791A - Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof - Google Patents
Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN117497791A CN117497791A CN202311094985.4A CN202311094985A CN117497791A CN 117497791 A CN117497791 A CN 117497791A CN 202311094985 A CN202311094985 A CN 202311094985A CN 117497791 A CN117497791 A CN 117497791A
- Authority
- CN
- China
- Prior art keywords
- gas diffusion
- diffusion layer
- membrane electrode
- integrated gas
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009792 diffusion process Methods 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 40
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 36
- 239000004917 carbon fiber Substances 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000005087 graphitization Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to the technical field of fuel cells, and discloses a preparation method of an integrated gas diffusion layer for PEMFC membrane electrodes, which comprises the following steps: carrying out resin impregnation and high-temperature carbonization treatment on carbon fiber base paper to obtain carbonized carbon fiber paper; preparing microporous layer slurry, coating the microporous layer slurry on the surface of the carbonized carbon fiber paper, and drying and graphitizing at high temperature to obtain the integrated gas diffusion layer for the PEMFC membrane electrode. The preparation method of the integrated gas diffusion layer improves the binding force of the microporous layer and the basal layer, and effectively solves the problem that the gas diffusion layer is easy to delaminate; in addition, the microporous layer is carbonized and subjected to high-temperature heat treatment after being coated, so that the conductivity of the gas diffusion layer is greatly improved; and the surface of the whole gas diffusion layer can be modified by adjusting the final heat treatment temperature and the gas atmosphere, so that the method is suitable for different fuel cell operation conditions.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to an integrated gas diffusion layer for PEMFC membrane electrodes, and a preparation method and application thereof.
Background
A gas diffusion layer (GDL for short) refers to an electrode layer made of cellulose fibers or polymer nanomaterials as raw materials, which is commonly used in fuel cells and other electrochemical applications. The gas diffusion layer is usually provided with micro-pores, and can allow gases such as hydrogen, oxygen and the like to flow and disperse to the electrolyte membrane, so that the gas diffusion layer not only can provide a gas conveying function in the electrochemical reaction process, but also can drive liquid water on the surface of the catalyst layer to be rapidly discharged so as to prevent the catalyst layer from flooding. That is, the GDL has the function of transferring gas and liquid, and can conduct heat and electricity with high efficiency, so that the electrochemical reaction is more efficient and stable. The gas diffusion layer plays an important role in the performance of the membrane electrode of the fuel cell.
The gas diffusion layer is mainly of a two-layer structure and comprises a substrate layer which is obtained by hydrophobic treatment of carbon paper or carbon cloth, and a microporous layer which is prepared by mixing carbon particles, a hydrophobic agent and a solvent, coating, drying and sintering. The conventional gas diffusion layer preparation method has the following problems that the microporous layer structure and the hydrophobe content are changed to carry out the adaptive matching of the working condition of the fuel cell: the binding force of the basal layer and the microporous layer is not firm, the microporous layer and the basal layer are easy to separate in the preparation process of the membrane electrode, the performance of the membrane electrode is influenced, the adhesive and the hydrophobic agent are required to be added in the microporous layer carbon particles, the conductivity of the microporous layer is reduced, and the ohmic resistance of the membrane electrode is improved.
Therefore, it is a problem to be solved by those skilled in the art how to provide an integrated gas diffusion layer with a stronger bonding of the substrate layer and the microporous layer.
Disclosure of Invention
In view of the above, the invention provides a method for preparing an integrated gas diffusion layer for PEMFC membrane electrodes, so as to solve the problem that the membrane electrode performance is affected due to easy separation between layers caused by weak combination of the existing basal layer and microporous layer.
In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect, the present invention provides a method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, comprising the steps of:
(1) Impregnating and predrying carbon fiber base paper by a resin impregnation process to obtain carbon fiber base paper impregnated paper, and carbonizing the carbon fiber base paper impregnated paper at high temperature to obtain carbonized carbon fiber paper;
(2) Preparing microporous layer slurry, coating the microporous layer slurry on the surface of the carbonized substrate carbon fiber paper, and performing drying and high-temperature graphitization heat treatment to obtain the integrated gas diffusion layer for the PEMFC membrane electrode. .
Preferably, in the above method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, the carbon fiber base paper is carbon fiber paper or carbon fiber cloth prepared by cutting, dispersing, papermaking or dry papermaking PAN-based carbon fibers;
further preferably, the thickness of the gas diffusion layer substrate is 120 to 300 μm.
Preferably, in the above method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, the high-temperature carbonization treatment in step (1) is performed under nitrogen atmosphere, and the carbonization treatment temperature is 800-1200 ℃.
Preferably, in the above method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, the microporous layer slurry in step (2) includes a carbon material, a thermoplastic resin adhesive, and a solvent;
further preferably, the mass fraction of the thermoplastic resin adhesive is 5-50% of that of the carbon material;
further preferably, the carbon loading of the microporous layer slurry is 5-15%.
Preferably, in the above method for preparing an integrated gas diffusion layer for a PEMFC membrane electrode, the carbon material includes any one or more of acetylene black, carbon black, conductive graphite, carbon nanotubes, and graphene;
further preferably, the thermoplastic resin adhesive comprises any one or more of polyvinyl acetate, polyvinyl acetal, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, perchloroethylene resin, polyacrylate, polyamide and polysulfone;
further preferably, the solvent comprises any one or more of ethanol, ethylene glycol and isopropanol.
Preferably, in the above method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, the drying temperature in step (2) is 80-120 ℃, and the thickness of the film after drying is controlled to be 15-80 μm.
Preferably, in the above method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, the high temperature graphitization treatment is performed under argon atmosphere, and the high temperature heat treatment temperature is 1800-2500 ℃.
On the other hand, the invention also provides an integrated gas diffusion layer for the PEMFC membrane electrode, which is prepared by any one of the methods.
The invention also provides an application of the integrated gas diffusion layer for PEMFC membrane electrode prepared by any method in fuel cells.
The invention provides a preparation method of an integrated gas diffusion layer for PEMFC membrane electrodes, which has the beneficial effects that compared with the prior art:
the preparation method of the integrated gas diffusion layer improves the binding force of the microporous layer and the basal layer, and effectively solves the problem that the gas diffusion layer is easy to delaminate;
the microporous layer is carbonized and subjected to high-temperature heat treatment after being coated, so that the conductivity of the gas diffusion layer is greatly improved; and the surface of the whole gas diffusion layer can be modified by adjusting the final heat treatment temperature and the gas atmosphere, so that the method is suitable for different fuel cell operation conditions.
Detailed Description
Examples of the present invention will be described in detail below, in which specific techniques or conditions are not noted, according to techniques or conditions described in the literature in the field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect of the present invention, the present invention provides a method for preparing an integrated gas diffusion layer for PEMFC membrane electrode, comprising the steps of:
and S100, carrying out resin impregnation process impregnation and predrying on the carbon fiber base paper to obtain carbon fiber base paper impregnation paper, and carrying out high-temperature carbonization treatment on the carbon fiber base paper impregnation paper to obtain carbonized carbon fiber paper.
In the step, the carbon fiber base paper is carbon fiber paper or carbon fiber cloth prepared by PAN-based carbon fibers through chopping, dispersing, papermaking or dry papermaking, and the specific dry or wet process is not particularly limited in the embodiment of the invention, and can be a conventional preparation process in industry, which is used as a conductive framework of a gas diffusion layer, provides a large number of water vapor transmission channels and influences the electric conductivity and the heat conductivity of the gas diffusion layer.
Further, the thickness of the carbon fiber base paper is 120-300 μm, preferably 150-200 μm, for example, 150 μm, 170 μm, 200 μm, etc., and the carbon fiber base paper in the invention can ensure better electric and heat conductivity in the thickness range and is convenient for subsequent combination with microporous layer slurry.
Further, the high-temperature carbonization treatment is performed in a nitrogen atmosphere, and the carbonization treatment temperature is 800-1200 ℃; the carbonization treatment temperature is preferably 850-950 ℃, for example, 850 ℃, 900 ℃, 950 ℃ and the like, and the carbonized carbon fiber paper subjected to the carbonization treatment at 800-1000 ℃ can be better combined with the microporous layer slurry, so that the combination firmness is higher, and the problem that the gas diffusion layer is easy to delaminate can be effectively solved.
And S200, preparing microporous layer slurry, coating the microporous layer slurry on the surface of the carbonized substrate, and performing drying and high-temperature heat treatment to obtain the integrated gas diffusion layer for the PEMFC membrane electrode.
In this step, the microporous layer slurry includes a carbon material, a thermoplastic resin adhesive, and a solvent for improving the pore structure of the base layer; wherein the mass fraction of the thermoplastic resin adhesive is 5-50%, preferably 10-40%, more preferably 20-30%, for example, 5%, 15%, 25%, 35%, 45%, 50% and the like of the carbon material; the carbon loading of the microporous layer slurry is 5 to 15%, preferably 8 to 12%, for example, 5%, 8%, 10%, 13%, 15%, etc., and the addition of a suitable thermoplastic resin adhesive and carbon material can make the gas diffusion layer more excellent in the firmness, the electric conductivity, etc.
Further, the carbon material comprises any one or more of acetylene black, carbon black, conductive graphite, carbon nanotubes and graphene; the thermoplastic resin adhesive comprises any one or more of polyvinyl acetate, polyvinyl acetal, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, perchloroethylene resin, polyacrylate, polyamide and polysulfone; the solvent comprises any one or more of ethanol, glycol and isopropanol.
Further, the drying temperature is 80-120 ℃, preferably 85-110 ℃, more preferably 90-105 ℃, for example, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃; the film thickness after drying is controlled to 15-80 μm, for example, 30 μm, 40 μm, 50 μm, 60 μm, etc., and specifically the drying time may be adjusted according to the actual situation to obtain the corresponding film thickness.
Further, the high temperature graphitization treatment is performed under an argon atmosphere, and the high temperature heat treatment temperature is 1800-2500 ℃, preferably 1800-2200 ℃, for example, 1800 ℃, 1850 ℃, 1950 ℃, 2000 ℃, 2050 ℃, 2100 ℃ and the like, and the high temperature graphitization treatment process can further provide the carbon fiber and the microporous layer with graphitization structures, thereby improving the conductivity and the durability.
In another aspect of the present invention, the present invention provides an integrated gas diffusion layer for PEMFC membrane electrode, the integrated gas diffusion layer being prepared by the method described above. Thus, the integrated gas diffusion layer for PEMFC membrane electrode has all the features and advantages of the method described above, and is not described in detail herein. In general, the base layer and the microporous layer of the integrated gas diffusion layer for the PEMFC membrane electrode have excellent binding force and good conductivity.
The embodiment of the invention also provides application of the integrated gas diffusion layer for the PEMFC membrane electrode, which is prepared by any method, in a fuel cell, wherein the fuel cell comprises the integrated gas diffusion layer for the PEMFC membrane electrode, which is prepared by the method. Thus, the fuel cell has all the features and advantages of the method described above, and will not be described in detail herein. In terms of the above, the fuel cell including the integrated gas diffusion layer for PEMFC membrane electrode has good electrical conductivity.
The invention is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the invention in any way, as will be understood by those skilled in the art. In addition, in the examples below, reagents and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
(1) Adopting PAN-based carbon fiber base paper with the thickness of 200 mu m, carrying out phenolic resin impregnation, drying and curing, and carrying out carbonization treatment in a nitrogen gas atmosphere, wherein the carbonization temperature is 900 ℃;
(2) Preparing microporous layer slurry, fully mixing acetylene black powder, polyvinyl acetate and an ethanol solvent, wherein the mass fraction of the thermoplastic resin adhesive is 30% of that of a carbon material, and the carbon loading of the slurry is 10%;
(3) Coating the microporous layer slurry on the surface of the carbonized substrate, drying at 100 ℃ and controlling the film thickness after drying to be 40 mu m;
(4) And (3) placing the dried gas diffusion layer in a graphitizing furnace in an argon atmosphere for high-temperature graphitizing treatment, wherein the heat treatment temperature is 2000 ℃, so that the integrated gas diffusion layer for the PEMFC membrane electrode is obtained.
Example 2
(1) Adopting PAN-based carbon fiber base paper with the thickness of 150 mu m, soaking and drying by using phenolic resin, and carbonizing in nitrogen atmosphere at the carbonization temperature of 800 ℃;
(2) Preparing microporous layer slurry, fully mixing carbon black powder, polyvinyl acetal and ethylene glycol solvent, wherein the mass fraction of the thermoplastic resin adhesive is 5% of that of the carbon material, and the carbon loading of the slurry is 5%;
(3) Coating the microporous layer slurry on the surface of the carbonized substrate, drying at 80 ℃ and controlling the film thickness after drying to be 30 mu m;
(4) And (3) placing the dried gas diffusion layer in a graphitizing furnace in an argon atmosphere for high-temperature graphitizing treatment, wherein the heat treatment temperature is 2200 ℃, and obtaining the integrated gas diffusion layer for the PEMFC membrane electrode.
Example 3
(1) Adopting PAN-based carbon fiber base paper with the thickness of 150 mu m, soaking and drying the base paper by using phenolic resin, and carbonizing the base paper in a nitrogen gas atmosphere at the carbonization temperature of 1000 ℃;
(2) Preparing microporous layer slurry, and fully mixing conductive graphite powder, ethylene-vinyl acetate copolymer resin and isopropanol solvent, wherein the mass fraction of the thermoplastic resin adhesive is 20% of that of a carbon material, and the carbon loading of the slurry is 15%;
(3) Coating the microporous layer slurry on the surface of the carbonized substrate, drying at 120 ℃ and controlling the film thickness after drying to be 30 mu m;
(4) And (3) placing the dried gas diffusion layer in a graphitizing furnace in an argon atmosphere for high-temperature graphitizing treatment, wherein the heat treatment temperature is 1800 ℃, and obtaining the integrated gas diffusion layer for the PEMFC membrane electrode.
Example 4
(1) Adopting PAN-based carbon fiber base paper with the thickness of 250 mu m, and carbonizing in nitrogen atmosphere at 850 ℃;
(2) Preparing microporous layer slurry, and fully mixing carbon nano tube powder, polyacrylate and an ethanol solvent, wherein the mass fraction of the thermoplastic resin adhesive is 50% of that of a carbon material, and the carbon loading amount of the slurry is 8%;
(3) Coating the microporous layer slurry on the surface of the carbonized substrate, drying at 110 ℃ and controlling the film thickness after drying to be 50 mu m;
(4) And (3) placing the dried gas diffusion layer in a graphitizing furnace in an argon atmosphere for graphitizing high-temperature treatment, wherein the heat treatment temperature is 2500 ℃, so that the integrated gas diffusion layer for the PEMFC membrane electrode is obtained.
The performance of the integrated gas diffusion layer for PEMFC membrane electrode prepared in examples 1-4 was tested, and the detachment of the microporous layer from the substrate layer during the membrane electrode preparation was counted, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the porosity of the basal layer and the microporous layer in the integrated gas diffusion layer for PEMFC membrane electrode prepared by the method is about 80%, the distribution is uniform, the air permeability is good, the conductivity and the tensile strength are good, the detachment condition of the microporous layer and the basal layer in the membrane electrode preparation process is obviously low, and the binding force between the microporous layer and the basal layer is effectively enhanced by the method.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that the high-temperature heat treatment temperature is set to 1800 ℃ in step (4).
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the high-temperature heat treatment temperature is set to 2000 deg.c in step (4).
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the high-temperature heat treatment temperature is set to 2200 c in step (4).
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that the high-temperature heat treatment temperature is set to 2300 deg.c in step (4).
The properties of the gas diffusion layers prepared in comparative examples 1 to 4 were tested, and the release of the microporous layer from the base layer during the membrane electrode preparation was counted, and the results are shown in table 2.
TABLE 2
As can be seen from table 2, the high temperature graphitization treatment process of the present invention has an important effect on the porosity and conductivity of the gas diffusion layer. Specifically, in a certain temperature range, as the heat treatment temperature increases, the porosity of the gas diffusion layer increases, and the conductivity becomes better, so that the gas diffusion layer with specific conductivity and air permeability can be obtained by adjusting the heat treatment temperature to be applied to different types of fuel cells.
In the description of the present specification, reference to the terms "one embodiment," "another embodiment," "yet another embodiment," "some embodiments," "other embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. A method for preparing an integrated gas diffusion layer for PEMFC membrane electrodes, comprising the steps of:
(1) Impregnating and predrying carbon fiber base paper by a resin impregnation process to obtain carbon fiber base paper impregnated paper, and carbonizing the carbon fiber base paper impregnated paper at high temperature to obtain carbonized carbon fiber paper;
(2) Preparing microporous layer slurry, coating the microporous layer slurry on the surface of the carbonized carbon fiber paper, and drying and graphitizing at high temperature to obtain the integrated gas diffusion layer for the PEMFC membrane electrode.
2. The method for preparing an integrated gas diffusion layer for PEMFC membrane electrode according to claim 1, wherein the carbon fiber base paper is prepared from PAN-based carbon fibers by chopping, dispersing, papermaking or dry papermaking;
and/or the thickness of the carbon fiber base paper is 120-300 mu m.
3. The method for preparing an integrated gas diffusion layer for PEMFC membrane electrode according to claim 1, wherein the high-temperature carbonization treatment in step (1) is performed under a nitrogen atmosphere, and the carbonization treatment temperature is 800-1200 ℃.
4. The method for preparing an integrated gas diffusion layer for PEMFC membrane electrode according to claim 1, wherein the microporous layer slurry in step (2) comprises a carbon material, a thermoplastic resin adhesive and a solvent;
and/or the mass fraction of the thermoplastic resin adhesive is 5-50% of that of the carbon material;
and/or the microporous layer slurry has a carbon loading of 5-15%.
5. The method for preparing an integrated gas diffusion layer for a PEMFC membrane electrode according to claim 4, wherein the carbon material includes any one or more of acetylene black, carbon black, conductive graphite, carbon nanotubes, and graphene;
and/or the thermoplastic resin adhesive comprises any one or more of polyvinyl acetate, polyvinyl acetal, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, perchloroethylene resin, polyacrylate, polyamide and polysulfone;
and/or the solvent comprises any one or more of ethanol, glycol and isopropanol.
6. The method for preparing an integrated gas diffusion layer for PEMFC membrane electrode according to claim 1, wherein the drying temperature in step (2) is 80-120 ℃, and the thickness of the film after drying is controlled to be 15-80 μm.
7. The method for preparing an integrated gas diffusion layer for PEMFC membrane electrode according to claim 1, wherein the high temperature graphitization treatment is performed under argon atmosphere, and the high temperature heat treatment temperature is 1800-2500 ℃.
8. An integrated gas diffusion layer for PEMFC membrane electrode, prepared by the method of any one of claims 1-7.
9. Use of the integrated gas diffusion layer for PEMFC membrane electrode prepared by the method of any one of claims 1-7 or the integrated gas diffusion layer for PEMFC membrane electrode of claim 8 in a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311094985.4A CN117497791A (en) | 2023-08-29 | 2023-08-29 | Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311094985.4A CN117497791A (en) | 2023-08-29 | 2023-08-29 | Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117497791A true CN117497791A (en) | 2024-02-02 |
Family
ID=89671442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311094985.4A Pending CN117497791A (en) | 2023-08-29 | 2023-08-29 | Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117497791A (en) |
-
2023
- 2023-08-29 CN CN202311094985.4A patent/CN117497791A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2424948C (en) | Carbon fiber electrode substrate for electrochemical cells | |
| JP2000299113A (en) | Conductive sheet and electrode base material for fuel cell using it | |
| JP6053251B2 (en) | Solid polymer fuel cell gas diffusion layer | |
| EP3902039A1 (en) | Graphitized carbon substrate and gas diffusion layer employing same | |
| CN111576079B (en) | Conductive carbon paper and preparation method thereof | |
| US20020058180A1 (en) | Fluid diffusion layers for fuel cells | |
| JP2003504822A (en) | Electrode substrate for electrochemical cell based on low cost manufacturing method | |
| JP4051714B2 (en) | Electrode substrate for polymer electrolyte fuel cell and method for producing the same | |
| JP5433147B2 (en) | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell | |
| CA2965802A1 (en) | Porous electrode substrate, membrane-electrode assembly using same, and polymer electrolyte fuel cell using same | |
| JP2001283865A (en) | Electrode catalyst layer, film-electrode complex and their manufacturing method and battery using same | |
| JP7031778B2 (en) | Gas diffusion layer and gas diffusion electrode for polymer electrolyte fuel cells and their manufacturing method | |
| CN111129555A (en) | Carbon paper material for high-toughness high-conductivity proton exchange membrane battery | |
| JP2009283259A (en) | Porous carbon electrode base material | |
| CN100550491C (en) | Gas diffusion media and fuel cell | |
| CN113882186B (en) | Carbon fiber paper and preparation method and application thereof | |
| JP5484777B2 (en) | Porous electrode substrate and method for producing the same | |
| CN117497791A (en) | Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof | |
| JP5336804B2 (en) | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell | |
| CN117063315A (en) | Electrode base material and method for producing same | |
| JP6183065B2 (en) | Porous carbon electrode and manufacturing method thereof | |
| JP6265028B2 (en) | Porous carbon electrode | |
| JP2014135270A (en) | Porous carbon electrode and method of manufacturing the same | |
| JP6212966B2 (en) | Porous carbon electrode | |
| JP5322212B2 (en) | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |