CN116314981A - Durable membrane electrode, preparation method thereof and fuel cell - Google Patents
Durable membrane electrode, preparation method thereof and fuel cell Download PDFInfo
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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]
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- 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
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a durable membrane electrode, a preparation method thereof and a fuel cell, wherein the durable membrane electrode comprises a second metal ion capturing layer arranged between a proton membrane and a catalytic layer, and a first metal ion capturing layer arranged between the catalytic layer and a gas diffusion layer; the first metal ion capturing layer and the second metal ion capturing layer both contain cation exchange resins. Through the double design of the inner and outer trapping layers, external metal ions can be trapped outside the catalytic layer in time, so that the catalytic reaction of free radicals is effectively prevented from occurring, and the catalytic performance is prevented from being deteriorated due to the invasion of the metal ions into active sites in the catalytic layer; meanwhile, the second metal ion capturing layer constructs a barrier for removing two metal ions outside the proton membrane, so that the metal ions generated in the catalytic layer are removed in time, the attack of free radicals is blocked for the proton exchange membrane in time, the chemical attenuation of the proton membrane is effectively reduced, and the service lives of the membrane electrode and the fuel cell are further prolonged.
Description
Technical Field
The invention belongs to the field of fuel cells, and relates to a durable membrane electrode, a preparation method thereof and a fuel cell.
Background
The proton exchange membrane fuel cell is a novel energy technology, and is considered as an automobile power source with great application prospect due to low working temperature, high power density and quick starting capability. However, the lifetime is one of the main factors limiting the commercialization progress of the proton exchange membrane fuel cell, wherein the pollution of the fuel cell by the metal ions is an important factor affecting the lifetime of the fuel cell.
The metal ions that affect the life are mainly derived from components of the fuel cell system, such as end plates, metallic bipolar plates, or catalyst-carried metal impurities, alloy catalyst corrosion, etc. When the generated metal cation impurities enter the membrane electrode in the operation process, on one hand, the metal cations generally have stronger chemical affinity to ion transmission sites in the polymer than protons, so that the metal cations occupy original proton sites, the mobility of the external cations is generally lower than that of the protons, and finally, the proton conductivity of the catalytic layer is reduced, and the performance of the catalytic layer is easily influenced; on the other hand, when the fuel cell is in an open circuit and idle condition, the anode of the fuel cell is in a low potential and oxygen permeation state, which is easy to generate H 2 O 2 When H 2 O 2 And metalIons move in the fuel cell, and some transition metal cations, such as iron, copper and the like, can cause Fenton reaction to generate free radicals, and the free radicals can attack carbon-carbon bonds, fluorocarbon bonds and the like of the ionomer, so that the main chain and the side chains of the ionomer are degraded or broken, the proton conductivity of the catalytic layer is finally reduced, the proton membrane is broken, thinned or pinholes are formed, and the service life of the fuel cell is accelerated.
CN114420987a discloses a composite proton exchange membrane and its preparation method and application, the composite proton exchange membrane includes a first ion exchange resin membrane, a second ion exchange resin membrane and a porous polymer membrane disposed between the first ion exchange resin membrane and the second ion exchange resin membrane, the two sides of the second ion exchange resin membrane are provided with free radical scavengers and metal ion adsorbents, one side of the porous polymer membrane is surface modified, the surface modified side is close to the second ion exchange resin membrane, the invention solves the problems of metal ion dissolution and migration by adding metal oxide free radical scavengers into the ion exchange resin and simultaneously adding metal ion adsorbing materials, the composite proton exchange membrane has the characteristics of low permeability and high durability;
CN101789509a proposes a durable fuel cell membrane electrode, and by adding a porous material with high specific surface area and high adsorption property, such as palygorskite-sepiolite mineral fiber, montmorillonite, diatomite, activated carbon, molecular sieve or silica gel, in the catalytic layer of the membrane electrode, impurities such as metal ions generated in the running process of the cell can be adsorbed, so that the attack of the impurities on a proton exchange membrane in the membrane electrode is prevented, and the service life of the proton exchange membrane is prolonged;
according to the scheme, the durability of the membrane electrode can be improved, the proton exchange membrane or the catalytic layer is improved, the effect of adsorbing metal ions generated in the catalytic layer is achieved by adding additional adsorption components, the treatment of impurity metal ions from parts such as end plates and metal bipolar plates is ignored, and the electrical performance of the fuel cell is easily affected by the additional inactive components.
Therefore, there is still a need to develop a new solution to provide a durable membrane electrode, which is of great importance for the life extension of fuel cells.
Disclosure of Invention
In view of the problems existing in the prior art, an object of the present invention is to provide a durable membrane electrode including a second metal ion capturing layer disposed between a proton membrane and a catalytic layer, a first metal ion capturing layer disposed between the catalytic layer and a gas diffusion layer, a method of manufacturing the same, and a fuel cell; the first metal ion capturing layer and the second metal ion capturing layer both contain cation exchange resins. Through the double design of the inner and outer trapping layers, external metal ions can be trapped outside the catalytic layer in time, so that the catalytic reaction of free radicals is effectively prevented from occurring, and the catalytic performance is prevented from being deteriorated due to the invasion of the metal ions into active sites in the catalytic layer; meanwhile, the second metal ion capturing layer constructs a barrier for removing two metal ions outside the proton membrane, so that the metal ions generated in the catalytic layer are removed in time, the attack of free radicals is blocked for the proton exchange membrane in time, the chemical attenuation of the proton membrane is effectively reduced, and the service lives of the membrane electrode and the fuel cell are further prolonged.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a durable membrane electrode comprising a second metal ion capturing layer disposed between a proton membrane and a catalytic layer, a first metal ion capturing layer disposed between the catalytic layer and a gas diffusion layer;
the first metal ion capturing layer and the second metal ion capturing layer both contain cation exchange resins.
Specifically, the durable membrane electrode is characterized in that an anode first metal ion capturing layer is arranged between a proton membrane and an anode catalytic layer, a cathode first metal ion capturing layer is arranged between the proton membrane and a cathode catalytic layer, an anode first metal ion capturing layer is arranged between the anode catalytic layer and an anode gas diffusion layer, and a cathode first metal ion capturing layer is arranged between the cathode catalytic layer and a cathode gas diffusion layer;
according to the invention, through the double design of the first metal ion capturing layer and the second metal ion capturing layer, external metal ions entering the catalytic layer can be captured outside the catalytic layer in time, so that the catalytic reaction of free radicals can be effectively prevented, and the proton conductivity of the catalytic layer is prevented from being reduced due to the invasion of the metal ions into proton sites of the ionomer; meanwhile, the second metal ion capturing layer constructs a barrier for removing two metal ions outside the proton membrane, so that the metal ions generated in the catalytic layer can be removed in time, the attack of free radicals can be blocked for the proton exchange membrane in time, the chemical attenuation of the proton membrane is effectively reduced, and the service lives of the membrane electrode and the fuel cell are further prolonged.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable embodiment of the present invention, the cation exchange resin in the second metal ion capturing layer is a perfluorosulfonic acid resin.
Preferably, the thickness of the second metal ion capturing layer is 0.05 to 0.2 μm, for example, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, or 0.2 μm, etc., but not limited to the listed values, and other values not listed in the above numerical ranges are equally applicable.
Too thick capturing layer is easy to reduce the power density of the membrane electrode, so that the impedance of the membrane electrode can be increased on one hand, and on the other hand, the first capturing layer can obstruct the water and gas transmission; too thin a metal trapping layer reduces trapping capacity, affecting membrane electrode durability.
As a preferable technical scheme of the invention, the first metal ion capturing layer also contains a gridding hydrophobic polymer.
Preferably, the network hydrophobic polymer comprises PTFE (polytetrafluoroethylene).
The addition of PTFE can enhance the hydrophobicity of the first metal ion capturing layer, enhance the water vapor transmission and prevent the reduction of the power density of the membrane electrode and the flooding of high electric density. Because PTFE cannot conduct protons and electrons, too much thickness of PTFE can increase the resistance of a capturing layer, reduce the proton conductivity of the capturing layer and further reduce the power density of a membrane electrode; too little PTFE can easily lead to the transmission of gas and water of the membrane electrode, reduce the power density of the membrane electrode and easily cause flooding.
Preferably, in the first metal ion capturing layer, the mass ratio of the cation exchange resin to the meshed hydrophobic polymer is 1 (1-4), for example, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, or 1:4, but not limited to the recited values, and other non-recited values within the above range are equally applicable.
Preferably, the thickness of the first metal ion capturing layer is 0.1 to 0.4 μm, for example, 0.1 μm, 0.12 μm, 0.14 μm, 0.16 μm, 0.18 μm, 0.2 μm, 0.22 μm, 0.24 μm, 0.26 μm, 0.28 μm, 0.3 μm, 0.32 μm, 0.34 μm, 0.36 μm, 0.38 μm or 0.4 μm, etc., but not limited to the listed values, and other values not listed in the above numerical range are equally applicable.
In a preferred embodiment of the present invention, the catalyst layer contains a catalyst and a perfluorosulfonic acid resin, and the mass ratio of the catalyst to the perfluorosulfonic acid resin is 1 (0.3-1), for example, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, or 1:1, but is not limited to the above-mentioned values, and other non-mentioned values in the above-mentioned value ranges are applicable.
Preferably, the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane.
For example, the perfluorosulfonic acid proton membrane of the present invention may be a nafion membrane manufactured by komu, a select membrane manufactured by gore, or a partially fluorinated proton exchange membrane, such as BAM3G membrane manufactured by Ballard, and the non-fluorinated proton exchange membrane may be a Pemion hydrocarbon proton exchange membrane manufactured by Ionomer, etc.
In a second aspect, the present invention provides a method for preparing a durable membrane electrode, the method comprising the steps of:
(1) Preparing a catalytic layer slurry, a first metal ion capturing layer slurry and a second metal ion capturing layer slurry respectively;
(2) Coating the second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of the proton membrane, drying to form a second metal ion capturing layer, coating the second metal ion capturing layer with the catalytic layer slurry, and drying to form a catalytic layer to obtain a first complex;
(3) Coating the slurry of the first metal ion capturing layer obtained in the step (1) on the surface of the gas diffusion layer, and drying to form a first metal ion capturing layer to obtain a second complex;
(4) And (3) bonding and hot-pressing one side of the catalytic layer of the first composite body obtained in the step (2) with one side of the first metal ion capturing layer of the second composite body obtained in the step (3) to obtain the durable membrane electrode.
As a preferable technical scheme of the invention, the preparation method of the catalyst layer slurry comprises the steps of wetting a catalyst by using water, adding a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin, and performing ultrasonic dispersion.
Preferably, in the catalyst layer slurry, the mass ratio of the catalyst, the hydroalcoholic dispersant and the perfluorinated sulfonic acid resin is 1: (50-120): (0.3-1), such as 1:50:0.3, 1:50:0.5, 1:50:0.7, 1:50:0.85, 1:50:1, 1:60:0.3, 1:60:0.5, 1:60:0.7, 1:60:0.85, 1:60:1, 1:70:0.3, 1:70:0.5, 1:70:0.7, 1:70:0.85, 1:70:1, 1:80:0.3, 1:80:0.5, 1:80:0.7, 1:80:0.85, 1:80:1, 1:90:0.3, 1:90:0.5, 1:90:0.7, 1:90:0.85, 1:90:1:100:0.3, 1:100:0.5, 1:100:0.7, 1:100:0.85, 1:100:0.3, 1:0.3, 1:80:0.5, 1:110:110:0.120, 110:0.120, 1:0.85, 1:120:110:0.5, 1:120:1:120.5, etc.):0.5; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the preparation method of the first metal ion capturing layer slurry comprises the steps of mixing cation exchange resin with a hydroalcoholic dispersing agent and performing ultrasonic dispersion.
Preferably, in the first metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersing agent to the cation exchange resin is 1 (0.05-0.1), for example, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, or 1:0.1, but not limited to the listed values, and other non-listed values within the above range are equally applicable.
Preferably, the preparation method of the first metal ion capturing layer slurry further comprises mixing the meshed hydrophobic polymer, the cation exchange resin and the hydroalcoholic dispersing agent together for ultrasonic dispersion.
Preferably, in the first metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersing agent, the cation exchange resin and the meshed hydrophobic polymer is 1: (0.05-0.1): (0.1-0.2), such as 1:0.05:0.1, 1:0.05:0.14, 1:0.05:0.17, 1:0.05:0.2, 1:0.06:0.1, 1:0.06:0.14, 1:0.06:0.17, 1:0.06:0.2, 1:0.07:0.1, 1:0.07:0.14, 1:0.07:0.17, 1:0.07:0.2, 1:0.08:0.1, 1:0.08:0.14, 1:0.08:0.17, 1:0.08:0.2, 1:0.09:0.1, 1:0.09:0.14, 1:0.09:0.17, 1:0.09:0.2, 1:0.1:0.1:0.14, 1:0.1:0.17, 1:0.17, 1:0.08:0.17, 1:0.9, 1:0.1, and the like, but the values are not limited to the ranges of the values recited herein, and the like.
Preferably, the network hydrophobic polymer comprises PTFE.
Preferably, the thickness of the first metal ion capturing layer is 0.1 to 0.4 μm, for example, 0.1 μm, 0.12 μm, 0.14 μm, 0.16 μm, 0.18 μm, 0.2 μm, 0.22 μm, 0.24 μm, 0.26 μm, 0.28 μm, 0.3 μm, 0.32 μm, 0.34 μm, 0.36 μm, 0.38 μm or 0.4 μm, etc., but not limited to the listed values, and other values not listed in the above numerical range are equally applicable.
Preferably, the preparation method of the second metal ion capturing layer slurry comprises the steps of mixing cation exchange resin with a hydroalcoholic dispersing agent and performing ultrasonic dispersion.
Preferably, the cation exchange resin is a perfluorinated sulfonic acid resin.
Preferably, in the second metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersant to the cation exchange resin is 1 (0.05-0.1), for example, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, or 1:0.1, but not limited to the above values, and other non-listed values within the above range are equally applicable.
Preferably, the thickness of the second metal ion capturing layer is 0.05 to 0.2 μm, for example, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, or 0.2 μm, etc., but not limited to the listed values, and other values not listed in the above numerical ranges are equally applicable.
In a preferred embodiment of the present invention, the power of the ultrasonic dispersion is 300 to 1000W, for example, 300W, 350W, 400W, 450W, 500W, 550W, 600W, 650W, 700W, 750W, 800W, 850W, 900W, 950W, 1000W, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the time of the ultrasonic dispersion is 10 to 30min, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the hydroalcoholic dispersant has a hydroalcoholic volume ratio of (0.5-6): 1, for example, 0.5:1, 0.7:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, etc., but not limited to the recited values, other non-recited values within the above range are equally applicable.
Preferably, the alcohol in the hydroalcoholic dispersant comprises any one or a combination of at least two of ethanol, isopropanol, n-propanol, or ethylene glycol, typical but non-limiting examples of which include a combination of ethanol and isopropanol, a combination of ethanol and n-propanol, a combination of ethanol and ethylene glycol, a combination of isopropanol and n-propanol, a combination of isopropanol and ethylene glycol, or a combination of n-propanol and ethylene glycol.
In the step (2), the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane.
Preferably, in step (2) and step (3), the coating method is independently selected from any one or a combination of at least two of spray coating, blade coating or slot coating, and typical but non-limiting examples of the combination include a combination of spray coating and blade coating, a combination of spray coating and slot coating or a combination of blade coating and slot coating.
Preferably, in the step (2), the drying temperature is 60 to 90 ℃, for example 60 ℃, 62 ℃, 64 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, or 90 ℃, etc., but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, in the step (3), the drying temperature is 60 to 100 ℃, for example 60 ℃, 62 ℃, 64 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, or 100 ℃, etc., but not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned value ranges are equally applicable.
Preferably, in the step (4), the pressure of the hot pressing is 0.1 to 0.6MPa, for example, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa or 0.6MPa, etc., but not limited to the values listed, and other values not listed in the above-mentioned numerical ranges are equally applicable.
Preferably, in the step (4), the hot pressing is performed at a temperature of 60 to 120 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃, 120 ℃, or the like, but the hot pressing is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are similarly applicable.
Preferably, in the step (4), the hot pressing time is 10 to 30 seconds, for example, 10 seconds, 12 seconds, 14 seconds, 16 seconds, 18 seconds, 20 seconds, 22 seconds, 24 seconds, 26 seconds, 28 seconds or 30 seconds, etc., but the hot pressing time is not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Preparation of the catalyst layer slurry: wetting a catalyst by using water, mixing the catalyst, a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin according to the mass ratio of (50-120) (0.3-1), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode catalytic layer slurry and cathode catalytic layer slurry;
Preparation of a first metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent, cation exchange resin and PTFE according to the mass ratio of (0.05-0.1) (0.1-0.2), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode first metal ion capturing layer slurry and cathode first metal ion capturing layer slurry;
preparing second metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin according to the mass ratio of 1 (0.05-0.1), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry;
the volume ratio of water to alcohol in the water to alcohol dispersing agent is (0.5-6): 1; the alcohol in the hydroalcoholic dispersant comprises any one or a combination of at least two of ethanol, isopropanol, n-propanol or ethylene glycol;
(2) Coating the anode second metal ion capturing layer slurry and the cathode second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of a proton membrane respectively, drying at 60-90 ℃ to form an anode second metal ion capturing layer and a cathode second metal ion capturing layer with the thickness of 0.05-0.2 mu m respectively, coating anode catalytic layer slurry and cathode catalytic layer slurry on the anode second metal ion capturing layer and the cathode second metal ion capturing layer respectively, and drying at 60-90 ℃ to form an anode catalytic layer and a cathode catalytic layer respectively to obtain a first composite;
In the step (2), the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane;
(3) Coating the anode first metal ion capturing layer slurry obtained in the step (1) on one side of an anode gas diffusion layer, and drying at 60-100 ℃ to form an anode first metal ion capturing layer with the thickness of 0.1-0.4 mu m, thereby obtaining an anode second complex; coating the slurry of the first metal ion capturing layer of the cathode obtained in the step (1) on one side of a cathode gas diffusion layer, and drying at 60-100 ℃ to form a first metal ion capturing layer of the cathode with the thickness of 0.1-0.4 mu m, thereby obtaining a second composite of the cathode;
in the step (2) and the step (3), the coating method is independently selected from any one or a combination of at least two of spraying, blade coating and slit coating;
(4) And (3) bonding one side of the anode first metal ion capturing layer of the anode second complex obtained in the step (3) with one side of the anode catalytic layer of the first complex obtained in the step (2), bonding one side of the cathode first metal ion capturing layer of the cathode second complex obtained in the step (3) with one side of the cathode catalytic layer of the first complex obtained in the step (2), and then carrying out hot pressing for 10-30 s at the temperature of 60-120 ℃ under the pressure of 0.1-0.6 MPa to obtain the durable membrane electrode.
In a third aspect, the present invention provides a fuel cell comprising the durable membrane electrode according to the second aspect or comprising the durable membrane electrode obtained by the production method according to the third aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the metal ion capturing layer is designed and arranged in the membrane electrode, so that metal ions can be removed in time, and metal impurity ions are prevented from occupying proton sites in the catalytic layer and the proton membrane, thereby improving the durability of the catalytic layer, simultaneously inhibiting Fenton reaction, reducing the generation speed of a free radical source, effectively inhibiting free radicals, and prolonging the service lives of the proton membrane and the ionomer of the catalytic layer. By adopting the design of the double-layer metal ion capturing layer, metal ions from spent fuel cell parts such as end plates, bipolar plates and the like can be captured, and metal ions corroded by the catalyst and the catalyst alloy can be captured at the same time, so that the proton membrane is doubly protected, and the chemical attenuation of the proton membrane is effectively reduced.
The preparation method of the durable membrane electrode provided by the invention has simple operation steps, and the obtained durable membrane electrode can improve the chemical durability of the membrane electrode by reducing the attack of free radicals on the proton membrane on the premise of not losing the proton conductivity of the proton exchange membrane, thereby prolonging the service life of the fuel cell and having better popularization prospect.
Drawings
FIG. 1 is a schematic view showing the hierarchical structure of a durable membrane electrode obtained in example 1;
in the figure, a 1-anode gas diffusion layer, a 2-anode first metal ion capturing layer, a 3-anode catalytic layer, a 4-anode second metal ion capturing layer, a 5-proton membrane, a 6-cathode second metal ion capturing layer, a 7-cathode catalytic layer, an 8-cathode first metal ion capturing layer and a 9-cathode gas diffusion layer are arranged.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The schematic layer structure of the durable membrane electrode is shown in fig. 1, and the durable membrane electrode comprises a proton membrane 5, and an anode second metal ion capturing layer 4 and a cathode second metal ion capturing layer 6 respectively arranged on the surfaces of two sides of the proton membrane 5; an anode catalytic layer 3, an anode first metal ion capturing layer 2 and an anode gas diffusion layer 1 are sequentially arranged on the surface of one side of the anode second metal ion capturing layer 4 far away from the proton membrane 5 from inside to outside; a cathode catalytic layer 7, a cathode first metal ion capturing layer 8 and a cathode gas diffusion layer 9 are sequentially arranged on one side surface of the cathode second metal ion capturing layer 6 far away from the proton membrane 5 from inside to outside.
The embodiment also provides a preparation method of the durable membrane electrode, which comprises the following steps:
(1) Preparation of the catalyst layer slurry: wetting 50% of platinum-carbon catalyst with water, mixing the catalyst, a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin (Nafion D520) according to the mass ratio of 1:80:0.7, and performing ultrasonic dispersion for 20min under the power of 600W to respectively prepare anode catalytic layer slurry and cathode catalytic layer slurry;
preparation of a first metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent, a cation exchange resin (Nafion D520) and PTFE (polytetrafluoroethylene) according to a mass ratio of 1:0.07:0.15, and performing ultrasonic dispersion for 20min under the power of 600W to respectively prepare anode first metal ion capturing layer slurry and cathode first metal ion capturing layer slurry;
preparing second metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin (Nafion D520) according to the mass ratio of 1:0.07, and performing ultrasonic dispersion for 20min under the power of 600W to respectively prepare anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry;
the hydroalcoholic dispersing agent is a solution prepared from water and isopropanol according to a volume ratio of 3:1;
(2) Spraying the anode second metal ion capturing layer slurry and the cathode second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of a proton membrane (Golgi membrane), respectively forming an anode second metal ion capturing layer and a cathode second metal ion capturing layer with the thickness of 0.12 mu m after drying at 80 ℃, respectively spraying anode catalytic layer slurry and cathode catalytic layer slurry on the anode second metal ion capturing layer and the cathode second metal ion capturing layer, respectively forming an anode catalytic layer and a cathode catalytic layer after drying at 80 ℃, and obtaining a first composite;
(3) Spraying the anode first metal ion capturing layer slurry obtained in the step (1) on one side of an anode gas diffusion layer, and drying at 80 ℃ to form an anode first metal ion capturing layer with the thickness of 0.25 mu m, so as to obtain an anode second complex; spraying the slurry of the first metal ion capturing layer of the cathode obtained in the step (1) on one side of a cathode gas diffusion layer, and drying at 80 ℃ to form a first metal ion capturing layer of the cathode with the thickness of 0.25 mu m, so as to obtain a second composite of the cathode;
(4) And (3) bonding one side of the anode first metal ion capturing layer of the anode second complex obtained in the step (3) with one side of the anode catalytic layer of the first complex obtained in the step (2), bonding one side of the cathode first metal ion capturing layer of the cathode second complex obtained in the step (3) with one side of the cathode catalytic layer of the first complex obtained in the step (2), and then performing hot pressing for 20s at the temperature of 100 ℃ under the pressure of 0.4MPa to obtain the durable membrane electrode.
Example 2
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment includes:
(1) Preparation of the catalyst layer slurry: wetting 40% of platinum-carbon catalyst with water, mixing the catalyst, a hydroalcoholic dispersing agent and perfluorosulfonic acid resin (Aquivion D72-25 BS) according to the mass ratio of 1:50:0.3, and performing ultrasonic dispersion for 30min under the power of 300W to respectively prepare anode catalytic layer slurry and cathode catalytic layer slurry;
preparation of a first metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent, a cation exchange resin (Mitsubishi HP2 MG) and PTFE according to a mass ratio of 1:0.05:0.1, and performing ultrasonic dispersion for 30min under the power of 300W to respectively prepare anode first metal ion capturing layer slurry and cathode first metal ion capturing layer slurry;
preparing second metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin (Aquivion D72-25 BS) according to the mass ratio of 1:0.05, and performing ultrasonic dispersion for 30min under the power of 300W to respectively prepare anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry;
the hydroalcoholic dispersing agent is a solution prepared by water and isopropanol according to a volume ratio of 0.5:1;
(2) Respectively coating anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of a proton membrane (Nafion proton membrane) in a slit way, drying at 60 ℃ to form an anode second metal ion capturing layer and a cathode second metal ion capturing layer with the thickness of 0.05 mu m respectively, respectively coating anode catalytic layer slurry and cathode catalytic layer slurry on the anode second metal ion capturing layer and the cathode second metal ion capturing layer in a slit way, drying at 60 ℃ to form an anode catalytic layer and a cathode catalytic layer respectively, and obtaining a first composite;
(3) Coating the slurry of the anode first metal ion capturing layer obtained in the step (1) on one side of an anode gas diffusion layer in a slit way, and drying at 60 ℃ to form an anode first metal ion capturing layer with the thickness of 0.1 mu m, thereby obtaining an anode second complex; coating the slurry of the first metal ion capturing layer of the cathode obtained in the step (1) on one side of a cathode gas diffusion layer in a slit way, and drying at 60 ℃ to form a first metal ion capturing layer of the cathode with the thickness of 0.1 mu m, thereby obtaining a second composite of the cathode;
(4) And (3) bonding one side of the anode first metal ion capturing layer of the anode second complex obtained in the step (3) with one side of the anode catalytic layer of the first complex obtained in the step (2), bonding one side of the cathode first metal ion capturing layer of the cathode second complex obtained in the step (3) with one side of the cathode catalytic layer of the first complex obtained in the step (2), and then performing hot pressing for 30s at the temperature of 0.1MPa and 60 ℃ to obtain the durable membrane electrode.
Example 3
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment includes:
(1) Preparation of the catalyst layer slurry: wetting 60% of platinum-carbon catalyst with water, mixing the catalyst, a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin (Xudi IC 154) according to the mass ratio of 1:120:0.1, and performing ultrasonic dispersion for 10min under the power of 1000W to respectively prepare anode catalytic layer slurry and cathode catalytic layer slurry;
preparation of a first metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent, cation exchange resin (Asahi nitro IC 154) and PTFE according to a mass ratio of 1:0.1:0.2, and performing ultrasonic dispersion for 10min under the power of 1000W to respectively prepare anode first metal ion capturing layer slurry and cathode first metal ion capturing layer slurry;
preparing second metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin (Asahi nitro IC 154) according to a mass ratio of 1:0.1, and performing ultrasonic dispersion for 10min under the power of 1000W to respectively prepare anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry;
the hydroalcoholic dispersing agent is a solution prepared from water, ethanol and glycol according to a volume ratio of 6:0.5:0.5;
(2) Spraying anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of a proton membrane (the Dongyue DMR100 proton membrane) respectively, drying at 90 ℃ to form an anode second metal ion capturing layer and a cathode second metal ion capturing layer with the thickness of 0.2 mu m respectively, spraying anode catalytic layer slurry and cathode catalytic layer slurry on the anode second metal ion capturing layer and the cathode second metal ion capturing layer respectively, drying at 90 ℃ to form an anode catalytic layer and a cathode catalytic layer respectively, and obtaining a first complex;
(3) Spraying the anode first metal ion capturing layer slurry obtained in the step (1) on one side of an anode gas diffusion layer, and drying at 100 ℃ to form an anode first metal ion capturing layer with the thickness of 0.4 mu m, thereby obtaining an anode second complex; spraying the slurry of the first metal ion capturing layer of the cathode obtained in the step (1) on one side of a cathode gas diffusion layer, and drying at 100 ℃ to form a first metal ion capturing layer of the cathode with the thickness of 0.4 mu m, thereby obtaining a second composite of the cathode;
(4) And (3) bonding one side of the anode first metal ion capturing layer of the anode second complex obtained in the step (3) with one side of the anode catalytic layer of the first complex obtained in the step (2), bonding one side of the cathode first metal ion capturing layer of the cathode second complex obtained in the step (3) with one side of the cathode catalytic layer of the first complex obtained in the step (2), and then performing hot pressing at 0.6MPa and 120 ℃ for 10s to obtain the durable membrane electrode.
Example 4
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is identical to embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent, the cation exchange resin (Nafion D520) and the PTFE (polytetrafluoroethylene) is adjusted from 1:0.07:0.15 to 1:0.07:0.07 during the preparation of the first metal ion capturing layer slurry in step (1).
Example 5
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is identical to embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent, the cation exchange resin (Nafion D520) and the PTFE (polytetrafluoroethylene) is adjusted from 1:0.07:0.15 to 1:0.07:0.1 during the preparation of the first metal ion capturing layer slurry in step (1).
Example 6
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is identical to embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent, the cation exchange resin (Nafion D520) and the PTFE (polytetrafluoroethylene) is adjusted from 1:0.07:0.15 to 1:0.07:0.2 during the preparation of the first metal ion capturing layer slurry in step (1).
Example 7
The present embodiment provides a durable membrane electrode having the same hierarchical structure as the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is identical to embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent, the cation exchange resin (Nafion D520) and the PTFE (polytetrafluoroethylene) is adjusted from 1:0.07:0.15 to 1:0.07:0.23 during the preparation of the first metal ion capturing layer slurry in step (1).
Example 8
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is exactly the same as that of embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent to the perfluorinated sulfonic acid resin (Nafion D520) is adjusted from 1:0.07 to 1:0.02 during the preparation of the second metal ion capturing layer slurry in step (1).
Example 9
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is exactly the same as that of embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent to the perfluorinated sulfonic acid resin (Nafion D520) is adjusted from 1:0.07 to 1:0.05 during the preparation of the second metal ion capturing layer slurry in step (1).
Example 10
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, specifically, the preparation method of the durable membrane electrode in this embodiment is exactly the same as that of embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent to the perfluorinated sulfonic acid resin (Nafion D520) is adjusted from 1:0.07 to 1:0.1 during the preparation of the second metal ion capturing layer slurry in step (1).
Example 11
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, specifically, the method for preparing the durable membrane electrode in this embodiment is exactly the same as that of embodiment 1 except that the mass ratio of the hydroalcoholic dispersing agent to the perfluorosulfonic acid resin (Nafion D520) is adjusted from 1:0.07 to 1:0.13 during the preparation of the second metal ion capturing layer slurry in step (1).
Example 12
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode second metal ion capturing layer and the cathode second metal ion capturing layer are adjusted from 0.12 μm to 0.02 μm in step (2).
Example 13
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode second metal ion capturing layer and the cathode second metal ion capturing layer are adjusted from 0.12 μm to 0.05 μm in step (2).
Example 14
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode second metal ion capturing layer and the cathode second metal ion capturing layer are adjusted from 0.12 μm to 0.2 μm in step (2).
Example 15
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode second metal ion capturing layer and the cathode second metal ion capturing layer are adjusted from 0.12 μm to 0.23 μm in step (2).
Example 16
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode first metal ion capturing layer and the cathode first metal ion capturing layer are adjusted from 0.25 μm to 0.07 μm in step (3).
Example 17
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode first metal ion capturing layer and the cathode first metal ion capturing layer are adjusted from 0.25 μm to 0.1 μm in step (3).
Example 18
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode first metal ion capturing layer and the cathode first metal ion capturing layer are adjusted from 0.25 μm to 0.4 μm in step (3).
Example 19
The present embodiment provides a durable membrane electrode having the same hierarchical structure as that of the durable membrane electrode provided in embodiment 1, and specifically, the method for preparing the durable membrane electrode according to the present embodiment is identical to embodiment 1 except that the thicknesses of the anode first metal ion capturing layer and the cathode first metal ion capturing layer are adjusted from 0.25 μm to 0.43 μm in step (3).
Comparative example 1
The comparative example provides a membrane electrode having a hierarchical structure that does not include an anode second metal ion capturing layer, a cathode second metal ion capturing layer, and an anode first metal ion capturing layer and a cathode first metal ion capturing layer, except that the conditions are exactly the same as in example 1.
Comparative example 2
This comparative example provides a membrane electrode having a hierarchical structure that does not include an anode first metal ion capturing layer and a cathode first metal ion capturing layer, and the other conditions are exactly the same as those of example 1.
Comparative example 3
This comparative example provides a membrane electrode having a hierarchical structure that does not include an anode second metal ion capturing layer and a cathode second metal ion capturing layer, and the other conditions are exactly the same as those of example 1.
The membrane electrodes obtained in each example and comparative example were assembled to form a single cell, and then subjected to chemical durability test, and open circuit voltage operation was performed under conditions of a cell temperature of 80 c, cathode and anode humidification of 70%,150kPa, and the membrane electrode power density and hydrogen permeation current density were tested every 25 hours, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1:
(1) It can be seen that the hydrogen permeation current of examples 1-3 increases at a slower rate, and the electrochemical active area decays less, which significantly slows down the decay of the proton exchange membrane and the catalytic layer resin when the metal ion capturing layer is added.
(2) From the embodiment 1 and the comparative example 1, it can be seen that the performance of the membrane electrode prepared in the embodiment 1 is reduced through the 100-hour open circuit voltage endurance test, because the metal ion capturing layer is designed to remove metal ions in time, metal impurity ions are prevented from occupying proton sites in the catalytic layer and the proton membrane, so that the endurance performance of the catalytic layer is improved, the power density of the membrane electrode is not affected between the proton membrane and the catalytic layer, and between the diffusion layer and the catalytic layer, meanwhile, the metal ion capturing layer can anchor the metal ions, the Fenton reagent is effectively prevented from being generated, the generation speed of free radicals is inhibited from the generation source of free radicals, the free radicals are effectively inhibited, and the ionomer life of the proton membrane and the catalytic layer is prolonged;
as can be seen from examples 1 and 2 and 3, the provision of the double metal trapping layer is better in that the outer metal trapping layer (first metal ion trapping layer) can trap metal ions from materials such as bipolar plates, and the inner metal ion trapping layer (second metal ion trapping layer) can trap metal ions from the corrosion of the catalyst and catalyst layer, double protecting the proton membrane, effectively reducing the chemical attenuation of the proton membrane, and thus further enhancing the durability of the membrane electrode.
(3) As can be seen from examples 1 and 4, 5, 6, and 7, the ratio of the first metal ion capturing layer cationic resin to PTFE is too large or too small, resulting in insufficient mass transfer and metal ion capturing, and examples 4 and 7 are inferior in performance and durability to examples 1, 5, and 6;
(4) As can be seen from examples 1 and 8, 9, 10 and 11, the reduction or increase of the hydroalcoholic dispersant ratio of the second metal ion capturing layer affects the concentration of the slurry of the metal ion capturing layer, the too high concentration of the cationic resin is not uniformly dispersed, but the too low concentration, the drying time is too long and is easy to agglomerate, the dispersion is not uniform, and finally mass transfer and metal ion capturing are not uniform, and the performances and durability of examples 8 and 11 are not better than those of examples 1, 9 and 10;
(5) As can be seen from example 1 and examples 12, 13, 14, 15, increasing the membrane electrode resistance by too thick a trapping layer reduces the membrane electrode power density, and too thin a trapping layer reduces the trapping ability of the metal, affecting the membrane electrode durability. Examples 12, 15 therefore perform less well and are less durable than examples 1, 13, 14;
(6) As can be seen from example 1 and examples 16, 17, 18, 19, too thick a trapping layer increases the membrane electrode resistance, while too thick a first trapping layer prevents water vapor transport, further reducing the membrane electrode power density; too thin a metal trapping layer reduces trapping capacity, affecting membrane electrode durability. Examples 16, 19 are therefore less good performing and durable than examples 1, 17, 18.
From the above, the invention can capture the external metal ions entering the catalytic layer in time outside the catalytic layer and prevent the metal ions from invading the proton sites of the ionomer, and can remove the metal ions generated in the catalytic layer in time, so that the attack of free radicals can be blocked for the proton exchange membrane in time, the chemical attenuation of the proton membrane is effectively reduced, and the service lives of the membrane electrode and the fuel cell are further prolonged.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A durable membrane electrode comprising a second metal ion capturing layer disposed between a proton membrane and a catalytic layer, and a first metal ion capturing layer disposed between the catalytic layer and a gas diffusion layer;
the first metal ion capturing layer and the second metal ion capturing layer both contain cation exchange resins.
2. The durable membrane electrode according to claim 1, wherein the cation exchange resin in the second metal ion capturing layer is a perfluorosulfonic acid resin;
preferably, the thickness of the second metal ion capturing layer is 0.05 to 0.2 μm.
3. The durable membrane electrode according to claim 1 or 2, wherein the first metal ion capturing layer further comprises a gridded hydrophobic polymer;
Preferably, the network hydrophobic polymer comprises PTFE;
preferably, in the first metal ion capturing layer, the mass ratio of the cation exchange resin to the meshed hydrophobic polymer is 1 (1-4);
preferably, the thickness of the first metal ion capturing layer is 0.1 to 0.4 μm.
4. The durable membrane electrode according to any one of claims 1 to 3, wherein the catalyst layer contains a catalyst and a perfluorosulfonic acid resin, and the mass ratio of the catalyst to the perfluorosulfonic acid resin is 1 (0.3 to 1);
preferably, the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane.
5. A method for preparing a durable membrane electrode, comprising the steps of:
(1) Preparing a catalytic layer slurry, a first metal ion capturing layer slurry and a second metal ion capturing layer slurry respectively;
(2) Coating the second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of the proton membrane, drying to form a second metal ion capturing layer, coating the second metal ion capturing layer with the catalytic layer slurry, and drying to form a catalytic layer to obtain a first complex;
(3) Coating the slurry of the first metal ion capturing layer obtained in the step (1) on the surface of the gas diffusion layer, and drying to form a first metal ion capturing layer to obtain a second complex;
(4) And (3) bonding and hot-pressing one side of the catalytic layer of the first composite body obtained in the step (2) with one side of the first metal ion capturing layer of the second composite body obtained in the step (3) to obtain the durable membrane electrode.
6. The method according to claim 5, wherein the method for preparing the catalyst layer slurry comprises wetting the catalyst with water, adding a hydroalcoholic dispersant and a perfluorosulfonic acid resin, and performing ultrasonic dispersion;
preferably, in the catalyst layer slurry, the mass ratio of the catalyst to the hydroalcoholic dispersing agent to the perfluorinated sulfonic acid resin is 1 (50-120) (0.3-1);
preferably, the preparation method of the first metal ion capturing layer slurry comprises the steps of mixing cation exchange resin with a hydroalcoholic dispersing agent for ultrasonic dispersion;
preferably, in the first metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersing agent to the cation exchange resin is 1 (0.05-0.1);
preferably, the preparation method of the first metal ion capturing layer slurry further comprises mixing a gridding hydrophobic polymer, the cation exchange resin and the hydroalcoholic dispersing agent together for ultrasonic dispersion;
preferably, in the first metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersing agent to the cation exchange resin to the grid hydrophobic polymer is 1 (0.05-0.1): (0.1-0.2);
Preferably, the network hydrophobic polymer comprises PTFE;
preferably, the thickness of the first metal ion capturing layer is 0.1-0.4 μm;
preferably, the preparation method of the second metal ion capturing layer slurry comprises the steps of mixing cation exchange resin with a hydroalcoholic dispersing agent for ultrasonic dispersion;
preferably, the cation exchange resin is a perfluorinated sulfonic acid resin;
preferably, in the second metal ion capturing layer slurry, the mass ratio of the hydroalcoholic dispersing agent to the cation exchange resin is 1 (0.05-0.1);
preferably, the thickness of the second metal ion capturing layer is 0.05 to 0.2 μm.
7. The method according to claim 6, wherein the power of the ultrasonic dispersion is 300 to 1000W;
preferably, the ultrasonic dispersion time is 10-30 min;
preferably, the volume ratio of water to alcohol in the water to alcohol dispersing agent is (0.5-6) 1;
preferably, the alcohol in the hydroalcoholic dispersant comprises any one or a combination of at least two of ethanol, isopropanol, n-propanol or ethylene glycol.
8. The method of any one of claims 5-7, wherein in step (2), the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane;
Preferably, in step (2) and step (3), the coating method is selected from any one or a combination of at least two of spraying, blade coating or slit coating;
preferably, in the step (2), the drying temperature is 60-90 ℃;
preferably, in the step (3), the drying temperature is 60-100 ℃;
preferably, in the step (4), the pressure of the hot pressing is 0.1-0.6 MPa;
preferably, in the step (4), the temperature of the hot pressing is 60-120 ℃;
preferably, in the step (4), the time of the hot pressing is 10 to 30 seconds.
9. The preparation method according to any one of claims 5 to 8, characterized in that the preparation method comprises the steps of:
(1) Preparation of the catalyst layer slurry: wetting a catalyst by using water, mixing the catalyst, a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin according to the mass ratio of (50-120) (0.3-1), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode catalytic layer slurry and cathode catalytic layer slurry;
preparation of a first metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent, cation exchange resin and PTFE according to the mass ratio of (0.05-0.1) (0.1-0.2), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode first metal ion capturing layer slurry and cathode first metal ion capturing layer slurry;
Preparing second metal ion capturing layer slurry: mixing a hydroalcoholic dispersing agent and perfluorinated sulfonic acid resin according to the mass ratio of 1 (0.05-0.1), and performing ultrasonic dispersion for 10-30 min under the power of 300-1000W to respectively prepare anode second metal ion capturing layer slurry and cathode second metal ion capturing layer slurry;
the volume ratio of water to alcohol in the water to alcohol dispersing agent is (0.5-6): 1; the alcohol in the hydroalcoholic dispersant comprises any one or a combination of at least two of ethanol, isopropanol, n-propanol or ethylene glycol;
(2) Coating the anode second metal ion capturing layer slurry and the cathode second metal ion capturing layer slurry obtained in the step (1) on the two side surfaces of a proton membrane respectively, drying at 60-90 ℃ to form an anode second metal ion capturing layer and a cathode second metal ion capturing layer with the thickness of 0.05-0.2 mu m respectively, coating anode catalytic layer slurry and cathode catalytic layer slurry on the anode second metal ion capturing layer and the cathode second metal ion capturing layer respectively, and drying at 60-90 ℃ to form an anode catalytic layer and a cathode catalytic layer respectively to obtain a first composite;
in the step (2), the proton membrane comprises a perfluorosulfonic acid proton membrane and/or a non-fluorine proton exchange membrane;
(3) Coating the anode first metal ion capturing layer slurry obtained in the step (1) on one side of an anode gas diffusion layer, and drying at 60-100 ℃ to form an anode first metal ion capturing layer with the thickness of 0.1-0.4 mu m, thereby obtaining an anode second complex; coating the slurry of the first metal ion capturing layer of the cathode obtained in the step (1) on one side of a cathode gas diffusion layer, and drying at 60-100 ℃ to form a first metal ion capturing layer of the cathode with the thickness of 0.1-0.4 mu m, thereby obtaining a second composite of the cathode;
in the step (2) and the step (3), the coating method is independently selected from any one or a combination of at least two of spraying, blade coating and slit coating;
(4) And (3) bonding one side of the anode first metal ion capturing layer of the anode second complex obtained in the step (3) with one side of the anode catalytic layer of the first complex obtained in the step (2), bonding one side of the cathode first metal ion capturing layer of the cathode second complex obtained in the step (3) with one side of the cathode catalytic layer of the first complex obtained in the step (2), and then carrying out hot pressing for 10-30 s at the temperature of 60-120 ℃ under the pressure of 0.1-0.6 MPa to obtain the durable membrane electrode.
10. A fuel cell comprising the durable membrane electrode according to any one of claims 1 to 4 or comprising the durable membrane electrode obtained by the production method according to any one of claims 5 to 9.
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| CN116759590A (en) * | 2023-08-17 | 2023-09-15 | 安徽明天新能源科技有限公司 | Preparation method of composite CCM with high durability and low activation time and different catalytic layers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116759590A (en) * | 2023-08-17 | 2023-09-15 | 安徽明天新能源科技有限公司 | Preparation method of composite CCM with high durability and low activation time and different catalytic layers |
| CN116759590B (en) * | 2023-08-17 | 2023-10-31 | 安徽明天新能源科技有限公司 | Preparation method of multi-layer catalytic layer structure CCM |
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