CN110783579B - Gas diffusion layer and preparation method and application thereof - Google Patents
Gas diffusion layer and preparation method and application thereof Download PDFInfo
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- CN110783579B CN110783579B CN201911072092.3A CN201911072092A CN110783579B CN 110783579 B CN110783579 B CN 110783579B CN 201911072092 A CN201911072092 A CN 201911072092A CN 110783579 B CN110783579 B CN 110783579B
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a gas diffusion layer and a preparation method and application thereof. The preparation method of the gas diffusion layer comprises the following steps: (1) adding a water electrolysis promoting catalyst precursor into the microporous layer slurry to obtain treated microporous layer slurry; (2) coating the microporous layer slurry treated in the step (1) on a substrate, and drying in an inert atmosphere until a precursor of a water electrolysis promoting catalyst is decomposed to obtain the gas diffusion layer; the microporous layer in the gas diffusion layer contains a water electrolysis promoting catalyst and is loose and porous; the gas diffusion electrode and the fuel cell provided by the invention comprise the gas diffusion layer; the invention also provides a method for reducing corrosion of the carbon carrier in the anode catalyst layer of the fuel cell under the working condition of the reverse electrode, which is realized by mixing a water electrolysis promoting catalyst precursor into the microporous layer slurry. The gas diffusion layer provided by the invention improves the electrolytic capacity of water on the surface of the electrode, slows down the corrosion of the carbon carrier in the catalyst layer on the surface of the electrode by the counter electrode and prolongs the service life of the electrode.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a gas diffusion layer and a preparation method and application thereof.
Background
The fuel cell is a device for directly converting chemical energy stored in fuel and oxidant into electric energy, and has the advantages of wide fuel source, cleanness, environmental protection, no limitation of Carnot cycle, high energy conversion efficiency, strong module structure flexibility, centralized power supply, decentralized power supply and the like, thereby meeting the requirements of environment and sustainable development of resources, and being highly valued. The fuel cell has wide application prospect in the fields of power stations, electric automobiles, spaceflight, submarines, space power supplies and the like, and particularly, the fuel cell is successfully applied to the electric automobiles in recent years and is considered to be a power source capable of replacing an internal combustion engine to be used as a transportation tool.
The fuel cell may use hydrogen, natural gas, methanol, etc. as fuel and pure oxygen or air as oxidant. During use, water produced by the reaction of the fuel and oxidant is removed through the gas diffusion layer. The support layer material generally used for the gas diffusion layer has a relatively rough surface and has a plurality of rugged lines, so that the contact area of the support layer material and the surface of the catalytic layer is small, the internal resistance of the battery is increased, and the performance of the battery is reduced. In order to improve the pore structure of the supporting layer and prevent the electrode flooding phenomenon in the working process of the fuel cell, a microporous layer is introduced into the diffusion layer, and the effective components of the microporous layer are carbon black powder and a water repellent material, so that the contact resistance between the electrode catalyst layer and the supporting layer can be reduced, the catalyst layer is prevented from leaking to the supporting layer in the preparation process, the utilization rate of the catalyst is improved, and the redistribution of gas and water is realized. However, researchers have found that when the gas distribution in the fuel cell stack is not reasonable, the gas supply is insufficient during operation, and the stack is started or shut down, some of the cells become extremely low in voltage and even become negative, which causes reverse polarity. When a plurality of single cells in the fuel cell stack generate reverse polarity, the voltage of the single cell anode generating the reverse polarity exceeds 0.207V firstly, the carbon corrosion is generated on the surface of the electrode firstly, and the irreversible damage is caused to the electrode; meanwhile, the anode voltage of the single cell with the reverse pole is rapidly increased to be more than 1.23V, and the water electrolysis reaction is carried out; when the water on the surface of the electrode is fully electrolyzed, the electrolysis voltage of the anode rises to be more than 2V, the anode of the battery only corrodes by carbon, and the anode of the battery is damaged most seriously. The reverse electrode causes the performance of the electric pile to be reduced, and fuel and oxidant in the reaction cavity are mixed with each other, so that the possibility of explosion exists. Therefore, in order to avoid the potential of the anode of the battery from rising to more than 2V, the water electrolysis catalytic capacity of the anode catalyst of the battery needs to be improved, so that the anode catalyst is beneficial to the occurrence of water electrolysis reaction, and the corrosion rate of carbon is slowed down as much as possible, thereby reducing the damage of the counter electrode to the electrode.
The prior art discloses a number of effective solutions to the phenomenon of pole reversal. CN109256569A discloses a microporous layer of a gas diffusion layer of a proton exchange membrane fuel cell and a preparation method thereof. Coating or spraying an organic solvent containing organic siloxane and carbon nano materials on the surface of the support layer subjected to hydrophobic treatment, and forming a gas diffusion layer microporous layer of the proton exchange membrane fuel cell through a microporous layer interface micro-nano structure and a coating layer; wherein, the dosage proportion of the organic siloxane and the carbon nano material is 10-100 wt%. The microporous layer prepared by the method has super-hydrophobic performance, so that gas transmission is guaranteed and water is effectively managed during reverse polarity, but the use of the organic siloxane increases the roughness of the surface of the microporous layer and increases the contact resistance between the microporous layer and the catalytic layer.
CN105074980A discloses a barrier layer for corrosion protection in electrochemical devices, such as a carbon-based Gas Diffusion Layer (GDL) in electrochemical devices, comprising electrically conductive ceramic material and a non-ionomeric polymer binder. The electrically conductive ceramic material has an electrical conductivity in an air atmosphere of >0.1S/cm, preferably >1S/cm (as detected by powder method) and is selected from the group consisting of: containing oxides, carbides, nitrides, borides of precious and/or base metals and mixtures and combinations thereof. The membrane-electrode assemblies (MEAs), Catalyst Coated Membranes (CCMs), Gas Diffusion Electrodes (GDEs) and Gas Diffusion Layers (GDLs) comprising the barrier layer of the present invention exhibit improved corrosion resistance, preferably against carbon corrosion; particularly during start/stop cycles and fuel starvation of PEM fuel cells. But the barrier layer is positioned between the catalyst layer and the gas diffusion layer, making the fabrication process cumbersome.
CN201523041U provides a self-shielding proton exchange membrane fuel cell, comprising one or more single cells, wherein the single cell comprises an anode, a cathode and a proton exchange membrane disposed between the anode and the cathode, and the anode and the cathode both contain a catalyst for accelerating electrochemical reaction of the electrodes, and the self-shielding proton exchange membrane fuel cell is characterized in that: the battery also comprises a diode connected with the single battery in parallel, wherein the anode of the diode is connected with the anode, and the cathode of the diode is connected with the cathode. The diode is conducted when the single cells in the proton exchange membrane fuel cell have reverse poles due to sudden change, and the fuel cell stack with the reverse poles can be automatically shielded by the diode because the resistance of the diode is far smaller than that of the single cells. The fuel cell can effectively avoid electrode corrosion of a single cell caused by reverse polarity, the service life of the cell is prolonged, but the complexity and the cost of a cell system are increased due to the introduction of the diode.
Based on the above documents, it is known how to improve the exhaust and drainage capabilities of the gas diffusion layer of the fuel cell and the water electrolysis catalytic capability of the catalytic layer without increasing the process steps and the complexity of the cell system, so as to facilitate the occurrence of water electrolysis reaction, effectively solve the problem of corrosion of carbon on the surface of the electrode when the single cell generates reverse polarity, and reduce the damage of the reverse polarity to the electrode, which is a technical problem to be solved urgently at present.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a gas diffusion layer, a method for preparing the same, and use thereof. The microporous layer in the gas diffusion layer is of a loose porous structure, so that the gas and water can be transmitted conveniently, and the mass transfer capacity of the gas diffusion layer is improved; in addition, the gas diffusion layer contains a water electrolysis promoting catalyst, so that the catalytic capability of water electrolysis on the surface of the electrode is improved, the catalytic layer is protected, and the corrosion problem of the carbon carrier of the catalytic layer on the surface of the electrode under the working condition of the counter electrode is solved; the gas diffusion electrode and the fuel cell not only have good anti-reversal capability, but also have significantly prolonged service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a gas diffusion layer, comprising the steps of:
(1) adding a water electrolysis promoting catalyst precursor into the microporous layer slurry to obtain treated microporous layer slurry;
(2) and (2) coating the microporous layer slurry treated in the step (1) on a substrate, and drying in an inert atmosphere until a precursor of the water electrolysis catalyst is promoted to be decomposed to obtain the gas diffusion layer.
According to the preparation method of the gas diffusion layer, the precursor of the water electrolysis promoting catalyst is added into the microporous layer slurry, the precursor is decomposed to generate the catalyst and gas in the drying process, and the gas is helpful for forming a loose porous structure on the microporous layer when escaping, so that the gas and the water can be transmitted easily, and the mass transfer capacity of the gas diffusion layer is improved.
Preferably, the water electrolysis catalyst precursor comprises any one or a combination of at least two of inorganic salts of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper, preferably any one or a combination of at least two of chloride, carbonate or nitrate of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper, and further preferably any one or a combination of at least two of ruthenium chloride, cobalt carbonate, nickel nitrate or palladium chloride, wherein typical but non-limiting combinations are ruthenium chloride and nickel nitrate, nickel nitrate and cobalt carbonate, ruthenium chloride and palladium chloride, ruthenium chloride, cobalt carbonate and nickel nitrate. The precursor of the water electrolysis promoting catalyst is decomposed to generate the catalyst and gas in the process of preparing the diffusion layer, when the gas escapes, the microporous layer forms a loose porous structure, so that the diffusion layer has enough gas channels and water channels, and the generated water can be captured and decomposed by the catalyst or discharged through the water channels, thereby achieving the effect of protecting the catalyst layer.
Preferably, the microporous layer slurry contains a carbon material and an auxiliary agent.
Preferably, the adjuvant is a hydrophobic agent.
Preferably, the mass ratio of the water electrolysis promoting catalyst precursor to the carbon material is 0.02 to 0.15, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15, and the mass ratio of the water electrolysis promoting catalyst precursor to the carbon material is more favorable for the formation of a porous structure, preferably 0.05 to 0.1.
The mass of the hydrophobizing agent is preferably 10 to 30% of the mass of the carbon material, and may be, for example, 10%, 11%, 12%, 15%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 29%, 30%, or the like, and preferably 15 to 28%.
In the present invention, the selection of the mass ratio of the hydrophobic agent to the mass of the carbon material in the microporous layer slurry is a commonly used adjustment by those skilled in the art, and the mass ratio is between 10-30% and contributes substantially the same to the microporous layer.
In the present invention, the specific types of the carbon material and the hydrophobizing agent used in the microporous layer slurry are not particularly limited, and the carbon material may be acetylene black, activated carbon or graphite powder; the hydrophobic agent may be polytetrafluoroethylene, polyvinylidene fluoride emulsion or polychlorotrifluoroethylene, of the kind used by those skilled in the art, and is suitable for use in the present invention.
Preferably, the preparation method of the microporous layer slurry in the step (1) comprises the following steps:
and adding a carbon material and a hydrophobic agent into a solvent, and dispersing to obtain microporous layer slurry.
Preferably, the solvent is an aqueous solution of polyvinylpyrrolidone, which enables a more uniform dispersion of the carbon material and the hydrophobizing agent.
Preferably, the dispersion is a stirred and/or ultrasonic dispersion.
Preferably, the ultrasonic dispersion time is 20 to 80 minutes, and may be, for example, 20 minutes, 22 minutes, 25 minutes, 28 minutes, 30 minutes, 33 minutes, 35 minutes, 37 minutes, 40 minutes, 42 minutes, 45 minutes, 48 minutes, 50 minutes, 53 minutes, 55 minutes, 57 minutes, 60 minutes, 62 minutes, 65 minutes, 68 minutes, 70 minutes, 72 minutes, 75 minutes, 77 minutes, 80 minutes, or the like, and the ultrasonic dispersion time is such that the carbon material and the hydrophobizing agent are uniformly dispersed, preferably 30 to 60 minutes.
Preferably, the power of the ultrasonic dispersion is 200-1000W, such as 200W, 220W, 260W, 300W, 320W, 350W, 380W, 400W, 420W, 450W, 480W, 500W, 530W, 550W, 570W, 600W, 620W, 660W, 700W, 730W, 750W, 770W, 800W, 820W, 860W, 900W, 920W, 940W, 960W, 980W or 1000W, and preferably 500-900W.
Preferably, the substrate in step (2) is selected from any one of a carbon substrate, a titanium substrate, a nickel substrate or a copper substrate, preferably any one of carbon paper, carbon felt, carbon fiber paper, carbon fiber woven cloth, a mesh titanium substrate, a mesh nickel substrate or a mesh copper substrate.
Preferably, the coating mode is any one or combination of at least two of coating, screen printing, spin coating or spray coating.
Preferably, the thickness of the coating is 10-60 μm, for example, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 24 μm, 27 μm, 30 μm, 32 μm, 35 μm, 37 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 57 μm or 60 μm, and the like, and the coating thickness can deal with the flooding problem of the electrode and can protect the catalytic layer, and is preferably 30-50 μm.
Preferably, the inert atmosphere is any one of nitrogen, argon or helium or a combination of at least two thereof.
Preferably, the drying temperature is 200-.
Preferably, the drying time is 30 to 90 minutes, and for example, may be 30 minutes, 33 minutes, 35 minutes, 37 minutes, 40 minutes, 42 minutes, 45 minutes, 48 minutes, 50 minutes, 53 minutes, 55 minutes, 57 minutes, 60 minutes, 62 minutes, 65 minutes, 68 minutes, 70 minutes, 72 minutes, 75 minutes, 77 minutes, 80 minutes, 82 minutes, 85 minutes, 88 minutes, 90 minutes, or the like, preferably 30 to 80 minutes.
The drying temperature and the drying time are determined by the specific component content in the microporous layer, the thickness and pore structure of the microporous layer, the decomposition temperature of the precursor of the water electrolysis promoting catalyst and the like, and are determined according to specific conditions.
Preferably, the loading of carbon material in the microporous layer slurry is 0.5-8.0mg/cm2For example, it may be 0.5mg/cm2、0.8mg/cm2、1.0mg/cm2、1.2mg/cm2、1.5mg/cm2、1.7mg/cm2、2.0mg/cm2、2.2mg/cm2、2.5mg/cm2、2.8mg/cm2、3.0mg/cm2、3.3mg/cm2、3.5mg/cm2、3.7mg/cm2、4.0mg/cm2、4.5mg/cm2、4.8mg/cm2、5.0mg/cm2、5.2mg/cm2、5.6mg/cm2、6.0mg/cm2、6.3mg/cm2、6.6mg/cm2、7.0mg/cm2、7.2mg/cm2、7.5mg/cm2、7.7mg/cm2Or 8.0mg/cm2Etc., the amount of the carbon material supported is such that the thickness of the microporous layer is secured, preferably 0.8 to 3.0mg/cm2。
Preferably, the preparation method comprises the following steps:
(1) adding a carbon material and a hydrophobic agent into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 20-80 minutes at the ultrasonic power of 200-1000W to obtain microporous layer slurry, adding a precursor of a water electrolysis promoting catalyst, stirring to obtain the treated microporous layer slurry, and controlling the loading amount of the carbon material in the microporous layer of the gas diffusion layer to be 0.5-8.0mg/cm2The mass of the water repellent agent is 10-30% of the mass of the carbon material, and the mass ratio of the precursor of the water electrolysis promoting catalyst to the carbon material is 0.02-0.15;
the water electrolysis promoting catalyst precursor comprises any one or combination of at least two of inorganic salts of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper;
(2) and (2) coating the microporous layer slurry treated in the step (1) on a substrate to ensure that the coating thickness is 10-60 mu m, and heating to 200-700 ℃ in an inert atmosphere for 30-90 minutes until the water electrolysis catalyst precursor is decomposed to obtain the gas diffusion layer.
In a second aspect, the present invention provides a gas diffusion layer produced by the production method according to the first aspect described above.
The gas diffusion layer provided by the invention is provided with the porous microporous layer, so that the exhaust and drainage capabilities of the gas diffusion layer are improved, meanwhile, the diffusion layer contains a water electrolysis promoting catalyst, the catalysis capability of water electrolysis on the surface of the electrode is improved, water begins to decompose in the diffusion layer, the catalyst layer is protected, and the problem of corrosion of the carbon carrier of the catalyst layer on the surface of the electrode under the reverse working condition is solved.
Preferably, the gas diffusion layer comprises a microporous layer having a pore size of 50-300nm, which may be, for example, 50nm, 60nm, 80nm, 90nm, 100nm, 102nm, 108nm, 115nm, 118nm, 120nm, 121nm, 124nm, 128nm, 130nm, 132nm, 135nm, 139nm, 140nm, 142nm, 144nm, 150nm, 155nm, 160nm, 166nm, 170nm, 177nm, 180nm, 188nm, 190nm, 195nm, 200nm, 260nm, 275nm, 280nm, 286nm, 288nm, 300nm, etc., preferably 80-120 nm.
Preferably, the mass ratio of the water electrolysis promoting catalyst to the carbon material in the microporous layer is 0.02 to 0.15, and may be, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15, and the like, and preferably 0.05 to 0.1.
Preferably, the thickness of the microporous layer is 10-60 μm, and may be, for example, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 24 μm, 27 μm, 30 μm, 32 μm, 35 μm, 37 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 57 μm, or 60 μm, and the like, preferably 30-50 μm.
In a third aspect, the present invention provides a gas diffusion electrode comprising a gas diffusion layer as described in the second aspect above.
The gas diffusion electrode provided by the invention has the advantages that the porous microporous layer is formed in the gas diffusion layer by mixing the water electrolysis promoting catalyst precursor into the microporous layer slurry, the mass transfer capacity of the electrode is enhanced, meanwhile, the diffusion layer of the electrode contains the water electrolysis promoting catalyst, so that the electrolytic capacity of the surface water of the gas diffusion electrode is higher than that of the conventional gas diffusion electrode, the gas diffusion electrode has good chemical and electrochemical stability and excellent anti-reversal capability, and can be widely applied to various fuel cell technologies such as proton exchange membrane fuel cells, methanol fuel cells and the like.
In a fourth aspect, the present invention provides a fuel cell comprising a gas diffusion electrode as described in the third aspect above.
The fuel cell provided by the invention is prepared by adopting the diffusion electrode containing the water electrolysis promoting catalyst, has the capability of resisting the reverse pole, and has more stable integral structure and performance and longer service life of the galvanic pile of the cell.
In a fifth aspect, the invention also provides a method for reducing carbon carrier corrosion in a fuel cell anode catalyst layer under a reverse working condition, which comprises the steps of mixing a water electrolysis promoting catalyst precursor into microporous layer slurry to obtain treated microporous layer slurry, coating the microporous layer slurry on a substrate, and drying in an inert atmosphere until the water electrolysis promoting catalyst precursor is decomposed to obtain the gas diffusion layer with the micropore size of 50-300 nm.
According to the method for reducing corrosion of the carbon carrier in the anode catalyst layer of the fuel cell under the reverse working condition, the water electrolysis promoting catalyst precursor is mixed into the slurry of the microporous layer, so that the microporous layer contains the water electrolysis promoting catalyst and is loose and porous, the water decomposition capacity and mass transfer capacity of the anode are improved, the carbon carrier in the catalyst layer is protected, and the corrosion of the carbon carrier under the reverse working condition is slowed down.
Preferably, the water electrolysis promoting catalyst precursor is selected from inorganic salts containing ruthenium, iridium, palladium, platinum, nickel, cobalt or copper or a combination of at least two of the inorganic salts, preferably chloride salts, carbonate salts or nitrate salts of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper or a combination of at least two of the chloride salts, carbonate salts or nitrate salts.
The microporous layer slurry of the present invention is not particularly limited, and any microporous layer slurry and the preparation method thereof, which are commonly used by those skilled in the art, are applicable to the present invention.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the preparation method of the gas diffusion layer, the precursor of the water electrolysis promoting catalyst is added into the microporous layer slurry, the precursor is decomposed to generate the catalyst and gas in the drying process, and the gas is helpful for forming more water channels and gas channels in the microporous layer when escaping;
(2) the gas diffusion layer provided by the invention is provided with a loose and porous microporous layer, the aperture is 50-300nm, the thickness is 10-60 mu m, the porous layer belongs to micron order, the gas diffusion layer is favorable for the transmission of gas and water, and simultaneously, the diffusion layer contains a water electrolysis promoting catalyst, so that the corrosion of a carbon carrier in a catalytic layer on the surface of a fuel cell electrode caused by the insufficient fuel supply due to the starting/stopping process of an engine is effectively prevented;
(3) according to the diffusion electrode provided by the invention, the diffusion layer containing the water electrolysis promoting catalyst is adopted, so that the chemical and electrochemical stability is good, when the counter electrode is generated, the moisture on the surface of the electrode starts to decompose in the diffusion layer, the catalytic layer is protected, and the diffusion electrode has excellent counter electrode resistance;
(4) the fuel cell provided by the invention has good stability of the whole structure and performance of the fuel cell stack by adopting the diffusion electrode which has good drainage and exhaust performance and can decompose water, and under the condition of a reverse electrode, the voltage drop value of the fuel cell provided by the invention is 15mV, and the voltage drop value is 85mV less than that of a fuel cell which does not adopt reverse electrode resistant operation; compared with a fuel cell formed by directly adding a water electrolysis promoting catalyst into the microporous layer, the voltage drop value of the fuel cell is less by 7mV, and the fuel cell has better anti-reversal performance;
(5) according to the method for reducing corrosion of the carbon carrier in the anode catalyst layer of the fuel cell under the reverse working condition, the water electrolysis promoting catalyst precursor is mixed into the slurry of the microporous layer, so that the microporous layer contains the water electrolysis promoting catalyst, more water channels and gas channels are provided, the mass transfer capacity and the water decomposition capacity of the anode are improved, the carbon carrier in the catalyst layer is protected, and the corrosion of the carbon carrier under the reverse working condition is slowed down.
Drawings
Fig. 1 is a schematic structural diagram of a gas diffusion layer prepared by the preparation method provided by the invention.
Fig. 2 is a comparative graph of performance tests before and after the cell counter electrode of the gas diffusion layer prepared in example 1 provided by the present invention.
FIG. 3 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 4 provided by the present invention is reversed.
FIG. 4 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 5 provided by the present invention is reversed.
FIG. 5 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 6 provided by the present invention is reversed.
FIG. 6 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 7 provided by the present invention is reversed.
FIG. 7 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 8 provided by the present invention is reversed.
FIG. 8 is a comparative graph of performance tests before and after the membrane electrode of the gas diffusion layer prepared in example 9 provided by the present invention is reversed.
Fig. 9 is a comparison graph of performance tests before and after cell reversal of the gas diffusion layers prepared in example 1 and comparative example 1 provided by the present invention.
Fig. 10 is a comparison graph of performance tests before and after the cell counter electrodes of the gas diffusion layers prepared in example 1 and example 3 provided by the present invention.
Fig. 11 is a comparative graph of performance tests before and after the cell counter electrode of the gas diffusion layer prepared in comparative example 2 provided by the present invention.
Detailed Description
The following further describes the technical means of the present invention to achieve the predetermined technical effects by means of embodiments with reference to the accompanying drawings, and the embodiments of the present invention are described in detail as follows.
The structure of the gas diffusion layer prepared by the preparation method provided by the invention is shown in figure 1. The gas diffusion layer comprises a substrate and a microporous layer, wherein the microporous layer comprises carbon materials and a water electrolysis promoting catalyst, the water electrolysis promoting catalyst is uniformly distributed among the carbon materials, and loose and porous structures are formed among the carbon materials and between the carbon materials and the water electrolysis promoting catalyst in the microporous layer, so that more channels are provided for the transmission of gas and moisture, the mass transfer capacity of the gas diffusion layer is improved, the water electrolysis promoting catalyst improves the decomposition capacity of the moisture, and the carbon carrier in the catalytic layer under the reverse working condition is protected.
Example 1
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding acetylene black and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 60 minutes at the ultrasonic power of 800W to obtain microporous layer slurry, adding ruthenium chloride, stirring to obtain treated microporous layer slurry, and controlling the loading amount of the acetylene black of the microporous layer of the gas diffusion layer to be 3mg/cm2The mass of the polytetrafluoroethylene is 25% of that of acetylene black, and the mass ratio of the ruthenium chloride to the acetylene black is 0.08;
(2) and (2) coating the microporous layer slurry treated in the step (1) on carbon paper to enable the coating thickness to be 45 micrometers, heating to 500 ℃ in nitrogen, and keeping for 60 minutes until ruthenium chloride is decomposed into simple substance ruthenium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
The results of the testing before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example are shown in FIG. 2, which shows that when the current density is less than 100mA/cm after the reversal of the electrode2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage was decreased, the decrease was small, about 15mV, indicating that the gas diffusion layer prepared in this example had the anti-bipolar capability.
Example 2
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding graphite powder and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 80 minutes at the ultrasonic power of 900W to obtain microporous layer slurry, adding ruthenium chloride, stirring to obtain treated microporous layer slurry, and controlling the loading amount of graphite powder of a microporous layer of a gas diffusion layer to be 8mg/cm2The mass of the polytetrafluoroethylene is 25% of that of graphite powder, and the mass ratio of the ruthenium chloride to the graphite powder is 0.02;
(2) and (2) spin-coating the microporous layer slurry treated in the step (1) on carbon paper to enable the coating thickness to be 60 micrometers, heating to 600 ℃ in nitrogen, and keeping for 90 minutes until ruthenium chloride is decomposed into simple substance ruthenium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
Example 3
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding activated carbon and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 20 minutes at the ultrasonic power of 800W to obtain microporous layer slurry, adding ruthenium chloride, stirring to obtain treated microporous layer slurry, and controlling the microporous layer activated carbon of a gas diffusion layerThe supporting amount of (B) is 0.5mg/cm2The mass of the polytetrafluoroethylene is 25% of that of the activated carbon, and the mass ratio of the ruthenium chloride to the activated carbon is 0.1;
(2) and (2) spin-coating the microporous layer slurry treated in the step (1) on a reticular titanium substrate to enable the coating thickness to be 10 microns, heating to 500 ℃ in nitrogen, and keeping for 30 minutes until ruthenium chloride is decomposed into simple substance ruthenium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
The results of the test before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example and example 1 at different current densities are shown in fig. 10, which shows that the initial voltage of the cell before the reversal is the same; after the electrode reversal, when the current density is less than 100mA/cm2When the current density is larger than 100mA/cm, the cell voltage drop value is small in difference2When the current density is increased, the voltage drop value of the battery is greatly different, and the current density is 1500mA/cm2When the voltage drop values of the two cells are different by 45mV, the gas diffusion layer prepared in example 1 has better anti-reversal capability than the gas diffusion layer prepared in this example.
Example 4
The mass ratio of ruthenium chloride to acetylene black in step (1) was replaced with 0.01 compared to example 1.
The results of the pre-and post-reversal test of the fuel cell assembled with the gas diffusion layer prepared in this example at different current densities are shown in fig. 3, which shows that the cell voltage is reduced significantly, about 75mV, after reversal, indicating that the gas diffusion layer prepared in this example has excellent anti-reversal capability.
Example 5
The mass ratio of ruthenium chloride to acetylene black in step (1) was replaced with 0.2 compared to example 1.
The results of the pre-and post-reversal test of the fuel cell assembled with the gas diffusion layer prepared in this example at different current densities are shown in fig. 4, which shows that the cell voltage is significant, about 90mV, after reversal, and shows that the gas diffusion layer prepared in this example has good resistance to reversal.
Example 6
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding acetylene black and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 60 minutes at the ultrasonic power of 800W to obtain microporous layer slurry, adding palladium chloride, stirring to obtain treated microporous layer slurry, and controlling the loading amount of the acetylene black of the microporous layer of the gas diffusion layer to be 3mg/cm2The mass of the polytetrafluoroethylene is 25% of that of acetylene black, and the mass ratio of the palladium chloride to the acetylene black is 0.05;
(2) and (2) coating the microporous layer slurry treated in the step (1) on carbon fiber paper by screen printing to enable the coating thickness to be 45 microns, heating to 500 ℃ in nitrogen, and keeping for 60 minutes until ruthenium chloride is decomposed into elemental palladium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
The results of the testing before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example are shown in FIG. 5, which shows that when the current density is less than 100mA/cm after the reversal of the electrode2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage was decreased, the decrease was small, about 17mV, indicating that the gas diffusion layer prepared in this example had excellent anti-bipolar capability.
Example 7
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding acetylene black and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 60 minutes at the ultrasonic power of 500W to obtain microporous layer slurry, adding ruthenium chloride, stirring to obtain treated microporous layer slurry, and controlling the loading amount of the acetylene black of the microporous layer of the gas diffusion layer to be 3mg/cm2The mass of the polytetrafluoroethylene is 25% of that of acetylene black, and the mass ratio of the ruthenium chloride to the acetylene black is 0.1;
(2) spraying the microporous layer slurry treated in the step (1) onto a reticular nickel substrate to enable the coating thickness to be 45 microns, heating to 500 ℃ in nitrogen, and keeping for 60 minutes until ruthenium chloride decomposes elementary ruthenium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
The results of the testing before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example are shown in FIG. 6, which shows that when the current density is less than 100mA/cm after the reversal of the electrode2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage was decreased, the decrease was small, about 22mV, indicating that the gas diffusion layer prepared in this example had good anti-bipolar capability.
Example 8
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding acetylene black and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 60 minutes at the ultrasonic power of 900W to obtain microporous layer slurry, adding ruthenium chloride, stirring to obtain treated microporous layer slurry, and controlling the loading amount of the acetylene black of the microporous layer of the gas diffusion layer to be 3mg/cm2The mass of the polytetrafluoroethylene is 25% of that of acetylene black, and the mass ratio of the ruthenium chloride to the acetylene black is 0.08;
(2) and (2) coating the microporous layer slurry treated in the step (1) on carbon paper to enable the coating thickness to be 45 micrometers, heating to 520 ℃ in nitrogen, and keeping for 60 minutes until ruthenium chloride is decomposed into simple substance ruthenium and hydrogen chloride gas, so as to obtain the gas diffusion layer.
The results of the testing before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example are shown in FIG. 7, which shows that when the current density is less than 100mA/cm after the reversal of the electrode2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage is decreased, the decrease value is smaller, and is about 27mV, which shows that the gas diffusion layer prepared by the embodiment has better anti-reversal pole capability.
Example 9
The embodiment provides a preparation method of a gas diffusion layer, which comprises the following steps:
(1) adding acetylene black and polytetrafluoroethylene into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 60 minutes at the ultrasonic power of 800W to obtain microporous layer slurry, adding ruthenium chloride and nickel nitrate, stirring to obtain treated microporous layer slurry, and controlling the loading amount of the acetylene black of the microporous layer of the gas diffusion layer to be 3mg/cm2The mass of the polytetrafluoroethylene is 25% of that of acetylene black, and the mass ratio of the ruthenium chloride and the nickel nitrate to the acetylene black is 0.05;
(2) and (2) screen-printing the microporous layer slurry treated in the step (1) on carbon fiber paper to ensure that the coating thickness is 45 microns, and heating to 500 ℃ in nitrogen for 60 minutes until ruthenium chloride and nickel nitrate are decomposed into elementary ruthenium, nickel oxide, hydrogen chloride and nitrogen dioxide gas to obtain the gas diffusion layer.
The results of the testing before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this example are shown in FIG. 8, which shows that when the current density is less than 100mA/cm after the reversal of the electrode2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage is reduced, the reduction value is smaller and is about 18mV, which shows that the gas diffusion layer prepared by the embodiment has excellent anti-reversal capability, namely that the anti-reversal capability of the gas diffusion layer is really improved by using the water electrolysis promoting catalyst precursors of ruthenium chloride and nickel nitrate.
Comparative example 1
The only difference compared to example 1 is that no ruthenium chloride was added in step (1).
The results of the test before and after the reversal of the electrode of the fuel cell assembled with the gas diffusion layer prepared in this comparative example and example 1 at different current densities are shown in fig. 9, which shows that the initial voltages of the cells before the reversal are the same; after the electrode reversal, when the current density is less than 100mA/cm2When the current density is larger than 100mA/cm, the cell voltage drop value is small in difference2When the current density is increased, the voltage drop value of the battery is greatly different, and the current density is higherIs 1500mA/cm2When the voltage drop values of the two cells differed by 85mV, the gas diffusion layer prepared in example 1 acted as a counter electrode.
Comparative example 2
The only difference compared to example 1 is that no ruthenium chloride was added in step (1), and elemental ruthenium was added directly.
The results of the test before and after the reversal at different current densities of the fuel cell assembled with the gas diffusion layer prepared in the present comparative example are shown in fig. 11, which shows that when the current density is less than 100mA/cm after the reversal2When the current density is more than 100mA/cm, the cell voltage is almost unchanged2When the cell voltage drop was about 22mV, the gas diffusion layer prepared in this comparative example was shown to have anti-bipolar capability.
Evaluation of gas diffusion layer anti-bipolar ability:
on the gas diffusion layers prepared in examples 1 to 9 and comparative examples 1 to 2 described above, catalyst layers were prepared, then gas diffusion electrodes were prepared, and then assembled into fuel cells, and a 20-minute reverse-polarity condition test was performed, the test method being as follows:
the air inlet pressure is 0.1-MPa, the metering ratio is 2, and the relative humidity is 100%; the pressure of a hydrogen inlet is 0.1-MPa, the metering ratio is 2, and the relative humidity is 100%; the cell was operated at 50 ℃ under different current density conditions.
The battery performances before and after the reversal were compared, and the battery voltage corresponding to 1500 current density was used as the basis for the performance measurement, and the test results are shown in tables 1 and 2.
TABLE 1
TABLE 2
As can be seen from the data in tables 1 and 2The followingThe following points are that:
(1) it can be seen from the combination of examples 1-9 that the fuel cell prepared by the gas diffusion layer provided by the embodiment of the invention has the voltage drop value of 15-90mV, and both have the function of anti-reversal; example 2 showed the most voltage drop compared to the other examples, which indicates that better anti-reversal performance can be achieved by optimizing the preparation conditions of the gas diffusion layer;
(2) by combining example 1 and comparative example 1, it can be seen that the gas diffusion layer prepared by adding ruthenium chloride to the microporous layer slurry in example 1 has a voltage drop value of 15mV compared with the gas diffusion layer prepared by not adopting the anti-reverse-polarity technology in comparative example 1, the voltage drop value of the fuel cell assembled by the gas diffusion layer provided in comparative example 1 is about 100mV, and the voltage drop value of example 1 is 15% compared with the voltage drop value of comparative example 1, thereby indicating that the gas diffusion layer provided in example 1 can play a role in improving the anti-reverse-polarity performance of the fuel cell;
(3) it can be seen from the combination of example 1 and comparative example 2 that the gas diffusion layer prepared by adding ruthenium chloride to the microporous layer slurry in example 1 has a 15mV drop value in the assembled fuel cell voltage of the gas diffusion layer compared with the direct addition of elemental ruthenium to the microporous layer slurry in comparative example 2, and the voltage drop of the assembled fuel cell voltage of the gas diffusion layer provided in comparative example 2 is about 22mV, thereby illustrating that the anti-reverse polarity performance of the gas diffusion layer provided in example 1 is better than that of the gas diffusion layer provided in comparative example 2.
(4) It can be seen from the combination of example 1, example 4 and example 5 that the mass ratio of ruthenium chloride to acetylene black in the gas diffusion layer prepared in example 1 is 0.08, the mass ratio of ruthenium chloride to acetylene black in the gas diffusion layer prepared in example 4 is 0.01, the mass ratio of ruthenium chloride to acetylene black in the gas diffusion layer prepared in example 5 is 0.2, the voltage drop of the fuel cell assembled with the gas diffusion layer provided in example 1 is 15mV, the voltage drop of the fuel cell assembled with the gas diffusion layer provided in example 4 is about 75mV, and the voltage drop of the fuel cell assembled with the gas diffusion layer provided in example 5 is about 90mV, which indicates that the anti-reversal capability of the gas diffusion layer provided in example 1 is stronger than that of the gas diffusion layers provided in examples 4 and 5.
In conclusion, the method for adding the precursor of the water electrolysis promoting catalyst into the microporous layer slurry provided by the invention enables the microporous layer to contain the water electrolysis promoting catalyst, has more water channels and gas channels, improves the mass transfer capacity and the water decomposition capacity of the anode, achieves the effect of improving the gas diffusion layer, and simultaneously plays a role in protecting the carbon carrier in the catalyst layer of the electrode. Under the condition of 20 minutes of counter electrode, the voltage drop value of the tested fuel cell is between 15 and 90mV, so that the counter electrode resistance effect is achieved, and better counter electrode resistance can be obtained through optimizing the preparation condition of the gas diffusion layer, so that the industrialization of the fuel cell is promoted.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through 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 understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (37)
1. A method of preparing a gas diffusion layer, comprising the steps of:
(1) adding a carbon material and a hydrophobic agent into a solvent, dispersing to obtain microporous layer slurry, adding a water electrolysis promoting catalyst precursor into the microporous layer slurry, wherein the mass ratio of the water electrolysis promoting catalyst precursor to the carbon material is 0.02-0.15, and obtaining the treated microporous layer slurry;
the water electrolysis promoting catalyst precursor comprises any one or combination of at least two of inorganic salts of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper;
(2) and (2) coating the microporous layer slurry treated in the step (1) on a substrate, and drying in an inert atmosphere until a precursor of the water electrolysis catalyst is promoted to be decomposed to obtain the gas diffusion layer.
2. The preparation method according to claim 1, wherein the water electrolysis catalyst precursor in step (1) is any one or a combination of at least two of chloride, carbonate or nitrate of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper.
3. The preparation method according to claim 2, wherein the precursor of the water electrolysis promoting catalyst in the step (1) is any one of ruthenium chloride, cobalt carbonate, nickel nitrate or palladium chloride or a combination of at least two of the ruthenium chloride, the cobalt carbonate, the nickel nitrate and the palladium chloride.
4. The production method according to claim 1, wherein the mass ratio of the water electrolysis promoting catalyst precursor to the carbon material is 0.05 to 0.1.
5. The production method according to claim 1, wherein the mass of the water repellent agent is 10 to 30% of the mass of the carbon material.
6. The production method according to claim 1, wherein the mass of the water repellent agent is 15 to 28% of the mass of the carbon material.
7. The method according to claim 1, wherein the solvent is an aqueous solution of polyvinylpyrrolidone.
8. The production method according to claim 1, wherein the dispersion is stirring and/or ultrasonic dispersion.
9. The method of claim 8, wherein the time of ultrasonic dispersion is 20 to 80 minutes.
10. The method of claim 9, wherein the time of ultrasonic dispersion is 30 to 60 minutes.
11. The method as claimed in claim 8, wherein the power of the ultrasonic dispersion is 200-1000W.
12. The method as claimed in claim 11, wherein the power of the ultrasonic dispersion is 500-900W.
13. The production method according to claim 1, wherein the substrate in the step (2) is selected from any one of a carbon substrate, a titanium substrate, a nickel substrate, or a copper substrate.
14. The method according to claim 13, wherein the substrate in the step (2) is selected from any one of carbon paper, carbon felt, carbon fiber paper, carbon fiber woven cloth, mesh titanium substrate, mesh nickel substrate and mesh copper substrate.
15. The method according to claim 1, wherein the coating is performed by any one or a combination of at least two of coating, screen printing, spin coating, and spray coating.
16. The method of claim 1, wherein the coating has a thickness of 10 to 60 μm.
17. The method of claim 16, wherein the coating has a thickness of 30 to 50 μm.
18. The method according to claim 1, wherein the inert gas atmosphere is any one of nitrogen, argon or helium or a combination of at least two thereof.
19. The method as claimed in claim 1, wherein the drying temperature is 200-700 ℃.
20. The method as claimed in claim 19, wherein the drying temperature is 400-600 ℃.
21. The method as claimed in claim 20, wherein the drying temperature is 500-580 ℃.
22. The method of claim 1, wherein the drying time is 30 to 90 minutes.
23. The method of claim 22, wherein the drying time is 30 to 80 minutes.
24. The method according to claim 1, wherein the carbon material is supported in the microporous layer of the gas diffusion layer in an amount of 0.5 to 8.0mg/cm2。
25. The method according to claim 24, wherein the carbon material is supported in the microporous layer of the gas diffusion layer in an amount of 0.8 to 3.0mg/cm2。
26. The method of claim 1, comprising the steps of:
(1) adding a carbon material and a hydrophobic agent into an aqueous solution of polyvinylpyrrolidone, stirring and ultrasonically dispersing for 20-80 minutes, wherein the power of ultrasonic is 200-1000W to obtain microporous layer slurry, adding a precursor of a water electrolysis promoting catalyst, stirring to obtain the treated microporous layer slurry, and controlling the loading amount of the carbon material in the microporous layer of the gas diffusion layer to be 0.5-8.0mg/cm2The mass of the water repellent agent is 10-30% of the mass of the carbon material, and the mass ratio of the precursor of the water electrolysis promoting catalyst to the carbon material is 0.02-0.15;
(2) and (2) coating the microporous layer slurry treated in the step (1) on a substrate to ensure that the coating thickness is 10-60 mu m, and heating to 200-700 ℃ in an inert atmosphere for 30-90 minutes until the water electrolysis catalyst precursor is decomposed to obtain the gas diffusion layer.
27. A gas diffusion layer produced by the production method according to any one of claims 1 to 26.
28. A gas diffusion layer according to claim 27 comprising a microporous layer having pore sizes in the range of 50 to 300 nm.
29. A gas diffusion layer according to claim 28, wherein the microporous layer has pore sizes in the range of 80 to 120 nm.
30. The gas diffusion layer of claim 28, wherein the microporous layer has a water electrolysis promoting catalyst to carbon material mass ratio of 0.02 to 0.15.
31. The gas diffusion layer of claim 30, wherein the microporous layer has a water electrolysis promoting catalyst to carbon material mass ratio of 0.05-0.1.
32. A gas diffusion layer according to claim 28, wherein the microporous layer has a thickness of 10 to 60 μm.
33. A gas diffusion layer according to claim 28, wherein the microporous layer has a thickness of 30 to 50 μm.
34. A gas diffusion electrode comprising a gas diffusion layer according to claim 27.
35. A fuel cell comprising a gas diffusion electrode according to claim 34.
36. A method for reducing corrosion of a carbon carrier in an anode catalyst layer of a fuel cell under a reverse working condition is characterized in that when a gas diffusion layer is prepared, a water electrolysis promoting catalyst precursor is mixed into microporous layer slurry to obtain treated microporous layer slurry, then the treated microporous layer slurry is coated on a substrate and dried in an inert atmosphere until the water electrolysis promoting catalyst precursor is decomposed to obtain the gas diffusion layer with the micropores of 50-300nm, wherein the water electrolysis promoting catalyst precursor is selected from any one or a combination of at least two of inorganic salts containing ruthenium, iridium, palladium, platinum, nickel, cobalt or copper.
37. The method of claim 36, wherein the water electrolysis catalyst precursor is any one of chloride, carbonate or nitrate salts or a combination of at least two of ruthenium, iridium, palladium, platinum, nickel, cobalt or copper.
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