CN113497235A - Fuel cell membrane electrode, preparation method thereof and fuel cell - Google Patents

Fuel cell membrane electrode, preparation method thereof and fuel cell Download PDF

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CN113497235A
CN113497235A CN202010191469.3A CN202010191469A CN113497235A CN 113497235 A CN113497235 A CN 113497235A CN 202010191469 A CN202010191469 A CN 202010191469A CN 113497235 A CN113497235 A CN 113497235A
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fuel cell
layer
membrane electrode
catalytic layer
cathode
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CN113497235B (en
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李目武
许永亮
周飞鲲
洪绍景
田冬伟
袁述
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Guangzhou Automobile Group Co Ltd
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • 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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    • 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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Abstract

为克服现有燃料电池中存在的反极现象，导致膜电极性能衰减的问题，本发明提供了一种燃料电池膜电极，包括质子交换膜和催化层，所述催化层包括阳极催化层和阴极催化层，所述阳极催化层和所述阴极催化层分别设置于所述质子交换膜的两侧，所述催化层的组分包括催化活性组分和抗反极材料，所述抗反极材料包括IrO2、RuO2、NiO和CoO中的一种或多种。同时，本发明还公开了上述燃料电池膜电极的制备方法及燃料电池。本发明提供的燃料电池膜电极有效抑制反极过程中反向电压对催化层中碳载体的腐蚀现象，从而延缓了燃料电池性能的衰减，延长了燃料电池的使用寿命。

Figure 202010191469

In order to overcome the problem of the reverse polarity phenomenon existing in the existing fuel cell, which leads to the performance degradation of the membrane electrode, the present invention provides a fuel cell membrane electrode, which includes a proton exchange membrane and a catalytic layer, and the catalytic layer includes an anode catalytic layer and a cathode. A catalytic layer, the anode catalytic layer and the cathode catalytic layer are respectively disposed on both sides of the proton exchange membrane, and the components of the catalytic layer include catalytically active components and anti-reverse materials, and the anti-reverse materials One or more of IrO 2 , RuO 2 , NiO and CoO are included. At the same time, the present invention also discloses a preparation method of the above-mentioned fuel cell membrane electrode and a fuel cell. The membrane electrode of the fuel cell provided by the invention effectively inhibits the corrosion phenomenon of the carbon carrier in the catalytic layer caused by the reverse voltage in the reverse process, thereby delaying the deterioration of the performance of the fuel cell and prolonging the service life of the fuel cell.

Figure 202010191469

Description

Fuel cell membrane electrode, preparation method thereof and fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a fuel cell membrane electrode, a preparation method thereof and a fuel cell.
Background
The fuel cell automobile has the advantages of environmental protection, high efficiency, short fuel filling time, long endurance and the like, and is an important development direction of new energy automobiles. The fuel cell stack is a core component of a fuel cell automobile, and the membrane electrode is one of the most important components in the fuel cell stack, and influences the service life and the performance of the fuel cell stack.
Under the dynamic working condition of a vehicle, the conditions of frequent start-stop and rapid load change can occur, particularly, when the load changes greatly, the situation that the fuel supply is insufficient or untimely can occur, so that the electric pile is in a hunger state, and serious gas shortage can cause that a certain single cell or a plurality of cells in the electric pile have extremely low voltage and even become negative voltage, so that the electric pile has a reverse pole phenomenon. In the reverse polarity process, two reactions of electrolytic water and carbon corrosion exist in the catalyst layer, and the carbon corrosion can destroy the structure of the catalyst layer, so that active metal particles on the carbon carrier can fall off and agglomerate, and the active area of the catalyst is reduced. Meanwhile, the hydrophilicity and hydrophobicity and porosity of the catalyst layer structure are also changed by the corrosion of the carbon carrier, so that the catalyst layer is possibly separated from the proton exchange membrane, and a microporous layer on a gas diffusion layer in contact with the catalyst layer is corroded by long-time reverse polarity, so that the structure of the whole membrane electrode is damaged. Therefore, the reverse electrode can cause the membrane electrode structure to generate irreversible damage, the internal resistance of the electric pile is increased, the attenuation of the electric pile performance is accelerated, and the performance and the service life of the fuel cell automobile electric pile are seriously influenced, so that the improvement of the reverse electrode resistance of the membrane electrode is one of the problems which are urgently needed to be solved by the current automobile electric pile.
Disclosure of Invention
Aiming at the problem of membrane electrode performance attenuation caused by a reverse pole phenomenon in the existing fuel cell, the membrane electrode of the fuel cell, the preparation method thereof and the fuel cell are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a fuel cell membrane electrode, which comprises a proton exchange membrane and a catalyst layer, wherein the catalyst layer comprises an anode catalyst layer and a cathode catalyst layer, the anode catalyst layer and the cathode catalyst layer are respectively arranged at two sides of the proton exchange membrane, the catalyst layer comprises a catalytic active component and an anti-reversal material, and the anti-reversal material comprises IrO2、RuO2NiO and CoO.
Optionally, the catalytic layer comprises the following components by weight:
1-40 parts of catalytic active component and 1-20 parts of anti-reversal electrode material.
Optionally, the mass fraction of the anti-reversal electrode material in the anode catalyst layer is 1-20%, and the mass fraction of the anti-reversal electrode material in the cathode catalyst layer is 1-10%.
Optionally, the thickness of the anode catalyst layer is 5-10 μm, and the thickness of the cathode catalyst layer is 8-20 μm.
Optionally, the catalytic active component and the anti-reversal electrode material are mixed in the catalytic layer in a granular manner, the grain size of the catalytic active component is 3-8 nm, and the grain size of the anti-reversal electrode material is 10-100 nm.
Optionally, the catalytic active component includes a carbon carrier and an active metal, the active metal includes one or more of Pt, Au, Ru, Rh, Pd, Ag, Ir, Co, Fe, Ni, and Mn, and the mass fraction of the active metal in the catalytic active component is 10-70%.
Optionally, the catalytic layer further comprises the following components by weight:
5-30 parts of proton conductor polymer.
Optionally, the current density reduction rate of the membrane electrode of the fuel cell is less than or equal to 7.8% under the same test condition after reverse voltage of-1.0V is applied and the reverse electrode is performed for 5 min.
Optionally, the gas diffusion layer is located outside the catalyst layer, the gas diffusion layer comprises an anode gas diffusion layer and a cathode gas diffusion layer, the anode gas diffusion layer is located outside the anode catalyst layer, the thickness of the anode gas diffusion layer is 50-200 μm, the cathode gas diffusion layer is located outside the cathode catalyst layer, and the thickness of the cathode gas diffusion layer is 20-150 μm.
Optionally, the gas diffusion layer includes a substrate layer and a microporous layer, the microporous layer is located on one side of the substrate layer facing the catalytic layer, the substrate layer is a porous carbon paper, the microporous layers are porous carbon layers, and an average pore diameter of the microporous layer is smaller than an average pore diameter of the substrate layer.
In another aspect, the present invention provides a method for preparing a fuel cell membrane electrode as described above, comprising the following steps:
dispersing a catalytic active component and an anti-counter electrode material in a solvent to prepare anode catalyst slurry and cathode catalyst slurry, wherein the anti-counter electrode material comprises IrO2、RuO2One or more of NiO and CoO;
and respectively applying the anode catalyst slurry and the cathode catalyst slurry to two side surfaces of the proton exchange membrane, and drying to obtain an anode catalyst layer and a cathode catalyst layer.
Optionally, before the anode catalyst slurry and the cathode catalyst slurry are applied, the proton exchange membrane is placed in 5% -10% hydrogen peroxide for soaking for 0.5-2 hours at the treatment temperature of 60-100 ℃, and is treated with 0.5-12 mol/L sulfuric acid for 0.5-1 hour after soaking at the treatment temperature of 60-80 ℃, and is dried at the temperature of 60-100 ℃ after being cleaned, so that the pretreated proton exchange membrane is obtained.
In another aspect, the present invention provides a fuel cell comprising a fuel cell membrane electrode as described above.
According to the fuel cell membrane electrode provided by the invention, the anti-reversal electrode material is added in the catalyst layer, and the catalyst layer added with the anti-reversal electrode material can effectively reduce the decomposition voltage of water in the catalyst layer and improve the decomposition reaction rate of water, so that when the reversal electrode phenomenon occurs, water can be preferentially electrolyzed to consume the reversal voltage generated by the reversal electrode, and the corrosion phenomenon of the reversal voltage to a carbon carrier in the catalyst layer is relatively inhibited, thereby effectively delaying the performance attenuation of the fuel cell and prolonging the service life of the fuel cell.
Drawings
FIG. 1 is a polarization characteristic curve before a reverse polarity test of a membrane electrode assembly for a fuel cell provided in example 1 of the present invention and comparative example 1;
fig. 2 is a polarization characteristic curve after a reverse polarity test of the fuel cell membrane electrode provided in example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a fuel cell membrane electrode, which comprises a proton exchange membrane and a catalyst layer, wherein the catalyst layer comprises an anode catalyst layer and a cathode catalyst layer, the anode catalyst layer and the cathode catalyst layer are respectively arranged at two sides of the proton exchange membrane, the catalyst layer comprises a catalytic active component and an anti-reversal material, and the anti-reversal material comprises IrO2、RuO2NiO and CoO.
The anti-reversal material is added in the catalyst layer of the fuel cell membrane electrode, and the catalyst layer added with the anti-reversal material can effectively reduce the decomposition voltage of water in the catalyst layer and improve the decomposition reaction rate of the water, so that when the reversal phenomenon occurs, the water can be preferentially consumed by the reverse voltage generated by the reversal electrode through electrolysis, the corrosion phenomenon of the reverse voltage to a carbon carrier in the catalyst layer is relatively inhibited, the performance attenuation of the fuel cell is effectively delayed, and the service life of the fuel cell is prolonged.
In some embodiments, the catalytic layer comprises the following components by weight:
1-40 parts of catalytic active component and 1-20 parts of anti-reversal electrode material.
If the content of the anti-electrode material is too low, the effect of inhibiting the corrosion of the carbon carrier is not obvious; if the content of the anti-reversal material is too high, the content of the catalytic active component is relatively reduced, and the electrical conversion efficiency of the catalytic layer is affected.
In some embodiments, the mass fraction of the anti-reversal material in the anode catalyst layer is 1-20%, and the mass fraction of the anti-reversal material in the cathode catalyst layer is 1-10%.
The anode catalyst layer is in a high potential under the action of reverse voltage, so that the corrosion of the carbon carrier is more easily caused, and correspondingly, the content of the anti-reversal electrode material in the anode catalyst layer is higher than that in the cathode catalyst layer, so that the corrosion of the carbon carrier in the anode catalyst layer can be effectively inhibited.
In some embodiments, the thickness of the proton exchange membrane is 8 to 50 μm.
In some embodiments, the thickness of the anode catalytic layer is 5-10 μm, and the thickness of the cathode catalytic layer is 8-20 μm.
In some embodiments, the catalytic active component and the anti-reversal electrode material are mixed in the catalytic layer in a granular form, the grain diameter of the catalytic active component is 3-8 nm, and the grain diameter of the anti-reversal electrode material is 10-100 nm.
It should be noted that by mixing the catalytically active component and the anti-reversal material with each other in the form of particles, functional interaction between the catalytically active component and the anti-reversal material can be avoided as much as possible.
In some embodiments, the catalytically active component comprises a carbon support and an active metal, the active metal comprises one or more of Pt, Au, Ru, Rh, Pd, Ag, Ir, Co, Fe, Ni and Mn, and the mass fraction of the active metal in the catalytically active component is 10-70%.
The content of impurities in the catalytic active component is not more than 0.1%.
In a more preferred embodiment, the catalytically active component is selected from one or more of Pt/C, PtNi/C, PtCo/C and PtPd/C.
The loading capacity of active metal in the cathode catalyst layer is 0.1-0.2 mg/cm2。
The loading capacity of active metal in the anode catalyst layer is 0.05-0.1 mg/cm2。
In some embodiments, the catalytic layer further comprises the following components by weight:
5-30 parts of proton conductor polymer.
The proton conductor polymer is selected from perfluorosulfonic acid polymers, the perfluorosulfonic acid polymers are added into the catalyst layer, so that the bonding strength between the catalytic active component and the anti-reversal electrode material can be effectively improved, a certain mechanical strength is kept, the catalytic active component and the anti-reversal electrode material are prevented from falling off the proton exchange membrane, and on the other hand, the perfluorosulfonic acid polymers can effectively improve the proton shuttling efficiency and reduce the internal resistance.
In some embodiments, the catalytic layer has a mass ratio of the catalytically active component to the proton conductor polymer of 2:1 to 6: 1.
In some embodiments, the proton exchange membrane further comprises a double-layer frame, the double-layer frame is arranged around the edge of the catalyst layer, and the proton exchange membrane is clamped in the double-layer frame.
Through double-deck frame can be right proton exchange membrane fixes, avoids the catalytic layer material to drop because proton exchange membrane's deformation, simultaneously double-deck frame is used for avoiding the anode gas diffusion layer and the cathode gas diffusion layer of both sides to produce the electricity and connects the short circuit.
In some embodiments, the thickness of the double-layer frame is 50-200 μm, and the double-layer frame is selected from thermoplastic resin.
In some preferred embodiments, the current density reduction rate of the fuel cell membrane electrode is less than or equal to 7.8% under the same test conditions after reverse voltage is applied for-1.0V and the time is 5min after reverse polarity.
In some embodiments, the gas diffusion layer is positioned on the outer side of the catalyst layer and comprises an anode gas diffusion layer and a cathode gas diffusion layer, the anode gas diffusion layer is positioned on the outer side of the anode catalyst layer, the thickness of the anode gas diffusion layer is 50-200 μm, the cathode gas diffusion layer is positioned on the outer side of the cathode catalyst layer, and the thickness of the cathode gas diffusion layer is 20-150 μm.
The gas diffusion layer can play a role in supporting the catalyst layer and providing an electronic channel, a gas channel and a drainage channel for electrode reaction.
In some embodiments, the gas diffusion layer comprises a substrate layer and a microporous layer, the microporous layer is located on the side of the substrate layer facing the catalytic layer, the substrate layer is a porous carbon paper, the microporous layers are porous carbon layers, and the average pore size of the microporous layer is smaller than the average pore size of the substrate layer.
The porous carbon paper has good air permeability and hydrophobicity, can effectively promote the diffusion of gas and moisture, and simultaneously plays a role in electronic conduction; the microporous layer with smaller pore diameter is arranged on one side of the porous carbon paper facing the catalytic layer, so that the contact area between the gas diffusion layer and the catalytic layer can be effectively increased, the contact resistance is further reduced, and substances in the catalytic layer can be prevented from being mixed into the gas diffusion layer.
Another embodiment of the present invention provides a method for preparing a fuel cell membrane electrode as described above, comprising the following steps of:
dispersing a catalytic active component and an anti-counter electrode material in a solvent to prepare anode catalyst slurry and cathode catalyst slurry, wherein the anti-counter electrode material comprises IrO2、RuO2One or more of NiO and CoO;
and respectively applying the anode catalyst slurry and the cathode catalyst slurry to two side surfaces of the proton exchange membrane, and drying to obtain an anode catalyst layer and a cathode catalyst layer.
In some embodiments, before the anode catalyst slurry and the cathode catalyst slurry are applied, the proton exchange membrane is soaked in 5-10% hydrogen peroxide for 0.5-2 hours at a treatment temperature of 60-100 ℃, then treated with 0.5-12 mol/L sulfuric acid for 0.5-1 hour at a treatment temperature of 60-80 ℃, cleaned, and dried at 60-100 ℃ to obtain the pretreated proton exchange membrane.
In some embodiments, the solvent comprises one or more of isopropanol, ethylene glycol, glycerol.
The solid content of the anode catalyst slurry and the solid content of the cathode catalyst slurry are both 1-5%.
In some embodiments, a perfluorosulfonic acid polymer is also added to the anode catalyst slurry and the cathode catalyst slurry.
Specifically, a solvent is placed in a container, a catalytic active component is added and stirred to be dispersed, the stirring speed is 1000-2000 rpm, a perfluorosulfonic acid polymer solution is added, ultrasonic dispersion is carried out, the frequency of ultrasonic dispersion is 20-40 KHz, an anti-reversal material is added into the slurry, and the mixture is uniformly mixed, so that anode catalyst slurry and cathode catalyst slurry are obtained.
In some embodiments, a proton exchange membrane covered with an anode catalyst layer and a cathode catalyst layer is placed between double-layer frames, and is packaged and clamped through the double-layer frames, an anode gas diffusion layer and a cathode gas diffusion layer are taken, the anode gas diffusion layer is placed on the outer side of the anode catalyst layer, the cathode gas diffusion layer is placed on the outer side of the cathode catalyst layer, and the fuel cell membrane electrode is obtained through hot press molding.
Another embodiment of the present invention provides a fuel cell comprising the fuel cell membrane electrode as described above.
Due to the adoption of the fuel cell membrane electrode, the fuel cell has better anti-reversal performance, can effectively relieve the corrosion condition of the carbon carrier in the actual working condition of a vehicle, and effectively prolongs the service life of the cell.
The present invention will be further illustrated by the following examples.
Example 1
This example is used to illustrate a membrane electrode assembly for a fuel cell and a method for manufacturing the same, which includes the following steps:
respectively taking the components with mass fraction of 40%Respectively adding Pt/C catalysts into two beakers, firstly adding a small amount of isopropanol solution into each beaker, stirring to dissolve the catalysts, respectively adding isopropanol into another two beakers, adding a perfluorinated sulfonic acid polymer solution with the mass content of 20% into the two beakers, ultrasonically stirring uniformly, respectively pouring the perfluorinated sulfonic acid polymer-containing solution into the two beakers containing the Pt/C catalysts, alternately carrying out ultrasonic and stirring mixing for 60min, preparing catalyst slurry which is uniformly dispersed and mixed, and weighing IrO2Adding into catalyst slurry, and alternately performing ultrasonic treatment and stirring for 60 min. In the catalyst slurry, Pt/C catalyst: perfluorosulfonic acid polymer: IrO2The mass ratio of (A) to (B) is 2.5: 1: 1.
preparing a three-in-one membrane electrode by adopting an ultrasonic automatic spraying mode, mounting a pretreated proton exchange membrane on a spraying clamp, fastening the membrane electrode by bolts, then placing the membrane electrode on the table surface of a spraying instrument, setting the spraying temperature to be 90 ℃, the spraying speed to be 2.0ml/min, the spraying air pressure to be 25psi and the nozzle moving speed to be 100mm/s, respectively spraying prepared catalyst slurry on two sides of the proton exchange membrane, sequentially forming a cathode catalyst layer and an anode catalyst layer, wherein the total content of Pt in the cathode catalyst layer is 0.2mg/cm2. The Pt content of the anode catalyst layer is 0.1mg/cm2. And after the spraying is finished, baking for 5 hours in a 60 ℃ oven, then packaging and clamping the three-in-one membrane electrode by using a double-layer frame to prepare a five-in-one membrane electrode, finally taking two cut gas diffusion layers, sticking the two gas diffusion layers on two sides of the five-in-one membrane electrode, performing hot press molding, and sealing the frame to finish the preparation of the single-sheet seven-in-one fuel cell membrane electrode.
Example 2
This example is used to illustrate a fuel cell membrane electrode and a method for manufacturing the same disclosed in the present invention, and most of the operation steps in example 1 are different in that:
in the catalyst slurry, Pt/C catalyst: perfluorosulfonic acid polymer: IrO2The mass ratio of (A) to (B) is 2.5: 1: 0.25.
example 3
This example is used to illustrate a fuel cell membrane electrode and a method for manufacturing the same disclosed in the present invention, and most of the operation steps in example 1 are different in that:
in the catalyst slurry, Pt/C catalyst: perfluorosulfonic acid polymer: IrO2The mass ratio of (A) to (B) is 2.5: 1: 0.5.
example 4
This example is used to illustrate a fuel cell membrane electrode and a method for manufacturing the same disclosed in the present invention, and most of the operation steps in example 1 are different in that:
in the catalyst slurry, Pt/C catalyst: perfluorosulfonic acid polymer: IrO2The mass ratio of (A) to (B) is 2.5: 1: 1.5.
comparative example 1
This example is for comparative illustration of a fuel cell membrane electrode and a method for preparing the same, which includes most of the steps of example 1, except that:
no IrO is added to the catalyst slurry2。
Performance testing
Firstly, the fuel cell membrane electrode prepared in example 1 and comparative example 1 was subjected to the following performance tests:
and (3) testing conditions are as follows: the cell temperature was set at 85 ℃, the anode inlet pressure was 1.7bar (gauge pressure), the anode inlet humidity was 50%, the anode metering ratio was 2.0, the cathode inlet pressure was 1.5bar (gauge pressure), the cathode inlet humidity was 50%, and the cathode metering ratio was 1.5.
The fuel cell membrane electrode was placed in a cell jig for performance testing, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the current density of the membrane electrode assembly for a fuel cell prepared in example 1 was 1298mA/cm2@0.6V, power density up to 778.8mW/cm2(ii) a The current density of the fuel cell membrane electrode prepared in comparative example 1 was 1289mA/cm2@0.6V, power density up to 773.4mW/cm2. The initial performance of both before doing the reversal is similar.
And then simulating the reverse polarity behavior of the membrane electrode of the fuel cell, applying reverse voltage of-1.0V to the membrane electrode, and performing performance test after reversing for 5min, wherein the performance is shown in figure 2.
As can be seen from FIG. 2, the current density of the membrane electrode of the fuel cell prepared in example 1 was 1250mA/cm2@0.6V, only a 3.7% decrease. The current density of the membrane electrode of the fuel cell prepared in the comparative example 1 is only 723mA/cm2@0.6V, a 44% reduction in performance compared to before reversal.
Secondly, the fuel cell membrane electrodes obtained in examples 1 to 4 and comparative example 1 were subjected to the above performance test, and the test results are filled in table 1.
TABLE 1
Figure BDA0002416071920000081
From the test results in table 1, the fuel cell membrane electrode provided by the invention can effectively inhibit the corrosion of carbon materials in the process of the counter electrode, and improve the service life of the fuel cell, and meanwhile, the counter electrode resistance effect is in positive correlation with the addition amount of the counter electrode resistance material, but the addition amount of the counter electrode resistance material is not too much, which can affect the original performance of the fuel cell.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (13)

1.一种燃料电池膜电极，其特征在于，包括质子交换膜和催化层，所述催化层包括阳极催化层和阴极催化层，所述阳极催化层和所述阴极催化层分别设置于所述质子交换膜的两侧，所述催化层的组分包括催化活性组分和抗反极材料，所述抗反极材料包括IrO2、RuO2、NiO和CoO中的一种或多种。1. A fuel cell membrane electrode, characterized in that it comprises a proton exchange membrane and a catalytic layer, the catalytic layer comprises an anode catalytic layer and a cathode catalytic layer, and the anode catalytic layer and the cathode catalytic layer are respectively arranged on the On both sides of the proton exchange membrane, the components of the catalytic layer include catalytically active components and anti-reverse pole materials, and the anti-reverse pole materials include one or more of IrO 2 , RuO 2 , NiO and CoO. 2.根据权利要求1所述的燃料电池膜电极，其特征在于，所述催化层包括以下重量组分：2. The fuel cell membrane electrode according to claim 1, wherein the catalytic layer comprises the following weight components: 催化活性组分1～40份和抗反极材料1～20份。1-40 parts of catalytic active components and 1-20 parts of anti-reverse material. 3.根据权利要求1所述的燃料电池膜电极，其特征在于，所述阳极催化层中抗反极材料的质量分数为1～20％，所述阴极催化层中抗反极材料的质量分数为1～10％。3 . The fuel cell membrane electrode according to claim 1 , wherein the mass fraction of the anti-reverse electrode material in the anode catalytic layer is 1-20%, and the mass fraction of the anti-reverse electrode material in the cathode catalytic layer is 1-20%. 4 . 1 to 10%. 4.根据权利要求1所述的燃料电池膜电极，其特征在于，所述阳极催化层的厚度为5-10μm，所述阴极催化层的厚度为8～20μm。4 . The fuel cell membrane electrode according to claim 1 , wherein the anode catalytic layer has a thickness of 5-10 μm, and the cathode catalytic layer has a thickness of 8-20 μm. 5 . 5.根据权利要求1所述的燃料电池膜电极，其特征在于，所述催化活性组分和所述抗反极材料以颗粒状混合于所述催化层中，所述催化活性组分的颗粒粒径为3～8nm，所述抗反极材料的颗粒粒径为10～100nm。5 . The fuel cell membrane electrode according to claim 1 , wherein the catalytically active component and the anti-reverse electrode material are mixed in the catalytic layer in granular form, and the particles of the catalytically active component are mixed in the catalytic layer. 6 . The particle size is 3-8 nm, and the particle size of the anti-reverse electrode material is 10-100 nm. 6.根据权利要求1所述的燃料电池膜电极，其特征在于，所述催化活性组分包括碳载体和活性金属，所述活性金属包括Pt、Au、Ru、Rh、Pd、Ag、Ir、Co、Fe、Ni、Mn中的一种或多种，所述催化活性组分中活性金属的质量分数为10～70％。6. The fuel cell membrane electrode according to claim 1, wherein the catalytically active component comprises a carbon support and an active metal, and the active metal comprises Pt, Au, Ru, Rh, Pd, Ag, Ir, One or more of Co, Fe, Ni, and Mn, and the mass fraction of the active metal in the catalytically active component is 10-70%. 7.根据权利要求2所述的燃料电池膜电极，其特征在于，所述催化层还包括以下重量组分：7. The fuel cell membrane electrode according to claim 2, wherein the catalytic layer further comprises the following weight components: 质子导体聚合物5～30份。5-30 parts of proton conductor polymer. 8.根据权利要求1所述的燃料电池膜电极，其特征在于，施加反向电压-1.0V，反极5min钟后，相同测试条件下，所述燃料电池膜电极的电流密度降低率≤7.8％。8 . The fuel cell membrane electrode according to claim 1 , wherein the current density reduction rate of the fuel cell membrane electrode is less than or equal to 7.8 under the same test conditions after applying a reverse voltage of -1.0V and reverse polarity for 5 minutes. 9 . %. 9.根据权利要求1所述的燃料电池膜电极，其特征在于，还包括有位于所述催化层外侧的气体扩散层，所述气体扩散层包括阳极气体扩散层和阴极气体扩散层，所述阳极气体扩散层位于所述阳极催化层的外侧，所述阳极气体扩散层的厚度为50～200μm，所述阴极气体扩散层位于所述阴极催化层的外侧，所述阴极气体扩散层的厚度为20～150μm。9 . The fuel cell membrane electrode according to claim 1 , further comprising a gas diffusion layer located outside the catalytic layer, the gas diffusion layer comprising an anode gas diffusion layer and a cathode gas diffusion layer, the The anode gas diffusion layer is located outside the anode catalytic layer, the thickness of the anode gas diffusion layer is 50-200 μm, the cathode gas diffusion layer is located outside the cathode catalytic layer, and the thickness of the cathode gas diffusion layer is 20～150μm. 10.根据权利要求9所述的燃料电池膜电极，其特征在于，所述气体扩散层包括基底层和微孔层，所述微孔层位于所述基底层朝向所述催化层的一侧，所述基底层为多孔碳纸，所述微孔层均为多孔碳层，且所述微孔层的平均孔径小于所述基底层的平均孔径。10 . The fuel cell membrane electrode according to claim 9 , wherein the gas diffusion layer comprises a base layer and a microporous layer, and the microporous layer is located on the side of the base layer facing the catalytic layer, 11 . The base layer is porous carbon paper, the microporous layers are all porous carbon layers, and the average pore size of the microporous layer is smaller than the average pore size of the base layer. 11.如权利要求1～10任意一项所述的燃料电池膜电极的制备方法，其特征在于，包括以下操作步骤：11. The method for preparing a membrane electrode for a fuel cell according to any one of claims 1 to 10, characterized in that it comprises the following operation steps: 将催化活性组分和抗反极材料分散于溶剂中制备得到阳极催化剂浆料和阴极催化剂浆料，所述抗反极材料包括IrO2、RuO2、NiO和CoO中的一种或多种；Dispersing the catalytically active component and the anti-reverse electrode material in a solvent to prepare an anode catalyst slurry and a cathode catalyst slurry, the anti-reverse electrode material includes one or more of IrO 2 , RuO 2 , NiO and CoO; 将阳极催化剂浆料和阴极催化剂浆料分别施加至质子交换膜的两个侧面，干燥后，得到阳极催化层和阴极催化层。The anode catalyst slurry and the cathode catalyst slurry are respectively applied to two sides of the proton exchange membrane, and after drying, an anode catalyst layer and a cathode catalyst layer are obtained. 12.根据权利要求11所述的燃料电池膜电极的制备方法，其特征在于，在施加阳极催化剂浆料和阴极催化剂浆料之前，将质子交换膜置于5％～10％的双氧水中浸泡0.5～2h，处理温度为60～100℃，浸泡后用0.5～12mol/L的硫酸处理0.5～1h，处理温度为60～80℃，清洗后在60～100℃下干燥，得到预处理的质子交换膜。12 . The method for preparing a membrane electrode for a fuel cell according to claim 11 , wherein before applying the anode catalyst slurry and the cathode catalyst slurry, the proton exchange membrane is immersed in 5% to 10% hydrogen peroxide for 0.5 % ～2h, the treatment temperature is 60～100℃, after soaking, it is treated with 0.5～12mol/L sulfuric acid for 0.5～1h, the treatment temperature is 60～80℃, and after cleaning, it is dried at 60～100℃ to obtain the pretreated proton exchange membrane. 13.一种燃料电池，其特征在于，包括如权利要求1～10任意一项所述的燃料电池膜电极。13. A fuel cell, characterized by comprising the fuel cell membrane electrode according to any one of claims 1 to 10.
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