Membrane electrode assembly and membrane electrode

Abstract

The application relates to the technical field of fuel cells, in particular to a membrane electrode assembly and a membrane electrode. The membrane electrode assembly provided by the application comprises a proton exchange membrane, an anode catalytic layer and a cathode catalytic layer arranged on the two sides of the proton exchange membrane respectively, and an oxidation-resistant layer arranged between the proton exchange membrane and the anode catalytic layer. The membrane electrode assembly of the application contains the oxidation-resistant layer, which can effectively reduce the oxygen content in the anode catalytic layer during the start-stop process, cut off the electric circuit generated by the "reverse current mechanism" of the anode hydrogen-air interface during the start-stop process, thereby effectively inhibiting the oxidation of the cathode carbon material, and further enabling the membrane electrode to have the "anti-start-stop" protection function, significantly reducing the damage to the fuel cell membrane electrode during the start-stop process, and preventing the performance degradation of the battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fuel cell technology, in particular to a membrane electrode assembly and a membrane electrode. BACKGROUND

[0002] A hydrogen fuel cell is a device that can directly convert the chemical energy in hydrogen into electricity, with high energy conversion efficiency and no pollution. The membrane electrode is the "heart" of the hydrogen fuel cell, and the electrochemical reaction occurs in the membrane electrode. The membrane electrode is usually composed of an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer and a cathode gas diffusion layer. The anode catalyst layer undergoes hydrogen oxidation reaction (HOR), and is usually composed of Pt / C catalyst and proton-conducting resin. The cathode catalyst layer undergoes oxygen reduction reaction (ORR), and is also usually composed of Pt / C catalyst and proton-conducting resin. The proton exchange membrane is usually composed of perfluorosulfonic acid resin, and mainly functions to conduct protons and insulate electrons and gases. The anode and cathode gas diffusion layers are usually composed of carbon paper or carbon cloth and a single layer of microporous layer, and are used to transport air and hydrogen to the anode and cathode catalyst layers, respectively, and to discharge excess water.

[0003] During the start-stop process of the fuel cell, a certain amount of air is easily mixed into the anode catalyst layer, thereby forming a hydrogen-air interface, as shown in FIG. 1. The air area of the anode catalyst layer can undergo oxygen reduction reaction under the catalysis of the Pt / C catalyst, thereby raising the local potential of the cathode catalyst layer. The local (IV) potential of the cathode catalyst layer can even reach 2.0 V, which forces the water in the region to undergo oxygen evolution reaction (OER) and the carbon carrier to undergo carbon oxidation reaction (COR). Oxidation of the carbon carrier as a catalyst and carrier and the skeleton of the catalyst layer will cause a large amount of Pt to be lost, and even cause the skeleton of the catalyst layer to collapse, thereby seriously damaging the performance of the fuel cell. Figure 1 In the prior art, CN201180061661.X discloses an improved membrane electrode assembly for a PEM fuel cell, which has two electrode layers (EL1 and / or EL2), at least one of which contains a first electrocatalyst (EC1) comprising a combination of an iridium oxide component and at least one other inorganic oxide component; and a second electrocatalyst (EC2 / EC2') which does not contain iridium. Preferably, an iridium oxide / titanium dioxide catalyst is used as EC1. These membrane electrodes exhibit good performance, especially under various severe operating conditions such as fuel shortage and start / stop cycles. However, this design inhibits the corrosion of the cathode carbon material by accelerating the water electrolysis reaction with iridium oxide to prevent the degradation of the performance of the fuel cell, which cannot fundamentally eliminate the degradation mechanism during the start-stop process, and the protection effect is limited.

[0004] SUMMARY

[0005] ​In view of the above, the present application provides a membrane electrode assembly, comprising: a proton exchange membrane;

[0006] and an anode catalytic layer and a cathode catalytic layer respectively arranged on two sides of the proton exchange membrane;

[0007] and an oxidation-resistant layer further arranged between the proton exchange membrane and the anode catalytic layer.

[0008] As a preferred embodiment of the present application, the membrane electrode assembly further comprises: an oxidation-resistant layer further arranged on a side of the anode catalytic layer away from the proton exchange membrane.

[0009] When two oxidation-resistant layers are contained, the oxidation-resistant agents therein can be the same or different.

[0010] As a preferred embodiment of the present application, the thickness ratio of the oxidation-resistant layer to the anode catalytic layer is less than 1:2.

[0011] As a preferred embodiment of the present application, the oxidation-resistant agent in the oxidation-resistant layer is at least one of polyphenol, butylated hydroxyanisole, butylated hydroxytoluene, tertiary butylated hydroquinone, and vitamin C.

[0012] As a preferred embodiment of the present application, the oxidation-resistant agent accounts for 10% to 70% of the weight percentage of the oxidation-resistant layer.

[0013] As a preferred embodiment of the present application, the oxidation-resistant layer contains a perfluorosulfonic acid resin.

[0014] As a preferred embodiment of the present application, the perfluorosulfonic acid resin accounts for 30% to 90% of the weight percentage of the oxidation-resistant layer.

[0015] As a preferred embodiment of the present application, the anode catalyst in the anode catalytic layer is a catalyst capable of catalyzing the hydrogen oxidation reaction, and is preferably at least one of Pt / C, PtRu / C, PtIr / C, PtCo / C, PtCoMn / C, PtNi / C, Ir / C, Ru / C, and IrRu / C.

[0016] As a preferred embodiment of the present application, the cathode catalyst in the cathode catalytic layer is Pt / C.

[0017] As a preferred embodiment of the present application, the anode catalytic layer further comprises: a perfluorosulfonic acid resin;

[0018] Preferably, the perfluorosulfonic acid resin accounts for 8% to 40% of the weight percentage of the anode catalytic layer.

[0019] As a preferred embodiment of the present application, the proton exchange membrane contains perfluorosulfonic acid resin.

[0020] Further, the present application provides a membrane electrode assembly comprising:

[0021] The membrane electrode assembly in any of the above embodiments; and gas diffusion layers arranged on both sides of the membrane electrode assembly.

[0022] As a preferred embodiment of the present application, the gas diffusion layer is carbon fiber paper or carbon fiber cloth coated with carbon powder on the surface.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] The membrane electrode assembly of the present application contains an antioxidant layer, which can effectively reduce the oxygen content in the anode catalytic layer during start-stop process (pipe penetration, cathode catalytic penetration, etc.), cut off the electric circuit generated by the "reverse current mechanism" of the anode hydrogen-air interface during start-stop process, thereby effectively inhibiting the oxidation of the cathode carbon material, and further providing the membrane electrode with "anti-start-stop" protection function, significantly reducing the damage to the fuel cell membrane electrode during start-stop process, and preventing the performance degradation of the cell. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0026] Figure 1 is a schematic diagram of the "reverse current mechanism" of the membrane electrode of the prior art.

[0027] Figure 2 is a schematic diagram of the design principle of the membrane electrode assembly with "anti-start-stop" protection function of the present application.

[0028] Figure 3 is a schematic diagram of the structure of the membrane electrode assembly provided by the present application.

[0029] Figure 4 is a schematic diagram of the structure of the membrane electrode assembly provided by the present application.

[0030] Figure 5 is a schematic diagram of the structure of the membrane electrode provided by the present application.

[0031] Figure 6 is a schematic diagram of the structure of the membrane electrode provided by the present application.

[0032] Figures 3-6In the figure, 1 represents a proton exchange membrane; 2 represents a cathode catalytic layer; 3 represents an anode catalytic layer; 4 and 5 represent oxidation-resistant layers; 6 represents a cathode gas diffusion layer; and 7 represents an anode gas diffusion layer. DETAILED DESCRIPTION

[0033] In order to make the objects, technical solutions and advantages of the present application clearer, the technical solutions in the present application will be clearly and completely described below with reference to the accompanying drawings in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0034] As an embodiment of the present application, the embodiment provides a membrane electrode assembly, comprising: a proton exchange membrane; and an anode catalytic layer and a cathode catalytic layer respectively arranged on two sides of the proton exchange membrane; and an oxidation-resistant layer further arranged between the proton exchange membrane and the anode catalytic layer. A structural schematic diagram of the membrane electrode assembly of the embodiment is shown in Figure 3 .

[0035] Through mechanism research, it is found that the "reverse current mechanism" shown in Figure 1 will occur on the membrane electrode used in the prior art. Specifically, a higher local high potential (>2.0V) is formed in the cathode catalytic layer, which accelerates the oxidation reaction of the carbon carrier, resulting in Pt loss and collapse of the cathode catalytic layer.

[0036] The present application designs a membrane electrode assembly, wherein an oxidation-resistant layer is arranged between the proton exchange membrane and the anode catalytic layer, which can effectively reduce the oxygen content (pipeline penetration, cathode catalytic penetration, etc.) in the anode catalytic layer during the start-stop process, cut off the electric circuit generated by the "reverse current mechanism" of the anode hydrogen-air interface during the start-stop process, thereby effectively inhibiting the oxidation of the cathode carbon material, and further enabling the membrane electrode to have a "start-stop resistant" protection function, significantly reducing the damage to the fuel cell membrane electrode during the start-stop process, and preventing the performance degradation of the battery. A design principle schematic diagram of the membrane electrode assembly with the "start-stop resistant" protection function of the present application is shown in Figure 2 .

[0037] As an embodiment of the present application, the membrane electrode assembly further comprises: an oxidation-resistant layer further arranged on the side of the anode catalytic layer away from the proton exchange membrane. A structural schematic diagram of the membrane electrode assembly of the embodiment is shown in Figure 4 .

[0038] As an embodiment of the present application, the oxidation-resistant agent in the oxidation-resistant layer is at least one of a polyphenol substance, butylated hydroxyanisole, dibutylhydroxytoluene, tertiary butyl hydroquinone, and vitamin C.

[0039] As an embodiment of the present application, the antioxidant accounts for 30% to 50% of the weight percentage of the antioxidant layer.

[0040] As an embodiment of the present application, the antioxidant layer contains a perfluorosulfonic acid resin.

[0041] As an embodiment of the present application, the perfluorosulfonic acid resin accounts for 50% to 70% of the weight percentage of the antioxidant layer.

[0042] As an embodiment of the present application, the anode catalyst in the anode catalytic layer is a catalyst capable of catalyzing the hydrogen oxidation reaction, preferably at least one of Pt / C, PtRu / C, PtIr / C, PtCo / C, PtCoMn / C, PtNi / C, Ir / C, Ru / C, and IrRu / C.

[0043] The present application finds that when a non-Pt catalyst is used to catalyze the hydrogen oxidation reaction, the non-Pt catalyst can work together with the antioxidant layer to further reduce the damage to the fuel cell membrane electrode during the start-stop process.

[0044] As an embodiment of the present application, the anode catalytic layer further comprises a perfluorosulfonic acid resin.

[0045] Preferably, the perfluorosulfonic acid resin accounts for 8% to 40% of the weight percentage of the anode catalytic layer.

[0046] As an embodiment of the present application, the proton exchange membrane contains a perfluorosulfonic acid resin.

[0047] As an embodiment of the present application, the cathode catalyst in the cathode catalytic layer is Pt / C.

[0048] As an embodiment of the present application, the present embodiment provides a membrane electrode, which has the structure of: a membrane electrode assembly of any of the above embodiments; and gas diffusion layers arranged on both sides of the membrane electrode assembly.

[0049] As an embodiment of the present application, the gas diffusion layer is a carbon fiber paper or carbon fiber cloth coated with carbon powder on the surface.

[0050] The structure of the above-mentioned membrane electrode is shown in Figure 5 or Figure 6 .

[0051] Since the membrane electrode of the present application contains the above-mentioned membrane electrode assembly with the "anti-start-stop" function, the membrane electrode in the above-mentioned embodiments also has the "anti-start-stop" function, which can significantly reduce the damage to the fuel cell membrane electrode during the start-stop process and prolong the service life of the membrane electrode.

[0052] The technical solutions and beneficial effects of the present application will be explained in more detail below in connection with more specific embodiments.

[0053] The specific techniques or conditions not specified in the following examples are all conventional methods or techniques described in the literature of the art or according to the product instructions. The reagents and instruments used, if not specified by the manufacturer, are all conventional products that can be purchased through regular channels.

[0054] Example 1

[0055] This embodiment provides a membrane electrode assembly, and the preparation method is as follows:

[0056] (1) 1 g of catalyst Pt / C (50 wt. % Pt) and 20 g of perfluorosulfonic acid resin solution (5 wt. %) are dispersed in 20 g of solvent, which is a mixture of water and n-propanol in a weight ratio of 1:1, and stirred at a speed of 8000 rpm after ultrasonic dispersion for 5 min to prepare an anode catalytic layer slurry;

[0057] 0.5 g of antioxidant tert-butyl-p-diphenol and 20 g of perfluorosulfonic acid resin solution (5 wt. %) are dispersed in 10 g of the above-mentioned solvent, and stirred at a speed of 8000 rpm after ultrasonic dispersion for 5 min to prepare an antioxidant layer slurry;

[0058] 1 g of catalyst Pt / C and 20 g of perfluorosulfonic acid resin solution (5 wt. %) are dispersed in 20 g of the above-mentioned solvent, and stirred at a speed of 8000 rpm after ultrasonic dispersion for 5 min to prepare a cathode catalytic layer slurry;

[0059] (2) The above-mentioned antioxidant layer slurry is sprayed on one side of the proton exchange membrane, and the above-mentioned anode catalytic layer slurry is sprayed after drying; and the above-mentioned cathode catalytic layer slurry is sprayed on the other side of the proton exchange membrane.

[0060] Further, the above-mentioned membrane electrode assembly is placed between two gas diffusion layers to prepare a membrane electrode, wherein the gas diffusion layer is a carbon fiber cloth.

[0061] Example 2

[0062] This embodiment provides a membrane electrode assembly, and the preparation method is as follows:

[0063] (1) 1 g of catalyst Pt / C (50 wt. % Pt) and 20 g of perfluorosulfonic acid resin solution (5 wt. %) are dispersed in 20 g of solvent, which is a mixture of water and n-propanol in a weight ratio of 1:1, and stirred at a speed of 8000 rpm after ultrasonic dispersion for 5 min to prepare an anode catalytic layer slurry;

[0064] An antioxidant layer slurry was prepared by dispersing 0.5 g of antioxidant butylated hydroxyanisole and 20 g of a perfluorosulfonic acid resin solution (5 wt.%) in 10 g of the above solvent, stirring at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min;

[0065] A cathode catalyst layer slurry was prepared by dispersing 1 g of catalyst Pt / C, 20 g of a perfluorosulfonic acid resin solution (5 wt.%) in 20 g of the above solvent, stirring at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min;

[0066] (2) The above antioxidant layer slurry was sprayed on one side of the proton exchange membrane, and the above anode catalyst layer slurry was sprayed after drying; the above cathode catalyst layer slurry was sprayed on the other side of the proton exchange membrane.

[0067] Further, the above membrane electrode assembly was placed between two gas diffusion layers to prepare a membrane electrode, wherein the gas diffusion layer was a carbon fiber cloth.

[0068] Example 3

[0069] The present example provides a membrane electrode assembly, and the preparation method is as follows:

[0070] (1) An anode catalyst layer slurry was prepared by dispersing 1 g of catalyst Pt / C (50 wt.% Pt) and 20 g of a perfluorosulfonic acid resin solution (5 wt.%) in 20 g of a solvent, which was a mixture of water and n-propanol in a weight ratio of 1:1, stirring at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min;

[0071] An antioxidant layer slurry was prepared by dispersing 0.5 g of antioxidant butylated hydroxyanisole and 20 g of a perfluorosulfonic acid resin solution (5 wt.%) in 10 g of the above solvent, stirring at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min;

[0072] A cathode catalyst layer slurry was prepared by dispersing 1 g of catalyst Pt / C, 20 g of a perfluorosulfonic acid resin solution (5 wt.%) in 20 g of the above solvent, stirring at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min;

[0073] (2) The above antioxidant layer slurry was sprayed on one side of the proton exchange membrane, and the above anode catalyst layer slurry was sprayed after drying; the above cathode catalyst layer slurry was sprayed on the other side of the proton exchange membrane.

[0074] Further, the above membrane electrode assembly was placed between two gas diffusion layers to prepare a membrane electrode, wherein the gas diffusion layer was a carbon fiber cloth.

[0075] Example 4

[0076] The present example provides a membrane electrode assembly, and the preparation method is as follows:

[0077] (1) 1 g of catalyst Ru / C (50 wt.% Pt) and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 20 g of solvent, which was a mixture of water and n-propanol in a weight ratio of 1:1, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare an anode catalytic layer slurry;

[0078] 0.5 g of antioxidant t-butyl-p-diphenol and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 10 g of the above-mentioned solvent, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare an antioxidant layer slurry;

[0079] 1 g of catalyst Pt / C and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 20 g of the above-mentioned solvent, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare a cathode catalytic layer slurry;

[0080] (2) The above-mentioned antioxidant layer slurry was sprayed on one side of a proton exchange membrane, and the above-mentioned anode catalytic layer slurry was sprayed after drying. The above-mentioned cathode catalytic layer slurry was sprayed on the other side of the proton exchange membrane.

[0081] Further, the above-mentioned membrane electrode assembly was placed between two gas diffusion layers, to prepare a membrane electrode, wherein the gas diffusion layers were carbon fiber papers coated with carbon powder on the surface.

[0082] Example 5

[0083] The present example provides a membrane electrode assembly, and the preparation method is as follows:

[0084] (1) 1 g of catalyst Ir / C (50 wt.% Ir) and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 20 g of solvent, which was a mixture of water and n-propanol in a weight ratio of 1:1, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare an anode catalytic layer slurry;

[0085] 0.5 g of antioxidant t-butyl-p-diphenol and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 10 g of the above-mentioned solvent, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare an antioxidant layer slurry;

[0086] 1 g of catalyst Pt / C and 20 g of perfluorosulfonic acid resin solution (5 wt.%) were dispersed in 20 g of the above-mentioned solvent, and stirred at a rotation speed of 8000 rpm after ultrasonic dispersion for 5 min, to prepare a cathode catalytic layer slurry;

[0087] (2) On one side of the proton exchange membrane, the above-mentioned oxidation-resistant layer slurry is sprayed, and after drying, the above-mentioned anode catalytic layer slurry is sprayed; on the other side of the proton exchange membrane, the above-mentioned cathode catalytic layer slurry is sprayed.

[0088] Further, the above-mentioned membrane electrode assembly is placed between two gas diffusion layers to obtain a membrane electrode, wherein the gas diffusion layers are carbon fiber papers coated with carbon powder.

[0089] Example 6

[0090] The present example provides a membrane electrode assembly, the preparation method of which is only different from that of Example 1 in that:

[0091] Step (2) On one side of the proton exchange membrane, the above-mentioned oxidation-resistant layer slurry is sprayed, and after drying, the above-mentioned anode catalytic layer slurry is sprayed, and after drying, a layer of the above-mentioned oxidation-resistant layer slurry is sprayed again; on the other side of the proton exchange membrane, the above-mentioned cathode catalytic layer slurry is sprayed.

[0092] Further, the above-mentioned membrane electrode assembly is placed between two gas diffusion layers to obtain a membrane electrode, wherein the gas diffusion layers are carbon fiber papers coated with carbon powder.

[0093] Comparative Example

[0094] The present comparative example provides a membrane electrode assembly, the preparation method of which is only different from that of Example 1 in that: no oxidation-resistant layer is provided.

[0095] Further, the above-mentioned membrane electrode assembly is placed between two gas diffusion layers to obtain a membrane electrode, wherein the gas diffusion layers are carbon fiber papers coated with carbon powder.

[0096] Test Example

[0097] The anti-start-stop ability of the membrane electrodes prepared in the examples and the comparative example is tested. Specifically:

[0098] The test method is as follows:

[0099] The membrane electrodes prepared in the examples and the comparative example with an active area of 25 cm 2 are assembled into a cell and activated. The activation conditions are: 80℃, anode hydrogen excess coefficient 1.5, cathode air excess coefficient 2.0, current density less than 400 mA / cm 2 , and the flow is supplied at a current density of 400 mA / cm 2 . The relative humidity is 100%, and the back pressure is 100 kPa / 100 kPa. After activation, the single cell polarization curve is tested, and the polarization curve is the same as the activation condition.

[0100] After the above experiment, start-stop acceleration experiment was started, and the acceleration experiment was referenced to the DOE test method, and the experimental conditions were as follows: 35°C, normal pressure. The whole acceleration experiment was 5000 cycles, and the steps in each cycle were shown in Table 1, and the air flow was a fixed value (excess coefficient 2.0, 1.0 A / cm 2 corresponding flow value under the current density). After the completion of the start-stop acceleration experiment, the polarization curve of the single cell was tested.

[0101] Table 1 Start-stop test method

[0102]

[0103] The test results are shown in Table 2.

[0104] Table 2 Comparison of anti-start-stop ability of examples and comparative examples

[0105]

[0106] As can be seen from Table 2, the membrane electrode of the application can effectively inhibit the oxidation of the cathode carbon material, and has the protection function of "anti-start-stop".

[0107] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the application, and not to limit them; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A membrane electrode assembly, characterized in that, include: Proton exchange membrane; And an anode catalyst layer and a cathode catalyst layer are respectively provided on both sides of the proton exchange membrane; An antioxidant layer is also provided between the proton exchange membrane and the anode catalyst layer; The anodic catalyst in the anodic catalyst layer is a non-Pt catalyst capable of catalyzing the hydrogenation reaction.

2. The membrane electrode assembly according to claim 1, characterized in that, Also includes: An antioxidant layer is also provided on the side of the anode catalyst layer away from the proton exchange membrane.

3. The membrane electrode assembly according to claim 1 or 2, characterized in that, The antioxidant in the antioxidant layer is at least one of polyphenols, butylated hydroxyanisole, butylated hydroxytoluene, tert-butyl-p-diphenol, and vitamin C.

4. The membrane electrode assembly according to claim 3, characterized in that, The antioxidant accounts for 10% to 70% of the weight of the antioxidant layer.

5. The membrane electrode assembly according to any one of claims 1, 2, or 4, characterized in that, The antioxidant layer contains perfluorosulfonic acid resin.

6. The membrane electrode assembly according to claim 3, characterized in that, The antioxidant layer contains perfluorosulfonic acid resin.

7. The membrane electrode assembly according to claim 5, characterized in that, The perfluorosulfonic acid resin accounts for 30% to 90% of the weight of the antioxidant layer.

8. The membrane electrode assembly according to claim 6, characterized in that, The perfluorosulfonic acid resin accounts for 30% to 90% of the weight of the antioxidant layer.

9. The membrane electrode assembly according to any one of claims 1, 2, 4, 6, 7 or 8, characterized in that, The non-Pt catalyst is at least one of Ir / C, Ru / C, and IrRu / C.

10. The membrane electrode assembly according to claim 3, characterized in that, The non-Pt catalyst is at least one of Ir / C, Ru / C, and IrRu / C.

11. The membrane electrode assembly according to claim 5, characterized in that, The non-Pt catalyst is at least one of Ir / C, Ru / C, and IrRu / C.

12. The membrane electrode assembly according to claim 9, characterized in that, The anode catalyst layer also includes: perfluorosulfonic acid resin.

13. The membrane electrode assembly according to claim 10 or 11, characterized in that, The anode catalyst layer also includes: perfluorosulfonic acid resin.

14. The membrane electrode assembly according to claim 12, characterized in that, The perfluorosulfonic acid resin accounts for 8% to 40% of the weight of the anode catalyst layer.

15. The membrane electrode assembly according to claim 13, characterized in that, The perfluorosulfonic acid resin accounts for 8% to 40% of the weight of the anode catalyst layer.

16. The membrane electrode assembly according to any one of claims 1, 2, 4, 6, 7, 8, 10, 11, 12, 14 or 15, characterized in that, The cathode catalyst in the cathode catalytic layer is Pt / C.

17. The membrane electrode assembly according to claim 3, characterized in that, The cathode catalyst in the cathode catalytic layer is Pt / C.

18. The membrane electrode assembly according to claim 5, characterized in that, The cathode catalyst in the cathode catalytic layer is Pt / C.

19. The membrane electrode assembly according to claim 9, characterized in that, The cathode catalyst in the cathode catalytic layer is Pt / C.

20. The membrane electrode assembly according to claim 13, characterized in that, The cathode catalyst in the cathode catalytic layer is Pt / C.

21. A membrane electrode, characterized in that, include: The membrane electrode assembly according to any one of claims 1 to 20; And a gas diffusion layer disposed on both sides of the membrane electrode assembly.

22. The membrane electrode according to claim 21, characterized in that, The gas diffusion layer is carbon fiber paper or carbon fiber cloth with carbon powder coated on its surface.

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