CN114937799A - Membrane electrode, preparation method thereof and fuel cell - Google Patents
Membrane electrode, preparation method thereof and fuel cell Download PDFInfo
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- CN114937799A CN114937799A CN202210616757.8A CN202210616757A CN114937799A CN 114937799 A CN114937799 A CN 114937799A CN 202210616757 A CN202210616757 A CN 202210616757A CN 114937799 A CN114937799 A CN 114937799A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- 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
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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 provides a membrane electrode, a preparation method thereof and a fuel cell, wherein the membrane electrode comprises an anode gas diffusion layer, an anode anti-toxicity layer, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a cathode gas diffusion layer and a sealing layer, the anode catalyst layer and the cathode catalyst layer are respectively arranged on two opposite surfaces of the proton membrane, the anode anti-toxicity layer is arranged on the anode catalyst layer, the sealing layer seals the proton membrane, the anode catalyst layer, the cathode catalyst layer and the side surface of the anode anti-toxicity layer, the anode gas diffusion layer is arranged on the anode anti-toxicity layer, and the cathode gas diffusion layer is arranged on the cathode catalyst layer. The membrane electrode has better CO poisoning resistance and can effectively prolong the service life of the fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a membrane electrode, a preparation method thereof and a fuel cell.
Background
A hydrogen fuel cell is a cell that directly converts chemical energy into electrical energy by using the reaction between hydrogen and oxygen. The proton exchange membrane fuel cell has the characteristics of low working temperature, quick start, high power density, mature application and the like, and is widely applied to automobiles.
At present, although the reserve of commercial vehicles in China only accounts for about 12 percent of the reserve of automobiles, the reserve of commercial vehicles in China causes CO (carbon monoxide) in road traffic 2 About 56% of the emissions. Therefore, hydrogen fuel cells would be an effective solution for commercial vehicles to achieve "carbon peaking" and "carbon neutralization". At present, the service life of the fuel cell of the commercial vehicle is about 15000h, and the service life requirement which is comparable with that of an internal combustion engine cannot be met. Therefore, how to improve the service life is one of the most important problems in the popularization and application of the fuel cell of the commercial vehicle.
The membrane electrode is an important component of a fuel cell, is a place where electrochemical reaction occurs, is compared with a chip of the fuel cell, and the cost thereof accounts for more than 60% of the total cost of the fuel cell. The cost and life of the membrane electrode therefore directly determine the cost and life of the fuel cell.
The working process of the membrane electrode is as follows: when passing through the anode catalyst layer, the high-purity hydrogen fuel from the hydrogen storage tank is decomposed into hydrogen protons and electrons by the action of the platinum catalyst, the hydrogen protons are transferred to the cathode side through the proton membrane, the electrons are transferred to the cathode side through the external circuit, and when reaching the cathode, the electrons are combined with the protons and the oxygen fuel from the ambient air by the action of the cathode platinum catalyst to generate water. The specific electrode reaction is as follows:
anode H 2 →2H + +2e - (1)
Cathode 1/2O 2 +2H + +2e - →H 2 O (2)
The total reaction formula is H 2 +1/2O 2 →H 2 O
Even if high-purity hydrogen is used for the anode, a trace amount of CO still exists, and the CO reacts with the platinum catalyst in the catalyst layer to generate Pt — CO which adheres to the surface of the catalyst, so that the CO carbon poisoning of the platinum catalyst occurs, and the catalytic action (1) cannot be performed any more, and the battery life is shortened. Therefore, how to improve the CO poisoning resistance of the fuel cell becomes a key point for commercial vehicle applications.
The following four methods are mainly adopted at present: (1) purifying the gas to remove CO; (2) adding oxygen or air into the raw material hydrogen to oxidize CO; (3) adopting a CO-resistant binary, ternary or quaternary platinum-ruthenium catalyst; (4) using a concentration of H 2 O 2 The CO is removed as a humidifying liquid of the humidifier. However, in practical applications, the adoption of the method (1) requires additional auxiliary equipment, and the complexity and cost of the vehicle system are significantly increased in order to achieve a CO concentration of 20ppm or less; the method (2) is adopted, and the hydrogen and the air are mixed difficultly, so that a greater safety risk exists; by adopting the method (3), the platinum-ruthenium catalyst system is adopted in the anode catalyst layer, so that the catalyst has a certain CO resistance effect, but the reaction activity of the anode can be greatly reduced, and the performance of the battery is remarkably reduced; by the method (4) H 2 O 2 Especially during the vehicle starting, stopping, idling and high potential dynamic circulation processes, the degradation of proton membrane, the dissolution and aggregation of platinum catalyst are accelerated, resulting in serious reduction of the durability of the fuel cell.
Disclosure of Invention
Therefore, it is necessary to provide a membrane electrode having a good CO poisoning resistance and capable of increasing the service life of a fuel cell, a method for manufacturing the membrane electrode, and a fuel cell.
According to one aspect of the present invention, a membrane electrode is provided, which includes an anode gas diffusion layer, an anode anti-poison layer, an anode catalytic layer, a proton membrane, a cathode catalytic layer, a cathode gas diffusion layer, and a sealing layer, wherein the anode catalytic layer and the cathode catalytic layer are respectively disposed on two opposite surfaces of the proton membrane, the anode anti-poison layer is disposed on the anode catalytic layer, the sealing layer seals the proton membrane, the anode catalytic layer, the cathode catalytic layer, and the side surfaces of the anode anti-poison layer, the anode gas diffusion layer is disposed on the anode anti-poison layer, and the cathode gas diffusion layer is disposed on the cathode catalytic layer.
In some of these embodiments, the anode anti-poison layer includes a first ionomer and a first catalyst supported on the first ionomer; the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8-7.0; the first ionic polymer has a side chain structure of-O (CF) 2 ) n SO 3 H, wherein n is 2-4.
In some of these embodiments, the first ionomer has an EW value of 830g/eq to 1000 g/eq.
In some of these embodiments, the first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst, and a Pt-Ir/C catalyst.
In some of these embodiments, the thickness of the anodic anti-poison layer is 1 μm to 3 μm.
In some of the embodiments, the sum of the loading amounts of Ru, Rh, Pd and Ir in the anode antitoxic layer is 0.02mg/cm 2 ～0.06mg/cm 2 。
In some of these embodiments, the mass percentage of Pt in the first catalyst is 20% to 60%.
In some of these embodiments, the anode catalytic layer comprises a second ionomer and a second catalyst supported on the second ionomer; the second ionic polymer has a main chain structure of- (CF) — (CF) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8 to 7.0; the side chain structure of the second ionic polymer is-O (CF) 2 ) n SO 3 H, wherein n is 2-4.
In some embodiments, the EW value of the second ionic polymer is 830g/eq to 1000 g/eq.
In some of these embodiments, the second catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst, a Pt-Ni/C catalyst.
In some embodiments, the mass percentage of the Pt in the second catalyst is 20% to 60%, and the loading amount of the Pt in the anode catalytic layer is 0.05mg/cm 2 ～0.1mg/cm 2 。
In some of these embodiments, the cathode catalytic layer comprises a third ionic polymer and a third catalyst supported on the third ionic polymer; the third ionic polymer has a main chain structure of- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 4.2-6.0; the side chain structure is-O (CF) 2 ) n SO 3 H, wherein n is 1-3.
In some of these embodiments, the EW of the third ionomer is from 750g/eq to 860 g/eq.
In some of these embodiments, the third catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst, a Pt-Ni/C catalyst.
In some embodiments, the mass percentage of the Pt in the third catalyst is 40-60%, and the loading amount of the Pt in the cathode catalytic layer is 0.1mg/cm 2 ～0.35mg/cm 2 。
In some of the embodiments, the proton membrane is a reinforced composite sulfate membrane, and the thickness of the proton membrane is 8-15 μm.
In some embodiments, the material of the sealing layer is polyethylene naphthalate or polyimide, and the thickness of the sealing layer is 45 μm to 75 μm.
In some of these embodiments, the anode gas diffusion layer has a thickness greater than a thickness of the cathode gas diffusion layer.
In some of these embodiments, the sum of the thicknesses of the anode catalytic layer, the anode anti-poison layer, and the anode gas diffusion layer is less than the sum of the thicknesses of the cathode catalytic layer and the cathode gas diffusion layer.
According to another aspect of the present invention, there is provided a method of preparing a membrane electrode, comprising the steps of:
respectively coating the cathode catalyst layer slurry and the anode catalyst layer slurry on two opposite surfaces of the proton membrane to respectively form a cathode catalyst layer and an anode catalyst layer;
coating the anode anti-virus layer slurry on the anode catalyst layer to form an anode anti-virus layer;
sealing the sides of the proton membrane, the anode catalyst layer, the cathode catalyst layer and the anode anti-virus layer by using a sealing frame to form a sealing layer; and
and an anode gas diffusion layer is packaged on the anode antitoxic layer, and a cathode gas diffusion layer is packaged on the cathode catalyst layer.
In some of these embodiments, the anode-catalyzed layer slurry comprises a second ionic polymer, a second catalyst, and a second solvent; the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, the solid content of the anode catalyst layer slurry is 1.0-1.5%.
In some of these embodiments, the cathode catalytic layer slurry comprises a third ionic polymer, a third catalyst, and a third solvent; the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalyst layer slurry is 1.8-2.5%.
In some embodiments, the anode anti-poison layer slurry comprises a first ionic polymer, a first catalyst and a first solvent, wherein the first solvent is one or more of water, isopropanol, n-propanol and ethanol, and the solid content of the anode anti-poison layer slurry is 1.0-1.5%.
According to another aspect of the present invention, there is provided a fuel cell comprising the membrane electrode described above.
Compared with the prior art, the invention has the following beneficial effects:
according to the membrane electrode, the anode anti-poison layer is arranged between the anode catalyst layer and the anode gas diffusion layer, the anode anti-poison layer can enable humidifying water in fuel to generate rich-OH, and the-OH can be exchanged with CO in CO-Pt to generate CO-OH, so that Pt is released, the Pt catalyst in the anode catalyst layer is not poisoned, the anti-poison capability of the anode catalyst layer is improved, and the service life of a fuel cell is prolonged. In addition, the anode anti-toxicity layer is arranged between the anode catalyst layer and the anode gas diffusion layer, so that the anti-toxicity capability of the anode catalyst layer is improved, and adverse effects on other performances of the membrane electrode can be avoided.
In addition, the proton transfer rate in the anode catalyst layer is improved by regulating and controlling the main chain molecular structure and the side chain sulfonic acid end molecular structure of the ionic polymer in the anode catalyst layer; the main chain and side chain structures of the ionic polymer in the cathode catalyst layer are regulated, so that the permeability of oxygen in the cathode catalyst layer and the removal of generated water are obviously improved, and the reduction of ohmic polarization and concentration polarization is facilitated.
Moreover, the fuel cell has smaller ohmic loss, concentration loss and activation loss and higher power density through the coupling anchoring between the cathode catalyst layer and the anode catalyst layer; through the anchoring and interlocking of the thickness of each film layer, water generated on the cathode side can permeate into the anode side, the quantity of-OH generated on the anode antitoxic layer is increased, the ohmic polarization and concentration polarization of the cell are further reduced, and the power density and the durability of the cell are remarkably improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a membrane electrode according to an embodiment of the present invention;
fig. 2 is a schematic cross-sectional view of a membrane electrode according to another embodiment of the present invention.
Description of the reference numerals:
10. a membrane electrode; 11. an anode gas diffusion layer; 12. an anode anti-virus layer; 13. an anode catalyst layer; 14. a proton membrane; 15. a cathode catalyst layer; 16. a cathode gas diffusion layer; 17. and (7) sealing the layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings, which illustrate embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Referring to fig. 1 and 2, an embodiment of the invention provides a membrane electrode 10, where the membrane electrode 10 includes an anode gas diffusion layer 11, an anode anti-poison layer 12, an anode catalyst layer 13, a proton membrane 14, a cathode catalyst layer 15, a cathode gas diffusion layer 16, and a sealing layer 17.
Wherein, the anode catalytic layer 13 and the cathode catalytic layer 15 are respectively arranged on two opposite surfaces of the proton membrane 14; the anode antitoxic layer 12 is arranged on the anode catalytic layer 13; the sealing layer 17 seals the side faces of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode antitoxic layer 12; the anode gas diffusion layer 11 is provided on the anode poisoning prevention layer 12, and the cathode gas diffusion layer 16 is provided on the cathode catalytic layer 15.
In the membrane electrode 10, the anode anti-poison layer 12 is arranged between the anode catalyst layer 13 and the anode gas diffusion layer 11, and the edge of the anode anti-poison layer 12 is covered by the sealing layer 17 to seal the anode anti-poison layer 12; the anode anti-poison layer 12 can enable the humidifying water in the fuel to generate an abundant-OH structure, and the-OH can exchange with CO in CO-Pt to generate CO-OH so as to release Pt, so that the Pt catalyst in the anode catalyst layer 13 is not poisoned, the anti-poison capability of the anode catalyst layer 13 is improved, and the service life of the fuel cell is prolonged.
In addition, by providing the anode catalytic layer 13 and the cathode catalytic layer 15 on the two opposite surfaces of the proton membrane 14, respectively, the power density of the fuel cell can be significantly improved by the coupling anchoring between the anode catalytic layer 13 and the cathode catalytic layer 15.
In some of these embodiments, the anode poisoning layer 12 includes a first ionomer and a first catalyst supported on the first ionomer; the backbone structure of the first ionic polymer is- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8-7.0; the first ionic polymer has a side chain structure of-O (CF) 2 ) n SO 3 H, wherein n is 2-4; the EW value (equivalent specific gravity) of the first ionic polymer is 830 g/eq-1000 g/eq; the first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst and a Pt-Ir/C catalyst. By adopting the anode anti-poisoning layer 12, a sufficient amount of-OH can be generated, so that the-OH can be fully exchanged with CO in CO-Pt to release Pt, the Pt catalyst in the anode catalyst layer 13 can be effectively prevented from being poisoned, and the anti-poisoning capability of the anode catalyst layer 13 is improved.
Specifically, the thickness of the anode antitoxic layer 12 is 1 μm to 3 μm. The sum of the loading amounts of Ru, Rh, Pd and Ir in the anode antitoxic layer 12 is 0.02mg/cm 2 ～0.06mg/cm 2 . The mass percentage content of Pt in the first catalyst in the anode antitoxic layer 12 is 20-60%.
In some of these embodiments, anode catalytic layer 13 comprises a second ionomer and a second catalyst supported on the second ionomer; the second ionic polymer has a main chain structure of- (CF) — ( 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8-7.0; the side chain structure of the second ionic polymer is-O (CF) 2 ) n SO 3 H, wherein n is 2-4; the EW value of the second ionic polymer is 830 g/eq-1000 g/eq; the second catalyst is one or more of Pt/C catalyst, Pt-Co/C catalyst and Pt-Ni/C catalyst.
By forming the anode catalyst layer 13 with the second ionic polymer having the main chain molecular structure and the side chain sulfonic acid terminal molecular structure, the proton transfer rate in the anode catalyst layer 13 can be effectively increased, thereby improving the performance of the fuel cell.
In some specific examples, the mass percentage content of Pt in the second catalyst of the anode catalytic layer 13 is 20% to 60%, and the loading amount of Pt in the anode catalytic layer 13 is 0.05mg/cm 2 ～0.1mg/cm 2 。
In some of these embodiments, the cathode catalytic layer 15 includes a third ionomer and a third catalyst supported on the third ionomer; the third ionic polymer has a main chain structure of- (CF) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 4.2-6.0; the side chain structure is-O (CF) 2 ) n SO 3 H, wherein n is 1-3; the EW value of the third ionic polymer is 750g/eq to 860 g/eq; the third catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst and a Pt-Ni/C catalyst; the mass percentage of Pt in the third catalyst is 40-60%, and the load amount of Pt in the cathode catalyst layer 15 is 0.1mg/cm 2 ～0.35mg/cm 2 。
By forming the cathode catalyst layer 15 with the third ionic polymer having the main chain molecular structure and the side chain sulfonic acid terminal molecular structure, the permeability of oxygen and the transmission rate of generated water in the cathode catalyst layer 15 can be effectively improved, and the performance of the fuel cell can be further improved.
Referring to fig. 1, in one specific example, the sealing layer 17 covers the edge of the lower surface of the anode anti-poison layer 12 and the edge of the upper surface of the cathode catalyst layer 15, and the sealing layer 17 can seal the side surfaces of the proton membrane 14, the anode catalyst layer 13, the cathode catalyst layer 15, and the anode anti-poison layer 12. The anode gas diffusion layer 11 covers the anode poisoning resistant layer 12 and the end of the sealing layer 17; the cathode gas diffusion layer 16 covers the cathode catalyst layer 15 and the end of the sealing layer 17.
Referring to fig. 2, in another specific example, the sealing layer 17 covers the side surface of the anode poisoning prevention layer 12 and covers the edge of the upper surface of the cathode catalysis layer 15, and the sealing layer 17 can seal the side surfaces of the proton membrane 14, the anode catalysis layer 13, the cathode catalysis layer 15, and the anode poisoning prevention layer 12. The anode gas diffusion layer 11 covers the anode poisoning resistant layer 12 and the end of the sealing layer 17; the cathode gas diffusion layer 16 covers the cathode catalytic layer 15 and the end of the sealing layer 17.
In some specific examples, the proton membrane 14 is a polymer proton membrane, specifically a reinforced composite sulfate membrane, and the thickness of the proton membrane 14 is 8 μm to 15 μm. The material used for the sealing layer 17 is polyethylene naphthalate (PEN) or Polyimide (PI), and the thickness of the sealing layer 17 is 45 μm to 75 μm. The sealing layer 17 of the above material and thickness can effectively seal the side surfaces of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15, and the anode poisoning prevention layer 12.
In some of these embodiments, the thickness of the anode gas diffusion layer 11 in the membrane electrode 10 is greater than the thickness of the cathode gas diffusion layer 16; the sum of the thicknesses of the anode catalytic layer 13, the anode antitoxic layer 12 and the anode gas diffusion layer 11 is less than the sum of the thicknesses of the cathode catalytic layer 15 and the cathode gas diffusion layer 16.
In the above manner, the thickness of the anode gas diffusion layer 11, the thickness of the anode catalytic layer 13, the thickness of the cathode catalytic layer 15, the thickness of the anode anti-poison layer 12 and the thickness of the cathode gas diffusion layer 16 are anchored and interlocked; water generated on the cathode side of the membrane electrode 10 can permeate into the anode side, the-OH amount in the anode anti-poison layer 12 can be increased, and the catalyst, the proton membrane 14 and the fuel in the anode catalyst layer 13 can be facilitated to construct a three-phase interface structure for optimization, so that the ohmic polarization and the concentration polarization of the fuel cell are reduced, and the power density and the durability of the fuel cell are remarkably improved.
The initial power density of the membrane electrode 10 of the present invention is 2200mA/cm for a simulated anode hydrogen composition of 99.99% +100ppm CO compared to a conventional commercial membrane electrode 2 @0.67V, 2.0A/cm after 6000q carrier durability test 2 The voltage attenuation under the condition is only 25mV, and the ECSA attenuation is only 28%; durable by catalyst 50000q, 0.8A/cm 2 The voltage attenuation is 20mV, and the ECSA attenuation is 35%, so that the battery has better battery performance and durability. The membrane electrode 10 is applied to a proton membrane fuel cell, can obviously improve the CO adaptability of the fuel cell, and meets the requirement of commercial useVehicle requirements for power and durability.
The membrane electrode 10 of the present invention can be prepared by the following method:
preparing anode catalyst layer slurry: the anode catalytic layer slurry comprises a second ionic polymer, a second catalyst and a second solvent; wherein the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, the solid content of the anode catalyst layer slurry is 1.0-1.5%.
Preparing cathode catalyst layer slurry: the cathode catalyst layer slurry comprises a third ionic polymer, a third catalyst and a third solvent; wherein the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalyst layer slurry is 1.8-2.5%.
Preparing anode anti-poison layer slurry: the anode anti-toxicity layer slurry comprises a first ionic polymer, a first catalyst and a first solvent, wherein the first solvent is one or more of water, isopropanol, n-propanol and ethanol, and the solid content of the anode anti-toxicity layer slurry is 1.0-1.5%.
Respectively coating the cathode catalyst layer slurry and the anode catalyst layer slurry on two opposite surfaces of a proton membrane 14 to respectively form a cathode catalyst layer 15 and an anode catalyst layer 13; coating the anode anti-virus layer slurry on the anode catalyst layer 13 to form an anode anti-virus layer 12; sealing the side surfaces of the proton membrane 14, the anode catalyst layer 13, the cathode catalyst layer 15 and the anode antitoxic layer 12 by using a sealing frame to form a sealing layer 17; an anode gas diffusion layer 11 is packaged on the anode antitoxic layer 12, and a cathode gas diffusion layer 16 is packaged on the cathode catalyst layer 15; thereby forming the membrane electrode 10 of the present invention.
Specifically, the cathode catalyst layer slurry, the anode catalyst layer slurry and the anode antitoxic layer slurry can be respectively coated on corresponding membrane layers in an ultrasonic spraying mode; and the anode gas diffusion layer 11 and the cathode gas diffusion layer 16 may be encapsulated on the respective membrane layers by a hot press encapsulation method. The anode gas diffusion layer 11 and the cathode gas diffusion layer 16 may be conventional gas diffusion layers.
The present invention will be further described with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the invention.
Example 1:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Slurry preparation of the cathode catalyst layer 15: 0.4g of a Pt-Ni/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionic polymer having y/x of 4.2, n of 1, and EW of 750 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of a cathode catalyst layer 15; wherein the third ionic polymer has a main chain structure of- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the anode anti-virus layer 12: 0.4g of 20 mass percent Pt-Ru/C catalyst; 1.0g of water; a first ionomer having y/x of 7.0, n of 4, and EW of 1000 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of the anode antitoxic layer 12; wherein the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H。
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13 thus prepared were applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalyst layer 15 is 15 μm, and the platinum loading is 0.2mg/cm 2 (ii) a The thickness of the anode catalyst layer 13 was 5 μm, and the platinum loading was0.05mg/cm 2 。
Coating the slurry of the anode antitoxic layer 12 on the anode catalyst layer 13 by adopting an ultrasonic spraying mode, wherein the thickness of the anode antitoxic layer 12 is 2 mu m, and the loading capacity of Ru is 20 mu g/cm 2 。
Sealing frames of 45 μm and PEN material are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalyst layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, anode catalytic layer 13, cathode catalytic layer 15, and anode anti-virus layer 12.
Respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode antitoxic layer 12 and the cathode catalyst layer 15 to obtain the membrane electrode 10.
The membrane electrode 10 prepared in example 1 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 1 shows the durability test conditions of 6000 circles of carriers of the battery; table 2 shows the results of the durability test of 6000 battery rings; table 3 shows the durability test conditions for 50000-turn battery carriers; table 4 shows the results of the 50000-turn carrier durability test for the battery.
Table 16000 circles Carrier Endurance test conditions
TABLE 26000 circles of Carrier durability test results
TABLE 350000 cycles of catalyst Endurance test conditions
TABLE 450000 catalyst durability test results
As can be seen from the data in tables 2 and 4, the fuel cell obtained by using the membrane electrode 10 prepared in example 1 of the present invention has high initial performance, after 50000 cycles of endurance test, the 0.68V performance decay is only 6%, the electrochemical active area ECSA decay is only 28.2%, and excellent adaptability to CO and endurance performance are exhibited. Can meet the use requirement of the commercial vehicle on durability. Exhibits excellent adaptability to CO and durability.
Example 2:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
slurry preparation of the anode catalyst layer 13: 0.4g of 20 mass percent Pt/C catalyst; 1.0g of water; a second ionomer having y/x of 7.0, n of 4, and EW of 830 g/eq; mixing 30g of n-propanol, dispersing for 15min in Primix dispersing equipment at a peripheral speed of 15m/s and a rotating speed of 7000rpm and at a cooler temperature of 5 ℃ to obtain anode catalyst layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the cathode catalyst layer 15: 0.4g of 52 mass percent Pt-Co/C catalyst; 1.0g of water; a third ionic polymer having y/x of 4.2, n of 1, and EW of 750 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of a cathode catalyst layer 15; wherein the third ionic polymer has a main chain structure of- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the anode anti-virus layer 12: 0.4g of Pt-Rd/C catalyst with the mass fraction of 20 percent; 1.0g of water; a first ionomer having y/x of 6, n of 3, and EW of 1000 g/eq; 30g of n-propanol were mixed and dispersed in a ball mill 8h, obtaining slurry of the anode antitoxic layer 12; wherein the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H。
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13 thus prepared were applied to the opposite surfaces of the proton membrane 14 having a thickness of 15 μm by slit pressing. Wherein the thickness of the cathode catalyst layer 15 is 12 μm, and the platinum loading is 0.15mg/cm 2 (ii) a The thickness of the anode catalyst layer 13 is 5 μm, and the platinum loading is 0.06mg/cm 2 。
Coating the slurry of the anode antitoxic layer 12 on the anode catalyst layer 13 by adopting an ultrasonic spraying mode, wherein the thickness of the anode antitoxic layer 12 is 3 mu m, and the Pd loading capacity is 40 mu g/cm 2 。
Sealing frames of 45 μm and PI material are respectively sealed at the edges of the anode antitoxic layer 12 and the cathode catalyst layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15, and the anode anti-virus layer 12.
And respectively hot-pressing and packaging the anode gas diffusion layer 11 with the thickness of 180 mu m and the cathode gas diffusion layer 16 with the thickness of 178 mu m on the anode antitoxic layer 12 and the cathode catalyst layer 15 to obtain the membrane electrode 10.
The membrane electrode 10 prepared in example 2 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 5 shows the durability test results of 6000 battery rings of carriers, and the test conditions are the same as example 1 (shown in table 1); table 6 shows the results of the durability test of 50000-turn carrier of the battery under the same test conditions as in example 1 (shown in table 3).
TABLE 56000 circle carrier durability test results
TABLE 650000 circles catalyst Endurance test results
As can be seen from the data in tables 5 and 6, the fuel cell obtained by using the membrane electrode 10 prepared in example 2 of the present invention has high initial performance, and after 50000 cycles of endurance test, the 0.68V performance decay is only 3%, the electrochemical active area ECSA decay is only 29.2%, and excellent adaptability to CO and endurance performance are exhibited. The using requirement of the commercial vehicle on durability can be met.
Example 3:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
slurry preparation of the anode catalyst layer 13: 0.4g of Pt-Co/C catalyst with the mass fraction of 40 percent; 1.0g of water; a second ionomer having y/x of 6.0, n of 3, and EW of 850 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalyst layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the cathode catalyst layer 15: 0.4g of 52 mass percent Pt-Co/C catalyst; 1.0g of water; a third ionic polymer having y/x of 4.8, n of 2, and an EW of 800 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalyst layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF) - ((CF)) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the anode anti-virus layer 12: 0.4g of 20 mass percent Pt-Rh/C catalyst; 1.0g of water; a first ionomer having y/x of 6.7, n of 4, and EW of 850 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of the anode antitoxic layer 12; wherein the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H。
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13 configured as described above are respectively applied to two opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalyst layer 15 is 15 μm, and the platinum loading is 0.1mg/cm 2 (ii) a The thickness of the anode catalyst layer 13 is 5 μm, and the platinum loading is 0.08mg/cm 2 。
Coating the slurry of the anode antitoxic layer 12 on the anode catalyst layer 13 by adopting an ultrasonic spraying mode, wherein the thickness of the anode antitoxic layer 12 is 1 mu m, and the loading capacity of Ru is 20 mu g/cm 2 。
Sealing frames of 45 μm and PEN material are respectively sealed at the edges of the anode anti-virus layer 12 and the cathode catalyst layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15, and the anode anti-virus layer 12.
And respectively hot-pressing and packaging the anode gas diffusion layer 11 with the thickness of 251 mu m and the cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode antitoxic layer 12 and the cathode catalyst layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 3 of the present invention exhibits excellent adaptability to CO and durability.
Example 4:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
slurry preparation of the anode catalyst layer 13: 0.4g of Pt-Ni/C catalyst with the mass fraction of 40 percent; 1.0g of water; a second ionic polymer with y/x of 6.0, n of 2 and EW value of 900 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalyst layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the cathode catalyst layer 15: 0.4g of Pt/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionic polymer having y/x of 5.0, n of 3, and an EW of 820 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalyst layer 15 slurry; wherein, the firstThe main chain structure of the tri-ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the anode anti-virus layer 12: 0.4g of 20 mass percent Pt-Pd/C catalyst; 1.0g of water; a first ionomer having y/x of 5.8, n of 2, and EW of 880 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of the anode anti-toxicity layer 12; wherein the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H。
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13 thus prepared were applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalyst layer 15 is 15 μm, and the platinum loading is 0.3mg/cm 2 (ii) a The thickness of the anode catalyst layer 13 is 5 μm, and the platinum loading is 0.1mg/cm 2 。
Coating the anode antitoxic layer 12 slurry on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, wherein the thickness of the anode antitoxic layer 12 is 2 mu m, and the Ru loading capacity is 20 mu g/cm 2 。
Sealing frames of 45 μm and PEN material are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalyst layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15, and the anode anti-virus layer 12.
Respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode antitoxic layer 12 and the cathode catalyst layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 4 of the present invention exhibits excellent adaptability to CO and durability.
Example 5:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Slurry preparation of the cathode catalyst layer 15: 0.4g of a Pt-Ni/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionic polymer having y/x of 5.2, n of 3, and an EW of 860 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalyst layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H；
Slurry preparation of the anode anti-virus layer 12: 0.4g of 20 mass percent Pt-Ru/C catalyst; 1.0g of water; a first ionomer having y/x of 6.8, n of 4, and EW of 900 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain slurry of the anode antitoxic layer 12; wherein the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y A; the side chain structure is-O (CF) 2 ) n SO 3 H。
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13 thus prepared were applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalyst layer 15 is 15 μm, and the platinum loading is 0.35mg/cm 2 (ii) a The thickness of the anode catalyst layer 13 is 5 μm, and the platinum loading is 0.09mg/cm 2 。
Coating the anode antitoxic layer 12 slurry on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, wherein the thickness of the anode antitoxic layer 12 is 2 mu m, and the Ru loading capacity is 20 mu g/cm 2 。
Sealing frames of 45 μm and PEN material are respectively sealed at the edges of the anode anti-virus layer 12 and the cathode catalyst layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15, and the anode anti-virus layer 12.
And respectively hot-pressing and packaging the anode gas diffusion layer 11 with the thickness of 251 mu m and the cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode antitoxic layer 12 and the cathode catalyst layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 5 of the present invention exhibits excellent adaptability to CO and durability.
Comparative example 1:
a method of producing a membrane electrode 10, which is substantially the same as in example 1, and differs from example 1 only in that: the anode poisoning resistant layer 12 is not provided between the anode catalytic layer 13 and the anode gas diffusion layer 11.
The membrane electrode 10 prepared in comparative example 1 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 7 shows the durability test results of 6000 battery rings of carriers, and the test conditions are the same as example 1 (shown in table 1); table 8 shows the results of the durability test of 50000-turn carrier of the battery under the same test conditions as in example 1 (shown in table 3).
TABLE 76000 circles Carrier durability test results
TABLE 850000 circles catalyst Endurance test results
As can be seen from the data in tables 7 and 8, the fuel cell obtained by using the membrane electrode 10 prepared in comparative example 1, in which the anode poisoning resistant layer 12 is eliminated, has little initial performance change under the idling condition of 0.8V, but has a greatly reduced initial performance under the rated condition of 0.68V. The open circuit voltage performance does not vary significantly. After 50000 circles of acceleration and durability, the performance attenuation amplitude of the idle speed working condition and the rated working condition is large, the performance is reduced by 12.5 percent, and the requirement of the commercial vehicle on long service life cannot be met.
Comparative example 2:
a method of producing a membrane electrode 10, which is substantially the same as in example 1, and differs from example 1 only in that: the thickness relationship between the anode gas diffusion layer 11 and the cathode gas diffusion layer 16 is different; the thickness relationship among the anode catalyst layer 13, the anode antitoxic layer 12, the anode gas diffusion layer 11, the cathode catalyst layer 15 and the cathode gas diffusion layer 16 is different.
Specifically, the thickness of the anode gas diffusion layer 11 in comparative example 2 was 168 μm, the thickness of the cathode gas diffusion layer 16 was 172 μm, and the thickness of the anode gas diffusion layer 11 was smaller than that of the cathode gas diffusion layer 16; the thickness of the anode catalyst layer 15 is 5 μm; the sum of the thicknesses of the anode catalytic layer 13, the anode anti-toxicity layer 12 and the anode gas diffusion layer 11 is 176 μm, and is larger than the sum of the thicknesses of the cathode catalytic layer 15 and the cathode gas diffusion layer 16 by 175 μm.
The membrane electrode 10 prepared in comparative example 2 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 9 shows the durability test results of 6000 battery rings of carriers, and the test conditions are the same as example 1 (shown in table 1); table 10 shows the results of the durability test of 50000-turn battery carriers under the same test conditions as in example 1 (see table 3).
TABLE 96000 Ring Carrier durability test results
TABLE 1050000 circles catalyst Endurance test results
As can be seen from the data in tables 9 and 10, the fuel cell obtained using the membrane electrode 10 prepared in comparative example 2 exhibited little change in initial performance under the idling condition of 0.8V, but exhibited a significant decrease in initial performance under the rated condition of 0.68V. The open circuit voltage performance does not vary significantly. After 50000 circles of acceleration and endurance, the performance attenuation amplitude of the idle speed working condition and the rated working condition is large, the performance is reduced by 11 percent, and the requirement of the commercial vehicle on long service life cannot be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (11)
1. The membrane electrode is characterized by comprising an anode gas diffusion layer, an anode anti-toxicity layer, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a cathode gas diffusion layer and a sealing layer, wherein the anode catalyst layer and the cathode catalyst layer are respectively arranged on two opposite surfaces of the proton membrane, the anode anti-toxicity layer is arranged on the anode catalyst layer, the sealing layer is sealed on the proton membrane, the anode catalyst layer, the cathode catalyst layer and the side surface of the anode anti-toxicity layer, the anode gas diffusion layer is arranged on the anode anti-toxicity layer, and the cathode gas diffusion layer is arranged on the cathode catalyst layer.
2. The membrane electrode of claim 1, wherein the anode anti-poison layer comprises a first ionic polymer and a first catalyst supported on the first ionic polymer; the main chain structure of the first ionic polymer is- (CF) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8-7.0; the first ionic polymer has a side chain structure of-O (CF) 2 ) n SO 3 H, wherein n is 2-4; the EW value of the first ionic polymer is 830 g/eq-1000 g/eq; and/or
The first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst and a Pt-Ir/C catalyst; the sum of the loading amounts of Ru, Rh, Pd and Ir in the anode antitoxic layer is 0.02mg/cm 2 ～0.06mg/cm 2 (ii) a The mass percentage of Pt in the first catalyst is 20-60%; and/or
The thickness of the anode antitoxic layer is 1-3 mu m.
3. The membrane electrode of claim 1, wherein the anode catalytic layer comprises a second ionomer and a second catalyst supported on the second ionomer; the second ionic polymer has a main chain structure of- (CF) — (CF) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 5.8-7.0; the side chain structure of the second ionic polymer is-O (CF) 2 ) n SO 3 H, wherein n is 2-4; the EW value of the second ionic polymer is 830 g/eq-1000 g/eq; and/or
The second catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst and a Pt-Ni/C catalyst; the mass percentage of Pt in the second catalyst is 20-60%, and the load amount of Pt in the anode catalyst layer is 0.05mg/cm 2 ～0.1mg/cm 2 。
4. The membrane electrode of claim 1, wherein the cathode catalytic layer comprises a third ionic polymer and a third catalyst supported on the third ionic polymer; the third ionic polymer has a main chain structure of- (CF) (-) 2 -CF) x (CF 2 -CF 2 ) y Wherein y/x is 4.2-6.0; the side chain structure is-O (CF) 2 ) n SO 3 H, wherein n is 1-3; the third separationThe EW value of the subpolymer is 750g/eq to 860 g/eq; and/or
The third catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst and a Pt-Ni/C catalyst; the mass percentage of Pt in the third catalyst is 40-60%, and the load amount of Pt in the cathode catalyst layer is 0.1mg/cm 2 ～0.35mg/cm 2 。
5. The membrane electrode according to claim 1, wherein the proton membrane is a reinforced composite sulfate membrane, and the thickness of the proton membrane is 8-15 μm; and/or
The sealing layer is made of polyethylene naphthalate or polyimide, and the thickness of the sealing layer is 45-75 micrometers.
6. The membrane electrode according to any one of claims 1 to 5, characterized in that the thickness of the anode gas diffusion layer is greater than the thickness of the cathode gas diffusion layer; and/or
The sum of the thicknesses of the anode catalyst layer, the anode antitoxic layer and the anode gas diffusion layer is smaller than the sum of the thicknesses of the cathode catalyst layer and the cathode gas diffusion layer.
7. A preparation method of a membrane electrode is characterized by comprising the following steps:
respectively coating the cathode catalyst layer slurry and the anode catalyst layer slurry on two opposite surfaces of the proton membrane to respectively form a cathode catalyst layer and an anode catalyst layer;
coating the anode anti-virus layer slurry on the anode catalyst layer to form an anode anti-virus layer;
sealing the side surfaces of the proton membrane, the anode catalyst layer, the cathode catalyst layer and the anode antitoxic layer by using a sealing frame to form a sealing layer; and
and an anode gas diffusion layer is packaged on the anode antitoxic layer, and a cathode gas diffusion layer is packaged on the cathode catalyst layer.
8. The method of preparing a membrane electrode assembly according to claim 7, wherein the anode-catalytic layer slurry comprises a second ionic polymer, a second catalyst, and a second solvent; the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, the solid content of the anode catalyst layer slurry is 1.0-1.5%.
9. The method of preparing a membrane electrode assembly according to claim 7, wherein the cathode catalyst layer slurry comprises a third ionic polymer, a third catalyst, and a third solvent; the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalyst layer slurry is 1.8-2.5%.
10. The method for preparing a membrane electrode according to claim 7, wherein the anode anti-poison layer slurry comprises a first ionic polymer, a first catalyst and a first solvent, the first solvent is one or more of water, isopropanol, n-propanol and ethanol, and the solid content of the anode anti-poison layer slurry is 1.0-1.5%.
11. A fuel cell comprising the membrane electrode according to any one of claims 1 to 6.
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