CN116565223A - Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell - Google Patents

Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell Download PDF

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Publication number
CN116565223A
CN116565223A CN202310610521.8A CN202310610521A CN116565223A CN 116565223 A CN116565223 A CN 116565223A CN 202310610521 A CN202310610521 A CN 202310610521A CN 116565223 A CN116565223 A CN 116565223A
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China
Prior art keywords
catalyst slurry
fuel cell
catalyst
coating
electrode
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Pending
Application number
CN202310610521.8A
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Chinese (zh)
Inventor
麦建明
白云飞
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Shanghai H Rise New Energy Technology Co Ltd
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Shanghai H Rise New Energy Technology Co Ltd
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Priority to CN202310610521.8A priority Critical patent/CN116565223A/en
Publication of CN116565223A publication Critical patent/CN116565223A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention provides an electrode catalyst layer, a membrane electrode for a fuel cell and the fuel cell, which belong to the field of fuel cells, wherein the electrode catalyst layer comprises a coating, hydrophilic catalyst slurry A and hydrophobic catalyst slurry B which are loaded on the coating, the coating area ratio of the catalyst slurry A and the catalyst slurry B on the coating is continuously changed according to the hydrophilicity of an active area of the cell, and the hydrophilicity refers to the contact angle of water drops on a material is smaller than 90 degrees; by hydrophobic is meant that the contact angle of the water droplet on the material is greater than 90 °. By the treatment scheme, the performance of the catalyst layer in the active area of the fuel cell is improved.

Description

Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell
Technical Field
The invention relates to the field of fuel cells, in particular to an electrode catalyst layer, a membrane electrode for a fuel cell and the fuel cell.
Background
In the prior art, the hydrophilicity control is mainly realized through the slurry component configuration of the catalyst layer, but the water content in the active area of the fuel cell is continuously changed along with the continuous reaction, and the water resistance of the conventional catalyst cannot meet the requirement of the active area. And the concentration of the reaction and the generated substances in different reaction areas is different, and the catalyst with a single formula needs to be compatible with all the areas to not exert the optimal performance, so that the performance of the fuel cell cannot be improved.
Disclosure of Invention
Accordingly, in order to overcome the above-described drawbacks of the prior art, the present invention provides an electrode catalyst layer, a membrane electrode for a fuel cell, and a fuel cell, which improve the performance of the catalyst layer in the active region of the fuel cell.
In order to achieve the above object, the present invention provides an electrode catalyst layer comprising a coating layer, and a hydrophilic catalyst slurry a and a hydrophobic catalyst slurry B supported on the coating layer, wherein the ratio of the coating areas of the catalyst slurry a and the catalyst slurry B on the coating layer is continuously changed according to the hydrophilicity of an active area of a battery, and the hydrophilicity means that the contact angle of water drops on a material is less than 90 °; the hydrophobicity refers to the contact angle of water drops on the material being greater than 90 degrees; the shape of at least one of the catalyst slurry A and the catalyst slurry B is an anisotropic island pattern, the anisotropic island pattern comprises at least one included angle, the angle of the included angle is not more than a right angle, and the direction of the included angle is the gas flow direction on the interface of the catalyst layer and the gas diffusion layer.
In one embodiment, the ratio of the coated areas of the catalyst slurry a and the catalyst slurry B on the coating layer is controlled according to the continuous change of the hydrophilicity in the cell active area, the ratio of the coated areas of the catalyst slurry a on the coating layer, which is arranged at the inlet of the fuel cell, is larger than the ratio of the coated areas of the catalyst slurry B on the coating layer, and the ratio of the coated areas of the catalyst slurry a on the inlet of the fuel cell is larger than the ratio of the coated areas of the catalyst slurry B on the outlet of the fuel cell.
In one embodiment, the ratio of the coated areas of the catalyst slurry A and the catalyst slurry B on the respective areas of the coating layer is controlled according to the humidity, the temperature, the pressure and/or the flow rate of the reaction gas stream.
In one embodiment, inkjet printing and/or shadow mask printing are used to achieve precise control of the ratio of the coated areas occupied by the two slurries.
In one embodiment, the catalyst on the cathode side and the anode side of the fuel cell are coated in different patterns.
In one embodiment, the coating shapes of the catalyst slurry a and the catalyst slurry B on the coating layer are square, triangular, circular and/or polygonal.
In one of the embodiments, the concentration of catalyst slurry a is different on the cathode side and the anode side of the fuel cell; and/or the catalyst slurry B is different in concentration on the cathode side and the anode side of the fuel cell.
A membrane electrode for a fuel cell has the above electrode catalyst layer.
A fuel cell having the membrane electrode for a fuel cell described above.
Compared with the prior art, the invention has the advantages that: the catalyst in the active area of the fuel cell is always in a better water content state by utilizing the characteristic that the hydrophilic catalyst slurry keeps stable higher water content in the active area of the fuel cell, the hydrophobic slurry keeps stable lower water content in the active area of the fuel cell, and the coating area proportion of the catalyst slurry A and the catalyst slurry B on the coating is continuously changed according to the hydrophilicity of the active area of the cell, in addition, when water drops formed on the surface of the catalyst layer are taken away by airflow from the pattern through an included angle which is consistent with the flowing direction of the gas on the catalyst slurry pattern, the adsorption force is gradually reduced due to gradual reduction of the adsorption area with the surface of the catalyst layer, so that the water drops are easy to separate from the surface of the catalyst layer and are discharged into the gas diffusion layer, thereby ensuring the performance of the catalyst layer in the active area of the fuel cell and further improving the performance of the fuel cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a coated pattern of an electrode catalyst layer in an embodiment of the present invention;
fig. 2 is a pattern of coating of a catalyst in an electrode catalyst layer in an embodiment of the invention;
FIG. 3 is a pattern of coating of an electrode catalyst layer in an embodiment of the invention;
FIG. 4 is a pattern of coating of an electrode catalyst layer in an embodiment of the invention;
FIG. 5 is a coating pattern of the electrode catalyst layer segment coating in the embodiment of the present invention;
fig. 6 is a coating pattern of the electrode catalyst layer segment coating in the embodiment of the present invention.
Detailed Description
Embodiments of the present application are described in detail below with reference to the accompanying drawings.
Other advantages and effects of the present application will become apparent to those skilled in the art from the present disclosure, when the following description of the embodiments is taken in conjunction with the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. The present application may be embodied or carried out in other specific embodiments, and the details of the present application may be modified or changed from various points of view and applications without departing from the spirit of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present application, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, apparatus may be implemented and/or methods practiced using any number and aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should also be noted that the illustrations provided in the following embodiments merely illustrate the basic concepts of the application by way of illustration, and only the components related to the application are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
In addition, in the following description, specific details are provided in order to provide a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects may be practiced without these specific details.
The membrane electrode assembly in the fuel cell may have a membrane electrode for the fuel cell, a pair of Gas Diffusion Layers (GDLs) sandwiching the membrane electrode for the fuel cell, and a pair of separators sandwiching the membrane electrode and the gas diffusion layers for the fuel cell. The GDL and the separator are paired on the anode side and the cathode side. The membrane electrode performs a power generating function, and the gas diffusion layer diffuses the supplied gas. The membrane electrode is sandwiched by a pair of Gas Diffusion Layers (GDLs). The pair of gas diffusion layers are also referred to as anode gas diffusion layers and cathode gas diffusion layers, respectively. Further, the membrane electrode for a fuel cell and the gas diffusion layer are sandwiched between a pair of separators. The pair of separators is also referred to as an anode separator and a cathode separator, respectively. The separator separates the fuel gas and the oxidant gas supplied to the anode and the cathode, and electrically connects the adjacent membrane electrodes to each other. In this way, the membrane electrodes for the fuel cell are stacked and connected to form the fuel cell.
The membrane electrode for a fuel cell may include a polymer electrolyte membrane and a pair of electrode catalyst layers sandwiching the polymer electrolyte membrane. The pair of electrode catalyst layers may be referred to as an anode electrode catalyst layer and a cathode electrode catalyst layer, respectively.
As shown in fig. 1 to 5, an embodiment of the present application provides an electrode catalyst layer, which includes a coating layer, and a hydrophilic catalyst slurry a and a hydrophobic catalyst slurry B supported on the coating layer, wherein the ratio of the coating areas of the catalyst slurry a and the catalyst slurry B on the coating layer is continuously changed according to the hydrophilicity of an active area of a battery, and the hydrophilicity refers to a contact angle of water drops on a material of less than 90 °; hydrophobic means that the contact angle of the water droplet on the material is greater than 90 °. In fig. 1 to 5, light gray and black represent two catalyst slurries with different hydrophilicity and hydrophobicity, respectively, and light gray represents a hydrophilic catalyst slurry a; black represents hydrophobic catalyst slurry B. The coating thickness of the catalyst slurry A and the catalyst slurry B on the coating layer can be 10 nanometers to 500 micrometers.
The hydrophilicity of catalyst slurry a means that the water droplet contact angle of catalyst slurry a is less than 90 °. The contact angle of the catalyst slurry A is in the range of 0 to 90 degrees, preferably 10 to 45 degrees. Catalyst slurry a may be selected from polytetrafluoroethylene (Poly tetra fluoroethylene, abbreviated as PTFE) and the like.
The hydrophobicity of catalyst slurry B means that the water droplet contact angle of catalyst slurry B is greater than 90 °. The contact angle of the catalyst slurry B is in the range of 90 to 180 DEG, preferably 135 to 170 deg. The catalyst slurry B may be, for example, a perfluorosulfonic acid resin film (Nafion) or the like that has been subjected to plasma treatment.
As shown in fig. 2, in the coating area of the catalyst, at least one of the catalyst slurry a and the catalyst slurry B is coated in an anisotropic island pattern, and the anisotropic island pattern includes at least one included angle, the included angle is not greater than a right angle, and the included angle direction is the gas flow direction at the interface between the catalyst layer and the gas diffusion layer. Arrows indicate the gas flow direction at the interface of the catalyst layer and the gas diffusion layer; the anisotropic island pattern has an angle pointing in the direction of the gas flow; after condensing the water vapor in the catalyst layer into micro droplets in the hydrophilic catalyst area, the micro droplets are driven by the airflow to move towards the direction pointed by the angle, and contact with the hydrophilic surface of the catalyst layer is reduced along with the movement, so that the adhesion force is gradually reduced, and the micro droplets are easy to separate from the catalyst layer and enter the gas diffusion layer. The shapes of the catalyst slurry A and the catalyst slurry B coating can be the same or different.
In one embodiment, the included angle of the anisotropic island pattern corresponding to catalyst slurry a is greater than the included angle of the anisotropic island pattern corresponding to catalyst slurry B.
In one embodiment, catalyst slurry a corresponds to an anisotropic island pattern having a greater number of included angles than the anisotropic island pattern corresponding to catalyst slurry B.
According to the structure, the hydrophilic catalyst slurry is utilized to keep a stable higher water content in the active area of the fuel cell, the hydrophobic slurry is utilized to keep a stable lower water content in the active area of the fuel cell, and the coating area proportion of the catalyst slurry A and the catalyst slurry B on the coating is distributed according to the continuous change of the hydrophilicity of the active area of the cell, so that the catalyst in the active area of the fuel cell is always in a better water content state.
In one embodiment, as shown in fig. 1 to 3, the coating shapes of the catalyst slurry a and the catalyst slurry B on the coating layer are square, triangle, circle and/or polygon. The coating shapes of the catalyst slurry A and the catalyst slurry B on the coating layer can be consistent or inconsistent, so long as the requirements of the catalytic performance of the membrane electrode are met. And the humidity control optimization of the membrane electrode can be further realized by adopting a plurality of layers of catalyst arrangements with different configurations or different grid shapes.
In one embodiment, the ratio of the coated areas of the catalyst slurry A and the catalyst slurry B on the coating layer is controlled according to the continuous change of the hydrophilicity in the active area of the cell, the ratio of the coated areas of the catalyst slurry A on the coating layer, which is arranged at the inlet of the fuel cell, is larger than the ratio of the coated areas of the catalyst slurry B on the coating layer, and the ratio of the coated areas of the catalyst slurry A on the inlet of the fuel cell is larger than the ratio of the coated areas of the catalyst slurry A on the outlet of the fuel cell. As shown in fig. 5, the left side is the active area of the fuel cell inlet and the right side is the active area of the fuel cell outlet. The hydrophilic catalyst occupies more configuration on the inlet side of the non-humidified air, so that the water content and the performance of the membrane electrode at the inlet side can be improved; the arrangement of the hydrophobic catalyst on the exhaust side with higher humidity occupies more space, so that the drainage property and performance of the exhaust side can be improved, and the performance of the fuel cell can be better improved.
In one embodiment, the ratio of the coated areas of catalyst slurry a and catalyst slurry B on the respective areas of the coating is controlled according to the humidity, temperature, pressure and/or flow rate of the reaction gas stream.
In one embodiment, inkjet printing and/or shadow mask printing are used to achieve precise control of the ratio of the coated areas occupied by the two slurries.
In one embodiment, the catalyst on the cathode side and the anode side of the fuel cell are coated in different patterns.
In one of the embodiments, the concentration of catalyst slurry a is different on the cathode side and the anode side of the fuel cell; and/or the concentration of the catalyst slurry B is different on the cathode side and the anode side of the fuel cell. As shown in fig. 5 and 6, the left side is the anode side of the fuel cell and the right side is the cathode side of the fuel cell. The concentration of the catalyst slurry a on the cathode side of the fuel cell is smaller than that on the anode side; the concentration of catalyst slurry B is greater on the cathode side than on the anode side of the fuel cell to accommodate the difference in gas conditions on both sides.
The concentration of the catalyst slurry A on the cathode side is different from that of the catalyst slurry A on the anode side, the catalyst slurry A with different concentrations can be prepared firstly, and then the catalyst slurry A is coated on the coating according to the humidity control requirement of the membrane electrode; the catalyst can also be obtained by coating different areas with the catalyst slurry A with the same concentration for multiple times.
The foregoing is merely specific embodiments of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (9)

1. An electrode catalyst layer comprising a coating layer, and a hydrophilic catalyst slurry A and a hydrophobic catalyst slurry B supported on the coating layer,
distributing the coating area ratio of the catalyst slurry A and the catalyst slurry B on the coating according to the continuous change of the hydrophilicity of the active area of the battery, wherein the hydrophilicity refers to the contact angle of water drops on the material is smaller than 90 degrees; the hydrophobicity refers to the contact angle of water drops on the material being greater than 90 degrees;
the shape of at least one of the catalyst slurry A and the catalyst slurry B is an anisotropic island pattern, the anisotropic island pattern comprises at least one included angle, the angle of the included angle is not more than a right angle, and the direction of the included angle is the gas flow direction on the interface of the catalyst layer and the gas diffusion layer.
2. The electrode catalyst layer according to claim 1, wherein the ratio of the coated areas of the catalyst slurry a and the catalyst slurry B on the coating layer is controlled in accordance with a continuous change in hydrophilicity in the cell active region, the ratio of the coated areas of the catalyst slurry a disposed at the fuel cell inlet on the coating layer is larger than the ratio of the coated areas of the catalyst slurry B on the coating layer, and the ratio of the coated areas of the catalyst slurry a at the fuel cell inlet is larger than the ratio of the coated areas at the fuel cell outlet.
3. The electrode catalyst layer according to claim 1, wherein the ratio of the coated areas of the catalyst slurry a and the catalyst slurry B on the respective areas on the coating layer is controlled according to the humidity, temperature, pressure, and/or flow rate of the reaction gas flow.
4. The electrode catalyst layer according to claim 1, wherein the precise control of the ratio of the coated areas occupied by the two pastes is achieved by inkjet printing and/or shadow mask printing.
5. The electrode catalyst layer according to claim 1, wherein the catalyst on the cathode side and the anode side of the fuel cell is coated in a different manner/pattern.
6. The electrode catalyst layer according to claim 1, wherein the coating shape of the catalyst slurry a and the catalyst slurry B on the coating layer is square, triangle, circle, and/or polygon.
7. The electrode catalyst layer according to claim 1, wherein the concentration of the catalyst slurry a is different on the cathode side and the anode side of the fuel cell;
and/or the catalyst slurry B is different in concentration on the cathode side and the anode side of the fuel cell.
8. A membrane electrode for a fuel cell, comprising the electrode catalyst layer according to any one of claims 1 to 7.
9. A fuel cell comprising the membrane electrode for a fuel cell according to claim 8.
CN202310610521.8A 2023-05-29 2023-05-29 Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell Pending CN116565223A (en)

Priority Applications (1)

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CN202310610521.8A CN116565223A (en) 2023-05-29 2023-05-29 Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell

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CN202310610521.8A CN116565223A (en) 2023-05-29 2023-05-29 Electrode catalyst layer, membrane electrode for fuel cell, and fuel cell

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006040767A (en) * 2004-07-28 2006-02-09 Nissan Motor Co Ltd Solid polymer fuel electrode
CN113140768A (en) * 2021-04-12 2021-07-20 上海交通大学 Cathode side structure of integrated reversible fuel cell membrane electrode
CN114824296A (en) * 2022-03-18 2022-07-29 福州大学 Gas diffusion layer with hydrophilic and hydrophobic structures and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006040767A (en) * 2004-07-28 2006-02-09 Nissan Motor Co Ltd Solid polymer fuel electrode
CN113140768A (en) * 2021-04-12 2021-07-20 上海交通大学 Cathode side structure of integrated reversible fuel cell membrane electrode
CN114824296A (en) * 2022-03-18 2022-07-29 福州大学 Gas diffusion layer with hydrophilic and hydrophobic structures and preparation method thereof

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