CN113013454A - Fuel cell membrane electrode and preparation method thereof - Google Patents
Fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- CN113013454A CN113013454A CN202110197047.1A CN202110197047A CN113013454A CN 113013454 A CN113013454 A CN 113013454A CN 202110197047 A CN202110197047 A CN 202110197047A CN 113013454 A CN113013454 A CN 113013454A
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- 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]
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Abstract
The invention relates to a fuel cell membrane electrode and a preparation method thereof, wherein the membrane electrode comprises a proton exchange membrane, a cathode catalyst layer and an anode catalyst layer which are respectively coated on two sides of the proton exchange membrane, and a diffusion layer which covers the outer sides of the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and the anode catalyst layer comprise catalysts and perfluorinated sulfonic acid resin, the perfluorinated sulfonic acid resin comprises long side chain resin, middle and long side chain resin and short side chain resin, and the types of the perfluorinated sulfonic acid resin used by the cathode catalyst layer and the anode catalyst layer are different. According to the fuel cell membrane electrode prepared by the invention, different types of perfluorinated sulfonic acid resin are adopted in the cathode and anode catalyst layers, and the proper gas diffusion layer is matched, so that the water management capacity of the fuel cell is improved, and the system matching difficulty is reduced.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell membrane electrode and a preparation method thereof.
Background
The proton exchange membrane fuel cell is an energy conversion device which does not need Carnot to circulate with high efficiency, directly converts the chemical energy of the hydrogen-oxygen reaction into electric energy in an electrochemical mode, and has the characteristics of environmental protection, low-temperature quick start and high smooth operation. The energy-saving power generation system has wide application prospect in the fields of automobiles, portable power sources, distributed power generation, aerospace and the like, and is considered as a novel, efficient and environment-friendly new energy in the 21 st century.
The Membrane Electrode (MEA) consists of a proton exchange membrane, a catalyst layer and a gas diffusion layer, is the core site of multiphase substance transmission and electrochemical reaction in the fuel cell, and the quality of the MEA directly determines the performance, the service life and the cost of the proton exchange membrane fuel cell. The proton exchange membrane adopted at present is mainly a perfluorosulfonic acid proton exchange membrane, the proton conductivity of perfluorosulfonic acid is seriously dependent on the hydration state of the membrane, when the membrane electrode loses water, the proton conductivity can be obviously reduced, so that the ohmic polarization is increased, the water content is overhigh, the transmission resistance of reaction gas is increased, and the performance of the cell is influenced. Therefore, whether the proton exchange membrane fuel cell membrane electrode can operate stably, with high performance and long service life is closely related to the water management in the electrode.
Perfluorosulfonic acid ionomers act primarily as binders and proton transporters in fuel cell membrane electrodes, but little research has been done on their water management of fuel cells. Therefore, there is a need in the art for a method of altering water management within an electrode by adjusting the perfluorosulfonic acid ionomer species and incorporating a diffusion layer.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned deficiencies of the prior art and to providing a fuel cell membrane electrode assembly having a wide operating window.
The invention also aims to provide a preparation method of the fuel cell membrane electrode.
In order to achieve the object of the present invention, the present application provides the following technical solutions.
In a first aspect, the present application provides a fuel cell membrane electrode, which includes a proton exchange membrane, a cathode catalyst layer and an anode catalyst layer coated on both sides of the proton exchange membrane, respectively, and a diffusion layer covering the outside of the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and the anode catalyst layer include a catalyst and perfluorosulfonic acid resin, the perfluorosulfonic acid resin includes long side chain resin, medium and long side chain resin, and short side chain resin, and the types of the perfluorosulfonic acid resin used by the cathode catalyst layer and the anode catalyst layer are different.
In one embodiment of the first aspect, the long side-chain resin has a side-chain molecular structure of-OCF2CF(CF3)OCF2CF2SO3H；
The side chain molecular structure of the medium-long side chain resin is-OCF2CF2CF2CF2SO3H；
The side chain molecular structure of the short side chain resin is-OCF2CF2SO3H。
In one embodiment of the first aspect, when the relative humidity of intake air is less than 30% during operation of the fuel cell, the perfluorosulfonic acid resin in the cathode catalyst layer is a short-side chain resin or a medium-side chain resin, and the perfluorosulfonic acid resin in the anode catalyst layer is a medium-side chain resin or a long-side chain resin; and the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types.
In one embodiment of the first aspect, when the relative humidity of the fuel cell during operation is 30% to 70%, the perfluorosulfonic acid resin in the cathode catalyst layer is a short-side chain resin or a long-side chain resin, and the perfluorosulfonic acid resin in the anode catalyst layer is a short-side chain resin or a long-side chain resin; and the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types.
In one embodiment of the first aspect, when the relative humidity at which the fuel cell operates is greater than 70%, the perfluorosulfonic acid resin in the cathode catalyst layer is a medium-long side chain resin or a long side chain resin, and the perfluorosulfonic acid resin in the anode catalyst layer is a short side chain resin or a medium-long side chain resin; and the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types.
The long side chain, mid-long side chain and short side chain perfluorosulfonic acid resins differ primarily in the length of the side chain, with the long side chain resin having the longest side chain and the short side chain resin having the shortest. At the same resin content, a reduction in the length of the side chains gives the polymer a higher exchange capacity. The higher exchange capacity minimizes hydrogen ion transport losses and optimizes cell performance under low humidity conditions. The sulfonic acid group with the hydrophilic cluster can absorb a large number of water molecules to form a hydration area, and when the inlet air humidity of the battery is high, the resin with high exchange capacity can easily absorb excessive water to cause electrode flooding, the transmission of reaction gas is blocked, and the performance of the battery is reduced. Therefore, the cathode-anode catalyst layer is matched with different resin types under different working conditions.
In one embodiment of the first aspect, the diffusion layer has a thickness of 0.20-0.30mm and a contact angle of greater than 120 ° when the relative humidity is less than 30% during operation of the fuel cell.
In one embodiment of the first aspect, the diffusion layer has a thickness of 0.18 to 0.25mm and a contact angle of greater than 130 ° when the relative humidity is 30% to 70% when the fuel cell is in operation.
In one embodiment of the first aspect, the diffusion layer has a thickness of 0.14 to 0.20mm and a contact angle of greater than 150 ° when the relative humidity is greater than 70% during operation of the fuel cell.
In one embodiment of the first aspect, the catalyst comprises platinum black, carbon-supported platinum or carbon-supported platinum alloy, and the platinum loading in the anode catalytic layer is 0.03-0.5 mg/cm2The platinum loading capacity in the cathode catalyst layer is 0.1-2 mg/cm2。
In one embodiment of the first aspect, the mass ratio of the catalyst to the perfluorosulfonic acid resin is (1 to 5): 1.
in one embodiment of the first aspect, the proton exchange membrane is a perfluorosulfonic acid resin composite membrane, and the proton exchange membrane has a thickness of 5 to 200 um.
In a second aspect, the present application also provides a method for preparing a fuel cell membrane electrode as described above, comprising the steps of:
(1) mixing a catalyst, perfluorinated sulfonic acid resin, water and an organic solvent, and preparing cathode catalyst slurry and anode catalyst slurry after ultrasonic, emulsifying, homogenizing and dispersing;
(2) respectively spraying cathode catalyst slurry and anode catalyst slurry on the surfaces of two sides of a proton exchange membrane to form a cathode catalyst layer and an anode catalyst layer;
(3) and covering diffusion layers on the outer sides of the cathode catalyst layer and the anode catalyst layer through hot pressing to obtain the fuel cell membrane electrode.
In one embodiment of the second aspect, the organic solvent comprises one or more of ethanol, isopropanol, n-propanol, n-butanol, isobutanol, t-butanol, ethylene glycol, glycerol, ethyl acetate, and the ratio of the organic solvent to water is (0.5-5): 1.
In one embodiment of the second aspect, the hot pressing temperature is 120 to 200 ℃, the hot pressing time is 10 to 300s, and the hot pressing pressure is 0.2 to 5 MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the fuel cell membrane electrode prepared by the invention, the cathode and anode catalyst layers are made of different types of perfluorinated sulfonic acid resin, and the gas diffusion layers are matched, so that the water management capacity of the fuel cell is improved, and the system matching difficulty is reduced.
(2) The fuel cell membrane electrode prepared by the invention has simple and quick process flow and is suitable for mass production.
Drawings
FIG. 1 is a polarization curve diagram of the membrane electrodes prepared in examples 1 to 10 and comparative examples 1 to 3 at a humidity of 30% RH;
FIG. 2 is a polarization curve of the membrane electrodes prepared in examples 1 to 10 and comparative examples 1 to 3 at 70% RH humidity.
Detailed Description
Unless otherwise defined, technical or scientific terms used herein in the specification and claims should have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All numerical values recited herein as between the lowest value and the highest value are intended to mean all values between the lowest value and the highest value in increments of one unit when there is more than two units difference between the lowest value and the highest value.
While specific embodiments of the invention will be described below, it should be noted that in the course of the detailed description of these embodiments, in order to provide a concise and concise description, all features of an actual implementation may not be described in detail. Modifications and substitutions to the embodiments of the present invention may be made by those skilled in the art without departing from the spirit and scope of the present invention, and the resulting embodiments are within the scope of the present invention.
The invention aims to improve the water management capacity of a proton exchange membrane fuel cell and provides a fuel cell membrane electrode with a wide operation interval and a preparation method thereof. According to the invention, different types of perfluorinated sulfonic acid resin are adopted in the cathode and anode catalyst layers, and the matching of the cathode and anode resin and the diffusion layer is optimized, so that the electrode can run stably with high performance in different operation intervals.
The purpose of the invention can be realized by the following technical scheme: a fuel cell membrane electrode with wide operation range is prepared through proportionally mixing catalyst, perfluoro-sulfonic acid resin, water and alcohol, ultrasonic emulsifying, homogenizing and dispersing. And spraying the uniformly dispersed cathode and anode catalyst slurry on the surface of a proton exchange membrane to form a cathode and anode catalyst layer coated on the membrane, and hot-pressing the CCM coated with the catalyst layer and the cathode and anode gas diffusion layers under a certain condition to form the five-in-one membrane electrode.
The cathode and anode catalysts are different types of catalysts in general, but can be the same type in some cases. Including platinum black, platinum on carbon, or platinum alloy on carbon.
If platinum-containing catalyst is adopted, the platinum loading capacity of the anode catalyst layer is 0.03-0.5 mg/cm2(ii) a The platinum loading capacity of the cathode catalyst layer is 0.1-2 mg/cm2。
The cathode and anode perfluorinated sulfonic acid resin is different types of resins, including perfluorinated sulfonic acid resin with long side chains, medium-long side chains and short side chains. The selection of the cathode and anode perfluorinated sulfonic acid resin is adjusted according to cathode and anode catalysts, a gas diffusion layer and electrode water management. The series of resins produced by Nafion, 3M, Asahi Glass, Asahi Kasei, Solvay, Shandong Yue and the like can be selected, wherein the mass ratio of the catalyst to the resin is (1-5) to 1.
The alcohol includes but is not limited to one or more of ethanol, isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, glycerol and ethyl acetate, and the ratio of the organic solvent to the water is (0.5-5): 1.
The proton exchange membrane is a perfluorinated sulfonic acid resin composite membrane, and the thickness of the proton exchange membrane is usually 5-200 um.
The cathode and anode diffusion layers are different in general condition and model, and are matched according to cathode and anode catalysts, perfluorinated sulfonic acid resin and electrode water management.
The hot pressing conditions are as follows: hot pressing temperature: 120-200 ℃; hot pressing time: 10-300 s; hot pressing pressure: 0.2 to 5 MPa.
Examples
The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, then 5% Nafion D2020 resin is added according to the weight ratio of 3.0 of the catalyst to the perfluorinated sulfonic acid resin, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry with uniform dispersion is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.16mm, the contact angle is about 150 degrees) and a cathode Avcarb MB30 (the thickness is about 0.16mm, the contact angle is about 150 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 2:
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.25mm, the contact angle is about 130 degrees) and a cathode Avcarb MB30 (the thickness is about 0.25mm, the contact angle is about 130 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 3:
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, then 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalysis slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.3mm, the contact angle is about 120 degrees) and a cathode Avcarb MB30 (the thickness is about 0.3mm, the contact angle is about 120 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 4
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, then 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalysis slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.3mm, the contact angle is about 120 degrees) and a cathode Avcarb MB30 (the thickness is about 0.3mm, the contact angle is about 120 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 5
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry with uniform dispersion is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.25mm, the contact angle is about 130 degrees) and a cathode Avcarb MB30 (the thickness is about 0.25mm, the contact angle is about 130 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 6
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.2mm, the contact angle is about 130 degrees) and a cathode Avcarb MB30 (the thickness is about 0.2mm, the contact angle is about 130 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 7
Weighing 50mg of 70% Pt/C catalyst, 3.5g of distilled water and 7g of n-propanol, adding 5% Nafion D2020 resin according to the weight ratio of 1 of the catalyst to the perfluorinated sulfonic acid resin, and performing ultrasonic emulsification to obtain uniformly dispersed cathode catalytic slurry.
Weighing 20mg of 30% Pt/C catalyst, 3.5g of distilled water and 7g of n-propanol, adding 5% short-side chain Solvay D72 resin according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin being 1, and carrying out ultrasonic emulsification to obtain uniformly dispersed anode catalytic slurry.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.3mm, the contact angle is about 120 degrees) and a cathode Avcarb MB30 (the thickness is about 0.3mm, the contact angle is about 120 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 8
Weighing 50mg of 70% Pt/C catalyst, 2g of distilled water and 10g of n-propanol, adding 5% Nafion D2020 resin according to the weight ratio of 5% of the catalyst to the perfluorinated sulfonic acid resin, and performing ultrasonic emulsification to obtain uniformly dispersed cathode catalytic slurry.
Weighing 20mg of 30% Pt/C catalyst, 2g of distilled water and 10g of n-propanol, adding 5% short-side chain Solvay D72 resin according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 5, and performing ultrasonic emulsification to obtain uniformly dispersed anode catalytic slurry.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of an 18um proton membrane, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.3mm, the contact angle is about 120 degrees) and a cathode Avcarb MB30 (the thickness is about 0.3mm, the contact angle is about 120 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 9
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry with uniform dispersion is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.2mm, the contact angle is about 130 degrees) and a cathode Avcarb MB30 (the thickness is about 0.2mm, the contact angle is about 130 degrees) to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Example 10:
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.14mm, the contact angle is about 150 degrees) and a cathode Avcarb MB30 (the thickness is about 0.14mm, the contact angle is about 150 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Comparative example 1:
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% long side chain Nafion D2020 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.16mm, the contact angle is about 150 degrees) and a cathode Avcarb MB30 (the thickness is about 0.16mm, the contact angle is about 150 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Comparative example 2
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalytic slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% of middle-side chain 3M 825 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry which is uniformly dispersed is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.16mm, the contact angle is about 150 degrees) and a cathode Avcarb MB30 (the thickness is about 0.16mm, the contact angle is about 150 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
Comparative example 3
50mg of 70% Pt/C catalyst, 2.8g of distilled water and 8.5g of n-propanol are weighed, then 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 3.0, and the uniformly dispersed cathode catalysis slurry is obtained after ultrasonic emulsification.
20mg of 30% Pt/C catalyst, 4.5g of distilled water and 12.1g of n-propanol are weighed, 5% short-side chain Solvay D72 resin is added according to the weight ratio of the catalyst to the perfluorinated sulfonic acid resin of 2.8, and the anode catalytic slurry with uniform dispersion is obtained after ultrasonic emulsification.
The dispersed cathode and anode catalyst slurry is respectively coated on the surface of a proton membrane of 18um, and then is hot-pressed with an anode Avcarb3260 (the thickness is about 0.16mm, the contact angle is about 150 degrees) and a cathode Avcarb MB30 (the thickness is about 0.16mm, the contact angle is about 150 degrees) diffusion layer to obtain a membrane electrode. The electrodes were tested for polarization curves at 30% RH and 70% RH, respectively.
In the testing process, except for different humidity, the gas conditions of the fuel cell in the operation process are ensured to be the same or equivalent, such as working temperature, hydrogen circulation ratio and the like. Comparing the polarization curves of examples 1 to 10 and comparative examples 1 to 3, as shown in FIGS. 1 and 2, we can see that: when the inlet air humidity is lower than 30%, the cathode and the anode should adopt perfluorinated sulfonic acid resin with short side chains or medium long side chains and match with a gas diffusion layer with thicker thickness. Short side chain or medium and long side chain resin can guarantee that the proton transmission loss is minimum when the humidity of admitting air is lower in the electrode, and the thick diffusion layer of collocation can prevent that electrode moisture loss from too much causing the increase of battery ohmic loss. On the contrary, when the humidity of the electrode is higher than 70%, the cathode and the anode should adopt medium-long side chain or long side chain resin and match with a gas diffusion layer with a thinner thickness, so as to improve the gas diffusion rate and prevent the electrode from flooding.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. The fuel cell membrane electrode is characterized by comprising a proton exchange membrane, a cathode catalyst layer and an anode catalyst layer which are respectively coated on two sides of the proton exchange membrane, and a diffusion layer which covers the outer sides of the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and the anode catalyst layer comprise catalysts and perfluorinated sulfonic acid resin, the perfluorinated sulfonic acid resin comprises long side chain resin, middle long side chain resin and short side chain resin, and the types of the perfluorinated sulfonic acid resin used by the cathode catalyst layer and the anode catalyst layer are different.
2. The fuel cell membrane electrode assembly according to claim 1 wherein said long side chain resin has a side chain molecular structure of-OCF2CF(CF3)OCF2CF2SO3H；
The side chain molecular structure of the medium-long side chain resin is-OCF2CF2CF2CF2SO3H；
The side chain molecular structure of the short side chain resin is-OCF2CF2SO3H。
3. The fuel cell membrane electrode assembly according to claim 2, wherein when the relative humidity of intake air during operation of the fuel cell is less than 30%, the perfluorosulfonic acid resin in the cathode catalyst layer is a short-side chain resin or a long-side chain resin, and the perfluorosulfonic acid resin in the anode catalyst layer is a long-side chain resin or a long-side chain resin; the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types;
when the relative humidity of the fuel cell during operation is 30-70%, the perfluorinated sulfonic acid resin in the cathode catalyst layer is short-side chain resin or long-side chain resin, and the perfluorinated sulfonic acid resin in the anode catalyst layer is short-side chain resin or long-side chain resin; the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types;
when the relative humidity of the fuel cell during operation is more than 70%, the perfluorinated sulfonic acid resin in the cathode catalyst layer is medium-long side chain resin or long side chain resin, and the perfluorinated sulfonic acid resin in the anode catalyst layer is short-side chain resin or medium-long side chain resin; and the perfluorinated sulfonic acid resin in the cathode catalyst layer and the perfluorinated sulfonic acid resin in the anode catalyst layer are different in types.
4. The fuel cell membrane electrode assembly according to claim 3 wherein said diffusion layer has a thickness of 0.20 to 0.30mm and a contact angle of greater than 120 ° when the relative humidity of the fuel cell is less than 30% during operation;
when the relative humidity of the fuel cell during operation is 30-70%, the thickness of the diffusion layer is 0.18-0.25mm, and the contact angle is larger than 130 degrees;
when the relative humidity of the fuel cell is more than 70 percent during operation, the thickness of the diffusion layer is 0.14-0.20mm, and the contact angle is more than 150 degrees.
5. The fuel cell membrane electrode of claim 1 wherein the catalyst comprises platinum black, platinum on carbon, or a platinum alloy on carbon, and the platinum loading in the anode catalytic layer is 0.03 to 0.5mg/cm2The platinum loading capacity in the cathode catalyst layer is 0.1-2 mg/cm2。
6. The fuel cell membrane electrode assembly according to claim 5, wherein the mass ratio of the catalyst to the perfluorosulfonic acid resin is (1 to 5): 1.
7. the fuel cell membrane electrode of claim 1, wherein said proton exchange membrane is a perfluorosulfonic acid resin composite membrane, said proton exchange membrane having a thickness of 5-200 um.
8. A method for preparing a fuel cell membrane electrode according to any one of claims 1 to 7, comprising the steps of:
(1) mixing a catalyst, perfluorinated sulfonic acid resin, water and an organic solvent, and preparing cathode catalyst slurry and anode catalyst slurry after ultrasonic, emulsifying, homogenizing and dispersing;
(2) respectively spraying cathode catalyst slurry and anode catalyst slurry on the surfaces of two sides of a proton exchange membrane to form a cathode catalyst layer and an anode catalyst layer;
(3) and covering diffusion layers on the outer sides of the cathode catalyst layer and the anode catalyst layer through hot pressing to obtain the fuel cell membrane electrode.
9. The method for preparing a fuel cell membrane electrode according to claim 8, wherein the organic solvent comprises one or more of ethanol, isopropanol, n-propanol, n-butanol, isobutanol, t-butanol, ethylene glycol, glycerol, and ethyl acetate, and the ratio of the organic solvent to water is (0.5-5): 1.
10. The method for preparing a fuel cell membrane electrode according to claim 8, wherein the hot-pressing temperature is 120 to 200 ℃, the hot-pressing time is 10 to 300s, and the hot-pressing pressure is 0.2 to 5 MPa.
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