CN114792811A - Fuel cell membrane electrode and preparation method thereof - Google Patents
Fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- 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 sequentially comprises an anode gas diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer, a first free radical quencher is arranged between the anode gas diffusion layer and the anode catalyst layer, and carbon-supported cerium oxide is uniformly distributed in the first free radical quencher. According to the invention, the free radical quenching agent is added on the anode diffusion layer, so that the damage of free radicals generated by the gas permeation of the membrane is reduced, and the service life of the membrane electrode is greatly prolonged. During preparation, the cathode catalyst layer adopts CCM, and the anode catalyst layer adopts GDE, so that the swelling, shrinkage and deformation of the proton exchange membrane in the catalyst layer preparation process are avoided, and the preparation and production of the membrane electrode are facilitated.
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 membrane electrode is a core component of the proton exchange membrane fuel cell and mainly comprises a catalyst layer, a proton exchange membrane and a gas diffusion layer, wherein the quality of the catalyst layer directly determines the performance and the service life of the fuel cell. The existing catalyst layer preparation process is mainly CCM, namely, catalyst slurry is directly coated on a proton exchange membrane to form a catalyst coating.
However, as fuel cells with higher power density are increasingly sought, the proton exchange membrane tends to be thin (lower ion conduction loss). Currently used proton exchange membranes are typically 12 μm in thickness, and it is expected that 8 μm, 5 μm will be used in large quantities in the near future. The film-forming puts higher requirements on the preparation process of the catalyst layer and the service life of the proton exchange membrane. Through a large amount of researches, the research of a CCM proton exchange membrane shows that when catalyst slurry is coated on the proton exchange membrane with the diameter of 8 μm or 5 μm, the proton exchange membrane has serious expansion and contraction deformation, and the coating of a catalyst layer and the service life of the proton membrane are influenced. In addition, thinner proton exchange membranes require caution against increased gas permeation. Gas permeation produces free radicals (. OH. OOH), which are highly reactive reagents known to attack polymeric materials causing decay. The proton exchange membrane decay reaction process is generally described by the following equation.
R f -CF 2 COOH+•OH→R f -CF 2 •+CO 2 +H 2 O
R f -CF 2 •+•OH→R f -CF 2 OH→R f -COF+H + +F -
R f -COF+H 2 O→R f -COOH+H + +F -
Therefore, there is a great need in the art for a membrane electrode for a thin proton exchange membrane.
Disclosure of Invention
The present invention is directed to a thin membrane electrode assembly for a fuel cell and a method for manufacturing the same, which overcomes the above-mentioned drawbacks of the prior art.
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, the membrane electrode sequentially includes an anode gas diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer, and a cathode gas diffusion layer, a first radical quencher is added between the anode gas diffusion layer and the anode catalyst layer or in the anode catalyst layer, and the first radical quencher includes carbon-supported cerium oxide. According to the membrane electrode, the free radical quencher is added on the anode diffusion layer, so that the harm of free radicals generated by gas permeation of the membrane is reduced, and the service life of the membrane electrode is greatly prolonged. The free radical quenching agent is sprayed in the anode diffusion layer instead of being added in the proton exchange membrane, so that continuous production of the electrode is facilitated, the carbon-supported cerium oxide is good in conductivity, conduction of electrons in the catalyst layer and the diffusion layer is not affected, and performance and service life of the electrode are guaranteed.
In one embodiment of the first aspect, the mass fraction of the carbon-supported cerium oxide in the first radical quencher is 1 to 70%, and the loading amount of the carbon-supported cerium oxide in the membrane electrode is 0.01 to 0.05mg/cm 2 。
In one embodiment of the first aspect, a second radical quencher is added between the cathode catalyst layer and the cathode gas diffusion layer or in the cathode catalyst layer, the second radical quencher comprises carbon-supported cerium oxide, the mass fraction of the carbon-supported cerium oxide in the second radical quencher is 1-70%, and the loading amount of the carbon-supported cerium oxide on the cathode diffusion layer is 0.01-0.03 mg/cm 2 。
In one embodiment of the first aspect, the carbon-supported cerium oxide is prepared as follows:
(1) mixing cerium nitrate, an organic solvent and carbon powder, and performing ultrasonic dispersion to obtain a mixed solution;
(2) and under the stirring condition, dropping sodium carbonate into the mixed solution, then continuously stirring for reaction, and sequentially carrying out sedimentation, suction filtration, washing, drying, grinding and roasting to obtain the carbon-supported cerium oxide.
The free radical quencher adopted by the application is carbon-supported cerium oxide, compared with pure cerium oxide, the electrical conductivity is better, the ohmic polarization loss of the electrode cannot be increased, and the supported amount on the diffusion layer cannot improve the gas transmission distance, so that no negative influence is caused on the electrode voltage.
In one embodiment of the first aspect, the method for preparing cerium oxide on carbon further comprises at least one of the following conditions: 1) the organic solvent comprises ethanol.
2) The using mass ratio of the cerium nitrate to the organic solvent to the carbon powder to the sodium carbonate is (10-20): (20-40): 1: (10-20).
3) The ultrasonic dispersion time is 20-60 min.
4) The stirring speed is 80-150 rpm.
5) The reaction time is 8-15 h.
6) And the settling time is 6-12 h.
7) The washing liquid used for washing is deionized water.
8) The drying temperature is 80-100 ℃, and the drying time is 3-6 h.
9) The roasting temperature is 500-700 ℃, the roasting time is 5-10 h, and the roasting is carried out in an inert atmosphere.
In a second aspect, the present application provides a method of making a fuel cell membrane electrode as described above, the method comprising the steps of:
(1) mixing carbon-supported cerium oxide, perfluorinated sulfonic acid resin, water and a first organic solvent, performing ultrasonic dispersion to obtain a first free radical quenching agent, and spraying the obtained first free radical quenching agent on the surface of one side of an anode gas diffusion layer;
(2) mixing a catalyst, perfluorinated sulfonic acid resin, water and a second organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain cathode catalyst slurry and anode catalyst slurry;
(3) spraying anode catalyst slurry on one side surface of the anode gas diffusion layer coated with the free radical quencher to form an anode catalyst layer; directly spraying cathode catalyst slurry on the surface of one side of the proton exchange membrane to form a cathode catalyst layer;
(4) and abutting the anode catalyst layer with the other side surface of the proton exchange membrane, abutting the cathode gas diffusion layer with the cathode catalyst layer, and then performing hot pressing to form the fuel cell membrane electrode.
According to the preparation method, the cathode catalysis layer is sprayed on one side of the proton exchange membrane in a CCM mode, then the anode catalysis layer is sprayed on the surface of the anode gas diffusion layer, and then the anode gas diffusion layer with the first free radical quencher and the anode catalysis layer, the proton exchange membrane with the cathode catalysis layer and the cathode gas diffusion layer (which can be sprayed with the second free radical quencher) are subjected to hot pressing, so that the swelling, shrinkage and deformation of the proton exchange membrane in the catalysis layer preparation process are avoided, and the preparation and production of the membrane electrode are facilitated.
In one embodiment of the second aspect, in step (1), the first organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol.
In one embodiment of the second aspect, in the step (1), in the first radical quencher, the mass ratio of the cerium oxide on carbon, the perfluorosulfonic acid resin, the water and the first organic solvent is (0.8-2): 1: (20-100): (30-200).
In one embodiment of the second aspect, in the step (1), the frequency of the ultrasound is 30 to 50kHZ, and the time is 20 to 60 min.
In one embodiment of the second aspect, in step (1), the preparation of the second radical quencher and the spraying of the second radical quencher on the surface of the cathode gas diffusion layer in step (1) are specifically as follows: mixing carbon-supported cerium oxide, perfluorinated sulfonic acid resin, water and a third organic solvent, performing ultrasonic dispersion to obtain a second free radical quencher, and spraying the obtained second free radical quencher on one side surface of the cathode gas diffusion layer.
In step (1), the third organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol.
In the step (1), in the second radical quencher, the mass ratio of the carbon-supported cerium oxide, the perfluorinated sulfonic acid resin, the water and the third organic solvent is (0.8-2): 1: (20-100): (30-200).
In the step (1), the frequency of the ultrasonic wave is 30-50 kHZ, and the time is 20-60 min.
In one embodiment of the second aspect, in step (2), the catalyst comprises one of platinum black, platinum on carbon, or a platinum alloy on carbon.
In one embodiment of the second aspect, in step (2), the second organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol.
In one embodiment of the second aspect, in the step (2), in the cathode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, water and the second organic solvent is (2-4): 1: (10-40): (20-90).
In one embodiment of the second aspect, in the step (2), in the anode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, water, and the second organic solvent is (3 to 5): 1: (40-100): (100-300).
In one embodiment of the second aspect, in the step (2), the frequency of the ultrasound is 30 to 50kHZ, and the time is 40 to 100 min.
In one embodiment of the second aspect, in the step (2), the high-pressure homogenization pressure is 300-800 bar, and the high-pressure homogenization time is 20-60 min.
In one embodiment of the second aspect, in the step (4), the hot pressing temperature is 120 to 170 ℃, the hot pressing time is 10 to 300s, and the hot pressing pressure is 0.2 to 3 MPa.
In a third aspect, the present application provides another fuel cell membrane electrode fabrication method, comprising the steps of:
(a) mixing carbon-supported cerium oxide, a catalyst, perfluorinated sulfonic acid resin, water and a fourth organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain anode catalyst slurry; mixing a catalyst, perfluorinated sulfonic acid resin, water and a fourth organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain cathode catalyst slurry;
(b) spraying anode catalyst slurry on the surface of the anode gas diffusion layer to form an anode catalyst layer; directly spraying cathode catalyst slurry on the surface of one side of the proton exchange membrane to form a cathode catalyst layer;
(c) and abutting the anode catalyst layer with the other side surface of the proton exchange membrane, abutting the cathode gas diffusion layer with the cathode catalyst layer, and then performing hot pressing to form the fuel cell membrane electrode.
In one embodiment of the third aspect, in step (a), the fourth organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol.
In one embodiment of the third aspect, in the step (a), in the anode catalyst slurry, the mass ratio of the cerium oxide on carbon, the catalyst, the perfluorosulfonic acid resin, water, and the fourth organic solvent is (1 to 4): (2-6): 1: (50-100): (100-200).
In one embodiment of the third aspect, in the step (a), the frequency of the ultrasound is 30 to 50kHZ, and the time is 20 to 100 min.
In one embodiment of the third aspect, in step (a), the high-pressure homogenizing pressure is 300-800 bar, and the high-pressure homogenizing time is 20-60 min.
In one embodiment of the third aspect, in step (a), the catalyst comprises one of platinum black, platinum on carbon, or a platinum alloy on carbon.
In one embodiment of the third aspect, in the step (a), in the cathode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, water, and the second organic solvent is (2 to 4): 1: (10-40): (20-90).
In one embodiment of the third aspect, in step (a), the carbon-supported cerium oxide is added to the cathode catalyst slurry, and the mass ratio of the carbon-supported cerium oxide to the catalyst in the cathode catalyst slurry is 1: (2-5).
In one embodiment of the third aspect, in the step (c), the hot pressing temperature is 120 to 170 ℃, the hot pressing time is 10 to 300s, and the hot pressing pressure is 0.2 to 3 MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) the cathode catalyst layer of the membrane electrode of the fuel cell prepared by the invention adopts CCM, and the anode catalyst layer adopts GDE, so that the swelling and shrinkage deformation of a proton exchange membrane in the catalyst layer preparation process is avoided, and the preparation and the production of the membrane electrode are facilitated.
(2) The free radical quenching agent is added on the anode diffusion layer, so that the harm of free radicals generated by the gas permeation of the film is reduced, and the service life of the film electrode is greatly prolonged. The free radical quencher is carbon-supported cerium oxide, and compared with pure cerium oxide, the free radical quencher has better conductivity and almost no influence on the performance of the electrode.
Drawings
FIG. 1 is a polarization graph of membrane electrodes prepared in examples 1 to 4 and comparative examples 1 to 3;
FIG. 2 is a graph showing the change of hydrogen permeation of the membrane electrodes prepared in examples 1 to 4 and comparative examples 1 to 3 under an open circuit voltage condition.
Detailed Description
Unless otherwise indicated, implicit from the context, or customary in the art, all parts and percentages herein are based on weight and the testing and characterization methods used are in step with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from a lower value to an upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not relevant to whether such other component, step or procedure is disclosed herein. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In a first aspect, the present application provides a high lifetime fuel cell membrane electrode comprising a cathode catalytic layer, an anode catalytic layer, a proton exchange membrane, and a cathode diffusion layer, an anode diffusion layer. The cathode catalyst layer is formed by directly coating cathode catalyst slurry on a proton exchange membrane, and the anode catalyst layer is formed by coating anode catalyst slurry on an anode gas diffusion layer.
In one embodiment of the first aspect, in the step of coating the cathode catalytic slurry on the surface of the proton exchange membrane, the proton membrane does not shrink and deform during the formation of the cathode catalytic layer due to the fixing effect of the PET base membrane attached to the proton membrane.
In one embodiment of the first aspect, the anode catalytic slurry is coated with a radical quencher on the surface of the microporous layer before the anode gas diffusion layer is coated with the anode catalytic slurry. The free radical quencher is carbon-supported cerium oxide, wherein the content of cerium oxide is 1-10 wt%. In order to prevent the hydrogen gas from reaching the Pt reaction site too far, the carbon-supported cerium oxide layer should be as thin as possible, and thus the amount of cerium oxide supported is controlled to be 0.01-0.05mg/cm 2 。
In one embodiment of the first aspect, the cathode/anode catalyst slurry comprises platinum black, platinum on carbon, or a platinum alloy on carbon, and the platinum loading in the cathode catalyst layer is 0.1-1.0mg/cm 2 The platinum loading in the anode catalyst layer is 0.02-0.5mg/cm 2 。
In one embodiment of the first aspect, the weight ratio of the catalyst to the perfluorosulfonic acid resin in the cathode-anode catalyst slurry is (1-5): 1.
in one embodiment of the first aspect, the weight ratio of the anodic diffusion layer coated radical quencher to perfluorosulfonic acid resin is (0.5-2): 1.
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) selecting carbon-supported cerium oxide, perfluorinated sulfonic acid resin, water and an organic solvent, mixing, performing ultrasonic dispersion, and spraying on the anode gas diffusion layer;
(2) mixing a catalyst, perfluorinated sulfonic acid resin, water and an organic solvent, and preparing cathode catalyst slurry and anode catalyst slurry after ultrasonic and high-pressure homogeneous dispersion;
(3) directly spraying the dispersed cathode catalyst slurry on a proton exchange membrane to form a cathode catalyst layer;
(4) spraying the dispersed anode catalyst slurry into a gas diffusion layer coated with carbon-supported cerium oxide to form an anode catalyst layer;
(5) the proton membrane PET base film coated with the cathode catalytic layer was torn off, with the side facing the gas diffusion layer of the anode catalytic layer. And hot-pressing the membrane electrode with a cathode diffusion layer which is not sprayed with a catalyst layer and faces a cathode catalyst layer to obtain the membrane electrode of the fuel cell.
In one embodiment of the second aspect, the organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol, glycerol, and the ratio of the organic solvent to water is (0.5-3): 1.
in one embodiment of the second aspect, the hot pressing conditions are: the temperature is 120 ℃ and 170 ℃, the time is 10-300s, and the pressure is 0.2-3 Mpa.
In the following examples, comparative examples, the carbon-supported cerium oxide used was prepared by the following steps:
weighing a certain amount of cerous nitrate, ethanol and carbon powder in a beaker, and carrying out ultrasonic dispersion for 30 min. Transferring the dispersed solution to a magnetic stirrer, stirring at normal temperature, and gradually dropwise adding a certain amount of sodium carbonate. And stirring the mixed solution for 12 hours, settling overnight, carrying out suction filtration, washing, and then placing the obtained cerium oxide supported by carbon in an air oven for drying. And grinding the dried carbon-supported cerium oxide, and roasting in a 600 ℃ tubular furnace in a nitrogen atmosphere for 8 hours to obtain the target product, namely the carbon-supported cerium oxide active free radical quencher.
In a third aspect, the present application provides a method of making a fuel cell membrane electrode as described above, the method comprising the steps of:
(1) mixing carbon-supported cerium oxide, a catalyst, perfluorinated sulfonic acid resin, water and a second organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain cathode catalyst slurry and anode catalyst slurry;
(3) spraying anode catalyst slurry on the surface of the anode gas diffusion layer to form an anode catalyst layer; directly spraying cathode catalyst slurry on the surface of one side of the proton exchange membrane to form a cathode catalyst layer;
(4) and abutting an anode catalyst layer with the other side surface of the proton exchange membrane, abutting a cathode gas diffusion layer with a cathode catalyst layer, and then performing hot pressing to form the fuel cell membrane electrode.
Examples
The following will describe in detail embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and give detailed implementation manners and specific operation procedures, but the scope of the present invention is not limited to the following embodiments.
Example 1
5% CeO was weighed 2 0.1g of a/C free radical quencher, 8g of n-propanol, 4g of distilled water, 0.1g of 5% Nafion, ultrasonically dispersed and sprayed on the anode gas diffusion layer, wherein the carbon-supported cerium oxide loading is 0.01mg/cm 2 。
Weighing 0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion, preparing anode catalyst slurry after ultrasonic and high-pressure homogeneous dispersion, and spraying the dispersed slurry until CeO is coated on the anode catalyst slurry 2 and/C on the anode gas diffusion layer. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore8 mu m proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And hot-pressing the proton membrane sprayed with the catalyst layer, the anode gas diffusion layer and the cathode gas diffusion layer to obtain a membrane electrode, wherein the hot-pressing conditions are as follows: the temperature is 150 ℃, the time is 100s, and the pressure is 1.5 Mpa.
Example 2
25% CeO was weighed 2 0.1g of/C free radical quenching agent, 8g of n-propanol, 4g of distilled water and 0.1g of 5% Nafion, wherein the carbon-supported cerium oxide loading is 0.05mg/cm after ultrasonic dispersion and spraying on an anode gas diffusion layer 2 。
Weighing 0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 0.128g of 5% Nafion, carrying out ultrasonic and high-pressure homogenization and dispersion to prepare anode catalyst slurry, and spraying the dispersed slurry to the position coated with CeO 2 and/C on the anode gas diffusion layer. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore8 mu m proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And carrying out hot pressing on the proton membrane sprayed with the catalyst layer, the anode gas diffusion layer and the cathode gas diffusion layer to obtain a membrane electrode, wherein the hot pressing conditions are as follows: the temperature is 120 ℃, the time is 300s, and the pressure is 0.2 Mpa.
Example 3
70% CeO was weighed 2 C radical quencher 0.1g, 8g n-propanol, 4g distilled water, 0.1g5% Nafion, ChaihongAfter sound dispersion, the mixture is respectively sprayed on an anode gas diffusion layer and a cathode gas diffusion layer, wherein the loading of carbon-supported cerium oxide on the cathode and the anode is 0.05mg/cm 2 。
Weighing 0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion, carrying out ultrasonic and high-pressure homogenization and dispersion to prepare anode catalyst slurry, and spraying the dispersed slurry to the position coated with CeO 2 On the anode gas diffusion layer of/C. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore8 mu m proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And (3) hot-pressing the proton membrane sprayed with the catalytic layer, the anode gas diffusion layer and the cathode gas diffusion layer (sprayed with a second free radical quenching agent) to obtain a membrane electrode, wherein the hot-pressing conditions are as follows: the temperature is 170 ℃, the time is 10s, and the pressure is 3 Mpa.
Example 4
Weighing 40% CeO 2 0.15g of/C free radical quenching agent, 0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion, preparing anode catalyst slurry after ultrasonic and high-pressure homogeneous dispersion, and spraying the dispersed slurry to the surface coated with CeO 2 and/C on the anode gas diffusion layer. Wherein the loading capacity of the carbon-supported cerium oxide is 0.05mg/cm2, and the loading capacity of the Pt is 0.1mg/cm 2 。
Weighing 40% CeO 2 0.15g of/C free radical quenching agent, 0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon, carrying out ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and spraying the dispersed slurry on the surface of a Gore8 mu m proton exchange membrane. Wherein the loading amount of the carbon-supported cerium oxide is 0.05mg/cm 2 The Pt loading is 0.3mg/cm 2 。
And carrying out hot pressing on the proton membrane sprayed with the catalyst layer, the anode gas diffusion layer and the cathode gas diffusion layer to obtain a membrane electrode, wherein the hot pressing conditions are as follows: the temperature is 170 ℃, the time is 10s, and the pressure is 3 Mpa.
Comparative example 1
5% CeO was weighed 2 C free radical quenching agent 0.1g, n-propanol 8g, distilled water 4g, Nafion 5% 0.1g, ultrasonic dispersing, and spray coating on anode gas diffusion layer, wherein the carbon-supported cerium oxide loading is 0.01mg/cm 2 。
0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare anode catalyst slurry, and the dispersed slurry is sprayed onto a Gore8um proton exchange membrane. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore8 mu m proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And respectively hot-pressing the proton membrane with the catalyst layers sprayed on the two sides with a cathode gas diffusion layer and an anode gas diffusion layer (coated with a first free radical quencher) to obtain a membrane electrode, wherein the hot-pressing conditions are as follows: the temperature is 150 ℃, the time is 100s, and the pressure is 1.5 Mpa.
Comparative example 2
0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion are weighed, subjected to ultrasonic and high-pressure homogenization and dispersion to prepare anode catalyst slurry, and the dispersed slurry is sprayed onto an anode gas diffusion layer. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore8 mu m proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And hot-pressing the proton membrane sprayed with the catalyst layer and the gas diffusion layer to obtain a membrane electrode, wherein the hot-pressing conditions are as follows: the temperature is 150 ℃, the time is 100s, and the pressure is 1.5 Mpa.
Comparative example 3
5% CeO was weighed 2 10mg of/C free radical quenching agent, 8g of n-propanol, 4g of distilled water and 0.1g of 5% Nafion, and the mixture is sprayed on an anode gas diffusion layer after ultrasonic dispersion, wherein the loading amount of the carbon-supported cerium oxide is 0.07mg/cm 2 。
Weighing 0.2g of 60% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 1.28g of 5% Nafion, carrying out ultrasonic and high-pressure homogenization and dispersion to prepare anode catalyst slurry, and spraying the dispersed slurry to the position coated with CeO 2 and/C on the anode gas diffusion layer. Wherein the Pt loading is 0.1mg/cm 2 。
0.5g of 70% Pt/C catalyst, 8g of n-propanol, 4g of distilled water and 2.7g of 5% Nafon are weighed, subjected to ultrasonic and high-pressure homogeneous dispersion to prepare cathode catalyst slurry, and the dispersed slurry is sprayed on the surface of a Gore and 8-micrometer proton exchange membrane. Wherein the Pt loading is 0.3mg/cm 2 。
And hot-pressing the proton membrane sprayed with the catalyst layer and the gas diffusion layer to obtain a membrane electrode, wherein the hot-pressing conditions are as follows: the temperature is 150 ℃, the time is 100s, and the pressure is 1.5 Mpa.
The membrane electrodes obtained in examples 1 to 3 and comparative examples 1 to 3 are subjected to electrode performance and hydrogen permeation current after OCV working condition by adopting a 25cm2 test fixture, and the specific experimental parameters are as follows:
electrode performance testing
OCV operating mode
Hydrogen permeation current test
The test results are shown in fig. 1 and fig. 2, respectively. From the graph, it can be seen that the open-circuit voltage of the electrode of example 1 is significantly higher than that of comparative example 1, and the hydrogen permeation current of the electrode of example 1 after 600hOCV working condition is 6.4mA/cm 2 Lower than 7.8mA/cm in comparative example 1 2 The application of GDE to the anode catalyst layer is demonstrated to reduce damage to the proton exchange membrane. Comparative example 2 electrode OCV attenuation after working condition is maximum, and 600h reaches 13.8mA/cm 2 This is because the radicals generated by the membrane electrode attack the proton exchange membrane. Comparative example 3 electrode at 2A/cm 2 The electrode performance was only 0.630V, lower than all examples, since excess free radicals increased the membrane electrode thickness, leading to increased gas transport resistance, affecting the electrode performance. Example 3 example 4 shows that the durability of the electrode can be significantly improved by adding cerium oxide on carbon to the catalytic layer, not only the electrode performance is very close, but also the OCV hydrogen permeation current change tendency is almost the same.
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. A fuel cell membrane electrode sequentially comprises an anode gas diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer, and is characterized in that a first free radical quencher is added between the anode gas diffusion layer and the anode catalyst layer or in the anode catalyst layer, and the first free radical quencher comprises carbon-supported cerium oxide.
2. The fuel cell membrane electrode assembly according to claim 1, wherein the mass fraction of the carbon-supported cerium oxide in the first radical quencher is 1-70%, and the loading of the carbon-supported cerium oxide on the anode diffusion layer is 0.01-0.05 mg/cm 2 。
3. The fuel cell membrane electrode assembly according to claim 1 wherein a second radical quencher is added between or within said cathode catalyst layer and cathode gas diffusion layer, said second radical quencher having a second radical quencher added theretoThe second free radical quencher comprises carbon-supported cerium oxide, the mass fraction of the carbon-supported cerium oxide in the second free radical quencher is 1-70%, and the loading amount of the carbon-supported cerium oxide on the cathode diffusion layer is 0.01-0.03 mg/cm 2 。
4. The fuel cell membrane electrode assembly according to claim 1 wherein said carbon-supported cerium oxide is prepared by the following process:
(1) mixing cerium nitrate, an organic solvent and carbon powder, and performing ultrasonic dispersion to obtain a mixed solution;
(2) and under the stirring condition, dropping sodium carbonate into the mixed solution, then continuously stirring for reaction, and sequentially carrying out sedimentation, suction filtration, washing, drying, grinding and roasting to obtain the carbon-supported cerium oxide.
5. The fuel cell membrane electrode assembly according to claim 4 wherein said method of making said carbon-supported cerium oxide further comprises at least one of the following conditions:
1) the organic solvent comprises ethanol;
2) the using mass ratio of the cerium nitrate to the organic solvent to the carbon powder to the sodium carbonate is (10-20): 20-40): 1: (10-20);
3) the ultrasonic dispersion time is 20-60 min;
4) the stirring speed is 80-150 rpm;
5) the reaction time is 8-15 h;
6) the settling time is 6-12 h;
7) the washing liquid used for washing is deionized water;
8) the drying temperature is 80-100 ℃, and the drying time is 3-6 h;
9) the roasting temperature is 500-700 ℃, the roasting time is 5-10 h, and the roasting is carried out in an inert atmosphere.
6. A method for preparing a fuel cell membrane electrode according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) mixing carbon-supported cerium oxide, perfluorinated sulfonic acid resin, water and a first organic solvent, performing ultrasonic dispersion to obtain a first free radical quenching agent, and spraying the obtained first free radical quenching agent on the surface of one side of an anode gas diffusion layer;
(2) mixing a catalyst, perfluorinated sulfonic acid resin, water and a second organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain cathode catalyst slurry and anode catalyst slurry;
(3) spraying anode catalyst slurry on one side surface of the anode gas diffusion layer coated with the free radical quencher to form an anode catalyst layer; directly spraying cathode catalyst slurry on the surface of one side of the proton exchange membrane to form a cathode catalyst layer;
(4) and abutting an anode catalyst layer with the other side surface of the proton exchange membrane, abutting a cathode gas diffusion layer with a cathode catalyst layer, and then performing hot pressing to form the fuel cell membrane electrode.
7. The method for preparing a fuel cell membrane electrode assembly according to claim 6, wherein said method further comprises at least one of the following technical features:
in step (1), the first organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol;
in the step (1), in the first radical quencher, the mass ratio of the carbon-supported cerium oxide, the perfluorinated sulfonic acid resin, the water and the first organic solvent is (0.8-2): 1: (20-100): (30-200);
in the step (1), the frequency of the ultrasound is 30-50 kHZ, and the time is 20-60 min;
in step (2), the catalyst comprises one of platinum black, platinum on carbon or platinum alloy on carbon;
in step (2), the second organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol;
in the step (2), in the cathode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, the water and the second organic solvent is (2-4): 1: (10-40): (20-90);
in the step (2), in the anode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, the water and the second organic solvent is (3-5): 1: (40-100): (100-300);
in the step (2), the frequency of the ultrasonic wave is 30-50 kHZ, and the time is 40-100 min;
in the step (2), the pressure of the high-pressure homogenization is 300-800 bar, and the time of the high-pressure homogenization is 20-60 min;
in the step (4), the hot pressing temperature is 120-170 ℃, the hot pressing time is 10-300s, and the hot pressing pressure is 0.2-3 MPa.
8. The method for preparing a membrane electrode assembly for a fuel cell according to claim 6, wherein the step (1) comprises preparing a second radical quencher and spraying the second radical quencher on one surface of the cathode gas diffusion layer, and the method comprises the following steps:
mixing carbon-supported cerium oxide, perfluorinated sulfonic acid resin, water and a third organic solvent, performing ultrasonic dispersion to obtain a second radical quencher, and spraying the obtained second radical quencher on one side surface of the cathode gas diffusion layer, wherein:
the third organic solvent comprises one or more of isopropanol, n-propanol, ethanol, ethylene glycol, tert-butanol or glycerol;
in the second radical quencher, the mass ratio of the carbon-supported cerium oxide, the perfluorinated sulfonic acid resin, the water and the third organic solvent is (0.8-2): 1: (20-100): (30-200);
the frequency of the ultrasonic wave is 30-50 kHZ, and the time is 20-60 min.
9. A method for preparing a fuel cell membrane electrode according to any one of claims 1 to 5, comprising the steps of:
(a) mixing carbon-supported cerium oxide, a catalyst, perfluorinated sulfonic acid resin, water and a fourth organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain anode catalyst slurry; mixing a catalyst, perfluorinated sulfonic acid resin, water and a fourth organic solvent, and carrying out ultrasonic and high-pressure homogenization to obtain cathode catalyst slurry;
(b) spraying anode catalyst slurry on the surface of the anode gas diffusion layer to form an anode catalyst layer; directly spraying cathode catalyst slurry on the surface of one side of the proton exchange membrane to form a cathode catalyst layer;
(c) and abutting an anode catalyst layer with the other side surface of the proton exchange membrane, abutting a cathode gas diffusion layer with a cathode catalyst layer, and then performing hot pressing to form the fuel cell membrane electrode.
10. The method for preparing a fuel cell membrane electrode assembly according to claim 9 wherein in step (a), said fourth organic solvent comprises one or more of isopropyl alcohol, n-propyl alcohol, ethyl alcohol, ethylene glycol, t-butyl alcohol, or glycerol;
in the step (a), in the anode catalyst slurry, the mass ratio of the cerium oxide on carbon, the catalyst, the perfluorosulfonic acid resin, water and the fourth organic solvent is (1-4): (2-6): 1: (50-100): (100-200);
in the step (a), the frequency of the ultrasonic is 30-50 kHZ, and the time is 20-100 min;
in the step (a), the pressure of the high-pressure homogenization is 300-800 bar, and the time of the high-pressure homogenization is 20-60 min;
in step (a), the catalyst comprises one of platinum black, platinum on carbon, or a platinum alloy on carbon;
in the step (a), in the cathode catalyst slurry, the mass ratio of the catalyst, the perfluorosulfonic acid resin, the water and the second organic solvent is (2-4): 1: (10-40): (20 to 90);
in the step (a), carbon-supported cerium oxide is added into the cathode catalyst slurry, and the mass ratio of the carbon-supported cerium oxide to the catalyst in the cathode catalyst slurry is (0.8-2): (2-6): 1: (20-70): (40-80);
in the step (c), the hot pressing temperature is 120-170 ℃, the hot pressing time is 10-300s, and the hot pressing pressure is 0.2-3 MPa.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104852003A (en) * | 2014-02-17 | 2015-08-19 | 三星Sdi株式会社 | Polymer electrolyte membrane, membrane electrode assembly and fuel cell including the same |
| JP2018085169A (en) * | 2016-11-21 | 2018-05-31 | パナソニックＩｐマネジメント株式会社 | Electrolyte membrane-electrode assembly and fuel cell |
| CN110190310A (en) * | 2019-05-16 | 2019-08-30 | 华南理工大学 | A method of promoting fuel-cell catalyst and membrane electrode durability |
| CN110256913A (en) * | 2019-06-17 | 2019-09-20 | 深圳市通用氢能科技有限公司 | A kind of preparation method of antioxidant, water-retaining agent, mixture, denatured fuel cell membrane-electrode |
| CN112909267A (en) * | 2021-02-04 | 2021-06-04 | 南京壹元新能源科技有限公司 | MEA for proton exchange membrane fuel cell and preparation method thereof |
| CN113140736A (en) * | 2020-06-08 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer structure, preparation method, membrane electrode assembly and fuel cell |
| CN113690450A (en) * | 2021-08-25 | 2021-11-23 | 中汽创智科技有限公司 | Free radical quenching agent, preparation method thereof and application thereof in membrane electrode |
| CN114300702A (en) * | 2022-01-01 | 2022-04-08 | 上海嘉资新材料科技有限公司 | Fuel cell gas diffusion layer structure containing cerium oxide modified carbon nanofiber and preparation method thereof |
-
2022
- 2022-06-27 CN CN202210735413.9A patent/CN114792811A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104852003A (en) * | 2014-02-17 | 2015-08-19 | 三星Sdi株式会社 | Polymer electrolyte membrane, membrane electrode assembly and fuel cell including the same |
| JP2018085169A (en) * | 2016-11-21 | 2018-05-31 | パナソニックＩｐマネジメント株式会社 | Electrolyte membrane-electrode assembly and fuel cell |
| CN110190310A (en) * | 2019-05-16 | 2019-08-30 | 华南理工大学 | A method of promoting fuel-cell catalyst and membrane electrode durability |
| CN110256913A (en) * | 2019-06-17 | 2019-09-20 | 深圳市通用氢能科技有限公司 | A kind of preparation method of antioxidant, water-retaining agent, mixture, denatured fuel cell membrane-electrode |
| CN113140736A (en) * | 2020-06-08 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer structure, preparation method, membrane electrode assembly and fuel cell |
| CN112909267A (en) * | 2021-02-04 | 2021-06-04 | 南京壹元新能源科技有限公司 | MEA for proton exchange membrane fuel cell and preparation method thereof |
| CN113690450A (en) * | 2021-08-25 | 2021-11-23 | 中汽创智科技有限公司 | Free radical quenching agent, preparation method thereof and application thereof in membrane electrode |
| CN114300702A (en) * | 2022-01-01 | 2022-04-08 | 上海嘉资新材料科技有限公司 | Fuel cell gas diffusion layer structure containing cerium oxide modified carbon nanofiber and preparation method thereof |
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