CN113921831B - Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell - Google Patents

Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell Download PDF

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CN113921831B
CN113921831B CN202111105302.1A CN202111105302A CN113921831B CN 113921831 B CN113921831 B CN 113921831B CN 202111105302 A CN202111105302 A CN 202111105302A CN 113921831 B CN113921831 B CN 113921831B
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catalyst
ionomer
electrode
catalyst slurry
membrane
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CN113921831A (en
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唐柳
于力娜
朱雅男
刘江唯
张中天
张克金
刘晓雪
王晶晶
苗梓航
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FAW Jiefang Automotive Co Ltd
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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
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method of electrode catalyst slurry, which comprises the following steps: carrying out first mixing dispersion on the catalyst and the ionomer solution, standing at 90-110 ℃ for self-assembly, filtering to obtain a solid, and carrying out freeze drying to obtain the ionomer-coated catalyst; and carrying out second mixing and dispersing on the ionomer-coated catalyst and the solvent to obtain the electrode catalyst slurry. Through mixing the dispersion with the ionomer solution earlier catalyst, and control and stew under certain condition self-assembly, and carry out freeze-drying, make the catalyst surface cladding have the ionomer membrane that the one deck has even hole, effectively solved traditional adding catalyst, ionomer and solvent and appear ionomer and catalyst uneven distribution problem together, effectively improve the catalyst utilization ratio through the mass transfer efficiency who improves the catalysis layer, reduce the platinum load volume.

Description

Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to electrode catalyst slurry and a preparation method thereof, a catalyst coating film and a fuel cell.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electric energy, and is also called an electrochemical generator, and from the viewpoint of energy saving and ecological environment protection, the fuel cell is considered to have a power generation technology with a great development prospect; the proton exchange membrane fuel cell has the advantages of low working temperature, high power density, quick starting capability and the like, and is considered as an ideal power source of the electric automobile. The core component of the proton exchange membrane fuel cell is a membrane electrode, wherein a catalyst layer is a main place of electrochemical reaction of the membrane electrode, the performance of the catalyst layer directly influences the performance of the membrane electrode, and the catalyst layer with good performance needs to have a good electron, proton and gas three-phase transmission channel. It is common practice to add an ionomer to the catalyst to provide adhesion and also to act as a proton transport channel for the reaction.
However, the traditional preparation method of adding ionomer into catalyst is to add catalyst, ionomer, solvent and the like together for stirring, so that the morphology of ionomer and catalyst cannot be controlled, the ionomer and catalyst are easily distributed unevenly in the drying process, a three-phase reaction channel is not smooth, the utilization rate of the fuel cell catalyst is reduced, and the efficiency of the fuel cell is reduced. Or, by adding a certain amount of thickening agent and adjusting the stirring dispersion mode, the agglomeration of catalyst particles is reduced, and the dispersion performance of the catalyst is improved. However, the thickener does not conduct electrons and protons, and may affect the performance of the membrane electrode.
Disclosure of Invention
Based on this, the present invention provides an electrode catalyst slurry, a method for preparing the same, a catalyst coated membrane, and a fuel cell, which allow uniform distribution of an ionomer and a catalyst.
The technical scheme of the invention for solving the technical problems is as follows.
A preparation method of electrode catalyst slurry comprises the following steps:
carrying out first mixing dispersion on the catalyst and the ionomer solution, standing at 90-110 ℃ for self-assembly, filtering to obtain a solid, and carrying out freeze drying to obtain the ionomer-coated catalyst;
and carrying out second mixing and dispersing on the ionomer-coated catalyst and the solvent to obtain the electrode catalyst slurry.
In some of the embodiments, the concentration of the ionomer solution in the preparation method of the electrode catalyst slurry is 0.03wt% to 8wt%.
In some of the embodiments, in the method of preparing an electrode catalyst slurry, the catalyst is selected from at least one of platinum carbon and platinum alloy carbon.
In some embodiments, in the preparation method of the electrode catalyst slurry, the mass ratio of the ionomer in the ionomer solution to the carbon in the catalyst is (0.5-3.6): 1.
In some of the embodiments, in the method of preparing an electrode catalyst slurry, the ionomer in the ionomer solution is a perfluorosulfonic acid resin.
In some of the embodiments, in the preparation method of the electrode catalyst slurry, the first mixing dispersion and/or the second mixing dispersion is shear dispersion;
the speed of the first mixed dispersion and the second mixed dispersion is 10000 r/min-30000 r/min, and the time is 10 min-30 min.
In some embodiments, in the preparation method of the electrode catalyst slurry, the standing self-assembly time is 8-24 h.
In some embodiments, in the preparation method of the electrode catalyst slurry, the freeze-drying temperature is-10 ℃ to-50 ℃ and the time is 24h to 48h.
The invention provides the electrode catalyst slurry prepared by the preparation method of the electrode catalyst slurry.
The invention provides a catalyst coating membrane which comprises a cathode catalyst layer, an anode catalyst layer and a proton exchange membrane, wherein the anode catalyst layer and the cathode catalyst layer are arranged on two sides of the proton exchange membrane, and the anode catalyst layer and/or the anode catalyst layer are/is prepared from the electrode catalyst slurry.
The invention provides a membrane electrode assembly, which comprises a gas diffusion layer and the catalyst coating membrane, wherein the gas diffusion layer is arranged on one side of the anode catalytic layer and one side of the cathode catalytic layer, which are far away from the proton exchange membrane, in the catalyst coating membrane.
The invention provides a fuel cell, which comprises an anode plate, a cathode plate and a membrane electrode assembly, wherein the anode plate and the cathode plate are arranged on two sides of the membrane electrode assembly.
Compared with the prior art, the preparation method of the electrode catalyst slurry has the following beneficial effects:
the preparation method of the electrode catalyst slurry provided by the invention comprises the steps of mixing and dispersing a catalyst and an ionomer solution, standing for self-assembly under specific conditions, and freeze-drying; under the specific condition, the surface of the catalyst is coated by a layer of ionomer film, after the temperature is suddenly reduced, the film is uniformly shrunk, so that the ionomer film on the surface of the catalyst is shrunk to expose holes, the surface of the catalyst is coated with the ionomer film with uniform holes, and the problem that the ionomer and the catalyst are not uniformly distributed when the catalyst, the ionomer and the solvent are added together in the prior art is effectively solved. Meanwhile, the ionomer membrane coated on the surface of the catalyst is provided with uniform holes, so that a transmission channel is added for gas in the catalyst layer, a uniform channel is also provided for protons and electrons, the utilization rate of the catalyst is improved, and the efficiency of the fuel cell is improved. And the ionomer membrane is uniformly coated around the catalyst, so that the binding force between the substrate and a catalyst layer formed by electrode catalyst slurry is increased, and the contact resistance between the catalyst layer and the substrate layer is reduced, thereby improving the performance of the membrane electrode.
Detailed Description
The electrode catalyst slurry, the production method thereof, the catalyst coated membrane, and the fuel cell according to the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated are in fact significant. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight of each component, therefore, the proportional enlargement or reduction of the content of the related components according to the description of the embodiments of the present invention is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical field, such as μ g, mg, g, kg, etc.
An embodiment of the present invention provides a method for preparing an electrode catalyst slurry, including the steps of:
carrying out first mixing dispersion on the catalyst and the ionomer solution, standing at 90-110 ℃ for self-assembly, filtering to obtain a solid, and carrying out freeze drying to obtain the ionomer-coated catalyst;
and carrying out second mixing and dispersing on the ionomer-coated catalyst and the solvent to obtain electrode catalyst slurry.
The catalyst, the ionomer and the solvent are mixed together, the ionomer is distributed among the catalysts, in the solvent evaporation process, particularly when the solvent is quickly evaporated, the ionomer is unevenly distributed due to different migration rates of the ionomer in the solvent caused by uneven heating, the ionomer is not arranged around some catalysts and cannot conduct protons, the ionomer is too much around some catalysts, and the efficiency of the catalyst is reduced due to the obstructed gas transmission. The catalyst and the ionomer solution are mixed and dispersed, standing self-assembly is carried out at the temperature of 90-110 ℃, and freeze drying is carried out, so that the surface of the catalyst is coated with an ionomer membrane with uniform holes.
In some examples, the concentration of the ionomer solution in the preparation method of the electrode catalyst slurry is 0.03wt% to 8wt%. The ionomer with specific concentration is adopted, so that the dispersion of the catalyst in the ionomer solution is facilitated, an ionomer membrane formed on the surface of the catalyst by subsequent self-assembly is more uniform, the membrane formation is uneven due to overhigh concentration, and the membrane formation is difficult due to overlow concentration. Alternatively, the concentration of the ionomer solution is in the range of 0.1wt% to 5wt%.
In some specific examples, the ionomer solution is prepared in a method of preparing an electrode catalyst slurry at a concentration of 1wt% to 5wt%. In some preferred examples, the ionomer solution is prepared in a method of preparing an electrode catalyst slurry having a concentration of 3wt% to 5wt%. Preferably, the ionomer solution has a concentration of 3wt%.
It is understood that an ionomer solution is one in which the ionomer is dissolved in a solvent; if the ionomer solution is purchased, it may be further diluted with a solvent to the desired concentration. In some examples, the method for preparing an electrode catalyst slurry includes a method for preparing an electrode catalyst slurry, in which a solvent for dissolving or diluting an ionomer solution is selected from at least one of isopropyl alcohol, methanol, n-propyl alcohol, ethanol, ethylene glycol, and propylene glycol.
In some of the examples, in the method of preparing the electrode catalyst slurry, the catalyst is selected from at least one of platinum carbon and platinum alloy carbon. Optionally, the platinum alloy carbon is selected from at least one of platinum cobalt carbon or platinum nickel carbon.
In some specific examples, in the preparation method of the electrode catalyst slurry, the mass percentage of platinum in the catalyst is 20-70%.
In some examples, the electrode catalyst slurry is prepared in a process wherein the mass ratio of ionomer in the ionomer solution to carbon in the catalyst is (0.5-3.6): 1. The thickness of the ionomer film formed on the surface of the antipolarity catalyst is proper by controlling the mass ratio of the ionomer in the ionomer solution to the carbon in the catalyst. Alternatively, the mass ratio of ionomer in the ionomer solution to carbon in the catalyst is (0.8-2.8): 1.
In some preferred examples, the electrode catalyst slurry is prepared in a process wherein the mass ratio of ionomer in the ionomer solution to carbon in the catalyst is (1-2.8): 1. Preferably, the mass ratio of ionomer in the ionomer solution to carbon in the catalyst is 2.8.
In some of these examples, the ionomer in the ionomer solution is a perfluorosulfonic acid resin in the method of preparing an electrode catalyst slurry.
It is to be understood that the ionomer perfluorosulfonic acid resin brand can be at least one of Nafion, aquivion, eastern yuen, and Fumion.
In some specific examples, the ionomer in the ionomer solution is selected from perfluorosulfonic acid resins in the method of preparing an electrode catalyst slurry.
In some examples, the solvent is selected from at least one of isopropyl alcohol, methanol, n-propyl alcohol, ethanol, ethylene glycol, and propylene glycol. It will be appreciated that the solvent used in the second mixing and dispersing step of the ionomer-coated catalyst and solvent may be the same or different than the solvent used to dissolve or dilute the ionomer solution. Alternatively, the solvent used in the second mixing and dispersing step of the ionomer-coated catalyst and solvent is the same solvent used to dissolve or dilute the ionomer solution. In some examples, in the preparation method of the electrode catalyst slurry, the mass ratio of the solvent to carbon in the catalyst is (200-500): 1; optionally, the mass ratio of the solvent to the carbon in the catalyst is (300-408): 1.
In some examples thereof, the first mixed dispersion and/or the second mixed dispersion is a shear dispersion; the speed of the first mixing and dispersing and the second mixing and dispersing is 10000 r/min-30000 r/min, and the time is 10 min-30 min. It is understood that the rate and time of the first mixing and dispersing and the second mixing and dispersing may be the same or different, and are controlled according to actual conditions. Optionally, the first mixing and dispersing and the second mixing and dispersing are both at a rate of 10000r/min to 20000r/min.
In some examples, in the preparation method of the electrode catalyst slurry, the temperature of standing self-assembly is 90-105 ℃; preferably, the temperature at which the self-assembly is allowed to stand is 100 ℃.
In some examples, in the preparation method of the electrode catalyst slurry, the standing self-assembly time is 8-24 h; optionally, the standing self-assembly time is 8-15 h.
In some examples, the electrode catalyst slurry is prepared at a temperature of-10 ℃ to-50 ℃ for 24h to 48h. Optionally, the temperature of freeze drying is-10 ℃ to-30 ℃; preferably, the temperature of freeze-drying is-20 ℃.
It will be appreciated that in some of the examples, the electrode catalyst slurry is prepared by wetting the catalyst with water prior to mixing and dispersing the catalyst and ionomer solution; or the ionomer-coated catalyst is wetted with water before subjecting the ionomer-coated catalyst and solvent to a second mixing dispersion. In some examples, in the preparation method of the electrode catalyst slurry, when the catalyst and the ionomer solution are subjected to first mixing dispersion, after the ionomer-coated catalyst is wetted with water, the ionomer solution is added dropwise; and when the ionomer-coated catalyst and the solvent are subjected to second mixing and dispersion, the solvent is also added dropwise.
In some examples, the electrode catalyst slurry is prepared by washing a solid obtained by filtration after standing for self-assembly with water and freeze-drying.
An embodiment of the present invention provides an electrode catalyst slurry prepared by the above method for preparing an electrode catalyst slurry.
The electrode catalyst slurry prepared by the invention has the advantages of uniform dispersion, good stability, good mass transfer and high performance, effectively improves the utilization rate of the catalyst and reduces the platinum loading capacity.
The invention provides a catalyst coating membrane, which comprises a cathode catalyst layer, an anode catalyst layer and a proton exchange membrane, wherein the anode catalyst layer and the cathode catalyst layer are arranged on two sides of the proton exchange membrane, and the anode catalyst layer and/or the anode catalyst layer are/is prepared from the electrode catalyst slurry.
An embodiment of the present invention provides a method for preparing a catalyst coated membrane, including steps S10 to S20.
Step S10: the electrode catalyst slurry was prepared according to the above-described preparation method of the electrode catalyst slurry.
Step S20: catalyst Coated Membranes (CCMs) were prepared. Specifically, the electrode catalyst slurry prepared in step S10 is sprayed on one side or both sides of the proton exchange membrane and dried. It can be understood that, in some examples, the electrode catalyst slurry prepared in step S10 is sprayed on one side of the proton exchange membrane and dried to form a cathode catalyst layer; alternatively, in other examples, the electrode catalyst slurry prepared in step S10 is sprayed on one side of the proton exchange membrane and dried to form the anode catalyst layer. It can be understood that when the electrode catalyst slurry prepared in step S10 is sprayed on one side of the proton exchange membrane and dried to form an anode catalyst layer, the cathode catalyst slurry commonly used in the art may be sprayed on the other side of the proton exchange membrane to prepare a catalyst coated membrane; or, when the electrode catalyst slurry prepared in step S10 is sprayed on one side of the proton exchange membrane and dried to form a cathode catalyst layer, the anode catalyst slurry commonly used in the art may be sprayed on the other side of the proton exchange membrane to prepare a catalyst coated membrane. Further, in some examples, the electrode catalyst slurry prepared in step S10 is sprayed on both sides of the proton exchange membrane, dried to form an anode catalytic layer and a cathode catalytic layer, and a catalyst coated membrane is prepared.
It is understood that the anode catalytic layer on one side of the proton exchange membrane may be used as the anode and the cathode catalytic layer on the other side of the proton exchange membrane may be used as the cathode.
In some examples, the cathode spray mass is 0.15mg/cm in step S20 2 ～0.2mg/cm 2 The anode spraying mass is 0.03mg/cm 2 ～0.08mg/cm 2 。
In some examples, the step of spraying the anode catalyst slurry and the cathode catalyst slurry is performed at 50 ℃ to 80 ℃ in step S20.
In some examples, in step S20, the drying is performed under vacuum at a temperature of 50 ℃ to 80 ℃ for 2min to 10min.
It is understood that, in some specific examples thereof, the temperature at which the anode catalyst slurry and the cathode catalyst slurry are sprayed is the same as the temperature at which they are dried under vacuum conditions.
An embodiment of the present invention provides a Membrane Electrode Assembly (MEA) including a gas diffusion layer and a catalyst coated Membrane as described above, wherein the gas diffusion layer is disposed on both sides of the anode catalyst layer and the cathode catalyst layer of the catalyst coated Membrane away from the proton exchange Membrane.
In some examples, the material of the gas diffusion layer in the membrane electrode assembly is selected from at least one of carbon fiber paper, carbon fiber woven cloth, non-woven cloth, and carbon black paper. Optionally, the material of the gas diffusion layer is selected from carbon fiber paper.
Accordingly, an embodiment of the present invention provides a method for preparing a membrane electrode assembly, including the steps of:
the catalyst coated membrane as described above is provided, and the materials of the gas diffusion layers are placed on both sides of the catalyst coated membrane and hot-pressed to form the gas diffusion layers, respectively, to obtain a membrane electrode assembly.
In some examples, the membrane electrode assembly is prepared by hot pressing at a pressure of 0.1MPa to 0.6MPa, at a temperature of 60 ℃ to 120 ℃ for 10s to 30s.
The membrane electrode prepared by the invention has simple preparation process and is suitable for large-scale and industrialized production.
An embodiment of the present invention provides a fuel cell including an anode plate, a cathode plate, and a membrane electrode assembly as described above, the anode plate and the cathode plate being provided on both sides of the membrane electrode assembly.
The preparation method of the electrode catalyst slurry provided by the invention mixes and disperses the catalyst and the ionomer solution, and the ionomer and the catalyst are uniformly distributed by controlling the concentration of the ionomer solution, the adding amount of the catalyst and the ionomer, controlling the parameters in the steps of standing self-assembly under specific conditions, freeze drying and the like to coat a layer of ionomer membrane with uniform holes on the surface of the catalyst; provide uniform channels for gas, protons and electrons in the catalyst layer, and improve the utilization rate of the catalyst, thereby improving the efficiency of the fuel cell.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, the electrode catalyst slurry, the preparation method thereof, the catalyst coating layer, and the fuel cell according to the present invention are exemplified, and it is understood that the electrode catalyst slurry, the preparation method thereof, the catalyst coating layer, and the fuel cell according to the present invention are not limited to the following examples.
The ionomer solutions used in the following examples were all ionomer solutions diluted with isopropanol.
Example 1
Preparing electrode catalyst slurry: weighing 1g of platinum alloy catalyst platinum cobalt carbon (the content of the carbon carrier is 78%) with the platinum content of 20%, wetting the platinum alloy catalyst platinum cobalt carbon with 0.1g of deionized water, then dropwise adding 5wt% of Nafion solution, wherein the mass ratio of Nafion in the Nafion solution to carbon in the platinum cobalt carbon is 2.8. 234g of isopropanol is dropwise added into the ionomer-coated catalyst, the mixture is stirred and mixed uniformly by ice bath and ultrasound, and shearing and dispersion are carried out for 30min under 10000min to prepare electrode catalyst slurry.
Preparing CCM: the prepared electrode catalyst slurry is sprayed on two sides of a proton exchange membrane at 50 ℃ by an ultrasonic spraying machine to be respectively used as a cathode and an anode. Wherein the cathode spraying mass is 0.2mg/cm 2 The anode spraying mass is 0.03mg/cm 2 (ii) a Drying under vacuum adsorption condition at 50 deg.C for 2min to obtain CCM.
Preparing a membrane electrode assembly: carbon paper is put on two sides of the prepared CCM, and hot pressing is carried out for 30s at the temperature of 60 ℃ under the pressure of 0.1MPa, so as to respectively form gas diffusion layers and obtain the membrane electrode assembly.
Example 2
Preparing electrode catalyst slurry: weighing 2.2g platinum nickel carbon (the content of a carbon carrier is 27%) of a platinum alloy catalyst with the platinum content of 70%, wetting the platinum nickel carbon with 0.1g deionized water, then dropwise adding 0.1wt.% of Aquivion solution, wherein the mass ratio of an ionomer in the Aquivion solution to carbon in the platinum nickel carbon is 0.8. 242g of isopropanol is added into the ionomer-coated catalyst drop by drop, ice bath ultrasonic stirring is carried out, the mixture is uniformly mixed, and shearing dispersion is carried out for 30min at 30000min, so as to prepare electrode catalyst slurry.
Preparing CCM: the prepared electrode catalyst slurry is sprayed on two sides of a proton exchange membrane at 80 ℃ by an ultrasonic spraying machine and respectively used as a cathode and an anode. Wherein the cathode spraying mass is 0.2mg/cm 2 The anode spraying mass is 0.03mg/cm 2 (ii) a Drying under vacuum adsorption condition at 80 deg.C for 10min to obtain CCM.
Preparing a membrane electrode assembly: carbon paper is put on two sides of the prepared CCM, and hot pressing is carried out for 10s at the temperature of 120 ℃ under the pressure of 0.6MPa, so as to form gas diffusion layers respectively, and the membrane electrode assembly is obtained.
Example 3
Preparing electrode catalyst slurry: weighing 1.5g of platinum-carbon catalyst with platinum content of 50%, wetting with 0.1g of deionized water, then dropwise adding 1wt% of Dongye perfluorosulfonic acid solution, wherein the mass ratio of ionomer in the Dongye perfluorosulfonic acid to carbon in platinum-carbon is 1.2. 263g of isopropanol is added into the ionomer-coated catalyst drop by drop, ice bath ultrasonic stirring is carried out to mix evenly, and shearing dispersion is carried out for 20min under 20000min to prepare the electrode catalyst slurry.
Preparing CCM: the prepared electrode catalyst slurry is sprayed on two sides of a proton exchange membrane at 60 ℃ by an ultrasonic spraying machine to be respectively used as a cathode and an anode. Wherein the cathode spraying mass is 0.2mg/cm 2 The anode spraying mass is 0.03mg/cm 2 (ii) a Drying under vacuum adsorption condition at 60 deg.C for 8min to obtain CCM.
Preparing a membrane electrode assembly: carbon paper is put on two sides of the prepared CCM, and the CCM is hot-pressed for 20s at the temperature of 100 ℃ under the pressure of 0.4MPa to respectively form gas diffusion layers, so that the membrane electrode assembly is obtained.
Example 4
Essentially the same as in example 1 except that the ionomer solution was at a concentration of 0.3wt%.
Example 5
The same as in example 1, except that the ionomer-to-catalyst mass ratio in the ionomer solution was 1.
Example 6
Substantially the same as in example 1, except that an electrode catalyst slurry was prepared and sealed at 90 ℃ for 8 hours for ionomer high temperature self-assembly.
Comparative example 1
Substantially the same as in example 1, except that the steps for preparing the electrode catalyst slurry were different as follows:
preparing electrode catalyst slurry: weighing 1g of platinum alloy catalyst platinum-cobalt-carbon with platinum content of 20%, wetting with 0.1g of deionized water, dropwise adding 5wt.% of ionomer solution, wherein the mass ratio of ionomer in the ionomer solution to carbon in the platinum-cobalt-carbon is 2.8.
Comparative example 2
Substantially the same as in example 1, except that in preparing the electrode catalyst slurry, the ionomer high temperature self-assembly was performed while hermetically standing at 70 ℃ for 8 hours. The method comprises the following specific steps:
preparing electrode catalyst slurry: weighing 1g of platinum alloy catalyst platinum cobalt carbon with platinum content of 20%, wetting with 0.1g of deionized water, then dropwise adding 5wt.% of Nafion solution, wherein the mass ratio of ionomer in the Nafion solution to carbon in the platinum cobalt carbon is 2.8. 234g of isopropanol is added into the ionomer-coated catalyst drop by drop, ice bath ultrasonic stirring is carried out, the mixture is uniformly mixed, and shearing dispersion is carried out for 30min under 10000min, so as to prepare electrode catalyst slurry.
The setting parameters of each example and comparative example are shown in table 1.
TABLE 1
Figure BDA0003272054090000131
Placing a gasket on a cathode end plate with a current collecting plate, respectively placing the membrane electrode assemblies prepared in the examples 1-6 and the comparative examples 1-2 in the middle part according to the cathode and the anode, and installing the gasket on the other side; the bipolar plate is well covered after being positioned and aligned, the end plate with the collector plate is arranged, the battery is locked by screws, and the torque wrench is screwed up to assemble the monocell.
And connecting the assembled single cell to a fuel cell testing platform for testing. And (3) testing conditions are as follows: the battery temperature is 70 ℃, and the gas excess coefficient is H 2 Air =1.5/2.5, humidity 70%, no back pressure. The results are shown in Table 2.
TABLE 2
Figure BDA0003272054090000141
As can be seen from table 2, the membrane electrode assemblies prepared in embodiments 1 to 6 of the present invention have a large power density at different voltages, i.e., have good electrochemical properties; in contrast, comparative example 1, the high-temperature self-assembly step was not performed, and the performance of the slurry prepared into the membrane electrode was poor, which indicates that the ionomer was uniformly distributed on the surface of the catalyst after self-assembly, thereby improving the utilization rate of platinum and improving the membrane electrode performance; in comparative example 2, since the self-assembly temperature is not high enough, the ionomer can form pores on the surface of the catalyst when the film is frozen at low temperature, but the pores of the ionomer are reduced or even disappear during the operation of the membrane electrode, the gas mass transfer is poor, the utilization rate of the catalyst is low, and the membrane electrode performance is low. The high temperature of this step is shown to contribute to ionomer pore formation and thus to improve catalyst platinum utilization.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent should be subject to the content of the appended claims, and the description can be used to interpret the content of the claims.

Claims (12)

1. A preparation method of electrode catalyst slurry is characterized by comprising the following steps:
carrying out first mixing dispersion on the catalyst and the ionomer solution, standing at 90-110 ℃ for self-assembly, filtering to obtain a solid, and carrying out freeze drying to obtain the ionomer-coated catalyst; the ionomer in the ionomer solution is perfluorinated sulfonic acid resin, the mass ratio of the ionomer in the ionomer solution to carbon in the catalyst is (0.5-3.6): 1, the standing self-assembly time is 8-24 h, the freeze-drying temperature is-10 ℃ to-50 ℃, and the freeze-drying time is 24-48 h;
and carrying out second mixing and dispersing on the ionomer-coated catalyst and the solvent to obtain the electrode catalyst slurry.
2. The method for preparing an electrode catalyst slurry according to claim 1, wherein the ionomer solution has a concentration of 0.03wt% to 8wt%.
3. The method for preparing an electrode catalyst slurry according to claim 1, wherein the catalyst is at least one selected from platinum carbon and platinum alloy carbon.
4. The method for preparing an electrode catalyst slurry according to claim 3, wherein the mass ratio of the ionomer in the ionomer solution to carbon in the catalyst is (0.8-2.8): 1.
5. The method for preparing an electrode catalyst slurry according to claim 1, wherein the solvent is at least one selected from the group consisting of isopropyl alcohol, methanol, n-propyl alcohol, ethanol, ethylene glycol, and propylene glycol.
6. The method for preparing an electrode catalyst slurry according to any one of claims 1 to 5, wherein the first mixed dispersion and/or the second mixed dispersion is a shear dispersion;
the speed of the first mixed dispersion and the second mixed dispersion is 10000 r/min-30000 r/min, and the time is 10 min-30 min.
7. The method for preparing an electrode catalyst slurry according to any one of claims 1 to 5, wherein the time for the standing self-assembly is 8 to 15 hours.
8. The method for preparing an electrode catalyst slurry according to any one of claims 1 to 5, wherein the temperature of the freeze-drying is from-10 ℃ to-30 ℃.
9. The electrode catalyst slurry prepared by the method for preparing an electrode catalyst slurry according to any one of claims 1 to 8.
10. A catalyst coated membrane comprising a cathode catalyst layer, an anode catalyst layer and a proton exchange membrane, wherein the anode catalyst layer and the cathode catalyst layer are provided on both sides of the proton exchange membrane, and the anode catalyst layer and/or the anode catalyst layer is made of the electrode catalyst slurry according to claim 9.
11. A membrane-electrode assembly, comprising a gas diffusion layer and a catalyst-coated membrane according to claim 10, wherein the gas diffusion layer is provided on both sides of the anode-and cathode-catalyst layers of the catalyst-coated membrane facing away from the proton-exchange membrane.
12. A fuel cell comprising an anode plate, a cathode plate, and the membrane electrode assembly according to claim 11, wherein the anode plate and the cathode plate are provided on both sides of the membrane electrode assembly.
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