CN113555568A - Membrane electrode and preparation method thereof - Google Patents

Membrane electrode and preparation method thereof Download PDF

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Publication number
CN113555568A
CN113555568A CN202110844884.9A CN202110844884A CN113555568A CN 113555568 A CN113555568 A CN 113555568A CN 202110844884 A CN202110844884 A CN 202110844884A CN 113555568 A CN113555568 A CN 113555568A
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conductive adhesive
membrane electrode
coating
catalyst
slurry
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李丰军
周剑光
漆海龙
杨成
周小草
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China Automotive Innovation Co Ltd
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China Automotive Innovation 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a membrane electrode with low interface contact resistance and a preparation method thereof. The preparation method of the membrane electrode comprises the following steps: 1) uniformly dispersing conductive particles, a hydrophobic polymer adhesive and solvent alcohol to prepare conductive adhesive slurry; 2) preparing catalyst slurry, and coating the catalyst slurry on the surface of a proton exchange membrane to prepare CCM; 3) and coating the conductive adhesive slurry on the side surface of the GDL microporous layer and/or the surface of the CCM, drying to form a conductive adhesive coating, bonding the CCM and the GDL through the conductive adhesive coating to form a membrane electrode, and assembling the membrane electrode to the fuel cell. The method of the invention coats the conductive adhesive layer on the surfaces of the CCM and the GDL microporous layer side, and utilizes the cell assembly and operation process to lead the CCM and the GDL to be tightly adhered together, thereby effectively reducing the interface contact impedance and improving the performance of the fuel cell.

Description

Membrane electrode and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a membrane electrode in a proton exchange membrane fuel cell and a preparation method thereof.
Background
A fuel cell is an electrochemical cell whose main principle is to convert chemical energy in a fuel and an oxidant directly into electrical energy through an oxidation-reduction reaction. The proton exchange membrane fuel cell is an important branch of the fuel cell field, and has the advantages of high starting speed at room temperature, small volume, no electrolyte loss, easy water drainage, long service life, high specific power and specific energy and the like besides the general characteristics of the fuel cell. The core component of a proton exchange membrane fuel cell is a membrane electrode, which is a place for the fuel cell to perform oxidation-reduction reaction, and mainly comprises a gas diffusion layer, a catalyst layer, a proton exchange membrane and the like.
The current Membrane electrode is generally prepared by directly coating a Catalyst layer on a Proton Exchange Membrane (PEM) to form a Catalyst Coated Membrane (CCM), and then bonding the CCM and a Gas Diffusion Layer (GDL) together to prepare a Membrane electrode; another membrane Electrode preparation method is to directly coat the catalyst slurry on the GDL to prepare a Gas Diffusion Electrode (GDE), and then combine the Gas Diffusion Electrode with a proton exchange membrane, namely the GDE preparation method. The CCM preparation method can overcome the problems of large interface resistance between the catalyst layer and the proton exchange membrane, blockage of gas diffusion layer pore channels by catalyst particles and the like in the GDE preparation method, so that the CCM preparation method is widely applied at the present stage.
In the CCM production method, there is mainly a large interfacial contact resistance between the catalytic layer and the gas diffusion layer, which seriously affects the performance of the fuel cell. In order to reduce the interfacial contact resistance between the catalytic layer and the gas diffusion layer and improve the performance of the fuel cell, hot press bonding of the CCM and the gas diffusion layer is generally performed. In such a hot press bonding process, the high temperature and pressure used often cause irreversible damage to the porous structures of the gas diffusion layer and the catalytic layer, which results in an increase in mass transfer resistance of the gas and a decrease in performance of the fuel cell. Meanwhile, in order to improve the bonding effect between the gas diffusion layer and the CCM, a layer of glue is usually coated around the gas diffusion layer, and the glue is usually a polyester hot-pressing glue. In the strong acid environment of the fuel cell, the structure of the hot-pressing adhesive can be decomposed to introduce new impurities into the cell to influence the activity of the catalyst, thereby causing the reduction of the performance of the cell. Therefore, the structure and the process of the fuel cell membrane electrode are optimized, the interface contact resistance between the catalyst layer and the gas diffusion layer is reduced, and the method has great significance for improving the performance of the fuel cell.
Disclosure of Invention
In the CCM preparation process, a large interface contact resistance exists between the catalytic layer electrode and the gas diffusion layer, so a hot-press bonding process is required in the membrane electrode preparation. The hot-press bonding between the gas diffusion layer and the catalytic layer electrode reduces the interface contact resistance between the gas diffusion layer and the catalytic layer electrode, but the pressure of the hot-press causes irreversible damage to the porous structures of the gas diffusion layer and the catalytic layer, so that the mass transfer resistance of the gas is increased, and the performance of the fuel cell is reduced. Meanwhile, the gas diffusion layer bonding glue used in the hot pressing process is decomposed in a strong acid environment in which the fuel cell operates for a long time, so that new impurities are introduced into the cell to influence the activity of the catalyst, thereby causing the degradation of the cell performance.
Aiming at the defects, the invention aims to provide a preparation method of a membrane electrode, which can overcome the defects of damage to the porous structures of a gas diffusion layer and a catalyst layer caused by a hot-pressing bonding process and the performance reduction of a battery caused by the decomposition of bonding glue by adopting the hot-pressing bonding process, enables the catalyst layer and the gas diffusion layer to be tightly bonded through the optimization of the surface structures of the gas diffusion layer and the catalyst layer, and simultaneously avoids the adverse effect on the pore structure, thereby effectively reducing the interface contact resistance between the catalyst layer and the gas diffusion layer and improving the performance of the fuel battery.
It is still another object of the present invention to provide a membrane electrode having low interfacial contact resistance prepared by the method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making a membrane electrode comprising the steps of:
1) preparation of conductive adhesive slurry
And uniformly dispersing the conductive particles, the hydrophobic polymer adhesive and the alcohol solvent to prepare the conductive adhesive slurry.
2) Preparation of Catalyst Coated Membranes (CCM)
Fully and uniformly mixing a platinum-carbon catalyst, deionized water, an alcohol solvent and a perfluorinated sulfonic acid resin solution to prepare catalyst slurry, and coating the catalyst slurry on the upper surface and the lower surface of a proton exchange membrane.
3) Preparation of membrane electrode
Coating the conductive adhesive slurry obtained in the step 1) on the side surface of the microporous layer of the GDL and/or the surface of the CCM obtained in the step 2), drying to form a conductive adhesive coating, bonding the CCM and the gas diffusion layer through the conductive adhesive coating to form a membrane electrode, and assembling the fuel cell.
After the membrane electrode, the collector plate, the flow passage plate and the like are assembled into the fuel cell, the CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded together by the pressure naturally generated in the process of assembling the cell, and the bonding performance between the CCM and the gas diffusion layer is further enhanced along with the high-temperature environment in the operation of the cell.
In the above method, the sequence of step 1) and step 2) is not limited. The catalyst-coated membrane (CCM) can be produced, among other things, by methods known in the art.
According to the method of the present invention, a preferred method for membrane electrode preparation may be a method of assembling a fuel cell after forming a membrane electrode by applying conductive adhesive slurries to the microporous layer side surface of a GDL and the surface of a CCM, respectively, and then bonding the conductive adhesive coating of the CCM and the conductive adhesive coating of the GDL, using the process flow shown in fig. 1.
Another method for preparing a membrane electrode can be to apply conductive adhesive slurry to the surface of the microporous layer of the GDL, and then to bond the conductive adhesive coatings of the CCM and the GDL to form a membrane electrode, followed by assembling the fuel cell, using the process shown in fig. 2.
The third method for preparing the membrane electrode can adopt the process flow shown in fig. 3, and the conductive adhesive slurry is coated on the surface of the CCM, and then the conductive adhesive coating of the CCM is bonded with the GDL to form the membrane electrode, and then the fuel cell is assembled.
In the step 1), the mass ratio of the conductive particles to the hydrophobic polymer adhesive is 1-10: 1, the solid content of the conductive adhesive slurry is between 1 and 50 percent.
In the step 1), the conductive particles are selected from one or more of platinum-carbon catalyst, platinum black, iridium black, graphene powder, carbon nanotube powder, carbon black powder, acetylene black and ketjen black; preferably, the size of the conductive particles is between 0.01um and 100um, preferably 0.05um and 0.5 um.
In the step 1), the hydrophobic adhesive may be liquid or solid powder, and is preferably one or more selected from styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyvinyl chloride, polythiophene and polyaniline.
In the step 2), preferably, the mass ratio of the platinum-carbon catalyst to the perfluorosulfonic acid resin is 1-5: 1, the mass ratio of the deionized water to the alcohol is 0.5-5: 1; the solid content of the catalyst slurry is 1-30%.
In the step 2), the catalyst slurry is preferably coated on the surface of the proton exchange membrane by a method such as spraying or direct coating.
In the step 3), the conductive adhesive may be applied by spraying or direct coating.
Preferably, the thickness of the conductive adhesive coating is between 0.05um and 50um, preferably 0.1um and 2 um.
In the method, the solvent alcohol is preferably selected from ethanol, isopropanol, n-propanol, n-butanol and the like.
The invention also relates to a membrane electrode prepared by the method and having low interface contact resistance.
According to the invention, the surfaces of the CCM and the gas diffusion layer are coated with the ultrathin conductive bonding layer with excellent performance, the gas diffusion layer and the catalytic layer surface structure are optimized, and the conductive bonding layer can be softened and has bonding property in the battery operation process, so that the CCM and the gas diffusion layer are tightly bonded, the interface contact resistance between the CCM and the gas diffusion layer can be greatly reduced, meanwhile, the damage of a hot-pressing bonding process to the porous structures of the gas diffusion layer and the catalytic layer is avoided, the porous structures of the gas diffusion layer and the catalytic layer are effectively maintained, and the performance of the fuel battery is improved. On the other hand, the conductive adhesive layer has hydrophobicity, so that the water management in the membrane electrode can be perfected, the mass transfer effect of gas can be improved, and the performance of the fuel cell can be further improved.
Has the advantages that: according to the preparation method of the membrane electrode with low interface contact resistance, the conductive bonding layer is coated on the surfaces of the CCM and the gas diffusion layer, so that the CCM and the gas diffusion layer can be tightly bonded together by using the pressure of an assembled battery, the interface contact resistance between the CCM and the gas diffusion layer is effectively reduced, and the performance of a fuel battery is improved. Meanwhile, the adhesion between the CCM and the gas diffusion layer is realized by utilizing the cell assembling pressure, the hot-pressing laminating process of the CCM and the gas diffusion layer is omitted, the preparation efficiency of the fuel cell can be improved, the influence of the hot-pressing pressure on the channel structure can be avoided, and the performance of the fuel cell is optimized.
Drawings
FIG. 1 is a flow chart of a process for preparing a low interfacial resistance membrane electrode (1);
FIG. 2 is a flow chart of a process for preparing a low interfacial resistance membrane electrode (2);
FIG. 3 is a flow chart of a process for preparing a low interfacial resistance membrane electrode (3);
FIG. 4 is a schematic view of polarization curves of membrane electrodes prepared in examples and comparative examples of the present invention applied to performance tests in fuel cells;
FIG. 5 is a schematic diagram of the high-frequency impedance of the membrane electrode prepared in the examples and comparative examples of the present invention applied to the performance test in the fuel cell.
Detailed Description
The present invention will be described in detail with reference to specific examples. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Example 1
8g of conductive graphene particles (0.1-0.2 um), 3g of hydrophobic polyvinylidene fluoride adhesive and 200mL of solvent ethanol are uniformly dispersed to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of the isopropanol is 1: 1. The resulting catalyst slurry had a solids content of 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
And (3) coating the conductive adhesive slurry on the microporous layer side of the GDL and the upper and lower surfaces of the CCM by ultrasonic spraying, wherein the dry thickness of the coating is 0.1 um. The CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded, and are assembled with a current collecting plate, a flow passage plate and the like to form the fuel cell, and the CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded together by assembly pressure to form the fuel cell.
The assembled fuel cell was tested to further activate the adhesion between the CCM and the gas diffusion layer in the high temperature environment in which the cell was operated.
Example 2
8g of conductive carbon nanotube particles (0.1-0.2 um), 3g of hydrophobic polytetrafluoroethylene adhesive and 200mL of ethanol solvent are uniformly dispersed to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of isopropyl alcohol was 1:1, and the solid content of the obtained catalyst slurry was 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane (wherein the Pt carrier on the cathode side)The amount is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
And (3) coating the conductive adhesive slurry on the microporous layer side of the GDL and the upper and lower surfaces of the CCM by ultrasonic spraying, wherein the dry thickness of the coating is 0.1 um. The CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded, and are assembled with a current collecting plate, a flow passage plate and the like to form the fuel cell, and the CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded together by assembly pressure to form the fuel cell.
The assembled fuel cell was tested to further activate the adhesion between the CCM and the gas diffusion layer in the high temperature environment in which the cell was operated.
Example 3
8g of conductive acetylene black particles (0.08um-0.15um), 4g of hydrophobic styrene-butadiene rubber adhesive and 300mL of ethanol solvent are uniformly dispersed to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of isopropyl alcohol was 1:1, and the solid content of the obtained catalyst slurry was 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
And (3) coating the conductive adhesive slurry on the microporous layer side of the GDL and the upper and lower surfaces of the CCM by ultrasonic spraying, wherein the dry thickness of the coating is 0.1 um. The CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded, and are assembled with a current collecting plate, a flow passage plate and the like to form the fuel cell, and the CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded together by assembly pressure to form the fuel cell.
The assembled fuel cell was tested to further activate the adhesion between the CCM and the gas diffusion layer in the high temperature environment in which the cell was operated.
Example 4
Uniformly dispersing 8g of carbon black nanoparticles (0.15-0.2 um), 3g of hydrophobic polyvinylidene fluoride adhesive and 200mL of ethanol solvent to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of the isopropanol is 1: 1. The resulting catalyst slurry had a solids content of 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
And (3) coating the conductive adhesive slurry on the microporous layer side of the GDL and the upper and lower surfaces of the CCM by ultrasonic spraying, wherein the dry thickness of the coating is 0.1 um. The CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded, and are assembled with a current collecting plate, a flow passage plate and the like to form the fuel cell, and the CCM coated with the conductive adhesive coating and the gas diffusion layer coated with the conductive adhesive coating are bonded together by assembly pressure to form the fuel cell.
The assembled fuel cell was tested to further activate the adhesion between the CCM and the gas diffusion layer in the high temperature environment in which the cell was operated.
Comparative example
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of the isopropanol is 1: 1. The resulting catalyst slurry had a solids content of 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2) And then, the electrode is formed by hot pressing with the frame film and the GDL.
The prepared membrane electrode, collector plate, flow channel plate and the like are assembled into a fuel cell and tested.
Example 5
8g of conductive Ketjen black particles (0.1-0.2 um), 3g of hydrophobic polyethylene adhesive and 200mL of solvent ethanol are uniformly dispersed to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of the isopropanol is 1: 1. The resulting catalyst slurry had a solids content of 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
The conductive adhesive slurry is coated on the microporous layer side of the GDL by ultrasonic spraying, and the dry thickness of the coating is 0.1 um. And bonding the CCM with the gas diffusion layer coated with the conductive adhesive coating, assembling the CCM with a current collecting plate, a flow channel plate and the like to form the fuel cell, and bonding the CCM with the gas diffusion layer coated with the conductive adhesive coating by assembling pressure to form the fuel cell.
Example 6
8g of conductive graphene particles (0.12-0.18 um), 3g of hydrophobic polypropylene adhesive and 200mL of solvent ethanol are uniformly dispersed to prepare conductive adhesive slurry.
1.2g of Pt/C (47% wt of Pt) catalyst, 39g of deionized water, 39g of isopropanol and 2g of Nafion solution (20% wt) are fully and uniformly mixed, and are stirred at a high speed for 2 hours to prepare catalyst slurry. Wherein the mass ratio of the Pt/C catalyst to Nafion is 3:1, and the mass ratio of deionized water: the mass ratio of the isopropanol is 1: 1. The resulting catalyst slurry had a solids content of 2%. Coating the catalyst slurry on the upper and lower surfaces of the proton exchange membrane by ultrasonic spraying (wherein the Pt loading on the cathode side is 0.4 mg/cm)2(ii) a The loading capacity of the anode side is 0.1mg/cm2)。
And (3) coating the conductive adhesive slurry on the upper surface and the lower surface of the CCM by ultrasonic spraying, wherein the dry thickness of the coating is 0.1 um. The CCM coated with the conductive adhesive coating is bonded with the gas diffusion layer, and is assembled with a current collecting plate, a flow channel plate and the like to form a fuel cell, and the CCM coated with the conductive adhesive coating is bonded with the gas diffusion layer by the assembling pressure to form the fuel cell.
The MEAs of examples 1 to 4 and comparative example were assembled into fuel cells respectively and subjected to performance test, and the polarization curve test and the high frequency impedance test are shown in fig. 4 and 5. The test conditions were: the temperature is 80 ℃, the humidity is 100%, the flow rate of hydrogen and air is 1.3/2.0 according to the metering ratio, the back pressure of a hydrogen end is 0.2MPa, and the back pressure of an air end is 0.2 MPa.
As can be seen from fig. 4: under the same current density, the voltage of the example 1, the example 2, the example 3 and the example 4 of the invention is larger than that of the comparative example, the power density of the example is higher than that of the comparative example, and the maximum power density of the example 1 to the example 4 is much higher than that of the comparative example, which shows that the performance of the fuel cell of the example 1, the example 2, the example 3 and the example 4 of the invention is better than that of the fuel cell of the comparative example. As can be seen from fig. 5: the high-frequency impedances in the embodiments of the present invention are all higher than those of the comparative examples, and the difference in the high-frequency impedances is mainly caused by the contact impedances between the catalytic layer and the gas diffusion layer in the membrane electrode, which indicates that the membrane electrode in the embodiments has a low interface contact impedance compared to the comparative examples, mainly because the conductive adhesive can enhance the interface contact between the catalytic layer and the gas diffusion layer in the membrane electrode.
In summary, in the embodiment of the invention, the surfaces of the CCM and the gas diffusion layer are respectively coated with the conductive bonding layers, so that the CCM and the gas diffusion layer can be tightly bonded together, the interface contact resistance between the CCM and the gas diffusion layer is effectively reduced, and the performance of the fuel cell is improved. Meanwhile, the adhesion between the CCM and the gas diffusion layer is realized by utilizing the assembly pressure of the battery, the hot-pressing and attaching process of the CCM and the gas diffusion layer is omitted, the porous structures of the gas diffusion layer and the catalyst layer are effectively kept, and the mass transfer of reaction gas is promoted, so that the performance of the fuel battery is improved.

Claims (10)

1. A preparation method of a membrane electrode is characterized by comprising the following steps:
1) preparation of conductive adhesive slurry
Uniformly dispersing conductive particles, a hydrophobic polymer adhesive and solvent alcohol to prepare conductive adhesive slurry;
2) preparation of catalyst coated membranes
Fully and uniformly mixing a platinum-carbon catalyst, deionized water, solvent alcohol and a perfluorinated sulfonic acid resin solution to prepare catalyst slurry, and coating the catalyst slurry on the upper surface and the lower surface of a proton exchange membrane;
3) preparation of membrane electrode
Coating the conductive adhesive slurry obtained in the step 1) on the side surface of the microporous layer of the gas diffusion layer and/or the surface of the catalyst coating film obtained in the step 2), drying to form a conductive adhesive coating, bonding the catalyst coating film and the gas diffusion layer through the conductive adhesive coating to form a film electrode, and assembling the film electrode to the fuel cell.
2. The method of preparing a membrane electrode according to claim 1, wherein in step 3), the conductive adhesive slurry obtained in step 1) is coated on the surface of the microporous layer side of the gas diffusion layer and the surface of the catalyst coated membrane obtained in step 2), respectively, and dried to form a conductive adhesive coating, and the conductive adhesive coating of the catalyst coated membrane and the conductive adhesive coating of the gas diffusion layer are bonded to constitute a membrane electrode and assembled to the fuel cell.
3. The preparation method of a membrane electrode according to claim 1, wherein in the step 1), the mass ratio of the conductive particles to the hydrophobic polymer binder is 1-10: 1, the solid content of the conductive adhesive slurry is 1-50%.
4. The method for preparing a membrane electrode according to claim 1, wherein in step 1), the conductive particles are selected from one or more of platinum-carbon catalyst, platinum black, iridium black, graphene powder, carbon nanotube powder, carbon black powder, acetylene black and ketjen black.
5. The method of claim 1, wherein in step 1), the conductive particles have a size of 0.01um to 100 um.
6. The method for preparing a membrane electrode according to claim 1, wherein in step 1), the hydrophobic binder is one or more selected from styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyvinyl chloride, polythiophene and polyaniline.
7. The membrane electrode preparation method according to claim 1, wherein in the step 2), the mass ratio of the platinum-carbon catalyst to the perfluorosulfonic acid resin is 1 to 5: 1, the mass ratio of the deionized water to the alcohol is 0.5-5: 1; the solid content of the catalyst slurry is 1-30%.
8. The method for preparing a membrane electrode according to claim 1, wherein in the step 3), the coating method of the conductive adhesive is spraying or direct coating, and the thickness of the conductive adhesive coating is 0.05um to 50 um.
9. The method of claim 8, wherein the thickness of the conductive adhesive coating layer is 0.1um to 2 um.
10. A membrane electrode obtained by the method for preparing a membrane electrode according to any one of claims 1 to 9.
CN202110844884.9A 2021-07-26 2021-07-26 Membrane electrode and preparation method thereof Pending CN113555568A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196967A (en) * 2021-12-03 2022-03-18 中国科学院大连化学物理研究所 Method for preparing membrane electrode for water electrolysis of high mass transfer PEM (proton exchange membrane)
CN114583227A (en) * 2022-02-25 2022-06-03 同济大学 Preparation method of multi-layer membrane electrode with complex structure based on ink-jet printing

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006277984A (en) * 2005-03-28 2006-10-12 Asahi Glass Co Ltd Manufacturing method of membrane electrode assembly
CN101212054A (en) * 2006-12-31 2008-07-02 比亚迪股份有限公司 Fuel cell membrane electrode and its preparation method
CN102823047A (en) * 2010-04-01 2012-12-12 丰田自动车株式会社 Bonding material for fuel cell, and fuel cell
CN106684395A (en) * 2016-11-22 2017-05-17 新源动力股份有限公司 Technique for manufacturing cathode catalyst layer with gradient porosity for fuel cell
CN110504472A (en) * 2019-07-16 2019-11-26 江苏大学 A kind of direct methanol fuel cell membrane electrode and preparation method thereof improving catalyst utilization
CN112048248A (en) * 2020-08-14 2020-12-08 上海文施绿极科技有限公司 Adhesive release film and method for producing same
CN112271301A (en) * 2020-10-16 2021-01-26 成都新柯力化工科技有限公司 Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion
CN112615033A (en) * 2021-01-19 2021-04-06 泰州市海创新能源研究院有限公司 Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof
CN213520049U (en) * 2020-12-21 2021-06-22 深圳市氢雄燃料电池有限公司 Fuel cell stack easy to disassemble and assemble

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006277984A (en) * 2005-03-28 2006-10-12 Asahi Glass Co Ltd Manufacturing method of membrane electrode assembly
CN101212054A (en) * 2006-12-31 2008-07-02 比亚迪股份有限公司 Fuel cell membrane electrode and its preparation method
CN102823047A (en) * 2010-04-01 2012-12-12 丰田自动车株式会社 Bonding material for fuel cell, and fuel cell
CN106684395A (en) * 2016-11-22 2017-05-17 新源动力股份有限公司 Technique for manufacturing cathode catalyst layer with gradient porosity for fuel cell
CN110504472A (en) * 2019-07-16 2019-11-26 江苏大学 A kind of direct methanol fuel cell membrane electrode and preparation method thereof improving catalyst utilization
CN112048248A (en) * 2020-08-14 2020-12-08 上海文施绿极科技有限公司 Adhesive release film and method for producing same
CN112271301A (en) * 2020-10-16 2021-01-26 成都新柯力化工科技有限公司 Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion
CN213520049U (en) * 2020-12-21 2021-06-22 深圳市氢雄燃料电池有限公司 Fuel cell stack easy to disassemble and assemble
CN112615033A (en) * 2021-01-19 2021-04-06 泰州市海创新能源研究院有限公司 Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196967A (en) * 2021-12-03 2022-03-18 中国科学院大连化学物理研究所 Method for preparing membrane electrode for water electrolysis of high mass transfer PEM (proton exchange membrane)
CN114196967B (en) * 2021-12-03 2022-12-13 中国科学院大连化学物理研究所 Method for preparing membrane electrode for water electrolysis of high mass transfer PEM (proton exchange membrane)
CN114583227A (en) * 2022-02-25 2022-06-03 同济大学 Preparation method of multi-layer membrane electrode with complex structure based on ink-jet printing

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Application publication date: 20211026