CN115275225A - Preparation method of membrane electrode catalyst coating - Google Patents
Preparation method of membrane electrode catalyst coating Download PDFInfo
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- CN115275225A CN115275225A CN202211049436.0A CN202211049436A CN115275225A CN 115275225 A CN115275225 A CN 115275225A CN 202211049436 A CN202211049436 A CN 202211049436A CN 115275225 A CN115275225 A CN 115275225A
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- coating
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- membrane electrode
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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
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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
- H01M4/90—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
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- 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 belongs to the field of fuel cells, and particularly relates to a preparation method of a membrane electrode catalyst coating, which comprises the following steps: dispersing a catalyst and an electrolyte resin solution in a mixed solvent to obtain slurry; coating the slurry on a proton exchange membrane to form a slurry coating; drying the slurry coating in sections to obtain the membrane electrode catalyst coating; the sectional drying comprises leveling drying, shaping drying and drying which are sequentially carried out. According to the invention, through optimizing the drying procedure, adopting three-stage drying and strictly controlling the temperature and time of each drying stage, a porous catalyst coating is formed, and compared with the catalyst coating obtained by a common coating and drying mode, the porous catalyst coating has the advantages of good drainage performance and good stability.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a membrane electrode catalyst coating.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. It is a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation. The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by Carnot cycle effect, so the efficiency is high; in addition, the fuel cell uses fuel and oxygen as raw materials, and has no mechanical transmission parts, so that the discharged harmful gas is extremely little, and the service life is long. Therefore, from the viewpoint of energy saving and ecological environment protection, fuel cells are the most promising power generation technology.
The Membrane Electrode (MEA), also known as the membrane electrode three-in-one or five-in-one component, is the core component of the proton exchange membrane fuel cell and the site for the internal energy conversion of the fuel cell, wherein the membrane electrode three-in-one component only contains a catalyst layer and a proton exchange membrane. The performance and cost of the membrane electrode greatly affects the performance, life and cost of the pem fuel cell.
The invention patent with the application number of CN202010127015.X discloses a fuel cell membrane electrode, wherein one surface of a proton exchange membrane is coated with a cathode catalyst layer, the other surface of the proton exchange membrane is coated with an anode catalyst layer, the outer sides of the cathode catalyst layer and the anode catalyst layer are respectively hot-pressed with a gas diffusion layer, the cathode catalyst layer is composed of more than two cathode sub-catalyst layers or/and the anode catalyst layer is composed of more than two anode sub-catalyst layers, and the porosity of the cathode sub-catalyst layers or/and the porosity of the anode sub-catalyst layers are gradually increased or decreased from one layer closest to the proton exchange membrane to the outside. Coating a layer of cathode catalyst slurry on one surface of a proton exchange membrane and drying to form a cathode catalyst layer; then, coating m layers of anode sub-catalyst slurry on the other surface of the proton exchange membrane in sequence, and drying the anode sub-catalyst slurry in sequence to form an anode sub-catalyst layer respectively.
The invention patent with application number 200510132153.2 provides a preparation method of a catalyst coating film, which comprises the following steps: contacting the microporous membrane with a catalyst dispersion liquid to obtain a catalyst-containing microporous membrane; contacting a microporous membrane containing a catalyst with a resin dispersion liquid to obtain a semi-catalyst coating membrane layer, wherein the semi-catalyst coating membrane layer comprises a catalyst layer and a resin membrane layer combined with the catalyst layer; and laminating the two semi-catalyst coated membrane layers to obtain the catalyst coated membrane. In the preparation method of the catalyst coating film provided by the invention, the catalyst and the resin are filled in the micropores of the microporous film step by step, so that the distribution of the catalyst and the resin in the microporous film is consistent, the combination of the catalyst and the resin is firm, the microporous film can play a role of hydrophobicity, and the problem of water drainage obstacle of a common catalyst coating film can be improved.
In the above applications, the problem that the cathode and anode catalyst layers prepared by the conventional coating and drying technology are too dense in coating and have small porosity, so that the catalyst layer is difficult to drain is not considered.
Disclosure of Invention
The present invention is directed to solving the above problems and provides a method for preparing a membrane electrode catalyst coating, which can increase the porosity of the catalyst coating while making the coating uniformly distributed without cracking by controlling the drying procedure.
According to the technical scheme of the invention, the preparation method of the membrane electrode catalyst coating comprises the following steps,
s1: dispersing a catalyst and an electrolyte resin solution in a mixed solvent to obtain slurry; the mixed solvent is a mixed solution of water and alcohol;
s2: coating the slurry on a proton exchange membrane to form a slurry coating;
s3: drying the slurry coating in sections to obtain the membrane electrode catalyst coating; the sectional drying comprises leveling drying, shaping drying and drying which are sequentially carried out.
Further, the catalyst comprises PtM/C catalyst or Pt/C catalyst, preferably, the catalyst comprises 40-80wt% of PtM/C catalyst (Pt accounts for 40-80% of the mass of the PtM/C catalyst) or 30-75wt% of Pt/C catalyst (Pt accounts for 30-75% of the mass of the Pt/C catalyst). Wherein M refers to copper, cobalt, nickel, palladium or ruthenium.
Further, the catalyst accounts for 1-10% of the total mass of the dispersion slurry.
Further, the electrolyte resin solution is AGC, dupont, sovlay and 3M brand electrolyte resin solution, and the solid mass in the electrolyte resin solution accounts for 1-5% of the total mass of the dispersion slurry.
Further, the alcohol is selected from one or more of methanol, ethanol, isopropanol, n-propanol, ethylene glycol and glycerol.
Further, the volume ratio of water to alcohol in the mixed solvent is 1-9:1.
further, in the step S1, the dispersion mode is ultrasonic, shearing, ball milling or homogenizing.
Further, in the step S2, the slurry coating is performed by slit coating, blade coating, air knife coating, dip coating, or roll coating.
Further, in the step S2, the thickness of the slurry coating is 80 to 200um.
Further, in the step S3, the temperature of leveling and drying is 30-40 ℃, the time is 0.4-0.6min, and the leveling stage is mainly to uniformly distribute the slurry on the coating surface.
Further, in the step S3, the temperature for shaping and drying is 40-50 ℃, the time is 0.8-1.2min, and the shaping stage is used for shaping the overall shape of the coating.
Further, in the step S3, the drying temperature is 80-100 ℃ and the drying time is 2.4-3.6min, and the drying stage is used for fast drying, so that the solvent is quickly volatilized, and the particles have no more time to be rearranged and large pores are left.
Compared with the prior art, the technical scheme of the invention has the following advantages: during the catalyst slurry coating process, a uniform wet slurry is applied to the proton exchange membrane and then the solvent in the wet coating is removed by drying. During drying, the coating undergoes some shrinkage as the solvent evaporates, and the solid materials approach each other in the wet coating, eventually forming a porous dried catalyst coating. The invention forms the porous catalyst coating by optimizing the drying procedure and adopting three-stage drying and strictly controlling the temperature and time of each drying stage.
Drawings
FIG. 1 is a scanning electron micrograph of the catalyst coating layer in example 1.
FIG. 2 is an external view of the catalyst coating layer in example 1.
Fig. 3 is an appearance view of the catalyst coating layer in comparative example 1.
Fig. 4 is an appearance view of the catalyst coating layer in comparative example 3.
Fig. 5 is a scanning electron micrograph of the catalyst coating in comparative example 4.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on the proton exchange membrane in a scraper coating mode to form a slurry coating with the thickness of 110 um;
three-stage drying is carried out on the slurry coating, wherein the temperature of leveling drying is 35 ℃, and the time is 0.5min; setting and drying at 45 deg.C for 1min; the drying temperature in the drying stage is 90 deg.C, and the drying time is 3min.
The appearance of the obtained catalyst coating is shown in figure 2, and the scanning electron microscope image of the catalyst coating is shown in figure 1, so that the catalyst layer has a large number of gaps, is uniformly distributed and has no cracks.
Example 2
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solids content 20%) were dispersed in a mixture of 320g of water and 130g of ethanol by means of ultrasonic dispersion to give a slurry.
2. Coating and drying
Coating the slurry on a proton exchange membrane by adopting a scraper coating mode to form a slurry coating with the thickness of 110 um;
three-stage drying is carried out on the slurry coating, wherein the temperature for leveling and drying is 30 ℃, and the time is 0.6min; setting and drying at 40 deg.C for 1.2min; the drying temperature in the drying stage is 80 ℃ and the time is 3.6min.
Example 3
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on a proton exchange membrane by adopting a scraper coating mode to form a slurry coating with the thickness of 110 um;
three-stage drying is carried out on the slurry coating, wherein the temperature of leveling drying is 40 ℃, and the time is 0.4min; setting and drying at 50 deg.C for 0.8min; the drying temperature in the drying stage is 100 ℃ and the time is 2.4min.
Comparative example 1
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on a proton exchange membrane by adopting a scraper coating mode to form a slurry coating with the thickness of 110 um;
and drying the slurry coating at 90 ℃ for 3min.
As shown in FIG. 3, the catalyst coating layer obtained was poor in the overall appearance and cracked.
Comparative example 2
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on a proton exchange membrane by adopting a scraper coating mode to form a slurry coating with the thickness of 110 um;
drying the slurry coating for two sections, wherein the first section drying temperature is 45 ℃ and 1min; the second stage drying temperature is 90 deg.C for 3min.
The resulting catalyst coating appeared thick on one side and thin on the other.
Comparative example 3
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on a proton exchange membrane by adopting a scraper coating mode to form a slurry coating with the thickness of 110 um;
drying the slurry coating for two sections, wherein the first section drying temperature is 35 ℃ and 0.5min; the second stage drying temperature is 90 deg.C for 3min.
The resulting catalyst coating was poor in overall appearance and cracked as shown in FIG. 4.
Comparative example 4
1. Slurry preparation
25g of 60wt% Pt/C catalyst and 40g of D2020 (Dupont, solid content: 20%) were dispersed in a mixed solution of 320g of water and 130g of ethanol by means of ultrasonic dispersion to obtain a slurry.
2. Coating and drying
Coating the slurry on the proton exchange membrane in a scraper coating mode to form a slurry coating (the thickness of a wet membrane is 110 um);
three-stage drying is carried out on the slurry coating, wherein the temperature of leveling drying is 35 ℃, and the time is 0.5min; setting and drying at 45 deg.C for 1min; the drying temperature in the drying stage is 50 deg.C, and the drying time is 3min.
The scanning electron micrograph of the obtained catalyst coating is shown in fig. 5, and it can be seen that the porosity is low.
The results of the average pore diameter and pore volume of the catalyst coatings obtained in examples 1-3 and comparative example 4 are shown in table 1.
Table 1 average pore diameter and pore volume of catalyst coatings in examples 1-3 and comparative example 4
| Average pore diameter/nm | Pore volume (cm) 3 /g) | |
| Example 1 | 1.872 | 0.133 |
| Example 2 | 1.835 | 0.130 |
| Example 3 | 2.023 | 0.155 |
| Comparative example 4 | 1.506 | 0.102 |
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a membrane electrode catalyst coating is characterized by comprising the following steps,
s1: dispersing a catalyst and an electrolyte resin solution in a mixed solvent to obtain slurry; the mixed solvent is a mixed solution of water and alcohol;
s2: coating the slurry on a proton exchange membrane to form a slurry coating;
s3: drying the slurry coating in sections to obtain the membrane electrode catalyst coating; the sectional drying comprises leveling drying, shaping drying and drying which are sequentially carried out.
2. The method for preparing a membrane electrode catalyst coating according to claim 1, wherein the catalyst comprises 40-80wt% of a PtM/C catalyst or 30-75wt% of a Pt/C catalyst, where M is copper, cobalt, nickel, palladium or ruthenium.
3. The method for preparing a membrane electrode catalyst coating according to claim 1 or 2, wherein the catalyst accounts for 1 to 10% of the total mass of the dispersion slurry; the mass of the solid in the electrolyte resin solution accounts for 1-5% of the total mass of the dispersion slurry.
4. The method of preparing a membrane electrode catalyst coating according to claim 1, wherein the alcohol is selected from one or more of methanol, ethanol, isopropanol, n-propanol, ethylene glycol and glycerol.
5. The method for preparing a membrane electrode catalyst coating according to claim 1 or 4, wherein the volume ratio of water and alcohol in the mixed solvent is 1 to 9:1.
6. the method for preparing a membrane electrode catalyst coating according to claim 1, wherein the slurry is applied by slit coating, blade coating, air knife coating, dip coating or roll coating in step S2.
7. The method for preparing a membrane electrode catalyst coating according to claim 1 or 6, wherein the slurry is coated to a thickness of 80-200um in the step S2.
8. The method for preparing a membrane electrode catalyst coating according to claim 1, wherein in the step S3, the temperature for leveling and drying is 30 to 40 ℃ and the time is 0.4 to 0.6min.
9. The method for preparing a membrane electrode catalyst coating according to claim 1, wherein in the step S3, the temperature for shaping and drying is 40 to 50 ℃ and the time is 0.8 to 1.2min.
10. The method for preparing a membrane electrode catalyst coating according to claim 1, wherein the drying temperature in step S3 is 80 to 100 ℃ and the time is 2.4 to 3.6min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013206676A (en) * | 2012-03-28 | 2013-10-07 | Toppan Printing Co Ltd | Method of manufacturing membrane electrode assembly and membrane electrode assembly |
| JP2018181671A (en) * | 2017-04-17 | 2018-11-15 | 凸版印刷株式会社 | Method for manufacturing membrane-electrode assembly |
| CN110993960A (en) * | 2019-11-11 | 2020-04-10 | 上海交通大学 | Cathode catalyst layer structure for enhancing catalyst durability and preparation method thereof |
| CN112259768A (en) * | 2020-10-21 | 2021-01-22 | 成都新柯力化工科技有限公司 | Fuel cell membrane electrode with gradient distribution catalyst layer and preparation method thereof |
| CN112599792A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation method of fuel cell membrane electrode catalyst layer |
| CN113839052A (en) * | 2021-11-29 | 2021-12-24 | 武汉氢能与燃料电池产业技术研究院有限公司 | Fuel cell membrane electrode and preparation method thereof |
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- 2022-08-30 CN CN202211049436.0A patent/CN115275225A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013206676A (en) * | 2012-03-28 | 2013-10-07 | Toppan Printing Co Ltd | Method of manufacturing membrane electrode assembly and membrane electrode assembly |
| JP2018181671A (en) * | 2017-04-17 | 2018-11-15 | 凸版印刷株式会社 | Method for manufacturing membrane-electrode assembly |
| CN110993960A (en) * | 2019-11-11 | 2020-04-10 | 上海交通大学 | Cathode catalyst layer structure for enhancing catalyst durability and preparation method thereof |
| CN112259768A (en) * | 2020-10-21 | 2021-01-22 | 成都新柯力化工科技有限公司 | Fuel cell membrane electrode with gradient distribution catalyst layer and preparation method thereof |
| CN112599792A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation method of fuel cell membrane electrode catalyst layer |
| CN113839052A (en) * | 2021-11-29 | 2021-12-24 | 武汉氢能与燃料电池产业技术研究院有限公司 | Fuel cell membrane electrode and preparation method thereof |
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