CN114899419B - Preparation method for improving proton conduction of fuel cell catalytic layer - Google Patents
Preparation method for improving proton conduction of fuel cell catalytic layer Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 54
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 109
- 239000010410 layer Substances 0.000 claims abstract description 96
- 229920000554 ionomer Polymers 0.000 claims abstract description 94
- 239000002002 slurry Substances 0.000 claims abstract description 80
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000011229 interlayer Substances 0.000 claims abstract description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002356 single layer Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000009792 diffusion process Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003937 Aquivion® Polymers 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
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- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 11
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material 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 application provides a preparation method for improving proton conduction of a fuel cell catalytic layer, which comprises the step of alternately spraying catalyst slurry and ionomer dispersion liquid to form the fuel cell catalytic layer with an interlayer structure. The alcohol-rich solvent is used as the ionomer dispersion liquid, the dispersibility is good, the characteristic of forming a continuous and uniform ionomer network in the catalytic layer is more favorable for solving the problem of poor proton conductivity of the catalytic layer, and meanwhile, gradient distribution of the ionomer of the catalytic layer can be realized, so that the output performance of the fuel cell is remarkably improved. The method can realize independent regulation and control of the content and configuration of the free ionomer in the catalyst slurry, and can flexibly improve the proton conduction network structure of the catalytic layer. In addition, the method is simple and feasible, can realize large-scale production, and is beneficial to commercialization of fuel cells.
Description
Technical Field
The application belongs to the field of fuel cells, and particularly relates to a preparation method for improving proton conduction of a catalytic layer of a fuel cell.
Background
The proton exchange membrane fuel cell has the characteristics of high conversion efficiency, high power density, zero emission and the like, so that the proton exchange membrane fuel cell becomes a clean energy source with great potential in the fields of new-generation automobiles, fixed power stations and electronics. However, the current cost is one of the important factors limiting the further development of fuel cells, where the catalyst cost occupies a significant proportion of the total stack cost. In order to reduce the cost of the catalyst, researchers have developed non-noble metal catalysts, but the use of platinum group metal catalysts is still dependent on the present use of non-noble metal catalysts because none of them fully meet the commercial demands in terms of performance, durability, stability, power density, etc. In this case, optimizing the catalytic layer structure, while maintaining or even improving the battery performance, reducing Pt loading is an effective way to reduce costs.
It is well known that the catalytic layer is prepared by depositing a catalyst slurry on a membrane or gas diffusion layer, so that the nature of the catalyst slurry largely determines the microstructure of the catalytic layer, thereby affecting the output performance of the fuel cell. The catalyst slurry typically consists of Pt/C catalyst, ionomer, and dispersant. However, under the catalytic action of Pt, the alcohol undergoes an oxidation reaction, resulting in degradation of the catalyst slurry. At the same time alcohols in solvents form hydrophobic products which lead to agglomeration of the Pt/C catalyst particles, thereby initiating cracking of the catalytic layer during drying, leading to degradation of fuel cell performance and durability. In order to prevent degradation of the catalyst slurry and to improve the storage stability of the slurry, it is most convenient to reduce the use of volatile alcohols during the preparation of the catalyst slurry. However, the catalytic layer prepared from the water-rich catalyst slurry has a problem of poor proton conductivity. Increasing the ionomer content directly in the catalyst slurry can in turn result in too much ionomer coverage on the catalyst surface, poisoning the catalyst, and affecting the electrochemical reactivity. In addition, free ionomer agglomerates in water-rich solvents, resulting in poor continuity and uniformity of ionomer network distribution in the catalytic layer, affecting proton conductivity.
Disclosure of Invention
The present application has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present application is to provide a method for improving proton conductivity of a catalytic layer of a fuel cell, which significantly improves proton conductivity of the catalytic layer by increasing formation of an ionomer network, thereby improving performance of the fuel cell.
In order to achieve the above object, the technical scheme of the present application is as follows:
a method of preparing a catalytic layer for a fuel cell, the method comprising: alternately spraying the catalyst slurry and the ionomer dispersion to form a fuel cell catalytic layer with an interlayer structure;
the catalyst slurry comprises a catalyst, a perfluorosulfonic acid ionomer and a dispersing agent, wherein the total mass fraction of the catalyst and the perfluorosulfonic acid ionomer in the catalyst slurry is 0.1-3%;
the ionomer dispersion comprises a perfluorosulfonic acid ionomer and a solvent, wherein the mass fraction of perfluorosulfonic acid ionomer in the ionomer dispersion is not higher than 3%.
Based on the technical scheme, preferably, the dispersing agent is a mixed solvent of water and volatile alcohol, and the mass percentage of the volatile alcohol in the mixed solvent is 5-30%.
Based on the above technical scheme, preferably, the solvent is a volatile alcohol, or a mixed solvent of water and a volatile alcohol; in the solvent, the mass percentage of the volatile alcohol is 50% -100%.
Based on the technical scheme, preferably, the catalyst comprises a carbon carrier and a catalytic active substance, wherein the mass percentage of the catalytic active substance in the catalyst is 10-70%;
in the catalyst slurry, the mass ratio of the perfluorosulfonic acid ionomer to the carbon carrier is 0.2-1.15:1;
in the ionomer dispersion liquid, the mass ratio of the perfluorosulfonic acid ionomer to the carbon carrier is 0.05-3:1.
Based on the above technical solution, preferably, the carbon carrier is one of Ketjen Black, vulcan XC-72, BP 2000; the catalytically active material is one of Pt, ptCo, ptIr, ptPd, ptRu, ptAu.
Based on the above technical solution, preferably, the perfluorosulfonic acid ionomer is one of Nafion and 3M, aquivion.
Based on the above technical scheme, preferably, the volatile alcohol is one or a mixture of at least two of methanol, ethanol, isopropanol and n-propanol.
Based on the technical scheme, preferably, in the alternate spraying, the ratio of the single-layer ionomer dispersion liquid discharge amount to the single-layer catalyst slurry discharge amount is x:1, wherein x is more than 0 and less than or equal to 5;
based on the above technical scheme, preferably, the single-layer catalyst slurry discharge amount is kept unchanged in the whole spraying process, and the ratio of the single-layer ionomer dispersion liquid discharge amount to the single-layer catalyst slurry discharge amount is decreased or increased gradually layer by layer according to different spraying substrates, wherein the decreased or increased value is y, and y is more than 0 and less than or equal to 0.4; the substrate is a proton exchange membrane and gradually decreases when the substrate is a diffusion layer.
The application also provides a membrane electrode for a fuel cell, which comprises a proton exchange membrane, a gas diffusion layer, a polyester frame and a catalytic layer, wherein the catalytic layer is the catalytic layer; the loading of Pt in the catalytic layer at the anode and the cathode is 0.05-0.4 mg/cm 2 。
The application also provides a fuel cell comprising the membrane electrode.
The beneficial effects of the application are as follows:
(1) The method of the application carries out transitional connection between the layer structures formed by spraying the catalyst slurry through the layer structure formed by the ionomer dispersion liquid, increases the formation of an ionomer network in the catalytic layer, improves the proton conductivity, and thus improves the performance of the fuel cell.
(2) The ionomer dispersion liquid in the method of the application is equivalent to free ionomer in slurry, and the ionomer dispersion liquid is independently formed into a layer structure, so that the independent control of the content and configuration of free ionomer in the catalyst slurry can be realized. Further, by dispersing the ionomer with an alcohol-rich solvent, a more extended ionomer chain structure can be obtained, and the agglomeration of the ionomer is reduced, so that the ionomer network formed after drying is more uniform and continuous. The catalyst slurry is formed by adopting the water-rich dispersing agent, so that the degradation of the catalyst slurry can be prevented, the storage stability of the slurry is improved, and meanwhile, the adsorption quantity of the ionomer on the carbon carrier in the water-rich catalyst slurry is sufficient, so that the interfacial conduction capacity of protons on the Pt/C surface is good. In addition, due to the volatilization characteristic of the water-rich dispersion, a more loose and porous catalytic layer structure is generated, and the transportation of gas and product water is facilitated. The combination of the alcohol-enriched ionomer dispersion liquid and the water-enriched catalyst slurry complements the advantages and complements each other, and the output performance of the fuel cell can be obviously improved.
(3) The method is simple and easy to implement, can break away from the limitation of the property of the catalyst slurry, and can flexibly and independently regulate and control the proton conduction network structure of the catalytic layer, so that any catalyst slurry formula can adopt the method to improve the proton conduction of the catalytic layer, can realize large-scale production, and is beneficial to commercialization of fuel cells.
Drawings
FIG. 1 is a schematic illustration of a method of preparing a catalytic layer of a fuel cell of the present application;
FIG. 2 is a schematic view of the structure of a catalytic layer made in accordance with the present application;
in the figure: 1. a proton exchange membrane, 2, a first catalyst slurry layer, 3, a first ionomer dispersion layer, 4, a second catalyst slurry layer, 5, a second ionomer dispersion layer, 6 and a third catalyst slurry layer;
FIG. 3 is a graph showing the polarization curves of the membrane electrodes of comparative examples 1-2 and examples 1-2 of the present application under hydrogen air conditions;
FIG. 4 is a proton conductivity resistance chart of the membrane electrode assembly catalytic layer of comparative examples 1-2 and examples 1-2 of the present application.
Detailed Description
The application will now be described in further detail with reference to the accompanying drawings.
The specific operation process is as follows:
in all of the following examples and comparative examples, the formulation parameters of the anode side catalyst slurry were: the carbon-supported platinum catalyst with the Pt content of 40wt.% has the mass ratio of perfluorosulfonic acid ionomer to catalyst carbon carrier of 0.65, the perfluorosulfonic acid ionomer adopts Nafion, the dispersant is a mixed solvent of water and isopropanol, wherein the mass percent of isopropanol is 50%, and the solid content of slurry, namely the total mass percent of the catalyst and the perfluorosulfonic acid ionomer, is 1%.
Filling the dispersed anode catalyst slurry into a spray gun, and spraying the anode catalyst slurry onto a proton exchange membrane to prepare an anode catalyst layer, wherein the Pt loading amount of the anode catalyst layer is 0.2mg/cm 2 。
Comparative example 1
The preparation parameters of the cathode side catalyst slurry are as follows: a carbon supported platinum catalyst having a Pt content of 40wt.%, the mass ratio of perfluorosulfonic acid ionomer to catalyst carbon support being 0.65:1, the perfluorosulfonic acid ionomer adopts Nafion, the mass percentage of isopropanol in the dispersing agent is 20%, and the solid content of the slurry, namely the total mass percentage of the catalyst and the perfluorosulfonic acid ionomer is 1%.
And loading the dispersed catalyst slurry into a spray gun, and spraying the catalyst slurry onto a proton exchange membrane to prepare the cathode catalytic layer. Wherein the Pt loading of the cathode catalytic layer is 0.1mg/cm 2 Finally, the membrane electrode is obtained by hot pressing with the gas diffusion layer.
Comparative example 2
The preparation parameters of the cathode side catalyst slurry are as follows: the carbon-supported platinum catalyst with the Pt content of 40wt.% has the mass ratio of perfluorosulfonic acid ionomer to catalyst carbon carrier of 1.25:1, the perfluorosulfonic acid ionomer adopts Nafion, the mass percent of isopropanol in the dispersant is 20%, and the solid content of the slurry, namely the total mass percent of the catalyst and the perfluorosulfonic acid ionomer, is 1%.
And loading the dispersed catalyst slurry into a spray gun, and spraying the catalyst slurry onto a proton exchange membrane to prepare the cathode catalytic layer. Wherein the Pt loading of the cathode catalytic layer is 0.1mg/cm 2 Finally, the membrane electrode is obtained by hot pressing with the gas diffusion layer.
Example 1
The preparation parameters of the cathode side slurry are as follows:
the preparation parameters of the catalyst slurry are as follows: the mass ratio of the perfluorosulfonic acid ionomer to the catalyst carbon carrier is 0.65:1, the perfluorosulfonic acid ionomer adopts Nafion, the mass percent of isopropanol in the dispersing agent is 20%, and the solid content of the slurry, namely the total mass percent of the catalyst and the perfluorosulfonic acid ionomer is 1%.
The formulation parameters of the ionomer dispersion were: the mass ratio of the perfluorosulfonic acid ionomer to the catalyst carbon carrier is 0.6:1, the added ionomer is dispersed by using a certain mixed solvent of water and isopropanol, the mass percent of the isopropanol in the mixed solvent is 80%, and the volume of the mixed solvent is the same as the volume of the dispersing agent in the slurry.
Loading the dispersed catalyst slurry into a spray gun, and spraying to the qualityPreparing a catalyst slurry layer on the sub-exchange membrane; and filling the dispersed ionomer dispersion liquid into another spray gun, spraying the ionomer dispersion liquid onto the catalyst slurry layer to form an ionomer dispersion liquid layer, and sequentially repeating the steps to form a structure that the catalyst slurry layer and the ionomer dispersion liquid layer are alternated layer by layer, so as to prepare the cathode catalytic layer. The single-layer catalyst slurry discharge and single-layer ionomer dispersion discharge were maintained at 0.1mL min throughout the spraying process -1 . Wherein the Pt loading of the cathode catalytic layer is 0.1mg/cm 2 Finally, the membrane electrode is obtained by hot pressing with the gas diffusion layer.
Example 2
The preparation parameters of the cathode side slurry are as follows:
the preparation parameters of the catalyst slurry are as follows: the mass ratio of the perfluorosulfonic acid ionomer to the catalyst carbon carrier is 0.65:1, the perfluorosulfonic acid ionomer adopts Nafion, the mass percent of isopropanol in the dispersing agent is 20%, and the solid content of the slurry, namely the total mass percent of the catalyst and the perfluorosulfonic acid ionomer is 1%.
The formulation parameters of the ionomer dispersion were: the mass ratio of the perfluorosulfonic acid ionomer to the catalyst carbon carrier is 0.6, the added ionomer is dispersed by a certain mixed solvent of water and isopropanol, the mass percent of the isopropanol in the mixed solvent is 80%, and the volume of the mixed solvent is the same as the volume of the dispersing agent in the slurry.
Loading the dispersed catalyst slurry into a spray gun, and spraying the catalyst slurry onto a proton exchange membrane to prepare a catalyst slurry layer; filling the dispersed ionomer dispersion liquid into another spray gun, spraying the ionomer dispersion liquid onto a catalyst slurry layer to form an ionomer dispersion liquid layer, and sequentially repeating the steps to form a structure with the catalyst slurry layer and the ionomer dispersion liquid layer alternately layer by layer, so as to prepare a cathode catalyst layer, wherein the discharge amount of the single-layer catalyst slurry is 0.1mL min in the whole spraying process -1 The initial discharge of the monolayer ionomer dispersion was 0.2mL min -1 The ratio of the single-layer ionomer dispersion to the single-layer catalyst slurry discharge was decreased from layer to layer during the spraying process by a value of 0.05. Wherein Pt is supported by the cathode catalytic layerThe amount was 0.1mg/cm 2 Finally, the membrane electrode is obtained by hot pressing with the gas diffusion layer.
FIG. 1 is a schematic illustration of a method of preparing a catalytic layer of a fuel cell according to the present application. The fuel cell catalyst layer was prepared by alternately spraying a water-rich catalyst slurry and an alcohol-rich ionomer dispersion to form an interlayer structure, and the prepared catalyst layer was shown in fig. 2. The catalyst layer prepared by the alternate spraying method can well utilize the advantages of the water-rich catalyst slurry, including preventing the degradation of the catalyst slurry, improving the storage stability of the slurry, having excellent interfacial proton conductivity and loose porous catalyst layer structure, facilitating the transportation of gas and products, and simultaneously utilizing the characteristic that the ionomer in the alcohol-rich solvent has good dispersibility, and being more beneficial to forming a continuous and uniform ionomer network in the catalyst layer to solve the problem of poor long-range proton conductivity of the catalyst layer prepared by the water-rich catalyst slurry. The combination of the two components complement each other, and can obviously improve the output performance of the fuel cell. In addition, the method is simple and feasible, can realize large-scale production, and is beneficial to commercialization of fuel cells.
Fig. 3 is a graph showing polarization curves of the membrane electrodes of comparative examples 1 and 2 and examples 1 and 2 under hydrogen air conditions. The battery performance of the examples 1 and 2 is obviously better than that of the comparative examples 1 and 2, so the membrane electrode prepared by the method of the application can obviously improve the battery performance. Among them, the performance of example 2 in which the ionomer is graded in the catalytic layer is optimal, mainly because the ionomer graded design is beneficial to improve the contact between the membrane and the catalytic layer, and increases the number of protons passing from the anode to the cathode through the membrane, so that the improvement effect of example 2 on the cell performance is better than that of example 1. While the cell performance of comparative example 2 in which the ionomer was directly added to the catalyst slurry was improved in the medium current density region controlled by proton conduction, the cell performance in the high current density region controlled by mass transfer was drastically reduced because the increased ionomer occupied the catalyst layer pore structure. In addition, the increased ionomer content in the catalyst slurry can also result in an increased ionomer coverage of Pt active sites, affecting ORR activity. Fig. 4 is a proton conduction resistance diagram of the catalytic layer of the membrane electrode of comparative examples 1 and 2 and examples 1 and 2. The proton conductivity of the catalytic layers of examples 1, 2 is significantly less than that of comparative example 1, but not much different from that of comparative example 2, which indicates that the formation of ionomer network can be significantly increased by the method of the present application, so that the proton conductivity of the catalytic layer is greatly reduced, and the fuel cell performance is improved. The method of the present application has the same proton conductivity as the manner of directly increasing the ionomer content in the catalyst slurry, but does not bring about other negative effects on the catalytic layer, such as a reduction in pore structure and a reduction in ORR activity, etc., and represents a unique advantage of the method of the present application. Therefore, the method of the application can be separated from the limitation of the property of the catalyst slurry, and can flexibly and independently regulate and control the proton conduction network structure of the catalytic layer, so that any catalyst slurry formula can be adopted to improve the proton conduction of the catalytic layer.
The present application is not limited to the above-mentioned embodiments, and any person skilled in the art, using the above-mentioned disclosure, can make various changes or modifications equivalent to the equivalent embodiments without departing from the scope of the present application.
Claims (10)
1. A method of preparing a catalytic layer for a fuel cell, the method comprising:
alternately spraying the catalyst slurry and the ionomer dispersion to form a fuel cell catalytic layer with an interlayer structure;
the catalyst slurry comprises a catalyst, a perfluorosulfonic acid ionomer and a dispersing agent, wherein the total mass fraction of the catalyst and the perfluorosulfonic acid ionomer in the catalyst slurry is 0.1-3%;
the ionomer dispersion comprises a perfluorosulfonic acid ionomer and a solvent, wherein the mass fraction of perfluorosulfonic acid ionomer in the ionomer dispersion is not higher than 3%.
2. The preparation method according to claim 1, wherein the dispersing agent is a mixed solvent of water and volatile alcohol, and the mass percentage of the volatile alcohol in the mixed solvent is 5-30%.
3. The method according to claim 1, wherein the solvent is a volatile alcohol or a mixed solvent of water and a volatile alcohol; in the solvent, the mass percentage of the volatile alcohol is 50% -100%.
4. The preparation method according to claim 1, wherein the catalyst comprises a carbon carrier and a catalytically active material, and the mass percentage of the catalytically active material in the catalyst is 10-70%;
in the catalyst slurry, the mass ratio of the perfluorosulfonic acid ionomer to the carbon carrier is 0.2-1.15:1;
in the ionomer dispersion liquid, the mass ratio of the perfluorosulfonic acid ionomer to the carbon carrier is 0.05-3:1.
5. The method according to claim 4, wherein the carbon carrier is one of Ketjen Black, vulcan XC-72, BP 2000; the catalytically active material is one of Pt, ptCo, ptIr, ptPd, ptRu, ptAu.
6. The method of claim 1, wherein the perfluorosulfonic acid ionomer is one of Nafion, 3M, aquivion.
7. The method according to claim 3, wherein the volatile alcohol is one or a mixture of at least two of methanol, ethanol, isopropanol, and n-propanol.
8. The method of claim 1, wherein the ratio of single layer ionomer dispersion to single layer catalyst slurry discharge in the alternating spray is x 1, wherein 0< x.ltoreq.5.
9. The method of claim 1, wherein the single-layer catalyst slurry discharge is maintained throughout the spraying process, and the ratio of single-layer ionomer dispersion discharge to single-layer catalyst slurry discharge is decreased or increased layer by layer according to the different spray substrates, the decreased or increased value being y, wherein 0< y is less than or equal to 0.4; the substrate is a proton exchange membrane and gradually decreases when the substrate is a diffusion layer.
10. A membrane electrode for a fuel cell comprising a proton exchange membrane, a gas diffusion layer, a polyester frame and a catalytic layer, wherein the catalytic layer is prepared by the preparation method of any one of claims 1 to 9; the loading of Pt in the catalytic layer at the anode and the cathode is 0.05-0.4 mg/cm 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210430704.7A CN114899419B (en) | 2022-04-22 | 2022-04-22 | Preparation method for improving proton conduction of fuel cell catalytic layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210430704.7A CN114899419B (en) | 2022-04-22 | 2022-04-22 | Preparation method for improving proton conduction of fuel cell catalytic layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114899419A CN114899419A (en) | 2022-08-12 |
| CN114899419B true CN114899419B (en) | 2023-11-03 |
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