CN118970124A - Method for preparing membrane electrode of proton exchange membrane fuel cell - Google Patents
Method for preparing membrane electrode of proton exchange membrane fuel cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 26
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- 229910052697 platinum Inorganic materials 0.000 claims abstract description 36
- 238000011068 loading method Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 21
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- 239000002002 slurry Substances 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 60
- 238000007731 hot pressing Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
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- 238000005507 spraying Methods 0.000 claims description 9
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 238000003487 electrochemical reaction Methods 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000011986 second-generation catalyst Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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
- 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]
-
- 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
- H01M4/88—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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a preparation method of a membrane electrode of a proton exchange membrane fuel cell, wherein the membrane electrode of the proton exchange membrane fuel cell comprises a proton exchange membrane and a gas diffusion layer electrode, the gas diffusion layer electrode sequentially comprises a resin thin layer, a catalyst layer and a gas diffusion layer which are attached to the proton exchange membrane from top to bottom, the catalyst layer is in an ordered straight pore structure, and the platinum loading capacity of the gas diffusion layer electrode is 0.02-0.3 mg/cm 2. According to the invention, an ordered pore canal structure is constructed on the catalyst layer, so that the performances of the membrane electrode with low platinum loading and the proton exchange membrane fuel cell under the condition of high current density are obviously improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a membrane electrode of a proton exchange membrane fuel cell.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) takes high-purity hydrogen and air as fuel and oxidant respectively, and directly converts chemical energy in the hydrogen into electric energy through electrochemical reaction between the fuel hydrogen and the oxidant air, is not limited by Carnot cycle, and has the advantages of high energy conversion efficiency, zero emission of pollutants, environmental friendliness and the like.
The proton exchange membrane fuel cell power generation system consists of a plurality of subsystems and parts. Wherein the Membrane Electrode Assembly (MEA) is the core component thereof and is the site where the electrochemical reaction occurs. The membrane electrode is generally composed of an electrolyte membrane and anodes and cathodes arranged on two sides, and the three components are in close contact. Wherein the anode is composed of an anode diffusion layer and an anode catalyst layer, the cathode is composed of a cathode diffusion layer and a cathode catalyst layer, and the cathode and the anode catalyst layer are in contact with the electrolyte membrane. Meanwhile, the anode diffusion layer and the cathode diffusion layer are both composed of a carbon paper layer containing hydrophobic polytetrafluoroethylene and a porous layer, the thickness and the structure of the carbon paper are the same, and the thickness and the structure of the porous layer can be the same or different.
Currently, electrolyte membranes and diffusion layers have been commercialized, and catalyst layers composed of catalysts and perfluorosulfonic acid resins are key to controlling the cost of proton exchange membrane fuel cells because noble metal platinum is commonly used in catalyst layers, reducing the amount of noble metal catalyst used in the catalyst. However, the performance of the membrane electrode with low platinum loading is obviously reduced under the condition of high current density, and particularly the oxygen reduction performance of the cathode side is obviously reduced.
Based on this, there is a need to provide a method for preparing a membrane electrode of a proton exchange membrane fuel cell to alleviate or solve the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the technical problem of performance degradation of a membrane electrode with low platinum loading in the common technology, and provides a preparation method of a membrane electrode of a proton exchange membrane fuel cell, which comprises the following steps:
Preparing a catalyst slurry, wherein the catalyst slurry comprises a solvent, resin and a catalyst, and the mass ratio of the resin to the catalyst is 0.04-0.6;
Coating the catalyst slurry and the resin slurry on a gas diffusion layer, and transferring the catalyst slurry and the resin slurry into a non-solvent bath to form a gas diffusion layer electrode;
And attaching the gas diffusion layer electrode to the proton exchange membrane, and performing hot pressing treatment to obtain a membrane electrode, wherein the membrane electrode comprises the proton exchange membrane and the gas diffusion layer electrode, the gas diffusion layer electrode sequentially comprises a resin thin layer, a catalyst layer and a gas diffusion layer from top to bottom, the resin thin layer is attached to the proton exchange membrane, the catalyst layer is of an ordered straight hole structure, and the platinum carrying capacity of the gas diffusion layer electrode is 0.02-0.3 mg/cm 2.
Further, the preparation method of the catalyst slurry comprises the following steps:
Uniformly mixing the catalyst, the solvent and the resin, and crushing to obtain catalyst slurry, wherein the mass ratio of the solvent to the catalyst is (10-70): 1.
Further, the catalyst comprises one or more of a low platinum loading carbon supported platinum catalyst, a carbon supported binary and above platinum alloy catalyst.
Further, the preparation of the resin slurry includes the steps of:
Mixing the solvent with the resin, and crushing to obtain resin slurry, wherein the mass ratio of the solvent in the resin slurry is 90% -99.9%, and the mass ratio of the resin in the resin slurry is 0.1% -10%.
Further, the solvent comprises one or more of N-methyl-2-pyrrolidone, 2-butanone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide or ethanol;
the resin comprises one or more of perfluorosulfonic acid resin, partial perfluorosulfonic acid resin and fluorine-free sulfonic acid resin.
Further, in the step of applying the catalyst slurry and the resin slurry on the gas diffusion layer and moving into a non-solvent bath to obtain the gas diffusion layer electrode, the method comprises the steps of:
sequentially coating the catalyst slurry and the resin slurry on the gas diffusion layer to obtain a resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode;
and (3) moving the resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode into the non-solvent bath, wherein the solvent and the non-solvent are subjected to exchange reaction to obtain the gas diffusion layer electrode, and the coating mode comprises a brushing method, a knife coating method or a spraying method.
Further, the duration of the exchange reaction is 10 s-24 h.
Further, the step of performing an exchange reaction between the solvent and the non-solvent to obtain the gas diffusion layer electrode further includes: taking the resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode after the exchange reaction out of the non-solvent bath, and drying to obtain the gas diffusion electrode;
The atmosphere environment of the drying treatment is composed of one or more of air, nitrogen and argon, and the duration of the drying treatment is 60 min-7 d.
Further, the hot pressing temperature in the hot pressing treatment is 80-155 ℃, the hot pressing pressure is 0.05-2MPa, and the hot pressing time is 90 s-7 d.
Compared with the prior art, the invention at least comprises the following advantages:
the types of membrane electrodes commonly used in the conventional technology are a second generation Catalyst Coated Membrane (CCM) type and a first generation Gas Diffusion Electrode (GDE) type, wherein the former is widely adopted and is the currently mainstream commercial membrane electrode preparation method. The catalyst layers with two configurations are randomly distributed, and the internal pore structures and the catalyst particles are in disordered states, wherein the disordered internal pore structures increase mass transfer resistance, and the performance of the membrane electrode with low platinum loading is greatly reduced under the condition of high current density.
Compared with the membrane electrode of the proton exchange membrane fuel cell, the invention provides an ordered pore canal structure which comprises a nano array structure or other shaped ordered structures on the catalyst layer, can provide ordered proton, electron or substance transmission channels, reduce mass transfer resistance, enlarge a three-phase interface of chemical reaction, remarkably improve the performance of the membrane electrode and the proton exchange membrane fuel cell under the condition of high current density, and optimize the application effect of the membrane electrode with low platinum loading (the platinum loading in the gas diffusion layer electrode is 0.02-0.3 mg/cm 2) in the proton exchange membrane fuel cell.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view showing the structure of a gas diffusion layer electrode produced in example 1 of the present invention; wherein 1-1 is a resin thin layer, 1-2 is a catalyst layer, and 1-3 is a gas diffusion layer;
FIG. 2 is a schematic structural diagram of a low platinum loading gas diffusion layer electrode prepared by the conventional method of comparative example 1 of the present invention; wherein 2-1 is a resin thin layer, 2-2 is a catalyst layer, and 2-3 is a gas diffusion layer;
FIG. 3 is a graph showing the gas permeation rate curves of examples 1 to 4 and comparative examples 1 to 2 according to the present invention, wherein the ordinate represents the nitrogen permeation flux, the unit 10 5Lm-2h-1, and the abscissa represents the pressure difference, the unit bar;
FIG. 4 is a graph showing the permeation rate of pure water in examples 1 to 4 and comparative examples 1 to 2, wherein the ordinate represents the permeation flux of pure water in 10 4kgm-2h-1 units and the abscissa represents the pressure difference in bar units;
Fig. 5 is a graph of power density in watt per square centimeter, and current density in amperes per square centimeter for examples 1-4 and comparative examples 1-2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the accompanying drawings, wherein it is apparent that the embodiments described are only some, but not all embodiments of the present invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. 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 and to which this invention belongs, and any method, apparatus, or material of the prior art similar or identical to the methods, apparatus, or materials of the embodiments of the invention may be used to practice the invention.
In the conventional technology, as shown in fig. 2, the pore structure inside the membrane electrode is disordered, the electrochemical performance of the membrane electrode is insufficient under the condition of high current density, and particularly the oxygen reduction performance of the cathode side is obviously reduced. Such as a second generation Catalyst Coated Membrane (CCM) type and a first generation Gas Diffusion Electrode (GDE) type, the catalyst layers of both configurations are randomly distributed, and the internal pore structure and the catalyst particles are in a disordered state, wherein the disordered internal pore structure increases the mass transfer resistance, and the performance of the membrane electrode is greatly reduced under the condition of high current density.
And as the platinum loading decreases, the mass transfer resistance increases further for the following reasons:
Low platinum loading results in increased oxygen transport resistance: as the platinum loading decreases, the platinum active sites within the catalyst layer decrease, resulting in more oxygen being required to partition onto fewer platinum surfaces for reduction reactions. This increases the transport path length of oxygen within the catalyst layer, which in turn increases the oxygen transport resistance. In addition, the low platinum loading may also cause structural changes in the catalyst layer, such as reduced porosity, complicated pore structure, etc., which further increase the difficulty of oxygen transport and thus affect electrochemical performance under high current density conditions.
In particular, mass transfer resistance within the catalyst layer directly affects the efficiency of oxygen (or other reactant gas) transport from the gas diffusion layer to the catalyst surface. The increased mass transfer resistance can result in limited oxygen transport, thereby reducing the performance of the fuel cell at high current densities. This is manifested as a decrease in the limiting current density, i.e. a decrease in the maximum current that the fuel cell can output under certain conditions, thereby affecting its power output.
Therefore, designing and preparing membrane electrodes with low platinum loading with low mass transfer resistance is a key to enhancing proton exchange membrane fuel cells under high current density conditions.
In order to solve the technical problems faced in the prior art, the invention provides a membrane electrode of a proton exchange membrane fuel cell, which comprises a proton exchange membrane and a gas diffusion layer electrode, wherein the gas diffusion layer electrode sequentially comprises a resin thin layer, a catalyst layer and a gas diffusion layer from top to bottom, the gas diffusion layer is in an ordered straight hole structure, and the platinum loading capacity of the gas diffusion layer electrode is 0.02-0.3 mg/cm 2.
Illustratively, the platinum loading of the gas diffusion layer electrode may be 0.1mg/cm 2.
Wherein the structure of the gas diffusion layer electrode is shown in fig. 1.
The catalyst layer is constructed into an ordered pore canal structure, which comprises a nano array structure or other shaped ordered structures, can provide ordered proton, electron or substance transmission channels, reduce mass transfer resistance, enlarge a three-phase interface of chemical reaction, and improve the performance of the membrane electrode with low platinum loading and the proton exchange membrane fuel cell under the condition of high current density.
Specifically, the ordered pore structure provides a rapid path for the transport of gases and liquids, accelerating the diffusion of reactants to the catalyst surface and the expulsion of products from the catalyst surface. This helps to reduce mass transfer limitations and increase reaction rates.
In addition, by optimizing the mass transfer performance, the ordered pore channel structure can reduce the performance loss caused by mass transfer polarization, thereby improving the overall performance of the membrane electrode.
The invention provides a preparation method of a membrane electrode of a proton exchange membrane fuel cell, which comprises the following steps:
S1, preparing catalyst slurry, wherein the catalyst slurry comprises a solvent, resin and a catalyst, and the mass ratio of the resin to the catalyst is 0.04-0.6.
For example, the mass ratio of the resin to the catalyst may be 0.1 to 0.5:1.
The preparation method of the catalyst slurry comprises the following steps:
Uniformly mixing the catalyst, the solvent and the resin, and crushing to obtain catalyst slurry, wherein the mass ratio of the solvent to the catalyst is (10-70): 1.
Illustratively, the mass ratio of solvent to catalyst may be from 20 to 40:1.
In some embodiments, the catalyst may be mixed with the solvent and resin particles uniformly and ball milled at 0-80 ℃ for more than 10 minutes to obtain a catalyst slurry.
The solvent comprises one or more of N-methyl-2-pyrrolidone, 2-butanone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide or ethanol;
the resin comprises one or more of perfluorosulfonic acid resin, partial perfluorosulfonic acid resin and fluorine-free sulfonic acid resin.
The catalyst comprises one or more of a low platinum loading carbon supported platinum catalyst, a carbon supported binary and above platinum alloy catalyst.
The carbon-supported binary and above includes one or a mixture of several of the carbon-supported binary/ternary/quaternary/penta and above platinum alloy catalysts.
The binary and above platinum alloy catalyst is a composite material formed by alloying platinum (Pt) with at least one other metal element (usually transition metal such as nickel, chromium, cobalt, vanadium, iron, etc.), and loading the alloy on a carbon material with high specific surface area.
In some embodiments, the mass concentration of platinum in the catalyst may be 20% -30%.
For example, the solvent and the resin species in the catalyst ink and the resin ink may be identical, respectively.
S2, coating the catalyst slurry and the resin slurry on a gas diffusion layer, and transferring the catalyst slurry and the resin slurry into a non-solvent bath to form a gas diffusion layer electrode.
For example, the catalyst paste and the resin paste may be applied to the gas diffusion layer in one step.
The preparation of the resin slurry comprises the following steps:
Mixing the solvent with the resin, and crushing to obtain resin slurry, wherein the mass ratio of the solvent in the resin slurry is 90% -99.9%, and the mass ratio of the resin in the resin slurry is 0.1% -10%.
In some embodiments, the solvent may be mixed with the resin particles uniformly and ball milled at 0-80 ℃ for more than 10 minutes to obtain a resin slurry.
The solvent comprises one or more of N-methyl-2-pyrrolidone, 2-butanone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide or ethanol;
the resin comprises one or more of perfluorosulfonic acid resin, partial perfluorosulfonic acid resin and fluorine-free sulfonic acid resin.
In the step S2, it includes:
s21, sequentially coating the catalyst slurry and the resin slurry on the gas diffusion layer to obtain a resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode;
S22, the resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode is moved into the non-solvent bath, the solvent and the non-solvent undergo an exchange reaction, and the gas diffusion layer electrode is obtained, and the coating mode comprises a brushing method, a knife coating method or a spraying method.
In some embodiments, the duration of the exchange reaction is 10s to 24 hours.
In other embodiments, the three-layer structure electrode of the resin thin layer/the catalyst layer/the gas diffusion layer after the exchange reaction is taken out of the non-solvent bath, and the gas diffusion electrode is obtained through drying treatment;
The atmosphere environment of the drying treatment is composed of one or more of air, nitrogen and argon, and the duration of the drying treatment is 60 min-7 d.
The non-solvent is water, alcohols, esters or a solution formed by a mixture of a plurality of the above.
In some embodiments, the catalyst slurry and resin slurry blade heights may each be set at 0.005-2mm.
In some embodiments, step S2 includes: the catalyst slurry is prepared on the gas diffusion layer by a brushing method, a knife coating method or a spraying method to obtain a wet gas diffusion layer electrode; then preparing the prepared resin slurry on the wet gas diffusion layer electrode prepared in the previous step by a brush coating method, a knife coating method or a spray coating method to obtain a resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode; transferring the three-layer structure electrode into a non-solvent bath to perform exchange reaction of solvent and non-solvent to obtain the ordered straight pore structure gas diffusion layer electrode with the resin thin layer, wherein the exchange time is 10 seconds to 24 hours, and then taking out the electrode from the non-solvent bath and drying the electrode in air, nitrogen, argon or a mixture of gases, wherein the drying time is 60 minutes to one week until the electrode is completely dried. The non-solvent is water, alcohols, esters or a solution formed by a mixture of a plurality of the above.
And S3, attaching the gas diffusion layer electrode to a proton exchange membrane, and performing hot pressing treatment to obtain the membrane electrode.
The hot pressing temperature in the hot pressing treatment is 80-155 ℃, the hot pressing pressure is 0.05-2MPa, and the hot pressing time is 90 s-7 d.
Wherein, the resin thin layer of the gas diffusion layer is closely attached to the proton exchange membrane.
In some embodiments, a membrane electrode with an effective area of 10-50 cm 2 is produced by hot pressing
The beneficial technical effects of the invention are as follows:
The invention controls the platinum carrying capacity of the gas diffusion layer electrode to be 0.02-0.3 mg/cm 2, and realizes cost saving on the premise of ensuring the application effect of the proton exchange membrane fuel cell.
According to the invention, through regulating and controlling the exchange rate of the solvent in the catalyst slurry and the non-solvent in the non-solvent bath, the technical prejudice of complicating the pore structure of the membrane electrode catalyst layer with low platinum loading is overcome, the ordered pore structure is efficiently constructed on the catalyst layer, and then a low-resistance straight pore channel is provided for material transmission, so that the mass transfer resistance in the catalyst layer is effectively reduced, and the purposes of improving the membrane electrode performance and the electrochemical performance of the proton exchange fuel cell are achieved.
According to the invention, the resin thin layer is introduced, so that the thermal matching performance and the hot press forming uniformity of the catalyst layer and the proton exchange membrane can be enhanced, and the yield of the membrane electrode is improved.
In the invention, the resin thin layer and the catalyst layer matched with the proton exchange membrane are obtained by one-step molding, so that the process flow and steps for manufacturing the membrane electrode are reduced, and the fixed investment and the manufacturing cost of the membrane electrode can be effectively reduced.
To facilitate a further understanding of the invention by those skilled in the art, reference is now made to the accompanying drawings, in which:
Example 1
1) Preparation of catalyst slurry: premetek 30% of platinum carbon catalyst (Vulcan XC-72 carrier) is used as a catalyst, perfluorinated sulfonic acid resin particles are used as resin raw materials, N-methyl-2-pyrrolidone is used as a solvent, and the mass ratio of the solvent to the catalyst is 30:1, the mass ratio of the catalyst to the resin is 1:0.5, preparing into mixed emulsion with certain viscosity.
2) Preparation of resin slurry: the perfluorinated sulfonic acid resin particles are used as resin raw materials, N-methyl-2-pyrrolidone is used as a solvent, and the mass ratio of the solvent to the resin is 40:1 is prepared into resin slurry with certain viscosity.
3) Preparation of an ordered straight pore structure gas diffusion layer electrode with a resin thin layer: the gas diffusion layer electrode with the ordered straight pore structure of the resin thin layer is prepared by a double-layer scraper through a scraper coating method in one step, the heights of the catalyst slurry and the scraper of the resin slurry are respectively 0.3mm and 0.05mm, the thickness of the prepared electrode is 0.15mm, the electrode is put into water for exchanging for 1 day, the electrode is taken out and dried for a week, and the platinum loading capacity of the catalyst is 0.1mg/cm 2.
4) Preparation of a membrane electrode: and (3) attaching the gas diffusion layer electrode to a proton exchange membrane, and hot-pressing to obtain the membrane electrode with the effective area of 4cm 2. The hot pressing temperature is 120 ℃, and the hot pressing pressure is as follows: 0.5MPa, hot pressing time: and 1 hour.
5) Electrode penetration performance evaluation: intercepting a circular gas diffusion layer electrode with an effective area of 1cm 2 and a resin thin layer and an ordered straight hole structure, placing the electrode on a membrane integrity tester, adjusting the pressure difference at two sides of the electrode by introducing N 2, and researching the N 2 permeation flux within the pressure difference range of 0-0.5 bar; pure water is introduced into one side of the electrode, the pure water is extruded by adopting N 2, and the pure water permeation flux of the electrode under the pressure difference condition of 0-2.5MPa is tested. The method is used for evaluating the mass transfer resistance of the membrane, and the larger the permeation flux is, the smaller the mass transfer resistance is.
6) Electrode electrochemical performance evaluation: the prepared membrane electrode is assembled into a proton exchange membrane fuel cell, the proton exchange membrane fuel cell is placed on a proton exchange membrane fuel cell test platform, the current-voltage relation of the cell is tested, a current-power density relation curve of the cell is obtained, and the test conditions are as follows: test temperature: 65 ℃, hydrogen flow rate: 0.1L/min, air flow rate: 1L/min.
Example 2
The mass ratio of the catalyst to the resin in the step 1) is 10:1 and the rest are the same as in example 1.
Example 3
The hot pressing temperature in step 4) was 140℃and the hot pressing pressure was 1.0MPa, and the hot pressing time was 2 hours, the same as in example 1.
Example 4
The use of Premetek% platinum carbon catalyst (Vulcan XC-72 support) as catalyst in step 1) and the catalyst slurry scraper height of 0.4mm in step 3) resulted in a decrease in permeability and cell performance, though increased in thickness, as seen in example 1, but still higher than conventional membrane electrodes.
The catalyst layer in the comparative sample membrane electrode is of a disordered pore structure and is prepared by adopting a spraying method, and the specific preparation process is as follows:
Comparative example 1
1) Preparation of catalyst slurry: premetek 30% of platinum carbon catalyst (Vulcan XC-72 carrier) is used as a catalyst, 5% of Nafion solution is used as a resin raw material, and isopropanol is used as a solvent, wherein the mass ratio of the solvent to the catalyst is 30:1, the mass ratio of the catalyst to the resin is 1:0.5, preparing into mixed emulsion with certain viscosity.
2) Preparation of resin slurry: adopting isopropanol solvent and 5% Nafion solution resin solution, and regulating and controlling the mass ratio of the resin to 40:1 is prepared into resin slurry with certain viscosity.
3) Preparation of a gas diffusion layer electrode: and spraying the catalyst slurry onto the gas diffusion layer by using a spraying method, spraying the resin slurry onto the surface of the catalyst slurry after drying, and forming a gas diffusion electrode after drying, wherein the catalyst loading amount is 0.1mg/cm 2.
4) Preparation of a membrane electrode: and (3) attaching the gas diffusion layer electrode to a proton exchange membrane, and hot-pressing to obtain the membrane electrode with the effective area of 4cm 2. The hot pressing temperature is 120 ℃, and the hot pressing pressure is as follows: 0.5MPa, hot pressing time: and 1 hour.
5) Electrode penetration performance evaluation: intercepting a circular gas diffusion layer electrode with an effective area of 1cm 2, placing the circular gas diffusion layer electrode on a membrane integrity tester, adjusting the pressure difference at two sides of the electrode by introducing N 2, and researching N 2 permeation flux within the pressure difference range of 0-0.5 bar; pure water is introduced into one side of the electrode, the pure water is extruded by adopting N 2, and the pure water permeation flux of the electrode under the pressure difference condition of 0-2.5MPa is tested. The method is used for evaluating the mass transfer resistance of the membrane, and the larger the permeation flux is, the smaller the mass transfer resistance is.
6) Electrode electrochemical performance evaluation: the prepared membrane electrode is assembled into a proton exchange membrane fuel cell, the proton exchange membrane fuel cell is placed on a proton exchange membrane fuel cell test platform, the current-voltage relation of the cell is tested, a current-power density relation curve of the cell is obtained, and the test conditions are as follows: test temperature: 65 ℃, hydrogen flow rate: 0.1L/min, air flow rate: 1L/min.
Comparative example 2
Premetek 20% platinum carbon catalyst (Vulcan XC-72 carrier) is used as catalyst in the step 1), the hot pressing temperature in the step 4) is 140 ℃, the hot pressing pressure is 1.0MPa, the hot pressing time is 2 hours, and the rest is the same as the comparative example 1.
Performance comparison and analysis:
1. the membrane electrode with low platinum carrying capacity prepared by the invention has obvious mass transfer advantages, and as shown in fig. 3 and 4, examples 1-4 have higher nitrogen flux and higher pure water permeation flux than comparative examples 1-2;
2. The membrane electrode with low platinum carrying capacity prepared by the invention has obvious electrochemical performance advantages, and as shown in fig. 5, examples 1-4 have higher electrochemical performance improvement than comparative examples 1-2;
The membrane electrode with low platinum loading capacity prepared by the invention can obviously enhance the mass transfer capacity in the membrane electrode, and can effectively solve the problem that the performance of the proton exchange membrane fuel cell is obviously reduced under the condition of low platinum loading capacity and high current density. In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (9)
1. The preparation method of the membrane electrode of the proton exchange membrane fuel cell is characterized by comprising the following steps:
Preparing a catalyst slurry, wherein the catalyst slurry comprises a solvent, resin and a catalyst, and the mass ratio of the resin to the catalyst is 0.04-0.6;
Coating the catalyst slurry and the resin slurry on a gas diffusion layer, and transferring the catalyst slurry and the resin slurry into a non-solvent bath to form a gas diffusion layer electrode;
And attaching the gas diffusion layer electrode to the proton exchange membrane, and performing hot pressing treatment to obtain a membrane electrode, wherein the membrane electrode comprises the proton exchange membrane and the gas diffusion layer electrode, the gas diffusion layer electrode sequentially comprises a resin thin layer, a catalyst layer and a gas diffusion layer from top to bottom, the resin thin layer is attached to the proton exchange membrane, the catalyst layer is of an ordered straight hole structure, and the platinum carrying capacity of the gas diffusion layer electrode is 0.02-0.3 mg/cm 2.
2. The method of preparing the catalyst slurry according to claim 1, wherein the method of preparing the catalyst slurry comprises the steps of:
Uniformly mixing the catalyst, the solvent and the resin, and crushing to obtain catalyst slurry, wherein the mass ratio of the solvent to the catalyst is (10-70): 1.
3. The method of preparation of claim 1, wherein the catalyst comprises one or more of a low platinum loading carbon supported platinum catalyst, a carbon supported binary and above platinum alloy catalyst.
4. The method of producing according to claim 2, wherein the preparation of the resin paste comprises the steps of:
Mixing the solvent with the resin, and crushing to obtain resin slurry, wherein the mass ratio of the solvent in the resin slurry is 90% -99.9%, and the mass ratio of the resin in the resin slurry is 0.1% -10%.
5. The method according to claim 4, wherein the solvent comprises one or more of N-methyl-2-pyrrolidone, 2-butanone, dimethylformamide, dimethylsulfoxide, dimethylacetamide, or ethanol;
the resin comprises one or more of perfluorosulfonic acid resin, partial perfluorosulfonic acid resin and fluorine-free sulfonic acid resin.
6. The method of manufacturing according to claim 1, wherein in the step of applying the catalyst slurry and resin slurry on a gas diffusion layer and moving into a non-solvent bath to obtain the gas diffusion layer electrode, comprising:
sequentially coating the catalyst slurry and the resin slurry on the gas diffusion layer to obtain a resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode;
and (3) moving the resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode into the non-solvent bath, wherein the solvent and the non-solvent are subjected to exchange reaction to obtain the gas diffusion layer electrode, and the coating mode comprises a brushing method, a knife coating method or a spraying method.
7. The method according to claim 6, wherein the exchange reaction is performed for 10s to 24 hours.
8. The method of claim 6, wherein the step of exchanging the solvent with the non-solvent to obtain the gas diffusion layer electrode further comprises: taking the resin thin layer/catalyst layer/gas diffusion layer three-layer structure electrode after the exchange reaction out of the non-solvent bath, and drying to obtain the gas diffusion electrode;
The atmosphere environment of the drying treatment is composed of one or more of air, nitrogen and argon, and the duration of the drying treatment is 60 min-7 d.
9. The method according to claim 1, wherein the hot pressing temperature in the hot pressing treatment is 80-155 ℃, the hot pressing pressure is 0.05-2MPa, and the hot pressing time is 90 s-7 d.
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| JPH10241701A (en) * | 1996-12-27 | 1998-09-11 | Japan Storage Battery Co Ltd | Gas diffusion electrode and solid polymer electrolyte film, manufacture thereof, and solid polymer electrolyte type fuel cell |
| KR20000046472A (en) * | 1998-12-31 | 2000-07-25 | 윤종용 | Method for manufacturing slurry for forming catalytic layers of proton exchange membrane(pem) fuel cell, and method for manufacturing pem fuel cell using the slurry manufacturing method, and pem fuel cell produced by the manufacturing method. |
| CN114204049A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Preparation method of low platinum-loading proton exchange membrane fuel cell membrane electrode |
| CN118156521A (en) * | 2024-03-25 | 2024-06-07 | 北京化工大学 | A method for preparing a high ion conductivity membrane electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10241701A (en) * | 1996-12-27 | 1998-09-11 | Japan Storage Battery Co Ltd | Gas diffusion electrode and solid polymer electrolyte film, manufacture thereof, and solid polymer electrolyte type fuel cell |
| KR20000046472A (en) * | 1998-12-31 | 2000-07-25 | 윤종용 | Method for manufacturing slurry for forming catalytic layers of proton exchange membrane(pem) fuel cell, and method for manufacturing pem fuel cell using the slurry manufacturing method, and pem fuel cell produced by the manufacturing method. |
| CN114204049A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Preparation method of low platinum-loading proton exchange membrane fuel cell membrane electrode |
| CN118156521A (en) * | 2024-03-25 | 2024-06-07 | 北京化工大学 | A method for preparing a high ion conductivity membrane electrode |
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