CN114583187A - Preparation method and application of ordered multi-layer cathode catalyst layer membrane electrode - Google Patents
Preparation method and application of ordered multi-layer cathode catalyst layer membrane electrode Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 166
- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000009792 diffusion process Methods 0.000 claims abstract description 21
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 150000003460 sulfonic acids Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to the technical field of proton exchange membrane fuel cells, and discloses a preparation method and application of an ordered multi-layer cathode catalytic layer membrane electrode. The membrane electrode comprises an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a gas diffusion layer, wherein the cathode catalyst layer is of a three-layer structure with different porosities, one layer close to the proton exchange membrane is a catalyst layer with a smaller porosity and is a catalyst layer prepared by using catalyst slurry with a low alcohol-water ratio, one side close to the gas diffusion layer is a catalyst layer with a larger porosity and is a catalyst layer prepared by using catalyst slurry with a high alcohol-water ratio, the middle of the two layers is the catalyst layer with a moderate porosity and is the catalyst slurry with a moderate alcohol-water ratio, and therefore different porosities are formed in the cathode catalyst layer and the cathode catalyst layer has an ordered gradient. The invention discloses a preparation method of an ordered multi-layer cathode catalyst layer membrane electrode, which considers proton conduction and a gas/liquid/solid three-phase interface in the catalyst layer, improves the water management of the cathode catalyst layer and greatly improves the performance of the membrane electrode.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to a membrane electrode for optimizing the porosity and water management of a cathode catalytic layer and a preparation method thereof.
Background
Although Proton Exchange Membrane Fuel Cells (PEMFCs) have many advantages such as high power density, high energy conversion efficiency, fast start-up, clean emission, etc., their mass application is limited due to the disadvantages such as high cost and poor durability. The MEA, which is a core component of the PEMFC, determines the performance and durability of the entire cell, and the oxygen reduction reaction occurring in the cathode catalyst layer is retarded compared to the hydrogen oxidation reaction at the anode, and the exchange current density is several orders of magnitude lower. Therefore, how to improve the structure of the cathode catalyst layer and increase the oxygen reduction reaction rate becomes a hot issue for researchers.
Patent publication No. CN106684395B discloses a process for manufacturing a cathode catalyst layer with gradient porosity for a fuel cell. And spraying the catalyst slurry on a proton exchange membrane to prepare a cathode catalyst layer, wherein the spraying frequency is controlled to be 2-4 times, the porosity of the cathode catalyst layer prepared by the process is gradually increased from the proton exchange membrane side to the gas diffusion layer side, and the catalyst layer with the gradient porosity structure is obtained. Although the catalyst layer with porosity gradient is prepared, the preparation process involves multi-step temperature control, and the preparation of one CCM requires more time and procedures, so that the method is not beneficial to industrial popularization.
The patent with publication number CN106229533B discloses a cathode catalyst layer with a three-layer composite structure with hydrophilic gradient, wherein one layer close to a proton exchange membrane is a hydrophilic modified layer, one layer close to a gas diffusion layer is a hydrophobic modified layer, and the middle is an unmodified layer; the hydrophilic modification of the hydrophilic modification layer is realized by doping silicon dioxide in the catalyst slurry; the hydrophobic modification of the hydrophobic modification layer is achieved by doping the catalyst slurry with PTFE. The optimization of the catalytic layer structure is achieved by adding silica and PTFE, but the additives undoubtedly increase the cost of the membrane electrode assembly, which is not favorable for the cost reduction of the fuel cell.
Disclosure of Invention
Based on the above background art, the present invention aims to provide a method for preparing an ordered multi-layer cathode catalyst layer membrane electrode, aiming at the defects existing in the prior art. According to the invention, catalyst slurry with different alcohol-water ratios is innovatively and sequentially sprayed/blade-coated on the proton exchange membrane to form an ordered pore structure, and the cathode catalyst layer with a gradient hydrophilic and hydrophobic multi-layer structure realizes a larger capillary pressure gradient, is more beneficial to the diffusion of liquid water to a single direction, and can effectively improve the water management of the cathode catalyst layer.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a preparation method of an ordered multi-layer cathode catalyst layer membrane electrode, wherein the cathode catalyst layer is a multi-layer cathode catalyst layer with gradient hydrophilic and hydrophobic properties, one layer close to a proton exchange membrane is a catalyst layer with small porosity and prepared by using catalyst slurry with low alcohol-water ratio (the mass ratio is 10 wt% -20 wt%), one side close to a gas diffusion layer is a catalyst layer with large porosity and prepared by using catalyst slurry with high alcohol-water ratio (the mass ratio is 80 wt% -90 wt%), the middle of the two layers is a catalyst layer with moderate porosity and prepared by using catalyst slurry with moderate alcohol-water ratio (the mass ratio is 40 wt% -50 wt%), and therefore an ordered pore structure is formed in the cathode catalyst layer. After catalyst slurry with different alcohol-water ratios is sprayed/blade-coated on a proton exchange membrane, the volatilization speed of the alcohol is higher than that of water, so that different pore sizes are generated, and the platinum loading capacity of each layer in the cathode catalyst layer is 0.05-0.1 mg/cm2. The ordered multi-layer cathode catalyst layer has different porosities, the porosity is sequentially increased from the proton exchange membrane side to the gas diffusion layer, the mass transfer of reaction gas is facilitated, the discharge of generated water is facilitated, and the performance of the membrane electrode is effectively improved.
The invention also relates to a preparation method of the ordered multi-layer cathode catalyst layer membrane electrode, which comprises the following steps:
s1: preparing three portions of catalyst slurry;
the first part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 10-20 wt%; the second part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 40-50 wt%; the third part of catalyst slurry is 80-90 wt% of catalyst slurry based on the mass ratio of alcohol to water;
s2: sequentially spraying or blade-coating the first part of catalyst slurry, the second part of catalyst slurry and the third part of catalyst slurry in the step S1 on the side surface of the cathode of the proton exchange membrane to form a cathode catalyst layer with a three-layer structure and porosity gradient;
s3: spraying or blade-coating any one of the three catalyst slurries in the step S1 to form an anode catalyst layer;
s4: the cathode catalyst layer and the anode catalyst layer are respectively attached with a gas diffusion layer and a frame and are hot-pressed into a membrane electrode.
The catalyst slurry comprises a Pt/C catalyst, a perfluorinated sulfonic acid resin solution, deionized water and alcohol, wherein the solid content of the catalyst slurry is 2 wt.% to 15 wt.%, the platinum content in the Pt/C catalyst is 20 wt.% to 70 wt.%, the i/C mass ratio is 0.5 to 1, the EW value of the perfluorinated sulfonic acid resin is 800 to 1200, and the alcohol is one or more of absolute ethyl alcohol, n-propyl alcohol and isopropyl alcohol.
The thickness of the proton exchange membrane is 8-18 mu m, the thickness of the gas diffusion layer is 150-300 mu m, and the thickness of the frame is 90-130 mu m made of PET material.
A proton exchange membrane fuel cell comprises the membrane electrode obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) at present, a single alcohol-water ratio is mostly adopted for preparing catalyst slurry in a cathode catalyst layer, and the prepared catalyst layer has narrow pore diameter distribution and no gradient distribution, and is not beneficial to water management; according to the invention, catalyst slurry with different alcohol-water ratios is innovatively and sequentially sprayed/blade-coated on the proton exchange membrane to form an ordered pore structure, and the cathode catalyst layer with a gradient hydrophilic and hydrophobic multi-layer structure realizes a larger capillary pressure gradient, is more beneficial to the diffusion of liquid water to a single direction, and can effectively improve the water management of the cathode catalyst layer.
(2) The cathode catalyst layer optimizes the gas/liquid/solid three-phase interface in the catalyst layer while considering proton conductivity, and has a gradient hydrophilic and hydrophobic multi-layer cathode catalyst layer, so that the performance of the membrane electrode of the fuel cell is improved, the utilization rate of the catalyst is effectively improved, and mass transfer in a high-electric-density area is facilitated, so that the performance of the fuel cell is remarkably improved.
Drawings
FIG. 1 is a schematic view of a CCM structure employed in the present invention;
FIG. 2 is a schematic of the porosity of a cathode side three-layer catalytic layer of an example CCM;
FIG. 3 is a schematic illustration of the polarization curves for hydrogen empty conditions for MEA's of comparative and example embodiments of the present invention.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings and tables in the embodiments of the present invention. The embodiments described are some, but not all embodiments of the inventions disclosed herein. All other embodiments obtained by others skilled in the art based on the embodiments in the patent of the invention without any inventive step are within the scope of the patent protection of the invention.
A preparation method of an ordered multi-layer cathode catalyst layer membrane electrode comprises the following steps:
s1: preparing three portions of catalyst slurry;
the first part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 10-20 wt%; the second part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 40-50 wt%; the third part of catalyst slurry is 80-90 wt% of catalyst slurry based on the mass ratio of alcohol to water;
s2: sequentially spraying or blade-coating the first part of catalyst slurry, the second part of catalyst slurry and the third part of catalyst slurry in the step S1 on the side surface of the cathode of the proton exchange membrane to form a cathode catalyst layer with a three-layer structure and porosity gradient;
s3: spraying or blade-coating any one of the three catalyst slurries in the step S1 to form an anode catalyst layer;
s4: the cathode catalyst layer and the anode catalyst layer are respectively attached with a gas diffusion layer and a frame and are hot-pressed into a membrane electrode.
The catalyst slurry comprises a Pt/C catalyst, a perfluorinated sulfonic acid resin solution, deionized water and alcohol, wherein the solid content of the catalyst slurry is 2-15 wt.%, the platinum content in the Pt/C catalyst is 20-70 wt.%, the i/C mass ratio is 0.5-1, the EW value of the perfluorinated sulfonic acid resin is 800-1200, and the alcohol is one or more of absolute ethyl alcohol, n-propyl alcohol and isopropyl alcohol.
The thickness of the proton exchange membrane is 8-18 mu m, the thickness of the gas diffusion layer is 150-300 mu m, and the thickness of the frame is 90-130 mu m made of PET material.
Example 1
Preparing three catalyst slurries according to an experimental scheme formulated at an earlier stage; first layer catalyst slurry (alcohol water ratio 20 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with the mass fraction of 10 wt%, adding 4g of anhydrous ethanol and 23g of deionized water, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form first catalyst slurry; second layer catalyst slurry (alcohol to water ratio 50 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with the mass fraction of 10 wt%, adding 15.5g of mixed solution of absolute ethyl alcohol and 11.5g of deionized water, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form the second part of catalyst slurry; the third layer of catalyst slurry (alcohol-water ratio 80 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with mass fraction of 10 wt%, adding 26g of absolute ethyl alcohol, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form the second catalyst slurry. Generally, the solids contents of the three catalyst slurries were formulated to a uniform value of 10 wt%. In this embodiment, a slit coating preparation process is adopted to coat a catalytic Layer on the surface of a gorem740.18 proton exchange membrane, and a first Layer 1 and a second Layer are sequentially arranged on the cathode sideLayer 2 and a third Layer of Layer3 catalyst slurry, a second Layer of catalyst slurry used on the anode side, and platinum loading of each Layer in the catalyst Layer is 0.1mg/cm2I.e. the cathode/anode platinum loading is 0.3/0.1mg/cm2And then the membrane electrode is obtained by hot pressing with the gas diffusion layer and the frame.
Example 2
Preparing three catalyst slurries according to an experimental scheme formulated at an earlier stage; first layer catalyst slurry (alcohol-water ratio 15 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with mass fraction of 10 wt%, adding a mixed solution of 2g of absolute ethyl alcohol and 25g of deionized water, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form a first part of catalyst slurry; second layer catalyst slurry (alcohol to water ratio 45 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with the mass fraction of 10 wt%, adding 13.5g of mixed solution of anhydrous ethanol and 13.5g of deionized water, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form the second part of catalyst slurry; the third layer of catalyst slurry (alcohol-water ratio 80 wt%): accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with mass fraction of 10 wt%, adding 26g of absolute ethyl alcohol, ultrasonically mixing for 10min, and mixing for 20min by using a high-speed mixer to form the second catalyst slurry. Generally, the solids contents of the three catalyst slurries were formulated to a uniform value of 10 wt%. In this embodiment, a slit coating preparation process is adopted to coat a catalytic Layer on the surface of a gorem740.18 proton exchange membrane, a first Layer of Layer 1, a second Layer of Layer 2 and a third Layer of Layer3 catalyst slurry are sequentially arranged on the cathode side, the second Layer of catalyst slurry is used on the anode side, and the platinum loading capacity of each Layer in the catalytic Layer is 0.1mg/cm2I.e. the cathode/anode platinum loading is 0.3/0.1mg/cm2The structure of CCM of the embodiment is shown in figure 1, and then the membrane electrode is obtained by hot pressing with a gas diffusion layer and a frame.
Comparative example 1
According to the earlier established experimental scheme, 3g of catalyst Pt/C with 47% of platinum content is accurately weighed, and 10 wt% of perfluorosulfonic acid resin solution 12 is added.72g, adding mixed solution of 15.5g of absolute ethyl alcohol and 11.5g of deionized water, then carrying out ultrasonic mixing for 10min, then mixing for 20min by using a high-speed mixer to form second catalyst slurry (the alcohol-water ratio is 50 wt%), respectively coating cathode and anode catalyst layers on the cathode surface and the anode surface of a Gorem740.18 proton exchange membrane by adopting a slit coating preparation process, wherein the cathode/anode platinum loading is 0.3/0.1mg/cm2And then the membrane electrode is obtained by hot pressing with the gas diffusion layer and the frame.
Comparative example 2
Accurately weighing 3g of catalyst Pt/C with platinum content of 47%, adding 12.72g of perfluorinated sulfonic acid resin solution with mass fraction of 10 wt%, adding 15.5g of absolute ethyl alcohol and 11.5g of deionized water, then ultrasonically mixing for 10min, mixing for 20min by using a high-speed mixer to form a second catalyst slurry (alcohol-water ratio is 50 wt%), respectively coating cathode and anode catalyst layers on the surface of a Gorem740.18 proton exchange membrane by adopting an ultrasonic spraying preparation process, placing the proton exchange membrane above a heating plate in the spraying process of the cathode catalyst layer, controlling the surface temperature of the heating plate to be 180 ℃, setting the height between the surface of the proton exchange membrane and the heating plate to be 15mm, heating the surface temperature of the catalyst layer to 45 ℃ before spraying, firstly spraying a first catalyst layer on a commercialized Gorem740.18 proton exchange membrane, and spraying Pt with the loading amount of 0.2mg/cm2(ii) a Setting the height between the surface of the proton exchange membrane and the heating plate to be 10mm, heating the surface of the proton exchange membrane to 80 ℃ before spraying, drying, and then spraying for the second time, wherein the Pt loading amount is 0.1mg/cm2. The total platinum loading capacity of the cathode catalyst layer after two times of spraying is 0.3mg/cm2. After the cathode spraying is finished, spraying an anode catalyst layer, controlling the surface temperature of the catalyst layer to be 80 ℃ before the spraying, spraying the anode catalyst layer twice in total, wherein the platinum carrying capacity of the spraying is 0.1mg/cm2The platinum loading of the cathode/anode is 0.3/0.1mg/cm2And then the membrane electrode is obtained by hot pressing with the gas diffusion layer and the frame.
Fig. 2 is porosity data of the cathode catalyst Layer with the three-Layer structure of the embodiment, and the porosities of Layer 1, Layer 2 and Layer3 are sequentially increased to form an ordered pore structure, so that not only is mass transfer of oxygen from the gas diffusion Layer to the catalyst Layer facilitated, but also discharge of water produced by the reaction is effectively improved, if the porosity of the cathode catalyst Layer is only one porosity of comparative example 1, and if the gradient porosity of the embodiment is not provided, the corresponding advantages are not provided.
The comparative example and the example of fig. 3 are tested and compared with the comparative examples 1 and 2 under the conditions of hydrogen empty RH-100% and 150KPa backpressure on both sides of the cathode and the anode, the performance of the comparative examples 1 and 2 is higher in a low-medium high electric density region than that of the comparative examples 1 and 2, the comparative example 1 is unfavorable for mass transfer and discharge of water generated by reaction due to single porosity, the comparative example 2 is CCM prepared according to the patent experimental scheme with the publication number of CN106684395B, the formed gradient aperture is not easy to control due to temperature control of a heating plate and a certain distance from a proton exchange membrane, the temperature of a catalytic layer is difficult to control, the mass ratio of alcohol to water in the formula of the catalyst slurry is optimized, the mass of the added alcohol to water can be accurately adjusted, the gradient aperture is formed by different volatilization speeds of alcohol and water, and fig. 3 also proves that the electrochemical performance of the examples is higher than that of the comparative examples 1 and 2.
In conclusion, the invention sprays/scrapes catalyst slurry with different alcohol-water ratios on the proton exchange membrane in sequence to form an ordered pore structure and a gradient hydrophilic-hydrophobic multi-layer cathode catalyst layer, thereby realizing larger capillary pressure gradient, being more beneficial to the diffusion of liquid water to a single direction and effectively improving the water management of the cathode catalyst layer.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. The membrane electrode comprises an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a gas diffusion layer; the method is characterized by comprising the following steps:
s1: preparing three parts of cathode catalyst slurry;
the first part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 10-20 wt%; the second part of catalyst slurry is catalyst slurry with the mass ratio of alcohol to water of 40-50 wt%; the third part of catalyst slurry is 80-90 wt% of catalyst slurry based on the mass ratio of alcohol to water;
s2: sequentially spraying or blade-coating the first part of catalyst slurry, the second part of catalyst slurry and the third part of catalyst slurry in the step S1 on the side surface of the cathode of the proton exchange membrane to form a cathode catalyst layer with a three-layer structure and porosity gradient;
s3: spraying or blade-coating any one of the three catalyst slurries in the step S1 to form an anode catalyst layer;
s4: the cathode catalyst layer and the anode catalyst layer are respectively attached with a gas diffusion layer and a frame and are hot-pressed into a membrane electrode.
2. The preparation method of claim 1, wherein the catalyst slurry comprises a Pt/C catalyst, a perfluorosulfonic acid resin solution, deionized water and alcohol, the solid content of the catalyst slurry is 2 wt.% to 15 wt.%, the platinum content in the Pt/C catalyst is 20 wt.% to 70 wt.%, the mass ratio of i to C is 0.5 to 1, the EW value of the perfluorosulfonic acid resin is 800 to 1200, and the alcohol is one or a mixture of two or more of absolute ethyl alcohol, n-propyl alcohol and isopropyl alcohol.
3. The method according to claim 1 or 2, wherein the thickness of the proton exchange membrane is 8 to 18 μm, the thickness of the gas diffusion layer is 150 to 300 μm, and the thickness of the frame is 90 to 130 μm.
4. The preparation method according to claim 1 or 2, wherein the platinum loading of each layer in the cathode catalyst layer is 0.05-0.1 mg/cm2。
5. The preparation method according to claim 3, wherein the platinum loading of each layer in the cathode catalyst layer is 0.05-0.1 mg/cm2。
6. A proton exchange membrane fuel cell comprising the membrane electrode obtained by the production method according to claims 1 to 5.
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| CN115133043A (en) * | 2022-07-07 | 2022-09-30 | 一汽解放汽车有限公司 | Membrane electrode containing gradient cathode catalyst layer and preparation method and application thereof |
| CN116364948A (en) * | 2023-03-24 | 2023-06-30 | 一汽解放汽车有限公司 | Pore-diameter gradient cathode catalytic layer and preparation method and application thereof |
| CN117810499A (en) * | 2023-12-29 | 2024-04-02 | 广州烯湾氢能科技有限公司 | Membrane electrode, preparation method thereof, fuel cell and electric equipment |
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