CN113078338B - Membrane electrode for fuel cell and preparation method and application thereof - Google Patents
Membrane electrode for fuel cell and preparation method and application thereof Download PDFInfo
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- CN113078338B CN113078338B CN202110328318.2A CN202110328318A CN113078338B CN 113078338 B CN113078338 B CN 113078338B CN 202110328318 A CN202110328318 A CN 202110328318A CN 113078338 B CN113078338 B CN 113078338B
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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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a membrane electrode for a fuel cell and a preparation method and application thereof. The preparation method of the membrane electrode comprises the following steps: (1) preparing anode and cathode catalyst layer slurry; (2) coating the cathode and anode catalyst layer slurry on two sides of a proton membrane to obtain the proton membrane simultaneously provided with an anode side catalyst layer and a cathode side catalyst layer; (3) sequentially arranging the sealing frame and the gas diffusion layer on the proton membrane to obtain a membrane electrode for the fuel cell; the preparation method of the cathode catalyst layer slurry comprises the following steps: and mixing the platinum-carbon catalyst and the solvent for the first time, adding the graphitized multi-walled carbon nanotube for the second time, and finally adding the perfluorinated sulfonic acid resin solution for the third time to obtain the slurry. According to the invention, through optimizing the structure in the catalyst layer, the falling of the catalyst carrier, the migration and the agglomeration distribution of platinum in the attenuation process are optimized, the proton mass transfer loss in the attenuation process is reduced, and the durability of the fuel cell is improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a membrane electrode for a fuel cell, and a preparation method and application thereof.
Background
The proton exchange membrane fuel cell directly converts chemical energy into electric energy by utilizing the reaction of hydrogen and oxygen, and is considered to be one of the best green energy sources in the 20 th century because of the advantages of high energy conversion efficiency, quick low-temperature start, no pollution, good durability, high specific power and the like. The membrane electrode mainly comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer, wherein the catalyst layer is the power generation center of the proton exchange membrane fuel cell, namely the electrochemical reaction generation place. When hydrogen passes through the anode catalyst layer, the hydrogen is decomposed into hydrogen protons and electrons under the action of the catalyst, the hydrogen protons are transferred to the cathode side through the proton membrane, the electrons are transferred to the cathode side through the external circuit, and when the electrons reach the cathode, the electrons, the protons and the introduced O2Under the action of cathode catalyst, combining to generate water, and specifically performing electrode reaction as follows:
anode H2→2H++2e- (1)
Cathode 1/2O2+2H++2e-→H2O (2)
The total reaction formula is H2+1/2O2→H2O
In a fuel cell, (2) the oxygen reduction reaction is the determining step in the whole electrochemical reaction process, and as can be seen from the chemical reaction formula, in order to accelerate the overall electrochemical reaction, the transport rates of protons, electrons and reactant gases must be increased simultaneously. However, in the current CCM membrane preparation process, the porosity inside the catalyst layer is low or no pore is caused in the step of preparing the catalyst layer and the gas diffusion layer by pressing, so that certain diffusion resistance is formed for the reactant gas transmission and the product transmission, the battery performance and the power density under high current are seriously affected, namely, the reactant gas cannot rapidly reach the catalyst layer under high current, and the reaction of the two electrodes (1) and (2) is seriously hindered. The effect of catalytic layer design on membrane electrode performance is therefore critical.
Typically, the catalytic layer is composed of catalysts, ionic polymers, solvents, additives, and the like. Wherein the catalyst is an active center, and accelerates the two reactions (1) and (2); the ionic polymer acts as a binder on one hand, the catalyst is wound and firmly attached to the surface of the proton membrane, on the other hand, the ionic polymer is an H proton conduction channel, but the content of the ionic polymer in the catalyst layer is too high, although the hydrogen proton conduction is fast, the ionic polymer can cover a large amount of the catalyst to block the electron transfer, and meanwhile, the transmission of product water and reaction gas can be caused, thus the performance of the battery can be seriously influenced; the solvent mainly serves as a medium for dispersing the catalyst and the ionic polymer in the catalytic layer; the additive is mainly used for adding pore-forming agent when preparing the catalyst layer, and can directly control the pore structure of the catalyst layer. Compared with anode Hydrogen Oxidation Reaction (HOR), cathode Oxygen Reduction Reaction (ORR) is slower, so the key to solving the performance of membrane electrode is the breakthrough of catalytic layer.
CN109713321A discloses a membrane electrode with an adjustable pore structure and a preparation method thereof, aiming at the problem of difficult oxygen mass transfer of a cathode of a proton exchange membrane fuel cell, a nanometer oxide is used for pore forming in a cathode catalyst layer, and after an additive used as a pore forming agent is washed away by acid, a large amount of pore structures are left in situ, so that the porosity of the cathode catalyst layer is greatly increased, the pore size distribution in the catalyst layer is changed, the gas diffusion resistance in the cathode catalyst layer is obviously reduced, and the performance of the cell under high current density is greatly improved.
CN109904469A discloses a membrane electrode preparation method for optimizing a cathode catalyst layer structure, which comprises the following steps: (1) preparing catalyst layer ink, adding PS microspheres with the particle size of 50-800 nm, and preparing a catalyst layer by adjusting the proportion of Pt/C and PS microspheres; (2) and (3) placing the catalyst layer into an organic solvent to remove PS microspheres, then carrying out hot-pressing transfer printing on the catalyst layer and the proton exchange membrane, and then carrying out hot-pressing on the catalyst layer and the diffusion layer to obtain the proton exchange membrane fuel cell membrane electrode with the optimized cathode catalyst layer structure.
CN110729494A discloses a catalyst slurry for a proton exchange membrane fuel cell and a preparation method thereof, the catalyst slurry for the proton exchange membrane fuel cell includes 5 wt.% to 30 wt.% of catalyst particles, 0 wt.% to 20 wt.% of pore-forming agent, 5 wt.% to 40 wt.% of polymer proton conductor polymer dispersion liquid, and 1 wt.% to 90 wt.% of solvent, wherein the pore-forming agent is a mixture of one or more of oxalic acid, malic acid, citric acid, and ethylenediaminetetraacetic acid, and the catalyst particles are platinum-containing catalyst particles or non-platinum catalyst particles.
However, the above documents have the following problems: (1) in the above documents, pore-forming agent cannot control pore size distribution of the catalyst layer during the removal process, which causes some large pore sizes to be generated inside or on the surface, which is not beneficial to the removal of product water, resulting in high interface contact resistance; (2) the high transfer temperature damages the proton membrane, and the transfer of the active ingredients is incomplete in the transfer process; (3) although the membrane electrode prepared by the above documents has good initial activity, in the actual use process, the requirements of an automobile on the operation power under different working conditions such as climbing, starting and stopping and the like cannot be met, particularly under a high current density, the output voltage of a fuel cell can frequently fluctuate, so that the activity of the membrane electrode is reduced and the service life is attenuated, which is specifically shown in that the quality activity and the power density of the membrane electrode are attenuated, and the durability is poor.
Therefore, the problems of poor durability of the fuel cell and the like caused by the loss of the mass activity of the catalyst in the potential scanning process, the falling off of the catalyst carrier in the attenuation process, the migration and aggregation distribution of platinum, and the proton mass transfer loss in the attenuation process in the membrane electrode are the technical problems to be solved at present.
Disclosure of Invention
The invention aims to provide a membrane electrode for a fuel cell and a preparation method and application thereof. The invention provides a preparation method of a membrane electrode with an improved catalyst layer, which reduces the mass activity loss of a catalyst in the potential scanning process by optimizing the structure in the catalyst layer, optimizes the falling of a catalyst carrier, the migration and the agglomeration distribution of platinum in the attenuation process, is beneficial to reducing the mass transfer loss of protons in the attenuation process and improves the durability of a fuel cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a membrane electrode for a fuel cell, the method comprising the steps of:
(1) preparing anode catalyst layer slurry and cathode catalyst layer slurry;
(2) respectively coating the cathode catalyst layer slurry and the anode catalyst layer slurry obtained in the step (1) on two sides of a proton membrane to obtain the proton membrane simultaneously provided with an anode side catalyst layer and a cathode side catalyst layer;
(3) sequentially arranging a sealing frame and a gas diffusion layer on the proton membrane which is provided with the anode side catalytic layer and the cathode side catalytic layer in the step (2) to obtain the membrane electrode for the fuel cell;
the preparation method of the cathode catalyst layer slurry in the step (1) comprises the following steps:
and (2) mixing a platinum-carbon catalyst and a solvent for the first time, adding the graphitized multi-walled carbon nanotube for the second time, and finally adding a perfluorinated sulfonic acid resin solution for the third time to obtain the cathode catalyst layer slurry in the step (1).
According to the invention, through the improvement of the cathode catalyst layer in the membrane electrode, a step-by-step mixing method is adopted, the stability of active components in the catalyst layer is favorably improved, only when the slurry formed by mixing the catalyst and the solvent is in an ink shape, the graphitized multi-walled carbon nano tube can be added, on one hand, the pore distribution in the catalyst layer is favorably realized, on the other hand, the three-phase interface optimization between the catalyst layer and the gas diffusion layer is favorably realized, the electron transmission and the water rapid elimination in the catalyst layer are favorably realized, and finally, the optimal combination configuration of the active components and the ionomer can be ensured by adding the perfluorinated sulfonic acid resin solution, and the proton and electron transmission rate is favorably improved.
The graphitized multiwalled carbon nanotube is added in the cathode catalyst layer, the hydrophobic capacity of the cathode catalyst layer can be improved by utilizing the strong hydrophobic property of the graphitized multiwalled carbon nanotube, particularly, generated water can be rapidly discharged under high current density without causing flooding, and meanwhile, the transmission rate of electrons is improved by adding the graphitized multiwalled carbon nanotube, so that the electrons rapidly reach the cathode to react with oxygen and hydrogen protons, the multiplying power performance of the battery is improved, the ohmic polarization of the battery is greatly reduced, and the power density of the battery is greatly improved; and after the graphitized multi-walled carbon nanotube is mixed with a catalyst, rich holes are formed in a cathode catalyst layer, so that the rapid transmission of reaction gas and the removal of water are facilitated, the proton mass transfer loss in the attenuation process is reduced, and the storage performance of the fuel cell is further improved.
Preferably, in the process of preparing the cathode catalytic slurry, the temperature of the primary mixing, the secondary mixing and the tertiary mixing is respectively and independently 8-22 ℃, such as 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃ or 22 ℃ and the like.
In the invention, the temperature cannot be too high when preparing the cathode slurry, and the high temperature can cause the active components in the slurry to agglomerate.
Preferably, the solvent comprises water and alcohols.
Preferably, the alcohol comprises ethanol, n-propanol or isopropanol.
Preferably, the mass of the ethanol, the n-propanol and the isopropanol is (0-1): 0.23-0.823, such as 0:0:0.23, 1:1:0.23 or 1:1: 0.823.
Preferably, the primary mixing and the secondary mixing are both ultrasonic.
Preferably, the power of the ultrasound in the primary mixing is 220-300W, such as 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W or 300W.
Preferably, the first mixing comprises firstly performing ultrasonic treatment on the platinum-carbon catalyst and water, and then adding the alcohol solvent.
Preferably, the method of mixing for three times comprises stirring, standing and ultrasound in sequence after the perfluorosulfonic acid resin solution is added.
Preferably, the rotation speed of the stirring is 8000-15000 r/min, such as 8000r/min, 10000r/min, 13000r/min or 15000 r/min.
Preferably, the standing time is 15-30 min, such as 15min, 20min, 25min or 30 min.
Preferably, the power of the ultrasound in the third mixing is 150-220W, such as 150W, 180W, 200W or 220W.
Preferably, the time of the ultrasound in the three mixing is 30-65 min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min or 65 min.
Preferably, the platinum in the platinum-carbon catalyst accounts for 40-70% of the mass fraction of the platinum-carbon catalyst, such as 40%, 50%, 60%, 70% or the like.
Preferably, the platinum-carbon catalyst further comprises an alloy.
The platinum-carbon catalyst provided by the invention can be diversified in types, and comprises Pt/C catalyst and/or Pt-alloy/C.
Preferably, the mass fraction of the alloy in the platinum-carbon catalyst is 0-4%, such as 0%, 1%, 2%, 3%, or 4%.
Preferably, the graphitized multi-walled carbon nanotube has an inner diameter of 9 to 15nm, such as 9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm, and an outer diameter of 15 to 25nm, such as 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm or 25 nm.
In the invention, the transmission rate of reaction gas in the catalyst layer is slow due to the small inner and outer diameters of the graphitized multi-walled carbon nanotube, and the conduction rate of protons and electrons in the catalyst layer is reduced due to the large inner and outer diameters of the graphitized multi-walled carbon nanotube, so that the power density of the membrane electrode is influenced.
Preferably, the length of the graphitized multi-walled carbon nanotube is 30-50 nm, such as 30nm, 35nm, 40nm, 45nm or 50 nm.
In the invention, the too long length of the graphitized multi-walled carbon nanotube can cause the ohmic polarization between the catalyst layer and the gas diffusion layer to be increased, and the too short length can cause the concentration polarization to be increased, which both affect the power density and the durability of the membrane electrode.
Preferably, the mass ratio of the platinum and the alloy in the platinum-carbon catalyst to the water to the alcohol to the resin in the graphitized multi-walled carbon nanotube to the perfluorinated sulfonic acid resin solution is (0.0067-0.009): (0.094-0.225): (0.71-0.823): 0.0002-0.0012): 0.0475-0.076, such as 0.0067:0.094:0.71:0.0002:0.0475, 0.009:0.225:0.823:0.0012:0.076 or 0.008:0.115:0.75:0.001: 0.06.
In the invention, the mass ratio of the slurry for preparing the cathode catalyst layer is not in the range, so that the power density and the durability can not meet the requirements of the membrane electrode for the vehicle.
Preferably, the preparation method of the anode catalytic layer slurry in the step (1) comprises the following steps:
and (2) mixing the platinum-carbon catalyst and the solvent for the first time, adding a perfluorinated sulfonic acid resin solution for the second time, and finally adding an anti-antipole inhibitor for the third time to obtain the anode catalyst layer slurry in the step (1).
Preferably, the temperature of the first mixing is 8 to 22 ℃, for example, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃ or 22 ℃.
Preferably, the solvent comprises water and alcohols.
Preferably, the alcohol comprises ethanol, n-propanol or isopropanol.
Preferably, the mass ratio of the ethanol, the n-propanol and the isopropanol is (0-1): 0.35-0.76, such as 0:0:0.35, 1:1:0.35 or 1:1: 0.76.
Preferably, the methods of primary mixing, secondary mixing and tertiary mixing are all ultrasonic.
Preferably, the first mixing comprises firstly performing ultrasonic treatment on the platinum-carbon catalyst and water, and then adding the alcohol solvent.
Preferably, the method of the secondary mixing comprises stirring, standing and ultrasound in sequence after the perfluorosulfonic acid resin solution is added.
Preferably, the standing time is 15-30 min, such as 15min, 20min, 25min or 30 min.
Preferably, the time of the ultrasound in the secondary mixing is 20-45 min, such as 20min, 25min, 30min, 35min, 40min or 45 min.
Preferably, the temperature of the third mixing is 5 to 12 ℃, such as 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃, 10 ℃, 11 ℃ or 12 ℃ and the like.
In the invention, when the anti-reversal inhibitor is added into the anode catalyst layer slurry, the temperature cannot be too high, and the active component agglomeration can be caused by the too high temperature.
Preferably, the power of the ultrasound in the third mixing is 160-240W, such as 160W, 180W, 200W, 220W or 240W.
Preferably, the time of the ultrasonic treatment in the three mixing processes is 30-45 min, such as 30min, 35min, 40min or 45 min.
Preferably, the mass fraction of platinum in the platinum-carbon catalyst is 20-60%, such as 20%, 30%, 40%, 50%, or 60%.
Preferably, the platinum-carbon catalyst further comprises an alloy.
Preferably, the mass fraction of the alloy in the platinum-carbon catalyst is 0-4%, such as 0%, 1%, 2%, 3%, or 4%.
Preferably, the mass ratio of the platinum and the alloy in the platinum-carbon catalyst to the water, the alcohol, the resin in the perfluorosulfonic acid resin solution and the anti-depolarization inhibitor is (0.006: 0.009): (0.15: 0.196): (0.68: 0.78): (0.06: 0.096): (0.0003: 0.0008), for example, 0.006:0.15:0.68:0.06:0.0003, 0.009:0.196:0.78:0.096:0.0008 or 0.008:0.175:0.75:0.08: 0.0006.
In the present invention, the mass ratio of the anode catalyst layer slurry to be prepared is not in the above range, which results in that the power density and durability of the prepared membrane electrode do not meet the requirements for vehicles.
Preferably, the coating method of the cathode catalyst layer slurry in the step (2) is spraying.
Preferably, the spraying concentration in the spraying process of the cathode catalyst layer slurry in the step (2) is 0.20-0.35 mg/cm2E.g. 0.2mg/cm2、0.25mg/cm2、0.3mg/cm2Or 0.35mg/cm2And the like.
Preferably, the temperature for spraying the cathode catalyst layer slurry is 85 to 105 ℃, for example, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or 105 ℃.
Preferably, the time for spraying the cathode catalyst layer slurry is 15-30 min, such as 15min, 20min, 25min or 30 min.
Preferably, the coating method of the anode catalytic layer slurry in the step (2) is spraying.
Preferably, the spraying concentration in the spraying process of the anode catalyst layer slurry in the step (2) is 0.05-0.08 mg/cm2For example 0.05mg/cm2、0.06mg/cm2、0.07mg/cm2Or 0.08mg/cm2And so on.
Preferably, the temperature for spraying the anode catalyst layer slurry is 80-95 ℃, for example, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, the time for spraying the anode catalyst layer slurry is 5-15 min, such as 5min, 8min, 10min, 12min or 15 min.
Preferably, the sealing frame in the step (3) is arranged on two sides of the proton membrane having both the anode side and the cathode side in the step (2) in a hot-pressing sealing manner.
Preferably, the temperature of the hot-press sealing is 85 to 105 ℃, such as 85 ℃, 90 ℃, 95 ℃, 100 ℃ or 105 ℃ and the like.
Preferably, the pressure of the hot-pressing sealing is 0.1 to 0.3Mpa, such as 0.1Mpa, 0.15Mpa, 0.2Mpa, 0.25Mpa or 0.3 Mpa.
Preferably, the time for the hot press sealing is 8-20 s, such as 8s, 10s, 12s, 15s, 18s or 20 s.
Preferably, after the sealing frame is sealed by hot pressing, the gas diffusion layer in step (3) is disposed on the surface of the sealing frame in a dispensing and pressing manner.
Preferably, the dispensing position is 1-2.3 mm, such as 1mm, 1.5mm, 2mm, or 2.3mm, at the edge of the gas diffusion layer.
Preferably, the width of the adhesive tape during dispensing is 0.5-1 mm, such as 0.5mm, 0.8mm or 1 mm.
Preferably, the pressing temperature is 65-85 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃ and the like.
Preferably, the pressing time is 5-8 s, such as 5s, 6s, 7s or 8 s.
Preferably, the pressing pressure is 0.05-0.15 Mpa, such as 0.05Mpa, 0.1Mpa or 0.15 Mpa.
As a preferable technical solution, the method for preparing the membrane electrode for a fuel cell comprises the steps of:
(1) preparing anode catalysis layer slurry and cathode catalysis layer slurry;
the preparation method of the anode catalysis layer slurry comprises the following steps:
carrying out ultrasonic treatment on a platinum-carbon catalyst and water at the temperature of 8-22 ℃, then adding an alcohol solvent, and continuing ultrasonic treatment; then adding a perfluorinated sulfonic acid resin solution, stirring, standing for 15-30 min, and then carrying out ultrasonic treatment for 20-45 min; finally, adding an anti-antipole inhibitor, and continuing performing ultrasound for 30-45 min at 5-12 ℃ with an ultrasound power of 160-240W to obtain anode catalyst layer slurry;
the preparation method of the cathode catalyst layer slurry comprises the following steps:
carrying out ultrasonic treatment on a platinum-carbon catalyst and water at the temperature of 8-22 ℃ and the ultrasonic power of 220-300W, then adding an alcohol solvent, and continuing ultrasonic treatment; adding the graphitized multi-walled carbon nanotube into the reactor, continuously performing ultrasonic treatment at 8-22 ℃ and with ultrasonic power of 220-300W, finally adding a perfluorinated sulfonic acid resin solution into the reactor, stirring at 8-22 ℃ and at a rotating speed of 8000-15000 r/min, standing for 15-30 min, and finally performing ultrasonic treatment at ultrasonic power of 150-220W for 30-65 min to obtain the cathode catalyst layer slurry in the step (1);
(2) the anode catalyst layer slurry in the step (1) is added at the temperature of 80-95 ℃ and the concentration is 0.05-0.08 mg/cm2Spraying the coating on one side of the proton membrane for 5-15 min at the spraying concentration; then, the slurry of the cathode catalyst layer in the step (1) is added at the temperature of 85-105 ℃ and at the concentration of 0.05-0.08 mg/cm2Spraying the other side of the proton membrane for 15-30 min according to the spraying concentration;
(3) sealing the sealing frame at 85-105 ℃ for 8-12 s under the pressure of 0.1-0.3 Mpa by hot pressing on two sides of the proton membrane which is provided with the anode side and the cathode side at the same time in the step (2); and (3) after hot-pressing and sealing the hot-melt adhesive sealing frame, placing an adhesive tape with the width of 0.5-1 mm at a position 1-2.3 mm away from the edge of the gas diffusion layer, and pressing the gas diffusion layer on the surface of the sealing frame at 65-85 ℃ for 5-8 s under the pressure of 0.05-0.15 Mpa to obtain the membrane electrode for the fuel cell.
In a second aspect, the present invention provides a membrane electrode for a fuel cell, which is produced by the method for producing a membrane electrode for a fuel cell according to the first aspect;
the membrane electrode comprises a first gas diffusion layer, a first sealing frame, an anode catalysis layer, a proton membrane, a cathode catalysis layer, a second sealing frame and a second gas diffusion layer which are sequentially stacked, wherein the cathode catalysis layer comprises a platinum carbon catalyst, a graphitized multi-walled carbon nanotube and perfluorosulfonic acid resin.
According to the membrane electrode provided by the invention, the graphitized multiwalled carbon nanotube is added in the cathode catalyst layer, so that the structure in the catalyst layer is optimized, the mass activity loss of the catalyst in the potential scanning process is reduced, the falling of a catalyst carrier, the migration and the agglomeration distribution of platinum in the attenuation process are optimized, the proton mass transfer loss in the attenuation process is reduced, and the durability of a fuel cell is improved.
In the invention, the sealing frame is attached to the edges of the two sides of the anode and cathode catalyst layers and is overlapped with the two catalyst layers to a certain extent, and the gas diffusion layer is correspondingly attached to the sealing frame, covers the active region and is overlapped with the sealing frame to a certain extent.
Preferably, the size of the overlapping part of the first sealing frame and the anode catalyst layer is 1.8-2.5 mm, such as 1.8mm, 2mm, 2.3mm or 2.5 mm.
Preferably, the size of the overlapping part of the second sealing frame and the cathode catalyst layer is 1.8-2.5 mm, such as 1.8mm, 2mm, 2.3mm or 2.5 mm.
Preferably, the size of the overlapping portion of the first gas diffusion layer and the first sealing frame is 0.5-2 mm, such as 0.5mm, 1mm, 1.5mm, or 2 mm.
Preferably, the size of the overlapping portion of the second gas diffusion layer and the second sealing frame is 0.5-2 mm, such as 0.5mm, 1mm, 1.5mm, or 2 mm.
Preferably, the thickness of each of the first gas diffusion layer and the second gas diffusion layer is 140 to 250 μm, such as 140 μm, 150 μm, 200 μm, or 250 μm.
In a third aspect, the present invention also provides a fuel cell including the membrane electrode for a fuel cell according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a membrane electrode with an improved catalyst layer, which reduces the mass activity loss of a catalyst in the potential scanning process by optimizing the structure in the catalyst layer, optimizes the falling of a catalyst carrier, the migration and the agglomeration distribution of platinum in the attenuation process, is beneficial to reducing the mass transfer loss of protons in the attenuation process and improves the durability of a fuel cell. The initial power density of the membrane electrode prepared by the invention can reach 1662W/cm2And above, the rated power density can still reach 1508W/cm after the 30000q endurance test2And above, the performance after durability is only attenuated within 9.95%, and better battery performance and durability are shown.
Drawings
FIG. 1 is a polarization curve of a cell prepared from the membrane electrode provided in example 1 and a polarization curve of a 30000q test after endurance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 1.8 mm; the size of the overlapped part of the second sealing frame and the cathode catalysis layer is 1.8 mm; the size of the overlapping part of the first gas diffusion layer and the first sealing frame is 0.8 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 0.8 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 140 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 0.6g of Pt/C catalyst with the mass fraction of 70% of platinum into 15g of deionized water for wetting, carrying out ultrasonic treatment at the temperature of 22 ℃ for 10min by using the ultrasonic power of 220W, then adding 47g of isopropanol, continuing the ultrasonic treatment for 120min, and after the solution is in an ink state, continuing adding 0.08g of graphitized multi-wall carbon nanotube powder with the inner diameter of 9nm, the outer diameter of 15nm and the length of 30nm, and continuing the ultrasonic treatment for 30min at the temperature of 22 ℃; and finally, adding 3.84g of 5% perfluorinated sulfonic acid resin solution, shearing and stirring at the rotating speed of 15000r/min for 35min by using a high-speed emulsification shearing machine at the temperature of 8 ℃, standing for 15min, and then carrying out ultrasonic treatment for 30min by using ultrasonic power of 150W to obtain cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 20g of deionized water into 0.6g of Pt/C catalyst with the mass fraction of platinum being 40% for wetting, carrying out ultrasonic treatment at 8 ℃ for 8min by using 220W ultrasonic power, and then adding 75g of isopropanol solvent for ultrasonic treatment for 75 min; then 8.64g of perfluorinated sulfonic acid resin solution with the mass concentration of 5 percent is added, a high-speed emulsification shearing machine is adopted to shear and stir for 45min at the rotating speed of 8000r/min, and after standing for 15min, ultrasonic treatment is carried out for 20min at the ultrasonic power of 150W; finally, adding 3ml of iridium oxide aqueous solution of 10mg/ml, and continuing to perform ultrasonic treatment at 5 ℃ for 30min under 160W of ultrasonic power to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was stirred at 85 ℃ at 0.35mg/cm2The spraying concentration is sprayed for 30min on one side of a Gole proton membrane with the thickness of 12 mu m, and the side is marked as the cathode side;
2) peeling off the release film, and subjecting the anode catalyst layer slurry to temperature of 95 deg.C at a concentration of 0.08mg/cm2Is sprayed on the other side of the proton membrane for 5min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and pressing for 20s under 0.3Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
Dispensing glue at the position of 1.0mm of the edge of the gas diffusion layer by using a glue dispenser, wherein the width of a glue strip is 0.5mm, and then respectively laminating 8s at 0.05Mpa on two sides of the 5-layer MEA to paste the gas diffusion layer with the thickness of 140 microns to obtain the membrane electrode.
The membrane electrode prepared in example 1 was subjected to a single cell polarization curve test under the following conditions: the battery temperature is 80 ℃, the battery is humidified at 100 percent, and the pressure is 100kPa and the H2/Air stoichiometric ratio is 2.0/2.0;
30000q Endurance Condition: cathode nitrogen, 100% RH, anode hydrogen, 100% RH, N2/H2 stoichiometric ratio 1.5/1.8, cell temperature 80 deg.C, pressure 50kPa, voltage 0.6-1.0V, scanning speed 0.05V/s, 16s per cycle.
As can be seen from FIG. 1, the open circuit voltage is about 0.96V, and the initial rated power density is 1.76W/cm2, which shows that the power density of the assembled battery of the membrane electrode prepared by the present example is better; 30000q accelerated durable membrane electrode rated power density is 1.58W/cm2, power density attenuation is only 10%, and the membrane electrode has good durability and can meet the requirements of vehicle-scale membrane electrode performance and durability.
Example 2
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 2.5 mm; the size of the overlapped part of the second sealing frame and the cathode catalyst layer is 2.5 mm; the size of the overlapped part of the first gas diffusion layer and the first sealing frame is 2 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 2 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 250 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 0.6g of Pt/C catalyst with the mass fraction of platinum being 40% into 8g of deionized water for wetting, carrying out ultrasonic treatment at the ultrasonic power of 300W for 8min at the temperature of 8 ℃, adding 70g of isopropanol, continuing the ultrasonic treatment for 75min, continuing to add 0.02g of graphitized multi-wall carbon nanotube powder with the inner diameter of 15nm, the outer diameter of 25nm and the length of 50nm after the solution is in an ink state, and continuing the ultrasonic treatment for 40min at the temperature of 8 ℃; and finally, 6.48g of 5% perfluorinated sulfonic acid resin solution is added, shearing and stirring are carried out at 8 ℃ for 60min at a rotating speed of 8000r/min by using a high-speed emulsification shearing machine, standing is carried out for 30min, and then ultrasonic treatment is carried out for 45min at an ultrasonic power of 220W, so as to obtain the cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 20g of deionized water into 0.6g of Pt/C catalyst with the mass fraction of platinum being 60% for wetting, carrying out ultrasonic treatment at 8 ℃ for 8min by using 220W ultrasonic power, and then adding 75g of isopropanol solvent for ultrasonic treatment for 75 min; then 6.48g of perfluorinated sulfonic acid resin solution with the mass concentration of 5 percent is added, a high-speed emulsification shearing machine is adopted to shear and stir for 45min at the rotating speed of 15000r/min, and after standing for 15min, ultrasonic treatment is carried out for 20min at the ultrasonic power of 150W; finally, 8ml of iridium oxide aqueous solution of 10mg/ml is added, and ultrasonic treatment is continuously carried out for 45min at 5 ℃ and the ultrasonic power of 240W, so as to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was stirred at 105 ℃ at 0.3mg/cm2The spraying concentration of the anode is sprayed for 15min on one side of a Gole proton membrane with the thickness of 12 mu m, and the anode is marked as the cathode side;
2) stripping off the release film, and subjecting the anode catalyst layer slurry to 0.08mg/cm at 80 deg.C2Is sprayed on the other side of the proton membrane for 15min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and carrying out hot-press sealing for 8s at 105 ℃ under the pressure of 0.1Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
And (3) dispensing at the position of 2.3mm of the edge of the gas diffusion layer by using a dispenser, wherein the width of the adhesive tape is 1mm, and then pressing 5s of 5-layer MEA (membrane electrode assembly) at 85 ℃ and under the pressure of 0.15Mpa to paste the gas diffusion layer with the thickness of 250 microns to obtain the membrane electrode.
Example 3
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 2 mm; the size of the overlapped part of the second sealing frame and the cathode catalyst layer is 2 mm; the size of the overlapped part of the first gas diffusion layer and the first sealing frame is 2 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 2 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 210 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 12g of deionized water into 0.6g of Pt-Co/C catalyst with the mass fraction of platinum being 48% and the mass fraction of Co being 4%, wetting, carrying out ultrasonic treatment at the ultrasonic power of 260W for 10min at the temperature of 15 ℃, adding 30g of isopropanol and 40g of ethanol, continuing the ultrasonic treatment for 100min, continuing adding 0.04g of graphitized multi-walled carbon nanotube powder with the inner diameter of 10nm and the outer diameter of 28nm and the length of 40nm after the solution is in an ink state, and continuing the ultrasonic treatment for 60min at the temperature of 15 ℃; and finally, 6.48g of 5% perfluorinated sulfonic acid resin solution is added, shearing and stirring are carried out at 8 ℃ for 60min at a rotating speed of 8000r/min by using a high-speed emulsification shearing machine, standing is carried out for 30min, and then ultrasonic treatment is carried out for 45min at an ultrasonic power of 220W, so as to obtain the cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 20g of deionized water into 0.6g of Pt/C catalyst with the mass fraction of platinum being 20% for wetting, carrying out ultrasonic treatment at 8 ℃ and the ultrasonic power of 220W for 8min, and then adding 35g of isopropanol and 40g of ethanol solvent for ultrasonic treatment for 75 min; then 4.9g of perfluorinated sulfonic acid resin solution with the mass concentration of 5% is added, a high-speed emulsification shearing machine is adopted to shear and stir at the rotating speed of 10000r/min for 40min, and after standing for 20min, ultrasonic treatment is carried out for 30min at the ultrasonic power of 240W; finally, 4ml of iridium oxide aqueous solution of 10mg/ml is added, and ultrasonic treatment is continuously carried out for 40min at 5 ℃ and the ultrasonic power of 240W, so as to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was heated at 95 ℃ to 0.2mg/cm2The spraying concentration of the anode is sprayed for 15min on one side of a Gole proton membrane with the thickness of 12 mu m, and the anode is marked as the cathode side;
2) stripping off the release film, and pasting the anode catalyst layer onAt 90 ℃ at 0.05mg/cm2Is sprayed on the other side of the proton membrane for 15min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and carrying out hot-press sealing for 10s at 105 ℃ under the pressure of 0.2Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
Dispensing glue at the position of 1.8mm of the edge of the gas diffusion layer by using a glue dispenser, wherein the width of a glue strip is 1mm, and then pressing 5s of 5-layer MEA (membrane electrode assembly) at 65 ℃ and under the pressure of 0.15Mpa to paste the gas diffusion layer with the thickness of 210 mu m to obtain the membrane electrode.
Example 4
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 2 mm; the size of the overlapped part of the second sealing frame and the cathode catalyst layer is 2 mm; the size of the overlapped part of the first gas diffusion layer and the first sealing frame is 2 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 2 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 210 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 0.6g of Pt/C catalyst with the mass fraction of platinum being 60% into 15g of deionized water for wetting, carrying out ultrasonic treatment at 15 ℃ for 5min under the ultrasonic power of 300W, then adding 10g of n-propanol, 20g of isopropanol and 35g of ethanol, continuing to carry out ultrasonic treatment for 90min, after the solution is in an ink state, continuing to add 0.04g of graphitized multi-walled carbon nanotube powder with the inner diameter of 10nm, the outer diameter of 18nm and the length of 40nm, and continuing to carry out ultrasonic treatment at 15 ℃ for 45 min; and finally, adding 4.02g of 5% perfluorinated sulfonic acid resin solution, shearing and stirring at 10 ℃ for 50min at a rotating speed of 10000r/min by using a high-speed emulsification shearing machine, standing for 20min, and then carrying out ultrasonic treatment for 65min at an ultrasonic power of 200W to obtain the cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 15g of deionized water into 0.6g of Pt/C catalyst with the mass fraction of platinum being 40% for wetting, carrying out ultrasonic treatment at 8 ℃ and the ultrasonic power of 220W for 8min, and then adding 35g of isopropanol, 35g of ethanol and 5g of n-propanol solvent for ultrasonic treatment for 75 min; then 9.6g of perfluorinated sulfonic acid resin solution with the mass concentration of 5 percent is added, a high-speed emulsification shearing machine is adopted to shear and stir at the rotating speed of 10000r/min for 40min, and after standing for 20min, ultrasonic treatment is carried out for 30min at the ultrasonic power of 240W; finally, adding 3ml of iridium oxide aqueous solution of 10mg/ml, and continuing to perform ultrasonic treatment at 5 ℃ for 40min under 240W of ultrasonic power to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was heated at 95 ℃ to 0.3mg/cm2The spraying concentration of the anode is sprayed for 15min on one side of a Gole proton membrane with the thickness of 12 mu m, and the anode is marked as the cathode side;
2) stripping off the release film, and subjecting the anode catalyst layer slurry to temperature of 90 deg.C at 0.08mg/cm2Is sprayed on the other side of the proton membrane for 15min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and carrying out hot-press sealing for 10s at 105 ℃ under the pressure of 0.2Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
Dispensing glue at the position of 1.8mm of the edge of the gas diffusion layer by using a glue dispenser, wherein the width of a glue strip is 1mm, and then pressing 5s of 5-layer MEA (membrane electrode assembly) at 85 ℃ and under the pressure of 0.15Mpa to paste the gas diffusion layer with the thickness of 210 mu m, so as to obtain the membrane electrode.
Example 5
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 2 mm; the size of the overlapped part of the second sealing frame and the cathode catalyst layer is 2 mm; the size of the overlapped part of the first gas diffusion layer and the first sealing frame is 2 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 2 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 190 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 0.6g of Pt/C catalyst with the mass fraction of 50% of platinum into 15g of deionized water for wetting, carrying out ultrasonic treatment at the ultrasonic power of 260W for 5min at the temperature of 15 ℃, then adding 10g of n-propanol, 20g of isopropanol and 35g of ethanol, continuing to carry out ultrasonic treatment for 90min, continuing to add 0.04g of graphitized multi-walled carbon nanotube powder with the inner diameter of 10nm and the outer diameter of 18nm and the length of 40nm after the solution is in an ink state, and continuing to carry out ultrasonic treatment for 45min at the temperature of 15 ℃; and finally, adding 5.2g of 5% perfluorinated sulfonic acid resin solution, shearing and stirring at 10 ℃ for 50min at a rotating speed of 10000r/min by using a high-speed emulsification shearing machine, standing for 20min, and then carrying out ultrasonic treatment for 65min at an ultrasonic power of 220W to obtain the cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 15g of deionized water into 0.6g of Pt/Co/C catalyst with 48 mass percent of platinum and 4 mass percent of cobalt for wetting, carrying out ultrasonic treatment at 8 ℃ and 220W of ultrasonic power for 5min, and then adding 35g of isopropanol, 25g of ethanol and 15g of n-propanol solvent for ultrasonic treatment for 60 min; then adding 5.76g of perfluorinated sulfonic acid resin solution with the mass concentration of 5%, shearing and stirring for 40min at the rotating speed of 15000r/min by using a high-speed emulsification shearing machine, standing for 20min, and then carrying out ultrasonic treatment for 30min at the ultrasonic power of 240W; finally, 4ml of iridium oxide aqueous solution of 10mg/ml is added, and ultrasonic treatment is continuously carried out for 42min at 5 ℃ and the ultrasonic power of 240W, so as to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was heated at 95 ℃ to 0.3mg/cm2The spraying concentration of the anode is sprayed for 15min on one side of a Gole proton membrane with the thickness of 12 mu m, and the anode is marked as the cathode side;
2) stripping off the release film, and subjecting the anode catalyst layer slurry to temperature of 90 deg.C at 0.05mg/cm2Is sprayed on the other side of the proton membrane for 15min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and carrying out hot-press sealing for 10s at 105 ℃ under the pressure of 0.2Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
Dispensing glue at the position of 1.8mm of the edge of the gas diffusion layer by using a glue dispenser, wherein the width of a glue strip is 1mm, and then pressing 5s of 5-layer MEA (membrane electrode assembly) at 85 ℃ and under the pressure of 0.15Mpa to paste the gas diffusion layer with the thickness of 190 microns to obtain the membrane electrode.
Example 6
The present embodiment provides a membrane electrode for a fuel cell, including a first gas diffusion layer, a first sealing frame, an anode catalyst layer, a proton membrane, a cathode catalyst layer, a second sealing frame, and a second gas diffusion layer, which are sequentially stacked;
wherein the size of the overlapping part of the first sealing frame and the anode catalysis layer is 2 mm; the size of the overlapped part of the second sealing frame and the cathode catalyst layer is 2 mm; the size of the overlapped part of the first gas diffusion layer and the first sealing frame is 2 mm; the size of the overlapped part of the second gas diffusion layer and the second sealing frame is 2 mm; preferably, the first gas diffusion layer and the second gas diffusion layer each have a thickness of 210 μm.
The preparation method of the membrane electrode comprises the following steps:
(1) preparation of cathode catalyst layer slurry and anode catalyst layer slurry
1) Preparing cathode catalyst layer slurry:
adding 12g of deionized water into 0.6g of Pt/Co/C catalyst with the mass fraction of platinum being 48% and the mass fraction of Co being 4%, wetting, carrying out ultrasonic treatment at the ultrasonic power of 260W for 10min at the temperature of 15 ℃, adding 30g of isopropanol and 40g of ethanol, continuing the ultrasonic treatment for 100min, continuing adding 0.04g of graphitized multi-walled carbon nanotube powder with the inner diameter of 10nm and the outer diameter of 28nm and the length of 35nm after the solution is in an ink state, and continuing the ultrasonic treatment for 60min at the temperature of 15 ℃; and finally, 6.48g of 5% perfluorinated sulfonic acid resin solution is added, shearing and stirring are carried out at 8 ℃ for 60min at a rotating speed of 8000r/min by using a high-speed emulsification shearing machine, standing is carried out for 30min, and then ultrasonic treatment is carried out for 45min at an ultrasonic power of 220W, so as to obtain the cathode catalyst layer slurry.
2) Preparing anode catalyst layer slurry:
adding 20g of deionized water into 0.6g of Pt/Co/C catalyst with 48 mass percent of platinum and 4 mass percent of cobalt for wetting, carrying out ultrasonic treatment at 15 ℃ for 8min by using 220W ultrasonic power, and then adding 35g of isopropanol and 40g of ethanol solvent for ultrasonic treatment for 75 min; then 6.9g of perfluorinated sulfonic acid resin solution with the mass concentration of 5% is added, a high-speed emulsification shearing machine is adopted to shear and stir at the rotating speed of 10000r/min for 40min, and after standing for 20min, ultrasonic treatment is carried out for 30min at the ultrasonic power of 240W; finally, 4ml of iridium oxide aqueous solution of 10mg/ml is added, and ultrasonic treatment is continuously carried out for 40min at 5 ℃ and the ultrasonic power of 240W, so as to obtain anode catalyst layer slurry;
(2) preparation of anode catalyst layer and cathode catalyst layer
1) The slurry of the cathode catalyst layer was heated at 95 ℃ to 0.2mg/cm2The spraying concentration of the anode is sprayed for 15min on one side of a Gole proton membrane with the thickness of 12 mu m, and the anode is marked as the cathode side;
2) stripping off the release film, and subjecting the anode catalyst layer slurry to temperature of 90 deg.C at 0.05mg/cm2Is sprayed on the other side of the proton membrane for 15min, and is marked as the anode side.
(3) Frame preparation
Respectively placing the cut sealing frames with hot melt adhesive on two sides of the proton membrane coated with the catalyst layer prepared in the step (2), and pressing and sealing for 8s at 105 ℃ under the pressure of 0.3Mpa to obtain 5 layers of MEA;
(4) gas diffusion layer preparation
Dispensing glue at the position of 1.8mm of the edge of the gas diffusion layer by using a glue dispenser, wherein the width of a glue strip is 1mm, and then pressing 5s of 5-layer MEA (membrane electrode assembly) at 85 ℃ and under the pressure of 0.15Mpa to paste the gas diffusion layer with the thickness of 210 mu m, so as to obtain the membrane electrode.
Comparative example 1
The comparative example is different from example 1 in that the graphitized multi-walled carbon nanotube is not added in the preparation of the cathode catalyst layer slurry.
The remaining preparation methods and parameters were in accordance with example 1.
The membrane electrode assembly single cell prepared in example 1 was tested, and the effective area was 25cm2Carrying out a catalyst accelerated durability test under the following test conditions: high-purity nitrogen and hydrogen with relative humidity RH of 100% are respectively introduced into the cathode and the anode, the flow rate is 0.5L/min, the air inlet pressure is 50Kpa, the temperature of the battery is 80 ℃, the scanning voltage is 0.6V-1.0V, the scanning speed is 50mV/s, and after 30000 circles are measured, a polarization curve test is carried out, the test result is shown in Table 1, and the polarization curve test conditions are the same as the above.
TABLE 1
From the data results of example 1 and comparative example 1, it can be seen that the power density and durability are greatly reduced without adding graphitized multi-walled carbon nanotubes during the preparation of the cathode catalyst layer.
In conclusion, the membrane electrode provided by the invention has the advantages that the structure in the catalyst layer is optimized, the mass activity loss of the catalyst in the potential scanning process is reduced, the durability of the fuel cell is improved, and the initial power density of the membrane electrode prepared by the invention can reach 1662W/cm2And above, through 300The rated power density can still reach 1508W/cm after 00q endurance test2And above, the performance after durability is only attenuated within 9.95%, and better battery performance and durability are shown.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (22)
1. A preparation method of a membrane electrode for a fuel cell is characterized by comprising the following steps:
(1) preparing anode catalyst layer slurry and cathode catalyst layer slurry;
the preparation method of the anode catalysis layer slurry comprises the following steps:
carrying out ultrasonic treatment on a platinum-carbon catalyst and water at the temperature of 8-22 ℃, then adding an alcohol solvent, and continuing ultrasonic treatment; then adding a perfluorinated sulfonic acid resin solution, stirring, standing for 15-30 min, and then carrying out ultrasonic treatment for 20-45 min; finally, adding an anti-reversal inhibitor, and continuing to perform ultrasonic treatment for 30-45 min at 5-12 ℃ and the ultrasonic power of 160-240W to obtain anode catalyst layer slurry;
the preparation method of the cathode catalyst layer slurry comprises the following steps:
carrying out ultrasonic treatment on a platinum-carbon catalyst and water at the temperature of 8-22 ℃ and the ultrasonic power of 220-300W, then adding an alcohol solvent, and continuing ultrasonic treatment; adding the graphitized multi-walled carbon nanotube into the reactor, continuously performing ultrasonic treatment at 8-22 ℃ and with ultrasonic power of 220-300W, finally adding a perfluorinated sulfonic acid resin solution into the reactor, stirring at 8-22 ℃ and at a rotating speed of 8000-15000 r/min, standing for 15-30 min, and finally performing ultrasonic treatment at ultrasonic power of 150-220W for 30-65 min to obtain the cathode catalyst layer slurry in the step (1);
(2) the anode catalyst layer slurry in the step (1) is added at the temperature of 80-95 ℃ and the concentration is 0.05-0.08 mg/cm2Spraying the coating on one side of the proton membrane for 5-15 min at the spraying concentration; then, the cathode catalyst layer is prepared in the step (1)The slurry is heated at 85-105 deg.C at a temperature of 0.05-0.08 mg/cm2Spraying the coating on the other side of the proton membrane for 15-30 min in the spraying concentration;
(3) sealing the sealing frame at 85-105 ℃ for 8-12 s under the pressure of 0.1-0.3 Mpa in a hot pressing manner at the two sides of the proton membrane which is provided with the anode side and the cathode side in the step (2); and (3) after hot-pressing and sealing the hot-melt adhesive sealing frame, placing an adhesive tape with the width of 0.5-1 mm at a position 1-2.3 mm away from the edge of the gas diffusion layer, and pressing the gas diffusion layer on the surface of the sealing frame at 65-85 ℃ for 5-8 s under the pressure of 0.05-0.15 Mpa to obtain the membrane electrode for the fuel cell.
2. The method of manufacturing a membrane electrode assembly for a fuel cell according to claim 1, wherein the alcohol includes ethanol, n-propanol or isopropanol in the cathode catalyst layer slurry manufacturing process.
3. The method for preparing a membrane electrode for a fuel cell according to claim 2, wherein the mass of the ethanol, the n-propanol and the isopropanol is (0-1): 0.23-0.823.
4. The method for preparing a membrane electrode for a fuel cell according to claim 1, wherein, in the process of preparing the cathode catalyst layer slurry, platinum in the platinum-carbon catalyst accounts for 40-70% by mass of the platinum-carbon catalyst.
5. The method of producing a membrane electrode for a fuel cell according to claim 4, wherein an alloy is further included in the platinum-carbon catalyst.
6. The method for producing a membrane electrode assembly for a fuel cell according to claim 5, wherein the alloy accounts for 0 to 4 mass% of the platinum-carbon catalyst.
7. The method for preparing a membrane electrode for a fuel cell according to claim 1, wherein the graphitized multi-walled carbon nanotube has an inner diameter of 9 to 15nm and an outer diameter of 15 to 25 nm.
8. The method for preparing a membrane electrode for a fuel cell according to claim 1, wherein the graphitized multi-walled carbon nanotubes have a length of 30 to 50 nm.
9. The method for preparing a membrane electrode for a fuel cell according to claim 1, wherein the mass ratio of the sum of the platinum and the alloy in the platinum-carbon catalyst to the mass ratio of the water to the alcohol to the resin in the graphitized multi-walled carbon nanotube to the perfluorinated sulfonic acid resin solution is (0.0067-0.009): 0.094-0.225): 0.71-0.823): 0.0002-0.0012): 0.0475-0.076.
10. The method of manufacturing a membrane electrode assembly for a fuel cell according to claim 1, wherein the alcohol includes ethanol, n-propanol or isopropanol in the anode catalyst layer slurry manufacturing process.
11. The method for preparing a membrane electrode for a fuel cell according to claim 10, wherein the mass of the ethanol, the n-propanol and the isopropanol is (0-1): 0.35-0.76.
12. The method for preparing a membrane electrode for a fuel cell according to claim 1, wherein, in the process of preparing the anode catalyst layer slurry, the mass fraction of platinum in the platinum-carbon catalyst is 20-60%.
13. The method of producing a membrane electrode for a fuel cell according to claim 12, wherein an alloy is further included in the platinum-carbon catalyst.
14. The method for producing a membrane electrode assembly for a fuel cell according to claim 13, wherein the alloy accounts for 0 to 4% by mass of the platinum-carbon catalyst.
15. The method for manufacturing a membrane electrode for a fuel cell according to claim 1, wherein the mass ratio of the sum of the platinum and the alloy in the platinum-carbon catalyst to the mass ratio of the water, the alcohol, the resin in the perfluorosulfonic acid resin solution, and the anti-depolarization inhibitor is (0.006-0.009): (0.15-0.196): (0.68-0.78): (0.06-0.096): (0.0003-0.0008).
16. A membrane electrode for a fuel cell, characterized in that it is produced by the method for producing a membrane electrode for a fuel cell according to any one of claims 1 to 15;
the membrane electrode comprises a first gas diffusion layer, a first sealing frame, an anode catalysis layer, a proton membrane, a cathode catalysis layer, a second sealing frame and a second gas diffusion layer which are sequentially stacked; the cathode catalyst layer comprises a platinum carbon catalyst, a graphitized multi-walled carbon nanotube and perfluorinated sulfonic acid resin.
17. The membrane electrode assembly for a fuel cell according to claim 16, wherein the size of the overlapping portion of the first seal frame and the anode catalyst layer is 1.8 to 2.5 mm.
18. The membrane electrode assembly for a fuel cell according to claim 16, wherein the size of the overlapping portion of the second seal frame and the cathode catalyst layer is 1.8 to 2.5 mm.
19. The membrane electrode assembly for a fuel cell according to claim 16, wherein the size of the overlapping portion of the first gas diffusion layer and the first sealing frame is 0.5 to 2 mm.
20. The membrane electrode assembly for a fuel cell according to claim 16, wherein the size of the overlapping portion of the second gas diffusion layer and the second sealing frame is 0.5 to 2 mm.
21. The membrane electrode assembly for a fuel cell according to claim 16, wherein the first gas diffusion layer and the second gas diffusion layer each have a thickness of 140 to 250 μm.
22. A fuel cell characterized by comprising the membrane electrode for a fuel cell according to any one of claims 17 to 21.
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| CN113745612A (en) * | 2021-07-30 | 2021-12-03 | 上海唐锋能源科技有限公司 | Membrane electrode with high-efficiency proton transmission network and preparation method thereof |
| CN114068955A (en) * | 2021-10-29 | 2022-02-18 | 浙江天能氢能源科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
| CN114420944B (en) * | 2022-01-19 | 2024-02-23 | 一汽解放汽车有限公司 | Fuel cell membrane electrode, preparation method thereof and fuel cell |
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| CN114899430B (en) * | 2022-04-07 | 2023-09-19 | 安徽明天氢能科技股份有限公司 | Fuel cell CCM with high durability and anti-counter pole and preparation method thereof |
| CN115011986A (en) * | 2022-05-25 | 2022-09-06 | 同济大学 | Electrolytic cell membrane electrode with controllable and adjustable pore structure and preparation method and application thereof |
| CN115799545B (en) * | 2022-11-30 | 2024-04-16 | 中汽创智科技有限公司 | Catalytic layer, preparation method thereof, membrane electrode, fuel cell and electricity utilization device |
| CN115939417A (en) * | 2023-01-06 | 2023-04-07 | 中国科学院长春应用化学研究所 | Membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN116344839A (en) * | 2023-01-13 | 2023-06-27 | 一汽解放汽车有限公司 | High-potential catalyst and preparation method and application thereof |
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| CN106784943B (en) * | 2016-12-19 | 2019-05-14 | 华南理工大学 | A kind of membrane electrode of fuel batter with proton exchange film of high power density and preparation method thereof |
| CN109713331A (en) * | 2018-12-18 | 2019-05-03 | 新源动力股份有限公司 | A kind of catalyst pulp, catalyst coated membranes, membrane electrode assembly and application thereof |
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