CN113948723A - Hydrogen fuel cell catalyst layer, preparation method thereof, hydrogen fuel cell and automobile - Google Patents

Hydrogen fuel cell catalyst layer, preparation method thereof, hydrogen fuel cell and automobile Download PDF

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CN113948723A
CN113948723A CN202111162081.1A CN202111162081A CN113948723A CN 113948723 A CN113948723 A CN 113948723A CN 202111162081 A CN202111162081 A CN 202111162081A CN 113948723 A CN113948723 A CN 113948723A
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fuel cell
hydrogen fuel
catalyst layer
microwave
irradiation
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CN113948723B (en
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中岛宏
元木寅雄
刘峰林
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Hong Kong Huaqing Technology Co ltd
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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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
    • 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
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—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
    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

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Abstract

A hydrogen fuel cell catalyst layer and a preparation method thereof, a hydrogen fuel cell and an automobile, wherein the preparation method comprises the following steps: s1, irradiating the polymer solution with the dispersed catalyst by ultrasonic waves to obtain a catalyst solution; s2, treating the catalyst solution in S1 by microwave irradiation; s3, coating the catalyst solution treated by the S2 on a proton exchange membrane; s4, irradiating the proton exchange membrane coated with the catalyst solution in S3 by ultrasonic waves and microwaves together to obtain a hydrogen fuel cell catalyst layer and a single fuel cell. Compared with the prior art, the hydrogen fuel cell catalyst layer and the preparation method thereof, the hydrogen fuel cell and the automobile provided by the invention have the following advantages: the catalytic performance of the prepared hydrogen fuel cell catalyst layer is improved by the same catalyst dosage; the hydrogen fuel cell catalyst layer with the same catalytic performance reduces the catalyst consumption.

Description

Hydrogen fuel cell catalyst layer, preparation method thereof, hydrogen fuel cell and automobile
Technical Field
The invention relates to the field of fuel cells, in particular to a hydrogen fuel cell catalyst layer, a preparation method thereof, a hydrogen fuel cell and an automobile.
Background
A fuel cell is a new type of energy conversion device that converts chemical energy into electrical energy, and generally consists of three parts: an anode, a cathode, and an electrolyte. The anode is subjected to oxidation reaction, hydrogen loses electrons and is changed into hydrogen ions and electrons, the hydrogen ions move to the cathode through the proton exchange membrane, the electrons move to the cathode through an external circuit, and at the moment, current is generated due to the movement of the electrons. In contrast, the cathode undergoes a reduction reaction, and oxygen, hydrogen ions and electrons are combined into water to be discharged. Due to the advantages of environmental friendliness, low noise, high-efficiency conversion and the like, the fuel cell is produced in the development of new energy, becomes a power generation device following water power, thermal power and nuclear power in the fourth generation, and is regarded as a future energy star.
However, the current hydrogen fuel cell has only 10000 hours of cycle service life, which is related to the performance of each component of the hydrogen fuel cell, the service life of the catalyst, the proton exchange membrane, the bipolar plate, the sealant, etc., wherein the service life of the catalyst is a main factor, and the current fuel cell catalyst has a short service life, which has become a main factor for restricting the long-term normal operation of the fuel cell.
The Membrane Electrode Assembly (MEA) is composed of a Gas Diffusion Layer (GDL), a Catalyst Layer (CL) and a Proton Exchange Membrane (PEM). The catalyst layer is a site where electrochemical reaction occurs inside the fuel cell. During operation of the fuel cell, proton and electron transfer, as well as reactant gas and product water gas-liquid two-phase flow, occur. The location where the reactant gas, Pt particles and high molecular polymer are combined is generally referred to as a three-phase reaction interface, which is essentially the junction of electron, proton and molecular (reactant gas) transport channels. Proton exchange membranes coated with catalytic layers are also commonly referred to in the industry as Membrane Electrodes (MEAs).
Generally, the more effective reaction active sites are exposed in the catalytic layer, the stronger the catalytic ability of the catalytic layer is, and the better the performance of the fuel cell is, and the distribution of the reaction active sites has an important relationship with the structure and morphology of the catalytic layer, so that the structure and morphology of the catalytic layer are generally considered to largely determine the performance of the fuel cell. Meanwhile, researchers also find that the structure of the catalyst layer is mainly influenced by the interaction between slurry components and components in the preparation process, so that the preparation process of the catalyst layer becomes a link which greatly influences the quality of the membrane electrode in the whole production process of the membrane electrode assembly.
Therefore, how to improve the activity of the fuel cell catalyst layer and reduce the amount of the catalyst has become an urgent technical problem to be solved in the technical field of fuel cells.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a hydrogen fuel cell catalyst layer, a preparation method thereof, a hydrogen fuel cell and an automobile.
The preparation method of the hydrogen fuel cell catalyst layer provided by the invention adopts the main technical scheme that: the preparation method comprises the following steps:
s1, irradiating the polymer solution with the dispersed catalyst by ultrasonic waves to obtain a catalyst solution;
s2, treating the catalyst solution in the S1 by microwave irradiation;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane;
and S4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves together to obtain the hydrogen fuel cell catalyst layer.
The preparation method of the hydrogen fuel cell catalyst layer also adopts the following subsidiary technical scheme:
the catalyst is platinum carbon, and the platinum carbon comprises a carbon carrier and platinum particles attached to the carbon carrier.
The macromolecule solution comprises the following components in percentage by weight: nafion 5%, isopropanol 50%, water 45%.
The proton exchange membrane is a DuPont proton exchange membrane N-117.
The ultrasonic wave and the microwave in the step S4 are irradiated towards the same side of the proton exchange membrane; or the two sides of the proton exchange membrane are respectively irradiated by ultrasonic waves and microwaves.
In the polymer solution in which the catalyst is dispersed in the step S1, the weight ratio of the catalyst to the polymer solution is 4:5 to 1: 1.
The frequency of ultrasonic irradiation in the step S1 is 10K-20 KHz, and the time is 5-10 min;
the frequency of the microwave irradiation in the step S2 is 1.5G-5 GHz, and the time is 2-15S.
The ultrasonic irradiation is ultrasonic emitted by an ultrasonic source, and the distance from the ultrasonic source to the polymer solution containing the catalyst in the step S1 is 0.5-3 cm;
the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the catalyst solution in the step S1 is 15-20 cm.
The irradiation frequency of the ultrasonic wave in the step S4 is 10K-20 KHz, and the irradiation time of each area of the proton exchange membrane covered by the ultrasonic wave is 5-10 min;
the frequency of the microwave irradiation in step S4 is 1.5G to 5GHz, and the irradiation time of each region of the proton exchange membrane covered by the microwave is 2 to 10S.
The ultrasonic irradiation is ultrasonic waves emitted by an ultrasonic source, and the distance from the ultrasonic source to the proton exchange membrane coated with the catalyst solution in the step S4 is 0.5-3 cm;
the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the proton exchange membrane coated with the catalyst solution in the step S4 is 15-20 cm.
The microwave irradiation is intermittent irradiation, in the process of continuously irradiating the area covered by the ultrasonic wave, the microwave intermittently irradiates the same area, the irradiation mode of the microwave is irradiation for 1-3s and stop for 5s, and then irradiation for 1-3s and stop for 5s, and the sum of the accumulated irradiation time is the irradiation time of the area covered by the proton exchange membrane by the microwave.
The hydrogen fuel cell catalyst layer provided by the invention adopts the main technical scheme that: the hydrogen fuel cell catalyst layer is prepared by the preparation method.
The hydrogen fuel cell provided by the invention adopts the main technical scheme that: comprises a hydrogen fuel cell catalyst layer, a diaphragm, a gas diffusion layer, a bipolar plate and an end plate; the hydrogen fuel cell catalyst layer is the hydrogen fuel cell catalyst layer.
The hydrogen fuel cell automobile provided by the invention adopts the main technical scheme that: the hydrogen storage device comprises a vehicle body, a control assembly, a storage battery, a hydrogen storage system and a hydrogen fuel cell, wherein the hydrogen fuel cell is the hydrogen fuel cell.
Compared with the prior art, the preparation method of the hydrogen fuel cell catalyst layer provided by the invention has the following advantages: in the catalyst layer prepared by the method, the polymer solution dispersed with the catalyst can be further ultrasonically dispersed by ultrasonic irradiation in the step S1, so that the catalyst and the polymer solution are more uniformly mixed, and the aggregation among the catalysts is reduced; in the microwave irradiation process in the step S2, the oxide film on the catalyst can be partially or completely vibrated and fallen off, so that the activity of the catalyst is maintained; in step S4, the coated catalyst solution is subjected to ultrasonic irradiation and microwave irradiation again, the first function of the microwave is to dry the coated catalyst solution, and the first function of the ultrasonic irradiation is to prevent the coated catalyst from re-aggregating; meanwhile, the polymer solution in the catalyst solution is gradually dried to form a polymer framework, and the second function of the ultrasonic wave is to increase the gaps of the polymer framework under the irradiation of the ultrasonic wave, so that the exposure rate of metal particles in the catalyst is improved; the second function of the microwave is to melt and shrink the polymer framework through high temperature, so that the gap in the framework can be further enlarged, the permeability between the framework gap and the outer side is improved, the contact area between the reaction gas and the metal particles in the catalyst is improved, and the efficiency of the catalyst layer of the hydrogen fuel cell is greatly improved. Compared with the prior art, the power generation performance of the catalyst layer of the hydrogen fuel cell prepared by the same catalyst dosage is improved; the hydrogen fuel cell catalyst layer has the same power generation performance, and the catalyst consumption is reduced.
Compared with the prior art, the hydrogen fuel cell catalyst layer provided by the invention has the following advantages: compared with the prior art, the power generation performance of the prepared hydrogen fuel cell catalyst layer is improved with the same catalyst dosage; the catalyst layer of the hydrogen fuel cell has the same power generation performance, and the amount of the catalyst is reduced.
Compared with the prior art, the hydrogen fuel cell provided by the invention has the following advantages: the hydrogen fuel cell adopts the hydrogen fuel cell catalyst layer, so that the power generation efficiency is higher, the catalyst consumption is less, the production cost is lower, the service life is longer, and the reliability is higher.
Compared with the prior art, the hydrogen fuel cell automobile provided by the invention has the following advantages: the hydrogen fuel cell automobile has the advantages of better power generation efficiency, less catalyst consumption, lower production cost, longer service life and higher reliability.
Drawings
Fig. 1 is a high-resolution electron micrograph of the catalyst layer of the hydrogen fuel cell in the comparative example.
Fig. 2 is a high-resolution electron microscope image of the hydrogen fuel cell catalyst layer in the first embodiment of the present invention.
Fig. 3 is a schematic diagram of the state of the hydrogen fuel cell catalyst layer in the comparative example.
Fig. 4 is a schematic view of the state of the hydrogen fuel cell catalyst layer in the present invention.
Fig. 5 is an I-V graph after 5 measurements when the hydrogen fuel cell catalyst layer in the first example of the present invention is used for a Membrane Electrode Assembly (MEA).
Fig. 6 is an I-P graph of a hydrogen fuel cell catalyst layer in accordance with a first embodiment of the present invention after 5 measurements when applied to a Membrane Electrode Assembly (MEA).
Fig. 7 is an I-V plot of 4 hydrogen fuel cell catalyst layers prepared in example one, example two, example three, and example four, for 4 Membrane Electrodes (MEAs), after measurement of 4 membrane electrodes, in accordance with the present invention.
Fig. 8 is an I-P graph of 4 hydrogen fuel cell catalyst layers prepared in example one, example two, example three, and example four, for 4 Membrane Electrodes (MEAs), after measurement of 4 membrane electrodes, in accordance with the present invention.
Detailed Description
Referring to fig. 2 and 4, according to an embodiment of the inventive method for preparing a catalyst layer of a hydrogen fuel cell, the method comprises the steps of:
s1, irradiating the polymer prepared solution with the dispersed catalyst by ultrasonic waves to obtain a catalyst solution;
s2, treating the catalyst solution in S1 by microwave irradiation;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane;
s4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves together to obtain the catalyst layer of the hydrogen fuel cell.
According to the catalyst prepared by the method, ultrasonic irradiation in the step S1 can further ultrasonically disperse the polymer mixed solution dispersed with the catalyst, so that the catalyst is more uniformly mixed in the polymer solution, and the aggregation among the catalysts is reduced; in the microwave irradiation process in the step S2, the oxide film on the catalyst can be partially or completely vibrated and fallen off, so that the activity of the catalyst is maintained; in step S4, the coated catalyst solution is subjected to ultrasonic irradiation and microwave irradiation again, the first function of the microwave is to dry the coated catalyst solution, and the first function of the ultrasonic irradiation is to prevent the coated catalyst from re-aggregating; meanwhile, the polymer solution in the catalyst solution is gradually dried to form a polymer framework 3, and the second function of the ultrasonic wave is to increase the gap 31 of the polymer framework 3 under the irradiation of the ultrasonic wave, so that the exposure rate of metal particles in the catalyst is improved; under the second action of the microwave, the high-molecular framework 3 is melted and contracted through high temperature, so that the gap 31 in the framework can be further expanded, the permeability of the framework gap 31 and the outer side is improved, the contact area of reaction gas and metal particles in the catalyst is improved, and the efficiency of the catalyst layer of the hydrogen fuel cell is greatly improved. Compared with the prior art, the power generation performance of the prepared hydrogen fuel cell catalyst layer is improved with the same catalyst dosage; the hydrogen fuel cell catalyst layer has the same power generation performance, and the catalyst consumption is reduced.
Referring to fig. 2 and 4, according to the above-described embodiment of the invention, the catalyst is platinum carbon including a carbon support 1 and platinum particles 2 attached to the carbon support 1. The oxide film is formed on the platinum particles 2. The catalyst has the advantages of good stability, mature technology, high reliability and high catalytic efficiency.
Referring to fig. 2 and 4, according to the above embodiment of the invention, the polymer solution comprises the following components in percentage by weight: nafion 5%, isopropanol 50%, water 45%. The components of the polymer solution are the same as those of a proton exchange membrane on the premise of ensuring the maximum efficiency of the catalyst, so that the associativity of the catalyst solution and the proton exchange membrane is ensured, and the catalyst can be better attached to the proton exchange membrane.
Referring to fig. 2 and 4, the pem is a dupont pem N-117 according to the above-described embodiments of the present invention.
Referring to fig. 2 and 4, according to the above embodiment of the invention, the ultrasonic waves and the microwaves in step S4 are irradiated toward the same side of the proton exchange membrane; or the two sides of the proton exchange membrane are respectively irradiated by ultrasonic waves and microwaves. The operation mode ensures that 1 ultrasonic irradiation is dispersed to prevent agglutination, 2 microwave irradiation helps the macromolecule solution to be converted into the macromolecule framework 3, ultrasonic irradiation improves the framework clearance rate, so that the exposure rate of the platinum particles 2 is improved, 4 microwave irradiation makes the macromolecule framework 3 melt and contract, the changes of the forms such as the expansion of the clearance 31 in the framework can be effectively connected step by step, and the production efficiency of the invention is improved.
Referring to fig. 2 and 4, in the polymer solution containing the catalyst in step S1, the weight ratio of the catalyst to the polymer solution is 4:5 to 1:1 according to the above embodiment of the invention.
Referring to fig. 2 and 4, according to the above embodiment of the invention, the frequency of the ultrasonic irradiation in step S1 is 10K-20 KHz, and the time is 5-10 min; the frequency of the microwave irradiation in the step S2 is 1.5G-5 GHz, and the time is 2-15S.
Referring to fig. 2 and 4, according to the above embodiment of the present invention, the ultrasonic irradiation is ultrasonic waves emitted from an ultrasonic source, and the distance from the ultrasonic source to the polymer solution in which the catalyst is dispersed in step S1 is 0.5 to 3 cm; the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the catalyst solution in the step S1 is 15-20 cm. The ultrasonic wave source can adopt an ultrasonic wave generator, and the microwave source can adopt a microwave generator.
Referring to fig. 2 and 4, according to the above-mentioned embodiment of the invention, the frequency of the ultrasonic irradiation in step S4 is 10KHz to 20KHz, and the irradiation time of each region of the proton exchange membrane covered by the ultrasonic wave is 5 to 10 min;
the frequency of the microwave irradiation in step S4 is 1.5GHz to 5GHz, and the irradiation time of each region of the proton exchange membrane covered by the microwave is 2 to 10S.
Referring to fig. 2 and 4, according to the above embodiment of the invention, the ultrasonic irradiation is ultrasonic waves emitted from an ultrasonic source, and the distance from the ultrasonic source to the proton exchange membrane coated with the catalyst solution in step S4 is 0.5-3 cm; the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the proton exchange membrane coated with the catalyst solution in the step S4 is 15-20 cm.
Referring to fig. 2 and 4, according to the above embodiment of the present invention, the microwave irradiation is intermittent irradiation, and during the continuous irradiation of the area covered by the ultrasonic wave, the microwave irradiates the same area intermittently, and the irradiation manner of the microwave is irradiation 1-3s for 5s, and then irradiation 1-3s for 5s, so that the sum of the accumulated irradiation time is the irradiation time of the area covered by the proton exchange membrane by the microwave. The microwave adopts an intermittent irradiation mode to ensure the melting and shrinking of the polymer framework 3, and the high-temperature damage to the polymer framework 3 can not be caused, thereby avoiding the falling of metal particles in the catalyst and having good energy-saving effect.
Referring to fig. 2 and 4, embodiments of a hydrogen fuel cell catalyst layer according to the invention are provided, which are the hydrogen fuel cell catalyst layers prepared in the above embodiments. Compared with the prior art, the power generation performance of the prepared hydrogen fuel cell catalyst layer is improved with the same catalyst dosage; the catalyst layer of the hydrogen fuel cell has the same power generation performance, and the amount of the catalyst is reduced.
Referring to fig. 2 and 4, a hydrogen fuel cell embodiment is provided in accordance with the invention, comprising a hydrogen fuel cell catalyst layer, a membrane, a gas diffusion layer, a bipolar plate, and an end plate; the gas diffusion layer is a mature technology in the prior art, and details are not repeated here, and the hydrogen fuel cell catalyst layer in this embodiment is the hydrogen fuel cell catalyst layer described in the above embodiment. The hydrogen fuel cell adopts the hydrogen fuel cell catalyst layer, so that the power generation efficiency is higher, the catalyst consumption is less, the production cost is lower, the service life is longer, and the reliability is higher.
Referring to fig. 2 and 4, an embodiment of a hydrogen fuel cell vehicle according to the invention includes a vehicle body, a control assembly, a storage battery, and a hydrogen fuel cell, where the vehicle body, the control assembly, and the storage battery are mature technologies in the prior art, and detailed description thereof is omitted here. The hydrogen fuel cell automobile has the advantages of better power generation efficiency, less catalyst consumption, lower production cost, longer service life and higher reliability.
Comparative example
Referring to fig. 1 and 3, a method for preparing a catalyst layer of a hydrogen fuel cell in the related art includes the steps of:
s1, irradiating the platinum-carbon polymer mixed solution by an ultrasonic source to obtain a catalyst solution;
wherein, the polymer solution is: a mixed solution of nafion 5%, isopropanol 50% and water 45%; the frequency of the ultrasonic wave is 15KHz, the irradiation time is 7min, and the distance from the ultrasonic wave to the solution is 1.5 cm; the platinum carbon includes a carbon support 1 and platinum particles 2 attached to the carbon support 1.
S2, coating the catalyst solution treated by the S1 on a proton exchange membrane;
and S3, drying or naturally airing the proton exchange membrane coated with the catalyst solution in the S2 to obtain the hydrogen fuel cell catalyst layer.
The difference between the present application and the preparation scheme of the catalyst layer of the hydrogen fuel cell in the prior art is that: the different conditions of irradiation are mainly reflected as: 1. the catalyst solution in the application needs to be subjected to microwave irradiation before being coated on a proton exchange membrane; 2. the proton exchange membrane coated with the catalyst solution is irradiated by ultrasonic waves and microwaves together.
Example one
S1, irradiating the platinum-carbon polymer mixed solution with the weight ratio of 1:1 by an ultrasonic source to obtain a catalyst solution;
wherein, the polymer solution is: a mixed solution of nafion 5%, isopropanol 50% and water 45%; the frequency of the ultrasonic wave is 15KHz, the irradiation time is 7min, and the distance from the ultrasonic wave to the solution is 1.5 cm; the platinum carbon includes a carbon support 1 and platinum particles 2 attached to the carbon support 1.
S2, irradiating the catalyst solution in the S1 by a microwave source; the oxide film on the platinum particles 2 is partially peeled off; the frequency of the microwave is 2GHz, the irradiation time is 2.5s, and the distance from the microwave to the catalyst solution is 17 cm;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane; the proton exchange membrane is DuPont proton exchange membrane N-117;
s4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves, wherein an ultrasonic wave source and a microwave source are positioned on two sides of the proton exchange membrane;
the frequency of the ultrasonic wave is 15KHz, and the irradiation time of the ultrasonic wave to each area of the proton exchange membrane covered by the ultrasonic wave is 7 min; the distance between the ultrasonic source and the proton exchange membrane is 1.5 cm;
the frequency of the microwave is 2GHz, and the irradiation time of the microwave to each area of the proton exchange membrane covered by the microwave is 9 s; the distance between the microwave source and the proton exchange membrane is 17 cm; and obtaining the hydrogen fuel cell catalyst layer. See fig. 5 and 6;
the hydrogen fuel cell catalyst layer prepared in the first implementation is used for I-V measurement after being used for a membrane electrode.
Fig. 5 is an I-V graph after 5 measurements when the hydrogen fuel cell catalyst layer in the first example of the present invention is used for a Membrane Electrode Assembly (MEA). The reproducibility of the measurement results showed a certain improvement compared to the untreated (Ref).
The hydrogen fuel cell catalyst layer prepared in the first embodiment is used for I-P measurement after being used for a membrane electrode.
Fig. 6 is an I-P graph of a hydrogen fuel cell catalyst layer in accordance with a first embodiment of the present invention after 5 measurements when applied to a Membrane Electrode Assembly (MEA). The reproducibility of the measurement results showed a certain improvement compared to the untreated (Ref).
Example two
S1, irradiating the platinum-carbon polymer mixed solution with the weight ratio of 4:5 by an ultrasonic source to obtain a catalyst solution;
wherein, the polymer solution is: a mixed solution of nafion 5%, isopropanol 50% and water 45%; the frequency of the ultrasonic wave is 10KHz, the irradiation time is 5min, and the distance from the ultrasonic wave to the solution is 0.5 cm; the platinum carbon includes a carbon support 1 and platinum particles 2 attached to the carbon support 1.
S2, irradiating the catalyst solution in the S1 by a microwave source; the oxide film on the platinum particles 2 is partially peeled off; the frequency of the microwave is 1.5GHz, the irradiation time is 5s, and the distance from the microwave to the catalyst solution is 15 cm;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane; the proton exchange membrane is DuPont proton exchange membrane N-117;
s4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves, wherein the ultrasonic wave source and the microwave source are positioned on the same side of the proton exchange membrane;
the frequency of the ultrasonic wave is 20KHz, and the irradiation time of the ultrasonic wave to each area of the proton exchange membrane covered by the ultrasonic wave is 10 min; the distance between the ultrasonic source and the proton exchange membrane is 3 cm;
the frequency of the microwave is 5GHz, and the irradiation time of the microwave to each area covered by the proton exchange membrane by the microwave is 6 s; the distance between the microwave source and the proton exchange membrane is 20 cm; and obtaining the hydrogen fuel cell catalyst layer.
EXAMPLE III
S1, irradiating the platinum-carbon polymer mixed solution with the weight ratio of 9:10 by an ultrasonic source to obtain a catalyst solution;
wherein, the polymer solution is: a mixed solution of nafion 5%, isopropanol 50% and water 45%; the frequency of the ultrasonic wave is 20KHz, the irradiation time is 10min, and the distance from the ultrasonic wave to the solution is 3 cm; the platinum carbon includes a carbon support 1 and platinum particles 2 attached to the carbon support 1.
S2, irradiating the catalyst solution in the S1 by a microwave source; the oxide film on the platinum particles 2 is partially peeled off; the frequency of the microwave is 5GHz, the irradiation time is 10s, and the distance from the microwave to the catalyst solution is 20 cm;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane; the proton exchange membrane is DuPont proton exchange membrane N-117;
s4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves, wherein an ultrasonic wave source and a microwave source are positioned on two sides of the proton exchange membrane;
the frequency of the ultrasonic wave is 10KHz, and the irradiation time of the ultrasonic wave to each area of the proton exchange membrane covered by the ultrasonic wave is 5 min; the distance between the ultrasonic source and the proton exchange membrane is 0.5 cm;
the frequency of the microwave is 1.5GHz, and the irradiation time of the microwave to each area of the proton exchange membrane covered by the microwave is 3 s; the distance between the microwave source and the proton exchange membrane is 15 cm; and obtaining the hydrogen fuel cell catalyst layer.
Example four
S1, irradiating the platinum-carbon polymer dispersion solution with the weight ratio of 1:1 by an ultrasonic source to obtain a catalyst solution;
wherein, the polymer solution is: a mixed solution of nafion 5%, isopropanol 50% and water 45%; the frequency of the ultrasonic wave is 15KHz, the irradiation time is 7min, and the distance from the ultrasonic wave to the solution is 1.5 cm; the platinum carbon includes a carbon support 1 and platinum particles 2 attached to the carbon support 1.
S2, irradiating the catalyst solution in the S1 by a microwave source; the oxide film on the platinum particles 2 is partially peeled off; the frequency of the microwave is 2GHz, the irradiation time is 15s, and the distance from the microwave to the catalyst solution is 17 cm;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane; the proton exchange membrane is DuPont proton exchange membrane N-117;
s4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves, wherein an ultrasonic wave source and a microwave source are positioned on two sides of the proton exchange membrane;
the frequency of the ultrasonic wave is 15KHz, and the irradiation time of the ultrasonic wave to each area of the proton exchange membrane covered by the ultrasonic wave is 7 min; the distance between the ultrasonic source and the proton exchange membrane is 1.5 cm;
the frequency of the microwave is 2GHz, the microwave irradiation is intermittent irradiation, the microwave intermittently irradiates the same area in the process of continuously irradiating the area covered by the ultrasonic, the irradiation mode of the microwave is that the irradiation is stopped for 5s for 3s, and the sum of the accumulated irradiation time is regarded as a prime 9 s; the distance between the microwave source and the proton exchange membrane is 17 cm; and obtaining the hydrogen fuel cell catalyst layer. The microwave adopts an intermittent irradiation mode to ensure the melting and shrinking of the polymer framework 3, and the high-temperature damage to the polymer framework 3 can not be caused, thereby avoiding the falling of metal particles in the catalyst and having good energy-saving effect.
Contact Angle test of Water
The hydrogen fuel cell catalyst layer a1 prepared in the comparative example;
the steps S1, S2, S3 of the first embodiment are adopted; step S4 is a hydrogen fuel cell catalyst layer a2 prepared by irradiation with only ultrasonic waves without irradiation with microwaves;
the steps S1, S2, S3 of the first embodiment are adopted; step S4 is a hydrogen fuel cell catalyst layer a3 prepared by only microwave irradiation without ultrasonic irradiation;
the hydrogen fuel cell catalyst layer a4 prepared using the first example described above;
the results of the contact angle test of water on the 4 hydrogen fuel cell catalyst layers a1, a2, a3 and a4 are as follows:
catalyst layer Contact angle (°)
a1 31.2
a2 23.4
a3 22.1
a4 20.5
Through the contact angle test of water, it can be known that the hydrogen fuel cell catalyst layer prepared in the first embodiment of the present application has a smaller contact angle of the membrane and better hydrophilicity than other hydrogen fuel cell catalyst layers, and water is more easily discharged to enter the catalyst layer for reaction, which is beneficial to improving the efficiency of the hydrogen fuel cell catalyst layer; the power generation performance of the prepared hydrogen fuel cell catalyst layer is improved by the same catalyst dosage; the hydrogen fuel cell catalyst layer has the same power generation performance, and the catalyst consumption is reduced.
The results of the specific surface area tests of Pt on the 4 hydrogen fuel cell catalyst layers a1, a2, a3 and a4 are as follows:
catalyst layer Pt amount ratio (%)
a1 16.51
a2 18.19
a3 18.55
a4 20.3
Through the specific surface area test of the Pt, the hydrogen fuel cell catalyst layer prepared by the first embodiment of the application has the advantages that the specific surface area of the Pt is increased compared with other hydrogen fuel cell catalyst layers, and the power generation performance of the prepared hydrogen fuel cell catalyst layer is improved with the same catalyst dosage; the hydrogen fuel cell catalyst layer has the same power generation performance, and the catalyst consumption is reduced.
I-V measurements were made on 4 hydrogen fuel cell catalyst layers prepared in the above-described examples one to four, after being applied to 4 membrane electrodes (MEA-A, MEA-B, MEA-C, MEA-D), and showed a certain improvement as compared to untreated (Ref) as shown in fig. 7. FIG. 7 is an I-V plot of 4 hydrogen fuel cell catalyst layers prepared in example one, example two, example three, and example four, for 4 membrane electrodes (MEA-A, MEA-B, MEA-C, MEA-D), after measurement.
The I-P measurements of 4 hydrogen fuel cell catalyst layers prepared in the above-described examples one to four, after being applied to 4 membrane electrodes (MEA-A, MEA-B, MEA-C, MEA-D), showed a certain improvement as compared to the untreated (Ref) as shown in fig. 8. FIG. 8 is an I-P plot of 4 hydrogen fuel cell catalyst layers prepared in example one, example two, example three, and example four, for 4 membrane electrodes (MEA-A, MEA-B, MEA-C, MEA-D), after measurement.
Although embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.

Claims (14)

1. A method of making a hydrogen fuel cell catalyst layer, characterized by: the preparation method comprises the following steps:
s1, irradiating the polymer solution with the dispersed catalyst by ultrasonic waves to obtain a catalyst solution;
s2, treating the catalyst solution in the S1 by microwave irradiation;
s3, coating the catalyst solution treated by the S2 on a proton exchange membrane;
and S4, irradiating the proton exchange membrane coated with the catalyst solution in the S3 by ultrasonic waves and microwaves together to obtain the hydrogen fuel cell catalyst layer.
2. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: the catalyst is platinum carbon, and the platinum carbon comprises a carbon carrier and platinum particles attached to the carbon carrier.
3. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: the macromolecule solution comprises the following components in percentage by weight: nafion 5%, isopropanol 50%, water 45%.
4. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: the proton exchange membrane is a DuPont proton exchange membrane N-117.
5. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: the ultrasonic wave and the microwave in the step S4 are irradiated towards the same side of the proton exchange membrane coated with the catalyst solution; or the two sides of the proton exchange membrane coated with the catalyst solution are respectively irradiated by ultrasonic waves and microwaves.
6. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: in the polymer solution in which the catalyst is dispersed in the step S1, the weight ratio of the catalyst to the polymer solution is 4:5 to 1: 1.
7. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that:
the frequency of ultrasonic irradiation in the step S1 is 10 KHz-20 KHz, and the time is 5-10 min;
the frequency of the microwave irradiation in the step S2 is 1.5 GHz-5 GHz, and the time is 2-15S.
8. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that: the ultrasonic irradiation is ultrasonic emitted by an ultrasonic source, and the distance from the ultrasonic source to the polymer solution containing the catalyst in the step S1 is 0.5-3 cm;
the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the catalyst solution in the step S1 is 15-20 cm.
9. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that:
the irradiation frequency of the ultrasonic wave in the step S4 is 10 KHz-20 KHz, and the irradiation time of each area of the proton exchange membrane covered by the ultrasonic wave is 5-10 min;
the frequency of the microwave irradiation in step S4 is 1.5GHz to 5GHz, and the irradiation time of each region of the proton exchange membrane covered by the microwave is 2 to 10S.
10. The method of producing a hydrogen fuel cell catalyst layer according to claim 1, characterized in that:
the ultrasonic irradiation is ultrasonic waves emitted by an ultrasonic source, and the distance from the ultrasonic source to the proton exchange membrane coated with the catalyst solution in the step S4 is 0.5-3 cm;
the microwave irradiation is the microwave emitted by a microwave source, and the distance from the microwave source to the proton exchange membrane coated with the catalyst solution in the step S4 is 15-20 cm.
11. The method of producing a hydrogen fuel cell catalyst layer according to claim 9, characterized in that: the microwave irradiation is intermittent irradiation, in the process of continuously irradiating the area covered by the ultrasonic wave, the microwave intermittently irradiates the same area, the irradiation mode of the microwave is irradiation for 1-3s and stop for 5s, and then irradiation for 1-3s and stop for 5s, and the sum of the accumulated irradiation time is the irradiation time of the area covered by the proton exchange membrane by the microwave.
12. A hydrogen fuel cell catalyst layer characterized by: the hydrogen fuel cell catalyst layer is a hydrogen fuel cell catalyst layer produced by the method for producing a hydrogen fuel cell catalyst layer according to any one of claims 1 to 11.
13. A hydrogen fuel cell comprises a hydrogen fuel cell catalyst layer, a diaphragm, a gas diffusion layer, a bipolar plate and an end plate; the method is characterized in that: the hydrogen fuel cell catalyst layer is a hydrogen fuel cell catalyst layer produced by the method for producing a hydrogen fuel cell catalyst layer according to claim 12.
14. The utility model provides a hydrogen fuel cell car, includes automobile body, control assembly, battery, hydrogen storage system and hydrogen fuel cell, its characterized in that: the hydrogen fuel cell according to claim 13.
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