CN117374292A - Gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof - Google Patents
Gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof Download PDFInfo
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- CN117374292A CN117374292A CN202311177831.1A CN202311177831A CN117374292A CN 117374292 A CN117374292 A CN 117374292A CN 202311177831 A CN202311177831 A CN 202311177831A CN 117374292 A CN117374292 A CN 117374292A
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 130
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 45
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 45
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 27
- -1 cerium ion Chemical class 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 150000000703 Cerium Chemical class 0.000 claims description 20
- 238000001652 electrophoretic deposition Methods 0.000 claims description 17
- 239000000693 micelle Substances 0.000 claims description 17
- 150000002503 iridium Chemical class 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 3
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 32
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 238000001962 electrophoresis Methods 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 108
- 230000000052 comparative effect Effects 0.000 description 45
- 230000008021 deposition Effects 0.000 description 19
- 239000002002 slurry Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- UIFPPCCBDYJNKI-UHFFFAOYSA-M Cl[Ir].[Na] Chemical compound Cl[Ir].[Na] UIFPPCCBDYJNKI-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8807—Gas diffusion layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to the technical field of fuel cells, and discloses a gas diffusion layer for PEMFC membrane electrodes and a preparation method thereof, wherein the gas diffusion layer comprises a basal layer and a microporous layer arranged on at least one side of the basal layer; the surface of the basal layer is deposited with shell-shaped cerium oxide particles, and the shell-shaped cerium oxide particles are positioned on one side of the basal layer, which is composited with the microporous layer; the surface of the microporous layer is deposited with shell-shaped iridium oxide particles. The invention adopts a soft template electrophoresis deposition method to uniformly distribute cerium oxide and iridium oxide on the expected positions of the gas diffusion layer, reduce particle agglomeration caused by direct doping of cerium oxide and iridium oxide particles and improve the utilization efficiency of the particles; by arranging the cerium oxide on the substrate layer, the dissolution of the cerium oxide by the acidic environment of the catalytic layer can be reduced, and the problem of ion pollution of the catalytic layer caused by cerium ion dissolution is reduced; the iridium oxide is arranged on the surface of the microporous layer, so that the iridium oxide on the surface of the microporous layer is contacted with the resin on the surface of the catalytic layer to form a three-phase interface, and the sufficiency of the electrochemical reaction condition of the iridium oxide is ensured.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a gas diffusion layer for PEMFC membrane electrodes, which is prepared by adopting a soft template electrophoretic deposition method.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of low working temperature, quick start-up and shutdown, high energy density and the like, and has good application prospect in the aspects of mobile power supply, vehicles and other equipment. As the range of fuel cells continues to expand, there is an increasing demand for initial performance and durability of the membrane electrode of the core power generation component of the fuel cell. In addition to the stability of the material itself, the factors affecting the durability of the membrane electrode are also greatly affected by the electrochemical additional reaction during operation of the membrane electrode.
The free radical formed under the anode potential environment of the membrane electrode attacks the sulfonic acid groups of the resin in the catalytic layer and the proton exchange membrane, so that the resin in the catalytic layer and the proton exchange membrane is degraded, and the service life of the membrane electrode is reduced. The cerium oxide can effectively capture free radicals, but due to strong acidity of a catalytic layer of the fuel cell, cerium ions are easily dissolved by directly doping the cerium oxide in the catalytic layer, so that the catalytic layer is polluted, and generally cerium oxide is doped in a microporous layer of a gas diffusion layer, but due to the fact that cerium oxide particles are insoluble in water, agglomeration of cerium oxide particles is easily caused by directly doping the cerium oxide in a pulping process, and slurry is unstable. In addition, the anode or cathode is extremely easy to be partially short of gas in the starting and stopping process of the fuel cell, the high potential at the gas-lack position is easy to cause carbon corrosion, catalyst particles are aggregated, the catalyst attenuation is accelerated, a certain amount of iridium oxide, iridium black and other electrolyzed water catalysts are doped in the anode catalytic layer to prevent carbon corrosion, the durability of the membrane electrode is improved, the doping of the iridium oxide and the iridium black greatly improves the cost of the membrane electrode, and the dispersing of the iridium oxide and the iridium black is uneven, so that the problems of low utilization rate and the like are easily caused.
Disclosure of Invention
In view of the above, the present invention provides a gas diffusion layer for PEMFC membrane electrode, to solve the problems of ion pollution of the catalytic layer caused by the dissolution of cerium oxide by the acidic environment of the catalytic layer, easy dispersion non-uniformity of the electrolyzed water catalyst, and low utilization rate;
the invention also provides a preparation method of the gas diffusion layer for the PEMFC membrane electrode, which is used for solving the problems of particle agglomeration and low utilization efficiency caused by direct doping of cerium oxide and iridium oxide particles.
In order to solve the technical problems, the invention adopts the following technical scheme:
a first object of the present invention is to provide a gas diffusion layer for PEMFC membrane electrode, comprising a base layer and a microporous layer disposed on at least one side of the base layer;
the surface of the basal layer is deposited with shell-shaped cerium oxide particles, and the shell-shaped cerium oxide particles are positioned on the composite side of the basal layer and the microporous layer; the surface of the microporous layer is deposited with shell-shaped iridium oxide particles.
The second object of the present invention is to provide a method for preparing the gas diffusion layer for PEMFC membrane electrode, comprising the following steps:
(1) Fully mixing cerium salt, amphiphilic block copolymer template agent and deionized water to obtain solution I, placing a gas diffusion layer substrate serving as a negative electrode in the solution I, and performing electrophoretic deposition to obtain a cerium ion surface modified gas diffusion layer substrate layer;
(2) Coating a microporous layer on the surface of the cerium ion surface modified gas diffusion layer substrate layer, drying and presintering to obtain a gas diffusion layer intermediate;
(3) Fully mixing iridium salt, amphiphilic block copolymer template agent and deionized water to obtain a solution II, and then placing the gas diffusion layer intermediate serving as a negative electrode in the solution II for electrophoretic deposition to obtain an iridium ion modified gas diffusion layer;
(4) Calcining the iridium ion modified gas diffusion layer.
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the cerium salt in step (1) includes any one or more of cerium ammonium nitrate, cerium acetate hydrate, and cerium nitrate hydrate;
further preferably, the mass ratio of the cerium salt, the amphiphilic block copolymer template agent and the deionized water is 1:1 (15-30).
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the iridium salt in step (3) includes any one or more of iridium chloride, iridium acetate, and sodium chloroiridate;
further preferably, the mass ratio of the iridium salt, the amphiphilic block copolymer template agent and the deionized water is 1:1 (15-30).
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the amphiphilic block copolymer template in step (1) and step (3) is a block copolymer P123 or F127;
further preferably, the concentration of the amphiphilic block copolymer template agent is 1-2 times of the critical micelle concentration.
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the voltage of the electrophoretic deposition in step (1) and step (3) is 1-25V.
Preferably, in the method for preparing a gas diffusion layer for a PEMFC membrane electrode, the gas diffusion layer substrate in the step (1) is any one of a carbon fiber paper substrate and a carbon cloth substrate.
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the pre-sintering temperature in step (2) is 200-300 ℃;
further preferably, the pre-sintering atmosphere is an air atmosphere;
further preferably, the presintering in step (2) comprises a primary presintering and a secondary presintering;
the primary presintering is as follows: sintering at 250-265 deg.c for 5-15min, cooling to 200-220 deg.c and secondary pre-sintering;
the secondary presintering is as follows: raising the temperature from 200-220 ℃ to 285-300 ℃ at a rate of 5-10 ℃/min, and sintering at the temperature of 285-300 ℃ for 5-10min.
Preferably, in the above method for preparing a gas diffusion layer for a PEMFC membrane electrode, the calcination temperature in step (4) is 340-400 ℃;
further preferably, the calcination atmosphere is an air atmosphere;
further preferably, the calcining in step (4) comprises a primary calcining and a secondary calcining;
the primary calcination is as follows: calcining at 340-365 deg.C for 30-45min;
the secondary calcination is as follows: raising the temperature from 340-365 ℃ to 390-400 ℃ at a rate of 3-5 ℃/min, and calcining at 390-400 ℃ for 15-30min.
A third object of the present invention is to provide an application of the gas diffusion layer for a PEMFC membrane electrode described above or the gas diffusion layer for a PEMFC membrane electrode obtained by any one of the above methods in a fuel cell.
The invention provides a gas diffusion layer for PEMFC membrane electrode and a preparation method thereof, which has the beneficial effects that compared with the prior art:
the invention adopts a soft template electrophoresis deposition method to uniformly distribute cerium oxide and iridium oxide on the expected positions of the gas diffusion layer, reduce particle agglomeration caused by direct doping of cerium oxide and iridium oxide particles and improve the utilization efficiency of the particles;
according to the invention, the cerium oxide is arranged on the surface of the substrate layer, so that the dissolution of the cerium oxide by the acidic environment of the catalytic layer can be reduced, and the problem of ion pollution of the catalytic layer caused by dissolution of cerium ions is reduced; by arranging the iridium oxide on the surface of the microporous layer, the iridium oxide on the surface of the microporous layer can be contacted with the resin on the surface of the catalytic layer to form a three-phase interface, so that the sufficiency of the electrochemical reaction condition of the iridium oxide is ensured, and the anti-counter electrode capability of the membrane electrode is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the anti-reverse-polarity performance of a gas diffusion layer according to example 1 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The conventional adding means of cerium oxide is to uniformly mix the cerium oxide into the microporous layer slurry to finally form stable distribution in the microporous layer, but the adding means is easy to cause particle agglomeration of the cerium oxide, and the cerium oxide close to one side of the catalytic layer is easy to dissolve due to the catalytic layer, so that ionomer pollution in the catalytic layer is caused; based on the above, the embodiment of the invention adopts a soft template electrophoresis deposition method to improve the dispersibility of cerium oxide, improve the utilization rate and reduce the pollution to the ionomer of the catalytic layer;
in addition, at present, iridium oxide is generally directly doped in the slurry of the catalytic layer to form stable distribution in the catalytic layer, but the iridium oxide also has the problems of uneven distribution and low utilization rate; based on the above, the embodiment of the invention electrophoretically deposits a thin iridium oxide layer on the surface of the microporous layer, so that the dispersibility of iridium oxide and the utilization rate of iridium oxide can be improved.
Based on the above, some embodiments of the present invention provide a gas diffusion layer for a PEMFC membrane electrode, including a base layer and a microporous layer disposed on at least one side of the base layer;
the surface of the basal layer is deposited with shell-shaped cerium oxide particles, and the shell-shaped cerium oxide particles are positioned on the composite side of the basal layer and the microporous layer; the surface of the microporous layer is deposited with shell-shaped iridium oxide particles.
The cerium oxide is arranged on the substrate layer, so that the dissolution of the cerium oxide by the acidic environment of the catalytic layer can be reduced, and the problem of ion pollution of the catalytic layer caused by cerium ion dissolution is reduced; the iridium oxide is arranged on the surface of the microporous layer, so that the iridium oxide on the surface of the microporous layer is contacted with the resin on the surface of the catalytic layer to form a three-phase interface, and the sufficiency of the electrochemical reaction condition of the iridium oxide is ensured.
According to other embodiments of the present invention, a method for preparing the gas diffusion layer for a PEMFC membrane electrode is provided, including the steps of:
and S100, fully mixing cerium salt, an amphiphilic block copolymer template agent and deionized water to obtain a solution I, placing a gas diffusion layer substrate serving as a negative electrode in the solution I, and performing electrophoretic deposition to obtain a cerium ion surface modified gas diffusion layer substrate layer.
In this step, the cerium salt includes, but is not limited to, ammonium cerium nitrate, hydrated cerium acetate, hydrated cerium nitrate, etc., and the mass ratio of cerium salt, amphiphilic block copolymer templating agent to deionized water is 1:1 (15-30), preferably 1:1: (15-25), more preferably 1:1: (15-20), for example, may be 1:1:15, 1:1:20, 1:1:25, 1:1:30, etc.
Further, the amphiphilic block copolymer template agents are block copolymers P123 or F127, and the concentration of the amphiphilic block copolymer template agents is 1-2 times of the critical micelle concentration of the amphiphilic block copolymer template agents, so that micelles in the solution self-assemble into stable spherical micelles, and Ce in the solution 4+ Uniformly adsorbing the core-shell structure outside the micelle structure to obtain the core-shell structure with the template agent as the core and the adsorption ions as the shell.
When the amphiphilic block copolymer is larger than the critical micelle concentration, the hydrophobic block is cohesive and nucleated, the hydrophilic block is coated on the outer side to form a shell, and the micelle is formed by self-assembly. According to different copolymer block structures, different copolymer concentrations and different temperatures, the assembled micelle structures are different, and the influence of the copolymer concentrations is considered, when the copolymer concentrations are changed from low to high, the formed micelle structures are gradually prolonged from a spherical shape to a rod shape, a cylindrical shape and a worm shape, and the stable micelle structures can form stable adsorption structures with ions in the solution, so that ordered chemical structures are obtained.
Further, the fully mixing mode can be ultrasonic dispersion, high-speed shearing, homogenizer stirring and the like, and the specific mode can be selected according to the actual situation, and the method is not particularly limited; the gas diffusion layer substrate is any one of a carbon fiber paper substrate and a carbon cloth substrate, and the carbon fiber paper substrate and the carbon cloth substrate have a good and uniform large number of pores, so that the gas diffusion layer substrate has good performance and low cost and is suitable for industrial production.
Further, the electrophoretic deposition is specifically performed by cathode electrophoretic deposition, the voltage is set to be 1-25V, preferably 2-20V, more preferably 3-15V, for example, 3V, 5V, 10V, 15V, etc., the electrophoretic deposition time can be determined according to the actual operation condition, preferably 20-150min, and Ce is adsorbed 4+ The micelle of the ions is deposited into the gas diffusion layer substrate layer to form a cerium ion surface modified gas diffusion layer substrate layer.
And S200, coating a microporous layer on the surface of the gas diffusion layer substrate layer modified on the surface of cerium ions, and drying and presintering to obtain a gas diffusion layer intermediate.
In the step, microporous layer slurry is prepared, microporous layer coating, drying and presintering are carried out on the surface of a gas diffusion layer substrate layer deposited by cerium salt, and then a gas diffusion layer intermediate is obtained. The microporous layer slurry according to the embodiment of the present invention is a conventional microporous layer slurry, and is not particularly limited.
Further, the presintering temperature is 200-300 ℃, and the presintering atmosphere is preferably air atmosphere;
more preferably, the pre-sintering comprises a primary pre-sintering and a secondary pre-sintering, wherein the primary pre-sintering is: sintering at 250-265deg.C for 5-15min, wherein the primary sintering temperature can be 250deg.C, 255 deg.C, 260 deg.C, 265 deg.C, etc., the sintering time can be 5min, 10min, 15min, etc., cooling to 200-220deg.C, and performing secondary pre-sintering; the secondary presintering is as follows: the temperature is raised from 200-220 ℃ to 285-300 ℃ at a rate of 5-10 ℃/min, and the mixture is sintered at 285-300 ℃ for 5-10min, wherein the secondary sintering temperature can be 285 ℃, 290 ℃, 295 ℃, 300 ℃ and the like, the sintering time can be 5min, 10min and the like, and the heating rate can be 5 ℃/min, 8 ℃/min, 10 ℃/min and the like. The porosity can be improved more effectively through the two presintering processes, and the agglomeration phenomenon is avoided.
And S300, fully mixing iridium salt, amphiphilic block copolymer template agent and deionized water to obtain a solution II, and then placing the gas diffusion layer intermediate serving as a negative electrode in the solution II for electrophoretic deposition to obtain the iridium ion modified gas diffusion layer.
In the step, the iridium salt comprises any one or more of iridium chloride, iridium acetate and sodium chloride, and the mass ratio of the iridium salt, the amphiphilic block copolymer template agent and deionized water is 1:1 (15-30), preferably 1:1: (15-25), more preferably 1:1: (15-20), for example, may be 1:1:15, 1:1:20, 1:1:25, 1:1:30, etc.
Further, the amphiphilic block copolymer template agents are block copolymers P123 or F127, and the concentration of the amphiphilic block copolymer template agents is 1-2 times of the critical micelle concentration of the amphiphilic block copolymer template agents, so that micelles in the solution self-assemble into stable spherical micelles, and Ir in the solution 4+ Uniformly adsorbing the core-shell structure outside the micelle structure to obtain the core-shell structure with the template agent as the core and the adsorption ions as the shell.
Further, the electrophoretic deposition is specifically performed by a cathodic electrophoretic deposition method, the voltage is set to be 1-25V, preferably 2-20V, more preferably 3-15V, for example, 3V, 5V, 10V, 15V, etc., the electrophoretic deposition time can be determined according to the actual operation condition, preferably 20-150min, ir is adsorbed 4+ The micelle of ions is deposited on the surface of the microporous layer to form an iridium deposition layer.
And further, placing the gas diffusion layer intermediate serving as a negative electrode in a second solution, performing cathode electrophoretic deposition, and then cleaning by deionized water to remove the gas diffusion layer intermediate.
And S400, calcining the iridium ion modified gas diffusion layer.
In the step, the gas diffusion layer modified by iridium ions is placed in an air atmosphere for calcination, cerium salt on the surface of the substrate layer is oxidized into cerium oxide, iridium salt on the surface of the microporous layer is oxidized into iridium oxide, and meanwhile, the hydrophobizing agent in the substrate layer and the microporous layer is melted and solidified to obtain the gas diffusion layer with hydrophobicity and free radical attack resistance and anti-polarity capability.
Furthermore, the calcining atmosphere in the embodiment of the invention is an air atmosphere, and compared with the conventional inert gas atmosphere such as nitrogen, the calcining atmosphere has the advantages of loose reaction conditions and lower cost;
further, the calcination temperature is 340-400 ℃, preferably, the calcination comprises primary calcination and secondary calcination; wherein the primary calcination is as follows: calcining at 340-365 deg.C for 30-45min, such as 340 deg.C, 345 deg.C, 350 deg.C, 360 deg.C, 365 deg.C, etc., for 30min, 35min, 40min, 45min, etc.; the secondary calcination is as follows: heating from 340-365 deg.C to 390-400 deg.C at a rate of 3-5 deg.C/min, and calcining at 390-400 deg.C for 15-30min, such as 390 deg.C, 395 deg.C, 400 deg.C, etc., for 15min, 20min, 25min, 30min, etc., and heating at 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, etc. The calcination operation of the step can oxidize cerium salt and iridium salt to obtain the gas diffusion layer with hydrophobicity, free radical attack resistance and anti-polar capability.
The invention is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the invention in any way, as will be understood by those skilled in the art. In addition, in the examples below, reagents and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
The embodiment provides a preparation method of a gas diffusion layer for PEMFC membrane electrodes, which comprises the following steps:
(1) Mixing cerium acetate hydrate, P123 and deionized water according to a mass ratio of 1:1:20, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution I; taking the hydrophobic gas diffusion layer substrate carbon paper as a negative electrode, placing the negative electrode into a solution I, setting a deposition voltage to be 5V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 1 h; then taking out the gas diffusion layer substrate, and cleaning with deionized water;
(2) Preparing microporous layer slurry, and coating, drying, primary presintering and secondary presintering microporous layers on one surface of a cerium salt deposited gas diffusion layer substrate to obtain a gas diffusion layer intermediate; wherein the primary presintering is to sinter at 260 ℃ for 10min, cool to 210 ℃ and then perform secondary presintering, the secondary presintering is to raise the temperature from 210 ℃ to 290 ℃ at a rate of 8 ℃/min and sinter at 290 ℃ for 8min;
(3) Iridium acetate, P123 and deionized water are mixed according to the mass ratio of 1:1:20, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution II; taking the intermediate of the gas diffusion layer as a negative electrode, placing the negative electrode in a second solution, setting the deposition voltage to be 5V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 1 h; then removing the intermediate of the gas diffusion layer, and cleaning with deionized water;
(4) Placing the gas diffusion layer in an air atmosphere, performing primary calcination at the temperature of 350 ℃ for 35min, then raising the temperature from 350 ℃ to 395 ℃ at the speed of 3 ℃/min, performing secondary calcination at the temperature of 395 ℃ for 20min, oxidizing cerium salt on the surface of the substrate layer into cerium oxide, oxidizing iridium salt on the surface of the microporous layer into iridium oxide, and simultaneously, melting and solidifying the hydrophobizing agent in the substrate layer and the microporous layer to obtain the gas diffusion layer with hydrophobicity and free radical attack resistance and anti-counter electrode capability; referring to fig. 1, after iridium oxide is deposited on the surface of the GDL, the membrane electrode has a counter electrode resistance of 35 min.
Example 2
The embodiment provides a preparation method of a gas diffusion layer for PEMFC membrane electrodes, which comprises the following steps:
(1) Cerium ammonium nitrate, P123 and deionized water according to the mass ratio of 1:1:15, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution I; taking the hydrophobic gas diffusion layer substrate carbon paper as a negative electrode, placing the negative electrode into a solution I, setting a deposition voltage to be 25V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 30 min; then taking out the gas diffusion layer substrate, and cleaning with deionized water;
(2) Preparing microporous layer slurry, and coating, drying, primary presintering and secondary presintering microporous layers on one surface of a cerium salt deposited gas diffusion layer substrate to obtain a gas diffusion layer intermediate; wherein the primary presintering is sintering at 250 ℃ for 15min, cooling to 200 ℃ and then carrying out secondary presintering, the secondary presintering is that the temperature is increased from 200 ℃ to 285 ℃ at a rate of 5 ℃/min, and sintering is carried out at 285 ℃ for 10min;
(3) The method comprises the steps of (1) mixing chloroiridium acid, P123 and deionized water according to a mass ratio of 1:1:15, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution II; taking the intermediate of the gas diffusion layer as a negative electrode, placing the negative electrode in a second solution, setting the deposition voltage to 25V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 30 min; then removing the intermediate of the gas diffusion layer, and cleaning with deionized water;
(4) Placing the gas diffusion layer in an air atmosphere, calcining for 45min at 340 ℃, then raising the temperature from 340 ℃ to 390 ℃ at a speed of 5 ℃/min, calcining for 30min at 390 ℃ for the second time, oxidizing cerium salt on the surface of the substrate layer into cerium oxide, oxidizing iridium salt on the surface of the microporous layer into iridium oxide, and simultaneously, melting and solidifying the hydrophobizing agent in the substrate layer and the microporous layer to obtain the gas diffusion layer with hydrophobicity, free radical attack resistance and anti-counter electrode capability; after iridium oxide is deposited on the surface of the GDL, the membrane electrode has the anti-counter electrode capability of 32 minutes.
Example 3
The embodiment provides a preparation method of a gas diffusion layer for PEMFC membrane electrodes, which comprises the following steps:
(1) Mixing cerium nitrate hydrate, F127 and deionized water according to a mass ratio of 1:1:30, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution I; taking the hydrophobic gas diffusion layer substrate carbon cloth as a negative electrode, placing the negative electrode into a solution I, setting a deposition voltage to be 1V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 2 hours; then taking out the gas diffusion layer substrate, and cleaning with deionized water;
(2) Preparing microporous layer slurry, and coating, drying, primary presintering and secondary presintering microporous layers on one surface of a cerium salt deposited gas diffusion layer substrate to obtain a gas diffusion layer intermediate; wherein the primary presintering is to sinter at 265 ℃ for 5min, cool to 220 ℃ and then perform secondary presintering, the secondary presintering is to raise the temperature from 220 ℃ to 300 ℃ at a rate of 7 ℃/min, and sinter at 300 ℃ for 5min;
(3) Iridium chloride, F127 and deionized water are mixed according to a mass ratio of 1:1:30, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution II; taking the intermediate of the gas diffusion layer as a negative electrode, placing the negative electrode in a second solution, setting the deposition voltage to be 1V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 2 hours; then removing the intermediate of the gas diffusion layer, and cleaning with deionized water;
(4) Placing the gas diffusion layer in an air atmosphere, performing primary calcination for 30min at 365 ℃, then raising the temperature from 365 ℃ to 400 ℃ at a rate of 4 ℃/min, performing secondary calcination for 15min at 400 ℃, oxidizing cerium salt on the surface of the substrate layer into cerium oxide, oxidizing iridium salt on the surface of the microporous layer into iridium oxide, and simultaneously, melting and solidifying hydrophobic agents in the substrate layer and the microporous layer to obtain the gas diffusion layer with hydrophobicity and free radical attack resistance and anti-polarity resistance; after iridium oxide is deposited on the surface of the GDL, the membrane electrode has the anti-counter electrode capability of 34 minutes.
Example 4
The embodiment provides a preparation method of a gas diffusion layer for PEMFC membrane electrodes, which comprises the following steps:
(1) Mixing cerium acetate hydrate, P123 and deionized water according to a mass ratio of 1:1:25, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution I; taking the hydrophobic gas diffusion layer substrate carbon paper as a negative electrode, placing the negative electrode into a solution I, setting a deposition voltage to be 10V by adopting a cathode electrophoresis deposition method, and carrying out electrophoresis deposition for 40 min; then taking out the gas diffusion layer substrate, and cleaning with deionized water;
(2) Preparing microporous layer slurry, and coating, drying, primary presintering and secondary presintering microporous layers on one surface of a cerium salt deposited gas diffusion layer substrate to obtain a gas diffusion layer intermediate; wherein the primary presintering is to sinter at 255 ℃ for 12min, cool to 205 ℃ and then perform secondary presintering, the secondary presintering is to raise the temperature from 205 ℃ to 295 ℃ at a rate of 10 ℃/min and sinter at 295 ℃ for 6min;
(3) Sodium chloroiridium, P123 and deionized water are mixed according to the mass ratio of 1:1:25, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution II; taking the intermediate of the gas diffusion layer as a negative electrode, placing the negative electrode in a second solution, setting the deposition voltage to be 10V by adopting a cathode electrophoresis deposition method, and carrying out electrophoresis deposition for 40 min; then removing the intermediate of the gas diffusion layer, and cleaning with deionized water;
(4) Placing the gas diffusion layer in an air atmosphere, performing primary calcination at 355 ℃ for 40min, then raising the temperature from 355 ℃ to 395 ℃ at a rate of 3 ℃/min, performing secondary calcination at 395 ℃ for 25min, oxidizing cerium salt on the surface of the substrate layer into cerium oxide, oxidizing iridium salt on the surface of the microporous layer into iridium oxide, and simultaneously, melting and solidifying hydrophobic agents in the substrate layer and the microporous layer to obtain the gas diffusion layer with hydrophobicity and free radical attack resistance and anti-counter electrode capability; after iridium oxide is deposited on the surface of the GDL, the membrane electrode has the anti-counter electrode capability of 35 min.
Physical properties of the gas diffusion layers prepared in examples 1 to 4 of the present invention were measured and summarized in table 1.
TABLE 1
| Anti-counter pole capability/min | Contact angle/° | Resistance/mΩ·cm 2 | GDL porosity/% | |
| Example 1 | 35 | 148.76 | 5.5 | 77 |
| Example 2 | 32 | 147.37 | 5.8 | 72 |
| Example 3 | 34 | 147.07 | 5.7 | 74 |
| Example 4 | 35 | 149.24 | 5.7 | 76 |
As shown in Table 1, the gas diffusion layer prepared by the method has good anti-reflection capability and excellent conductivity, and in addition, the contact angle can reach more than 145 degrees, which indicates that the gas diffusion layer has good hydrophobic performance; and the GDL can reach more than 70, the pore structure is not obviously reduced, and the mass transfer characteristic of the GDL is not obviously changed.
Comparative example 1
Comparative example 1 provides a method for preparing a gas diffusion layer for PEMFC membrane electrode, comprising the steps of:
(1) The cerium oxide equivalent to that of the embodiment 1 is doped into the microporous layer slurry for full mixing, microporous layer coating, drying, primary presintering and secondary presintering are carried out on the surface of the gas diffusion layer substrate carbon paper, and a gas diffusion layer intermediate is obtained; wherein the primary presintering is to sinter at 260 ℃ for 10min, cool to 210 ℃ and then perform secondary presintering, the secondary presintering is to raise the temperature from 210 ℃ to 290 ℃ at a rate of 8 ℃/min and sinter at 290 ℃ for 8min;
(2) The gas diffusion layer intermediate was put in an air atmosphere, primary calcination was performed at a temperature of 350 ℃ for 35min, then the temperature was increased from 350 ℃ to 395 ℃ at a rate of 3 ℃/min, and secondary calcination was performed at a temperature of 395 ℃ for 20min, to obtain a gas diffusion layer.
Comparative example 2
Comparative example 2 provides a method for preparing a gas diffusion layer for PEMFC membrane electrode, comprising the steps of:
(1) The cerium oxide equivalent to that of the embodiment 1 is doped into the microporous layer slurry for full mixing, microporous layer coating, drying, primary presintering and secondary presintering are carried out on the surface of the gas diffusion layer substrate carbon paper, and a gas diffusion layer intermediate is obtained; wherein the primary presintering is to sinter at 260 ℃ for 10min, cool to 210 ℃ and then perform secondary presintering, the secondary presintering is to raise the temperature from 210 ℃ to 290 ℃ at a rate of 8 ℃/min and sinter at 290 ℃ for 8min;
(2) Iridium acetate, P123 and deionized water are mixed according to the mass ratio of 1:1:20, fully mixing, and performing ultrasonic dispersion for 24 hours to obtain a uniform solution II; taking the intermediate of the gas diffusion layer as a negative electrode, placing the negative electrode in a second solution, setting the deposition voltage to be 5V by adopting a cathode electrophoresis deposition method, and performing electrophoresis deposition for 1 h; then removing the intermediate of the gas diffusion layer, and cleaning with deionized water;
(3) The gas diffusion layer was put in an air atmosphere, primary calcination was performed at a temperature of 350 ℃ for 35min, then the temperature was increased from 350 ℃ to 395 ℃ at a rate of 3 ℃/min, and secondary calcination was performed at a temperature of 395 ℃ for 20min, to obtain the gas diffusion layer.
Comparative example 3
Comparative example 3 is substantially the same as example 1, except that: the mass ratio of the hydrated cerium acetate to the P123 to the deionized water is 1:0.5:20.
comparative example 4
Comparative example 4 is substantially the same as example 1, except that: the mass ratio of the hydrated cerium acetate to the P123 to the deionized water is 1:2:20.
comparative example 5
Comparative example 5 is substantially the same as example 1, except that: iridium acetate, P123 and deionized water according to the mass ratio of 1:0.5:20.
comparative example 6
Comparative example 6 is substantially the same as example 1, except that: iridium acetate, P123 and deionized water according to the mass ratio of 1:2:20.
comparative example 7
Comparative example 7 is substantially the same as example 1, except that: the calcination atmosphere is a nitrogen atmosphere.
Comparative example 8
Comparative example 8 is substantially the same as example 1, except that: the calcination in the step (4) is calcination at 350 ℃ for 55min.
Comparative example 9
Comparative example 9 is substantially the same as example 1, except that: the calcination in step (4) is calcination at 395℃for 55min.
Comparative example 10
Comparative example 10 is substantially the same as example 1, except that: the calcination in step (4) is a primary calcination at a temperature of 320℃for 35min, followed by a secondary calcination at a temperature of 395℃for 20min at a rate of 3℃per min, with the temperature being increased from 320℃to 395 ℃.
Comparative example 11
Comparative example 11 is substantially the same as example 1, except that: the calcination in step (4) is a primary calcination at a temperature of 350℃for 35min, followed by a secondary calcination at a temperature of 410℃for 20min at a rate of 3℃per min by raising the temperature from 350℃to 395 ℃.
Comparative example 12
Comparative example 12 is substantially the same as example 1 except that: in the step (2), the pre-sintering is directly performed for 20 minutes at 290 ℃, and the staged sintering process is not involved.
Comparative example 13
Comparative example 13 is substantially the same as example 1 except that: the primary pre-sintering in the step (2) is sintering at 260 ℃ for 10min, the secondary pre-sintering is that the temperature is increased from 260 ℃ to 290 ℃ at the speed of 8 ℃/min, and sintering is performed at 290 ℃ for 8min.
Physical properties of the gas diffusion layers prepared in comparative examples 1 to 13 of the present invention were measured and summarized in table 2.
Physical properties of the gas diffusion layers prepared in comparative examples 1 to 13 of the present invention were measured and summarized in table 2.
TABLE 2
| Anti-counter pole capability/min | Contact angle/° | Resistance/mΩ·cm 2 | GDL porosity/% | |
| Comparative example 1 | 0 | 142.9 | 9.6 | 77 |
| Comparative example 2 | 23 | 155.9 | 8.9 | 72 |
| Comparative example 3 | 26 | 147.09 | 6.8 | 76 |
| Comparative example 4 | 34 | 148.29 | 7.2 | 75 |
| Comparative example 5 | 28 | 148.16 | 6.5 | 76 |
| Comparative example 6 | 35 | 149.01 | 7.4 | 77 |
| Comparative example 7 | 34 | 148.06 | 5.5 | 77 |
| Comparative example 8 | 26 | 144.95 | 8.1 | 68 |
| Comparative example 9 | 23 | 146.87 | 7.9 | 70 |
| Comparative example 10 | 29 | 147.04 | 6.9 | 73 |
| Comparative example 11 | 28 | 147.52 | 7.1 | 73 |
| Comparative example 12 | 34 | 148.24 | 6.3 | 63 |
| Comparative example 13 | 34 | 148.19 | 6.1 | 72 |
As is clear from comparative examples 1-2, the GDL prepared by doping cerium oxide directly into the microporous layer has increased resistance, indicating that direct entanglement leads to maldistribution of cerium oxide, affecting GDL conductivity. According to the invention, the soft template electrophoretic deposition method is adopted to arrange cerium oxide on the substrate layer and iridium oxide on the surface of the microporous layer, so that the particle agglomeration phenomenon can be effectively reduced, and the sufficiency of electrochemical reaction conditions is ensured;
as is clear from comparative examples 3 to 6, the amphiphilic block copolymer template agent is added in an excessively small amount, so that the anti-reverse polarity performance and the electrical conductivity of the gas diffusion layer are reduced, and if the amount is added in an excessively large amount, positive feedback is not always provided to the anti-reverse polarity, the hydrophobic performance and the pore uniformity, and even the electrical conductivity is reduced to some extent, so that the ratio of cerium salt/iridium salt to the amphiphilic block copolymer template agent is preferably 1:1;
as is clear from comparative examples 7 to 11, the use of the method of the present invention does not have a great influence on the physical properties of the product during calcination, either in an air atmosphere or in a nitrogen atmosphere, and therefore, in view of cost, an air atmosphere is preferable; in addition, when the calcination process is one-step calcination, the anti-counter electrode performance and the conductivity of the gas diffusion layer are greatly influenced, and the porosity is obviously reduced; if the temperature control is not good, the anti-polarity performance of the gas diffusion layer is reduced and the conductivity performance is affected by adopting a secondary calcination method, so that the calcination process is limited to secondary calcination, and the sectional calcination temperature needs to be strictly controlled;
as is apparent from comparative examples 12 to 13, the pre-sintering process has a great influence on the conductivity and porosity of the final gas diffusion layer, particularly on the porosity, in the process of preparing the gas diffusion layer intermediate by using the method of the present invention, so the present invention defines the pre-sintering process as the secondary sintering, and the temperature of the secondary sintering process needs to be strictly controlled so that the gas diffusion layer has good porosity and excellent conductivity.
In conclusion, the invention adopts a soft template electrophoresis deposition method to uniformly distribute cerium oxide and iridium oxide in the gas diffusion layer, reduce particle agglomeration caused by direct doping of particles and improve the utilization efficiency of the iridium oxide and the cerium oxide; by arranging the cerium oxide on the substrate layer, the dissolution of the cerium oxide by the acidic environment of the catalytic layer can be reduced, and the problem of ion pollution of the catalytic layer caused by cerium ion dissolution can be reduced; by arranging the iridium oxide on the surface of the microporous layer, the iridium oxide on the surface of the microporous layer can be contacted with the resin on the surface of the catalytic layer to form a three-phase interface, so that the sufficiency of the electrochemical reaction condition of the iridium oxide is ensured.
In the description of the present specification, reference to the terms "one embodiment," "another embodiment," "yet another embodiment," "some embodiments," "other embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A gas diffusion layer for a PEMFC membrane electrode, comprising a substrate layer and a microporous layer disposed on at least one side of the substrate layer;
the surface of the basal layer is deposited with shell-shaped cerium oxide particles, and the shell-shaped cerium oxide particles are positioned on the composite side of the basal layer and the microporous layer; the surface of the microporous layer is deposited with shell-shaped iridium oxide particles.
2. A method for preparing a gas diffusion layer for PEMFC membrane electrode as claimed in claim 1, comprising the steps of:
(1) Fully mixing cerium salt, amphiphilic block copolymer template agent and deionized water to obtain solution I, placing a gas diffusion layer substrate serving as a negative electrode in the solution I, and performing electrophoretic deposition to obtain a cerium ion surface modified gas diffusion layer substrate layer;
(2) Coating a microporous layer on the surface of the cerium ion surface modified gas diffusion layer substrate layer, drying and presintering to obtain a gas diffusion layer intermediate;
(3) Fully mixing iridium salt, amphiphilic block copolymer template agent and deionized water to obtain a solution II, and then placing the gas diffusion layer intermediate serving as a negative electrode in the solution II for electrophoretic deposition to obtain an iridium ion modified gas diffusion layer;
(4) Calcining the iridium ion modified gas diffusion layer.
3. The method for preparing a gas diffusion layer for PEMFC membrane electrode according to claim 2, wherein the cerium salt in step (1) includes any one or more of cerium ammonium nitrate, cerium acetate hydrate, and cerium nitrate hydrate;
and/or the mass ratio of the cerium salt, the amphiphilic block copolymer template agent and deionized water is 1:1 (15-30);
the gas diffusion layer substrate is any one of carbon fiber paper substrate and carbon cloth substrate.
4. The method for preparing a gas diffusion layer for a PEMFC membrane electrode according to claim 2, wherein the iridium salt in step (3) includes any one or more of iridium chloride, iridium acetate, and sodium chloride;
and/or the mass ratio of the iridium salt, the amphiphilic block copolymer template agent and deionized water is 1:1 (15-30).
5. The method for preparing a gas diffusion layer for a PEMFC membrane electrode according to claim 2, wherein the amphiphilic block copolymer templating agent in step (1) and step (3) is a block copolymer P123 or F127, and the concentration of the amphiphilic block copolymer templating agent is 1-2 times the critical micelle concentration thereof;
and/or the voltage of the electrophoretic deposition in the step (1) and the step (3) is 1-25V.
6. The method for preparing a gas diffusion layer for PEMFC membrane electrode according to claim 2, wherein the pre-sintering temperature in step (2) is 200-300 ℃;
and/or the pre-sintering atmosphere is an air atmosphere.
7. The method for preparing a gas diffusion layer for PEMFC membrane electrode according to claim 2 or 6, wherein the pre-sintering in step (2) includes a primary pre-sintering and a secondary pre-sintering;
the primary presintering is as follows: sintering at 250-265 deg.c for 5-15min, cooling to 200-220 deg.c and secondary pre-sintering;
the secondary presintering is as follows: raising the temperature from 200-220 ℃ to 285-300 ℃ at a rate of 5-10 ℃/min, and sintering at the temperature of 285-300 ℃ for 5-10min.
8. The method for preparing a gas diffusion layer for PEMFC membrane electrode according to claim 2, wherein the calcination temperature in step (4) is 340-400 ℃;
and/or the calcination atmosphere is an air atmosphere.
9. The method for preparing a gas diffusion layer for a PEMFC membrane electrode according to claim 2 or 8, wherein the calcination in step (4) includes primary calcination and secondary calcination;
the primary calcination is as follows: calcining at 340-365 deg.C for 30-45min;
the secondary calcination is as follows: raising the temperature from 340-365 ℃ to 390-400 ℃ at a rate of 3-5 ℃/min, and calcining at 390-400 ℃ for 15-30min.
10. Use of the gas diffusion layer for a PEMFC membrane electrode according to claim 1 or the gas diffusion layer for a PEMFC membrane electrode prepared by the method of any one of claims 2 to 8 in a fuel cell.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112563516A (en) * | 2020-12-28 | 2021-03-26 | 浙江唐锋能源科技有限公司 | Gas diffusion layer of environment-friendly fuel cell and preparation method thereof |
| KR20210076754A (en) * | 2019-12-16 | 2021-06-24 | 현대자동차주식회사 | Gas diffusion layer for fuel cell applications and unit cell of fuel cell having the same and fuel cell stack having the same |
| CN113140736A (en) * | 2020-06-08 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer structure, preparation method, membrane electrode assembly and fuel cell |
| CN113140739A (en) * | 2021-01-28 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer, preparation method thereof, membrane electrode assembly and fuel cell |
| CN114300702A (en) * | 2022-01-01 | 2022-04-08 | 上海嘉资新材料科技有限公司 | Fuel cell gas diffusion layer structure containing cerium oxide modified carbon nanofiber and preparation method thereof |
| CN115198293A (en) * | 2022-08-29 | 2022-10-18 | 上海交通大学 | Proton exchange membrane electrolyzer comprising a bifunctional porous layer |
-
2023
- 2023-09-13 CN CN202311177831.1A patent/CN117374292B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210076754A (en) * | 2019-12-16 | 2021-06-24 | 현대자동차주식회사 | Gas diffusion layer for fuel cell applications and unit cell of fuel cell having the same and fuel cell stack having the same |
| CN113140736A (en) * | 2020-06-08 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer structure, preparation method, membrane electrode assembly and fuel cell |
| CN112563516A (en) * | 2020-12-28 | 2021-03-26 | 浙江唐锋能源科技有限公司 | Gas diffusion layer of environment-friendly fuel cell and preparation method thereof |
| CN113140739A (en) * | 2021-01-28 | 2021-07-20 | 上海嘉资新材料有限公司 | Fuel cell gas diffusion layer, preparation method thereof, membrane electrode assembly and fuel cell |
| CN114300702A (en) * | 2022-01-01 | 2022-04-08 | 上海嘉资新材料科技有限公司 | Fuel cell gas diffusion layer structure containing cerium oxide modified carbon nanofiber and preparation method thereof |
| CN115198293A (en) * | 2022-08-29 | 2022-10-18 | 上海交通大学 | Proton exchange membrane electrolyzer comprising a bifunctional porous layer |
Non-Patent Citations (1)
| Title |
|---|
| LIANG CHEN ET AL.: "Microporous Layer Containing CeO2‑Doped 3D Graphene Foam for Proton Exchange Membrane Fuel Cells at Varying Operating Conditions", APPLIED MATERILAS INTERFACES, 26 April 2021 (2021-04-26), pages 20201 - 20212 * |
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