CN109618561B - Fuel cell device and method for manufacturing electrode material for fuel cell - Google Patents

Fuel cell device and method for manufacturing electrode material for fuel cell Download PDF

Info

Publication number
CN109618561B
CN109618561B CN201580078974.4A CN201580078974A CN109618561B CN 109618561 B CN109618561 B CN 109618561B CN 201580078974 A CN201580078974 A CN 201580078974A CN 109618561 B CN109618561 B CN 109618561B
Authority
CN
China
Prior art keywords
fuel cell
anode
cathode
layer
catalyst layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201580078974.4A
Other languages
Chinese (zh)
Other versions
CN109618561A (en
Inventor
林科闯
黄苡叡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CN109618561A publication Critical patent/CN109618561A/en
Application granted granted Critical
Publication of CN109618561B publication Critical patent/CN109618561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • 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
    • H01M4/8832—Ink jet printing
    • 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
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0236—Glass; Ceramics; Cermets
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A fuel cell electrode material is disclosed herein comprising a plurality of pores having a substantially uniform size of about 500nm to 5mm, having a variation of less than 20%, having a porosity of about 40-85%. The fuel cell electrode material may be used in a catalyst layer, a gas fusion layer, or a water treatment layer in a fuel cell device. A plurality of fuel cell devices comprising such fine array porous fuel cell electrode materials having different designs and methods of preparing such fine array porous fuel cell electrode materials are also disclosed.

Description

Fuel cell device and method for manufacturing electrode material for fuel cell
Technical Field
The present invention relates to a fuel cell electrode material for a plurality of fuel cell devices, and in particular to a fine array porous fuel cell electrode material and additionally to the use of the fuel cell electrode material in a plurality of fuel cell devices.
Background
Fuel cells are electrochemical devices that convert chemical energy from a fuel, including hydrogen and hydrocarbons such as diesel and methanol, into electrical energy by performing a chemical reaction using an oxidant such as oxygen or hydrogen peroxide. Due to his high energy efficiency and the ability to continue to generate electricity as long as the fuel supply is available, a fuel cell has a wide range of applications, including transportation, material handling, stationary, mobile, and emergency back-up power applications.
A fuel cell typically requires the presence of multiple catalyst layers on its cathode and anode electrode assemblies to reduce the activation energy required to perform the chemical reactions that generate electricity. The catalyst layer is typically designed with a plurality of crystallites of a noble metal catalyst, such as platinum, finely dispersed on a conductive support with a high surface area, such as carbon paper, carbon cloth, and carbon nanotubes, to increase both the active surface area and the electrocatalytic activity of the catalyst. However, such a configuration generally has problems such as high cost and insufficient reliability, and thus practical application of a plurality of fuel cells is greatly limited.
Disclosure of Invention
A fuel cell electrode material for a fuel cell device is provided. The fuel cell electrode material typically comprises a fine array of porous material comprising a plurality of pores, wherein the plurality of pores have a size of about 500nm to 5mm, and preferably about 1000nm and 50000 nm; the size of the plurality of holes is substantially uniform and has a variation of less than about 20%; and the fine array porous material has a porosity of about 40-85%. In some embodiments, the fine array porous material may be composed of a metal such as nickel, aluminum, copper, gold, silver, titanium, iron, platinum, palladium, ruthenium, manganese, cobalt, or chromium. In some embodiments, the fine array porous material may be made of, for example, stainless steel, platinum-cobalt, platinum-iron, platinum-chromium, platinum-nickel, platinum-titanium, platinum-manganese, platinum-copper, platinum-vanadium, platinum-chromium-cobalt, platinum-iron-chromium, platinum-iron-manganese, platinum-iron-cobalt, platinum-iron-chromium, platinum-chromium, platinum-nickel-cobalt, platinum-iron-cobalt, platinum-chromium, platinum-iron-cobalt, or combinations thereof-an alloy of iron-nickel, platinum-iron-copper, platinum-chromium-copper or platinum-cobalt-gallium. In some embodiments, the fine array porous material may be made of a material selected from the group consisting of CoTMPP-TiO2、MnOx-CoTMPP、CoFe2O4、Pt-WO3、Pt-TiO2、Pt-Cu-MOx、MnO2、CrO2、CuxMnyOz,LaMnO3And La1-xSrxFeO3A metal oxide in the group.
In some embodiments, a fuel cell electrode material may be used in the cathode or anode catalyst layer, and typically comprises a fine array of porous materials having a porosity of about 74%. In some embodiments, the fine array porous material is substantially entirely comprised of a catalyst material: such as a metal (e.g., ruthenium, palladium, nickel, aluminum, copper, gold, silver, titanium, iron, platinum, manganese, cobalt, and chromium), an alloy (e.g., platinum-series alloys, such as platinum-cobalt, platinum-iron, platinum-chromium, platinum-nickel, platinum-titanium, platinum-manganese, platinum-copper, platinum-vanadium, platinum-chromium-cobalt, platinum-iron-chromium, platinum-iron-manganese, platinum-iron-cobalt, platinum-iron-nickel, platinum-iron-copper, platinum-chromium-copper, platinum-cobalt-gallium), or a metal oxide (e.g., CoTMPP-TiO)2、MnOx-CoTMPP、CoFe2O4、Pt-WO3、Pt-TiO2、Pt-Cu-MOxMnO2、CrO2、CuxMnyOz、LaMnO3And La1-xSrxFeO3). In some other embodiments, the fine-array porous material may include a catalyst carrier composed of a metal (e.g., nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt, and zinc), a conductive ceramic material (e.g., zinc oxide, copper monoxide, indium tin oxide, AZO, IZO, IGZO) or a conductive polymer (e.g., polypyrrole, polyphenylene sulfide, phthalocyanine, polyaniline, and polythiophene) with high cost efficiency, and a catalyst component including platinum, ruthenium, palladium, CoPc, CoTMPP-TiO2、MnOx-CoTMPP or CoFe2O4At least one of them. In some embodiments, the catalyst component may be coated on the surface of the catalyst support. But in some other embodiments, asThe plurality of particles of the catalyst component may be disposed in the plurality of pores of the fine-array porous catalyst carrier. In some other embodiments, the particles as catalyst components may be attached to the surface of a plurality of particles as a second catalyst carrier, such as carbon nanotubes or carbon nanospheres, and they are disposed together in the plurality of pores of the micro-array porous catalyst carrier.
In some embodiments, a fuel cell electrode material may be used in the water treatment layer of the cathode or the anode, and it is typically surface-treated, for example, by oxidation of the metal composition or coating a hydrophilic material on a designated area of the fine array porous fuel cell electrode material to become hydrophilic. The hydrophilic surface treatment of the water treatment layer electrode material may be accomplished in some embodiments by a hydrophilic plasma coating of the electrode material, in some embodiments by treating the electrode material with a surfactant such as ammonium dodecyl sulfonate, Sodium Dodecyl Sulfonate (SDS), dioctyl sodium sulfosuccinate, perfluorooctane sulfonate (PFOS), perfluorobutyl sulfonate, sodium lauroyl sarcosinate, perfluorononanoate, or perfluorooctanoate, or in some embodiments by chemically modifying the electrode material with a chemical agent having hydrophilic functional groups such as hydroxyl (-OH) or carboxylic acid groups (-COOH).
In some embodiments, a fuel cell electrode material may be used in the gas diffusion layer of the cathode or the anode, and is typically surface treated, for example by coating with a hydrophobic material in a specified area, to become hydrophobic. The hydrophobic surface treatment of the gas diffusion layer electrode material may be accomplished in some embodiments by a hydrophobic plasma coating on the electrode material, and in some other embodiments by treating the electrode material with fluorosilicone, silicone, or fluorocarbon.
Also provided herein is a fuel cell device using the above-mentioned fine array porous fuel cell electrode material. The fuel cell device includes a Membrane Electrolyte Assembly (MEA). The membrane electrolyte assembly comprises a Polymer Electrolyte Membrane (PEM), an anode catalyst layer and a cathode catalyst layer, wherein the PEM is sandwiched between the anode layer and the cathode layer; at least one of the anode catalyst layer and the cathode catalyst layer comprises a fine array of porous fuel cell electrode material having a porosity of about 74% and a catalyst.
In some embodiments of the fuel cell device, the fuel cell electrode material is comprised of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt, and zinc; the catalyst is platinum, ruthenium, palladium, CoPc, CoTMPP-TiO2、MnOx-CoTMPP or CoFe2O4At least one of them. In some embodiments, the catalyst is uniformly coated on the surface of the fine array porous material; in some other embodiments, a plurality of particles as the catalyst are disposed within the plurality of pores of the micro-array porous material. In some other embodiments, however, at least one of the anode catalyst layer and the cathode catalyst layer further comprises a catalyst carrier, such as carbon nanotubes or carbon nanospheres, wherein particles of the catalyst carrier carrying particles of the catalyst particles on outer surfaces of the particles of the catalyst carrier are disposed in the pores of the fine array porous material in at least one of the anode catalyst layer and the cathode catalyst layer.
In some embodiments, the fuel cell device includes a combined catalyst-gas diffusion layer design. In these embodiments, at least one of the anode catalyst layer and the cathode catalyst layer is further configured to diffuse the reactant gas therethrough. In some embodiments, a designated area of the anode catalyst layer, the cathode catalyst layer, or both is further surface treated to become hydrophobic to facilitate diffusion of the reactant gas therethrough. In some embodiments, the fuel cell device may include a split catalyst-gas diffusion layer design. In these embodiments, the fuel cell device further comprises an anode gas diffusion layer and a cathode gas diffusion layer, wherein the anode gas diffusion layer and the cathode gas diffusion layer are respectively arranged on a side of the anode catalyst layer and the cathode catalyst layer opposite to the Polymer Electrolyte Membrane (PEM); and at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a second fine array of fuel cell electrode materials as described above. In some embodiments, the pore size of the second fine array porous fuel cell electrode material in at least one of the anode gas diffusion layer and the cathode gas diffusion layer is less than the pore size of the fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer; and at least one of the anode gas diffusion layer and the cathode gas diffusion layer further comprises a second catalyst selected from at least one of ruthenium and palladium.
In some embodiments, the fuel cell device further comprises a water treatment layer disposed at the bottom of the anode gas diffusion layer, the anode catalyst layer, the cathode catalyst layer and the cathode gas diffusion layer, wherein the water treatment layer comprises a third micro-array porous fuel cell electrode material as disclosed above, wherein the pore size of the third micro-array porous fuel cell electrode material in the water treatment layer is larger than the pore size of the micro-array porous fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer and is larger than the pore size of the second micro-array porous fuel cell electrode material in at least one of the anode gas diffusion layer and the cathode gas diffusion layer; and the third fine array porous fuel cell electrode material in the water treatment layer is selectively surface-treated to form hydrophilicity. In some embodiments, the fuel cell device further comprises an anode water treatment layer and a cathode water treatment layer, wherein the anode water treatment layer and the cathode water treatment layer are respectively arranged between the anode catalyst layer and the polymer electrolyte membrane, and between the cathode catalyst layer and the polymer electrolyte membrane; at least one of the anode water treatment layer and the cathode water treatment layer comprises a second micro-array porous fuel cell electrode material, and the pore size of the second micro-array porous fuel cell electrode material is larger than the pore size of the micro-array porous fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer; and the anode catalyst layer and the cathode catalyst layer are configured to allow the reaction gas to diffuse therein.
In some embodiments, the fuel cell device comprises a Membrane Electrolyte Assembly (MEA), wherein the MEA comprises, in order from anode to cathode, an anode gas diffusion layer, an anode catalyst layer, a Polymer Electrolyte Membrane (PEM), and a cathode catalyst layer, wherein at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a fine array of porous fuel cell electrode material. In some embodiments of the fuel cell device, at least one of the anode catalyst layer and the cathode catalyst layer comprises a catalyst support selected from carbon nanotubes or carbon nanospheres.
Also provided herein are methods of making a fine array of porous fuel cell electrode material as described above, comprising the step of (i) preparing the fine array of porous material by 3D printing or by template fabrication methods. In some embodiments of the method, the fine array of porous material may be fabricated by 3D printing. In some other embodiments, the fine array of porous material may be prepared by a template fabrication method, comprising the following sub-steps: a) electrophoretically fabricating a colloidal particle template; b) infiltrating an electrode material into the colloidal particle template; and c) removing the colloidal particle template. In some embodiments, the sub-step b) is performed by at least one of electrodeposition, PVD (physical vapor deposition), CVD (chemical vapor deposition) or Sol-Gel (Sol-Gel method).
In some embodiments, the method further comprises the step (ii) of manufacturing a second micro-array porous material on top of the micro-array porous material by 3D printing or by a template manufacturing method. In some embodiments, the second microarrayed porous material of step (ii) is configured with a pore size that is larger than the pore size of the microarrayed porous material, and the second microarrayed porous material is configured with a hydrophilic surface. The second fine array porous material may be composed of a hydrophilic conductive polymer in some embodiments, or may be surface-treated to be hydrophilic in some other embodiments. In one example, the second micro-array porous material is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt and zinc, and a surface of the second micro-array porous material is treated by an oxidation reaction. In another example, the second fine array porous material may be coated with a hydrophilic material.
In some embodiments, the method may further comprise the step of (ii) dispersing particles of a catalyst carrier carrying particles of a catalyst onto the surface or into the plurality of pores of the fine array porous material. The catalyst carrier can be a plurality of carbon nanotubes or a plurality of carbon nanospheres. In some embodiments, the method may further comprise a step (iii) performed immediately after the step (ii), of combining the particles as a catalyst with the fine array of porous material in the fuel cell electrode material, and in some embodiments may be accomplished by heating.
In some embodiments, the method may further comprise the step of (ii) subjecting the microarray porous material to an etching resist. For example, when the fine array porous material is composed of a metal such as zinc, titanium or nickel, the etching-resistant treatment in step (ii) may be an oxidation treatment in some embodiments, and a surface-coated with a resist material in some other embodiments.
The fine array porous fuel cell electrode material described herein can also be applied to other kinds of fuel cell devices, such as SOFC (solid oxide fuel cell), DMFC (direct methanol fuel cell), PAFC (phosphoric acid fuel cell), fuel cell, MCFC (molten carbonate fuel cell), or PFC. Also provided herein is a fuel cell device comprising a fine array of porous fuel cell electrode materials, wherein the fuel cell device is at least one of a SOFC (solid oxide fuel cell), DMFC (direct methanol fuel cell), PAFC (phosphoric acid fuel cell), fuel cell, MCFC (molten carbonate fuel cell), or PFC.
A fine array porous fuel cell electrode material disclosed herein has the following advantages over existing fuel cell electrode materials such as carbon paper/coating/nanotubes coated with a plurality of catalyst particles. First, the microarrayed porous structure has a very high effective electrocatalytic area due to its significantly higher surface-to-area-to-volume ratio. Second, its membrane structure eliminates the problem of gradual loss of reliability due to the catalyst particles of a conventional fuel cell falling off from the conductive carrier. Third, it eliminates the binder used in an existing fuel cell for tightly adhering the catalyst particles to the conductive carrier, greatly reduces the amount of catalyst used and the cost incurred in manufacturing a plurality of fuel cells, and greatly improves reliability. Fourth, the design is to use a less expensive metal or metal oxide (e.g., copper, iron, aluminum, CoPc, CoTMPP-TiO)2、MnOx-CoTMPP、CoFe2O4Etc.) to form a fine array of porous conductive carriers coated with expensive noble metal catalysts (e.g., platinum), can further reduce the manufacturing cost of a plurality of fuel cells, and can achieve a higher conductivity than the carbon paper/cloth/nanotube/nanosphere currently used. Fifth, the presence of a periodic structure of a fine array porous fuel cell electrode material eliminates the problem of thermal buildup at some locations due to local defects or uneven distribution of a plurality of catalyst particles on a plurality of carbon-based conductive supports. Sixth, the presence of a periodic structure of a fine array of porous fuel cell electrode material further allows the reaction gas or reactive solvent (e.g., H) to cross/pass through the material2、O2Ethanol, methanol), waste liquid products (such as water), and electrons. Finally, some concepts may be made to combine multiple catalyst layers and multiple gas diffusion layers in the fuel cell, which may simplify the design, reduce cost, and improve reliability.
Drawings
FIG. 1 illustrates a conventional Proton Exchange Membrane Fuel Cell (PEMFC) device having a multi-layered catalyst layer formed of a plurality of carbon nanotubes coated with a plurality of finely dispersed catalyst particles;
FIG. 2 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine arrays of porous electrode materials, according to some embodiments herein;
FIG. 3 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine arrays of porous electrode materials, according to some embodiments herein;
FIG. 4 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine arrays of porous electrode materials, according to some embodiments herein;
figure 5 illustrates a plurality of fuel cell membrane electrode assemblies comprising a plurality of fine arrays of porous electrode materials, according to some embodiments herein; and
figure 6 illustrates another membrane electrode assembly including a plurality of fine arrays of porous electrode materials, according to some embodiments herein.
Detailed Description
FIG. 1 illustrates a conventional Proton Exchange Membrane Fuel Cell (PEMFC) device having a plurality of catalyst layers composed of carbon nanotubes coated with a plurality of finely dispersed catalyst particles. The PEMFC device 100 includes an anode end plate 101, an anode bipolar plate 102, an anode gasket 103, an anode gas diffusion layer 104, a Membrane Electrode Assembly (MEA)105, a cathode gas diffusion layer 106, a cathode gasket 107, a cathode bipolar plate 108, and a cathode end plate 109, in this order from anode to cathode. Gas channels are typically provided on both the anode bipolar plate 102 and the cathode bipolar plate 108 as paths for injecting hydrogen and oxygen into the anode and cathode of the fuel cell, respectively. By way of illustration, FIG. 1 illustrates only the oxygen gas channels 110 on the cathode bipolar plate 108. The MEA105 typically includes a Polymer Electrolyte Membrane (PEM)111 sandwiched between an anode catalyst layer 112 and a cathode catalyst layer 113. Typically both the anode catalyst layer and the cathode catalyst layer comprise a catalyst support coated with very fine powder as an anode catalyst and a cathode catalyst, respectively. The catalyst carrier is typically composed of a carbon paper, a carbon cloth or a carbon nanotube film; the anode catalyst may be formed from a metal such as platinum, e.g., Pt-RAn alloy of u, e.g. a metal oxide of cerium (IV) oxide, e.g. MoxRuySzAnd MoxRhySzA metal sulfide of, or e.g. (Ru)1-xMox)SeOzA chalcogenide; and the cathode catalyst may be composed of platinum or nickel. FIG. 1 also shows a picture of a typical anode catalyst layer comprising a carbon nanotube film 114 coated with platinum nanoparticles 115.
A conventional fuel cell as described in fig. 1 has the following disadvantages. First, it is generally necessary to stably attach and effectively disperse the catalyst particles on the surface of the conductive carrier using a binder. And the presence of a binder reduces the effective electrocatalytic area of the catalyst in the fuel cell, so to compensate for this reduction, a large amount of catalyst is required to achieve a level of electrical output. Second, catalyst particles coated on the surface of the conductive support may easily become loose and easily fall off the support under a shock/impact environment or even during periods of multiple gas ingress or when water/other reaction products are being processed from the fuel cell. These pose a reliability problem for the fuel cell.
Figure 2 illustrates a fuel cell Membrane Electrode Assembly (MEA) comprising a plurality of fine arrays of porous electrode materials according to some embodiments herein. As shown in fig. 2, the Membrane Electrode Assembly (MEA)200 includes a Polymer Electrolyte Membrane (PEM)201 sandwiched between an anode catalyst layer 202 and a cathode catalyst layer 203. Both the anode catalyst layer 202 and the cathode catalyst layer 203 may comprise a fuel cell electrode material having a fine array of porous structures 204. The fuel cell electrode material 204 typically comprises a fine array of porous material having a plurality of pores with a pore size of about 500nm-5 mm; the size of the plurality of holes is substantially uniform and has a variation of less than about 20%; and the fine array porous material has a porosity of about 40-85%. In some preferred embodiments, a fuel cell electrode material may comprise a highly dense microarrayed porous material having a porosity of about 74%, which has a theoretically high surface-to-area-to-volume ratio for a porous material.
In some embodiments, as described in 205, a fine array of porous material may be composed entirely of platinum or some other fuel cell catalyst material and thus may be used directly as a catalyst layer material in an MEA of a fuel cell. In some other embodiments, made of a metal/alloy such as copper, aluminum, iron, nickel, and stainless steel, or Zn, for examplexO1-xA fine array of porous supports composed of a conductive metal oxide of (a) may be uniformly coated on its surface with a fuel cell catalyst material, such as platinum, also shown in 205. In some other embodiments, a fine array of porous materials may be used as a high surface-area conductive carrier to carry particles of catalysts in the catalyst layer of a fuel cell. In some other embodiments, as described at 206, is made of a metal/alloy such as copper, aluminum, iron, stainless steel, and nickel, or Zn, for examplexO1-xA fine array of porous supports composed of a conductive metal oxide can be coated with a plurality of nanoparticles of a fuel cell catalyst, such as platinum, within the pores thereof. However, in some other embodiments, as described in 207, a second conductive carrier, such as carbon nanotubes, graphene and carbon nanospheres, along with the catalyst particles supported on the surfaces of the two conductive carriers, is disposed on a first fine-array porous conductive carrier composed of copper, aluminum, iron, stainless steel or nickel or made of, for example, ZnxO1-xIn the hole of the substrate, is formed by a conductive metal oxide.
Due to the presence of the periodic plurality of pores in the micro-array porous structure, the fuel cell electrode material as described above may also be used as a gas diffusion layer material, allowing the reactant gases, such as hydrogen and oxygen, to be uniformly and efficiently dispersed through the pores of the micro-array porous structure, while at the same time, the presence of a catalyst on the surface of the micro-array porous electrically conductive support or within the pores, allows for efficient catalytic reactions to occur in the fuel cell. These features allow for the design of a single combined catalyst-gas diffusion layer in a fuel cell device, and the single combined catalyst-gas diffusion layer functions as both a catalyst layer and a gas diffusion layer in the fuel cell. The combined catalyst-gas diffusion layer with a fine array of porous structures can greatly simplify the module design and manufacture of multiple fuel cells. Furthermore, it is also possible to facilitate the treatment of the final reaction product (e.g. water) by the engineered regions of the micro-array porous fuel cell electrode material of the fuel cell based on the engineering of treating specific regions of the micro-array porous fuel cell electrode material to become hydrophobic/hydrophilic. Figure 3 illustrates a fuel cell Membrane Electrode Assembly (MEA) comprising a plurality of fine arrays of porous electrode materials according to some embodiments herein. The fuel cell membrane electrode assembly 300 includes a Polymer Electrolyte Membrane (PEM)301, a combined anode catalyst-gas diffusion layer 302, a combined cathode catalyst-gas diffusion layer 303, and a water treatment layer 304, wherein the PEM301 is sandwiched between the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303, and the water treatment layer 304 is disposed at the bottom of the PEM301, the combined anode catalyst-gas diffusion layer 302, and the combined cathode catalyst-gas diffusion layer 303. Both the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 comprise a fine array of porous fuel cell electrode material, either entirely comprised of an anode catalyst or a cathode catalyst, or alternatively comprise a fine array of porous metal supports, such as 205, 206 and 207 shown in fig. 2, coated or impregnated with particles of an anode or cathode catalyst with or without a second catalyst support. In addition to functioning as a multi-layer catalyst layer, the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 also function as a multi-layer gas diffusion layer in the fuel cell Membrane Electrode Assembly (MEA). Optionally, to further increase the gas diffusion efficiency of the layers in the fuel cell, the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 may be surface treated to increase the hydrophobicity of some regions located in both layers. The water treatment layer 304 also comprises a fine array of porous materials and is designed to treat the final reaction product, such as water, within the fuel cell and is optionally surface treated to increase hydrophilicity in order to further increase the water treatment efficiency.
Fig. 4 illustrates a fuel cell Membrane Electrode Assembly (MEA) comprising a plurality of fine array porous electrode materials according to some embodiments herein. Referring to fig. 4A, the fuel cell Membrane Electrode Assembly (MEA)400 includes components arranged sequentially from anode to cathode: an anode gas diffusion layer 401, an anode catalyst layer 402, a Polymer Electrolyte Membrane (PEM)403, a cathode catalyst layer 404, and a cathode gas diffusion layer 405. In some embodiments, both the anode catalyst layer 402 and the cathode catalyst layer 404 may comprise a plurality of fine array porous fuel cell electrode materials as disclosed in fig. 2(205, 206, and 207), respectively comprising anode catalyst and cathode catalyst, while the anode gas diffusion layer 401 and the cathode gas diffusion layer 405 may comprise a gas diffusion material that does not have a fine array porous structure. In some other embodiments, however, both the anode gas diffusion layer 401 and the cathode gas diffusion layer 405 may comprise a plurality of fine array porous electrode materials, and the anode catalyst layer 402 and the cathode catalyst layer 404 may comprise an existing catalyst layer material that does not have a fine array porous structure, such as carbon paper, carbon cloth, or carbon nanotubes, coated with a plurality of anode and cathode catalysts, respectively. In some other embodiments, however, the anode catalyst layer 402, the cathode catalyst layer 404, the anode gas diffusion layer 401, and the cathode gas diffusion layer 405 may all comprise a plurality of fine array porous fuel cell electrode materials, but with different pore sizes or compositions. In some embodiments, however, the anode catalyst layer 402 and the anode gas diffusion layer 401, or the cathode catalyst layer 404 and the cathode gas diffusion layer 405 may comprise a cake of a fine array of porous fuel cell electrode material with a uniform pore size, coated or impregnated with particles of an anode/cathode catalyst with or without a second catalyst support, the portion immediately adjacent to the Polymer Electrolyte Membrane (PEM)403 forming the anode/cathode catalyst layer 402/404; and the portion without catalyst components forms the anode/cathode gas diffusion layer 401/405. In some embodiments, the fuel cell Membrane Electrode Assembly (MEA) may also include an additional anode/cathode catalyst layer between the Polymer Electrolyte Membrane (PEM)403 and the anode/cathode catalyst layer 402/404. In one example, as illustrated in fig. 4C, a layer of conventional carbon-derived catalyst layer 423 comprising a carbon paper/cloth/nanotube coated with an anode/cathode catalyst is disposed on one side of the micro-array porous catalyst layer 422, the micro-array porous catalyst layer 422 comprises a plurality of particles in the pores that are a plurality of carbon carriers carrying a plurality of anode/cathode catalyst particles, and the micro-array porous gas diffusion layer 421 is disposed on the other side of the micro-array porous catalyst layer 422.
In one embodiment as depicted in fig. 4B, the fuel cell Membrane Electrode Assembly (MEA)410 comprises, in order from anode to cathode, an anode gas diffusion layer 411, an anode catalyst layer 412, a Polymer Electrolyte Membrane (PEM)413, a cathode catalyst layer 414, and a cathode gas diffusion layer 415, wherein both the anode catalyst layer 412 and the cathode catalyst layer 414 comprise a fine array of porous fuel cell electrode material with the platinum catalyst; both the anode gas diffusion layer 411 and the cathode gas diffusion layer 415 comprise a fine array of porous fuel cell electrode material having smaller pore sizes than those of the fine array of porous fuel cell electrode materials used in the anode catalyst layers 412 and 414 and are coated with the ruthenium/palladium catalyst. With such a configuration, the anode and cathode gas diffusion layers 411 and 415 not only provide diffusion paths to allow the reaction gases, such as hydrogen and oxygen, to react on the surfaces of the anode and cathode catalyst layers 412 and 414 of the fuel cell, but also serve as a filter layer to remove the carbon monoxide from the reaction gases by the presence of the ruthenium/palladium, so as to prevent the carbon monoxide present in the reaction gases from poisoning the platinum catalyst in the anode and cathode catalyst layers 412 and 414.
Figure 5 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials according to some embodiments herein. Referring to fig. 5A, the fuel cell Membrane Electrode Assembly (MEA)500 comprises the components arranged sequentially from anode to cathode: an anode gas diffusion layer 501, an anode catalyst layer 502, a Polymer Electrolyte Membrane (PEM)503, a cathode catalyst layer 504, and a cathode gas diffusion layer 505, and also a water treatment layer 506 disposed at the bottom of the MEA component 501 and 505. The composition and structure of the MEA part 501 and 505 are similar to the MEA components of the fuel cell MEA described in FIG. 4A. The water treatment layer 506 comprises a fine array of porous material having a pore size of about 0.5-100 times the pore size of the anode gas diffusion layer 501 and the cathode gas diffusion layer 505, and is designed to treat the final liquid reaction product, such as water, within the fuel cell, and is optionally surface treated to increase hydrophilicity in order to further increase the treatment efficiency.
In another embodiment, as depicted in fig. 5B, the fuel cell Membrane Electrode Assembly (MEA)510 includes the components of an anode combined catalyst-gas diffusion layer 511, an anode water treatment layer 512, a Polymer Electrolyte Membrane (PEM)513, a cathode water treatment layer 514, and a cathode combined catalyst-gas diffusion layer 515 arranged sequentially from anode to cathode. Both the anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion layer 515 comprise a plurality of fine array porous fuel cell electrode materials as described in fig. 3, having a plurality of smaller pore sizes, and are coated with a plurality of anode and cathode catalysts, respectively. Both of which serve as catalyst layers and diffusion layers in the fuel cell. Both the anode water treatment layer 512 and the cathode water treatment layer 514 comprise a fine array of porous materials and are designed to treat the final liquid reaction product, such as water, within the fuel cell. The fine array of porous materials in the anode water treatment layer 512 and the cathode water treatment layer 514 may optionally have a larger or alternatively and preferably smaller pore size than the fine array of porous fuel cell electrode materials in the anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion layer 515. The anode and cathode water treatment layers 512 and 514 may optionally be surface treated to be more hydrophilic on the surface, which in turn increases the water treatment benefit; alternatively and preferably, they may be surface treated to be more hydrophobic on the surface to keep water away from the anode/cathode combined catalyst-gas diffusion layers 511 and 515, allowing efficient flow of reactant gases to effectively contact the catalyst in the anode/cathode combined catalyst-gas diffusion layers 511 and 515.
Figure 6 illustrates a fuel cell membrane electrode assembly comprising a fine array of porous electrode materials according to some embodiments herein. The fuel cell Membrane Electrode Assembly (MEA)600 includes the components of an anode gas diffusion layer 601, an anode catalyst layer 602, a Polymer Electrolyte Membrane (PEM)603, a cathode catalyst layer 604, and a cathode gas diffusion layer 605 arranged sequentially from anode to cathode. Both the anode catalyst layer 602 and the cathode catalyst layer 604 comprise a catalyst carrier, such as a carbon paper, a carbon cloth, a carbon nanotube membrane, or a carbon nanosphere membrane, coated with a plurality of anode catalysts and a plurality of cathode catalysts, respectively. Both the anode gas diffusion layer 601 and the cathode gas diffusion layer 605 comprise a fine array of porous material that is selectively surface treated to increase the hydrophobicity of the surface of the layer in order to further increase the gas diffusion efficiency of the layer in the fuel cell.
In some embodiments of a fuel cell device comprising a microarrayed porous fuel cell electrode material, whether it be a catalyst layer, a gas diffusion layer, or a water treatment layer, the microarrayed porous fuel cell electrode material may be surface treated by oxidation of all or a portion of the electrode material to avoid corrosion by acids and bases present in the fuel cell device or generated by electrochemical reactions occurring in the fuel cell.
Although specific embodiments have been described in detail above, this description is for illustrative purposes only. It should be understood, therefore, that many of the aspects described above are not intended as required or essential elements unless explicitly described as such. Various modifications and equivalent actions to the disclosed aspects of the exemplary embodiments, in addition to those described above, may be made by those skilled in the art having the benefit of the present disclosure without departing from the spirit and scope of the present disclosure, which is defined in the following claims, the scope of which is to be accorded the broadest interpretation so as to encompass such modifications and equivalent structures.

Claims (25)

1. A fuel cell device comprising a Membrane Electrolyte Assembly (MEA) comprising a Polymer Electrolyte Membrane (PEM), an anode catalyst layer, a cathode catalyst layer, an anode water treatment layer, and a cathode water treatment layer, wherein:
the Polymer Electrolyte Membrane (PEM) is sandwiched between the anode catalyst layer and the cathode catalyst layer;
at least one of the anode catalyst layer and the cathode catalyst layer comprises a fuel cell electrode material and a catalyst, the fuel cell electrode material comprising a fine array porous material comprising a plurality of pores, wherein the plurality of pores have a pore size of 1000nm to 50000nm, the plurality of pores are substantially uniform in size and have a variation of less than 20%, and the fine array porous material has a porosity of about 74%;
the anode water treatment layer and the cathode water treatment layer are respectively arranged between the anode catalyst layer and the polymer electrolyte membrane and between the cathode catalyst layer and the polymer electrolyte membrane;
at least one of the anode water treatment layer and the cathode water treatment layer comprises a fuel cell electrode material comprising a fine array porous material having a porosity of 40% -85% and comprising a plurality of pores having a pore size of 500nm to 5mm, being substantially uniform in size and having a variation of less than 20%;
the pore size of the fuel cell electrode material of at least one of the anode water treatment layer and the cathode water treatment layer is greater than the pore size of the fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer; and
the anode catalyst layer and the cathode catalyst layer are configured to allow a reaction gas to diffuse therein.
2. The fuel cell device according to claim 1, characterized in that: the fine array porous material in the fuel cell electrode material of at least one of the anode catalyst layer and the cathode catalyst layer is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt and zinc; and the catalyst is platinum, ruthenium, palladium, CoPc, CoTMPP-TiO2、MnOx-CoTMPP or CoFe2O4At least one of them.
3. The fuel cell device according to claim 2, characterized in that: the catalyst is uniformly coated on the surface of the fine array porous material of at least one of the anode catalyst layer and the cathode catalyst layer.
4. The fuel cell device according to claim 2, characterized in that: a plurality of particles of the catalyst are disposed within the plurality of pores of the micro-array porous material of at least one of the anode catalyst layer and the cathode catalyst layer.
5. The fuel cell device according to claim 2, characterized in that: at least one of the anode catalyst layer and the cathode catalyst layer further comprises a catalyst carrier selected from at least one of carbon nanotubes, graphene or carbon nanospheres, wherein a plurality of particles of the catalyst carrier carrying a plurality of particles of catalyst particles on outer surfaces of the plurality of particles of catalyst carrier are disposed in the plurality of pores of the fine array porous material of at least one of the anode catalyst layer and the cathode catalyst layer.
6. The fuel cell device according to claim 1, characterized in that: a prescribed region of at least one of the anode catalyst layer and the cathode catalyst layer is surface-treated to become hydrophobic to facilitate diffusion of the reaction gas therethrough.
7. The fuel cell device according to claim 1, characterized in that: the fuel cell device further comprises an anode gas diffusion layer and a cathode gas diffusion layer, wherein:
the anode gas diffusion layer and the cathode gas diffusion layer are respectively arranged on one sides of the anode catalyst layer and the cathode catalyst layer opposite to the Polymer Electrolyte Membrane (PEM); and is
At least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a second fuel cell electrode material comprising a micro-array porous material having a porosity of 40% -85%, the micro-array porous material of the second fuel cell electrode material comprising a plurality of pores having a pore size of 500nm to 5mm, being substantially uniform in size, and having a variation of less than 20%.
8. The fuel cell device according to claim 7, characterized in that:
the pore size of the second fuel cell electrode material in at least one of the anode gas diffusion layer and the cathode gas diffusion layer is less than the pore size of the fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer; and is
At least one of the anode gas diffusion layer and the cathode gas diffusion layer further comprises a second catalyst selected from at least one of ruthenium and palladium.
9. The fuel cell device according to claim 7, characterized in that: the fuel cell device further comprises a water treatment layer arranged at the bottom of the anode gas diffusion layer, the anode catalyst layer, the cathode catalyst layer and the cathode gas diffusion layer, wherein:
the water treatment layer comprises a third fuel cell electrode material comprising a fine array of porous material having a porosity of 40% -85%, the fine array of porous material of the third fuel cell electrode material comprising a plurality of pores having a pore size of 500nm to 5mm, being substantially uniform in size, and having a variation of less than 20%, wherein:
the pore size of the third fuel cell electrode material in the water treatment layer is greater than the pore size of the fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer and is greater than the pore size of the second fuel cell electrode material in at least one of the anode gas diffusion layer and the cathode gas diffusion layer; and
the third fuel cell electrode material in the water treatment layer is selectively surface-treated to form hydrophilicity.
10. The fuel cell device according to claim 1, characterized in that: the fuel cell device further comprises an anode gas diffusion layer and a cathode gas diffusion layer, wherein the fuel cell device comprises the anode gas diffusion layer, the anode catalyst layer, the Polymer Electrolyte Membrane (PEM), the cathode catalyst layer and the cathode gas diffusion layer from the anode to the cathode in sequence, wherein:
the fuel cell electrode material included in at least one of the anode gas diffusion layer and the cathode gas diffusion layer includes a fine array porous material having a porosity of 40% -85% and including a plurality of pores having a pore size of 500nm to 5mm, being substantially uniform in size, and having a variation of less than 20%.
11. The fuel cell device according to claim 10, characterized in that: at least one of the anode catalyst layer and the cathode catalyst layer includes a catalyst carrier selected from carbon nanotubes or carbon nanospheres.
12. A method of manufacturing a fuel cell electrode material comprising a fine array porous material including a plurality of pores having a pore size of 500nm to 5mm, the plurality of pores being substantially uniform in size and having a variation of less than 20%, the fine array porous material having a porosity of 40% -85%, the method of manufacturing a fuel cell electrode material comprising the following step (i) and step (ii) performed immediately after step (i):
(i) a step of preparing the fine array porous material by 3D printing or by a template manufacturing method; wherein the template manufacturing method comprises the following substeps:
a) electrophoretically fabricating a colloidal particle template;
b) infiltrating an electrode material into the colloidal particle template; and
c) removing the colloidal particle template;
(ii) a second fine array porous material is fabricated on top of the fine array porous material by 3D printing or by a stencil fabrication method.
13. The method of claim 12, wherein: in the template manufacturing method, sub-step b) is accomplished by at least one of electrodeposition, PVD (physical vapor deposition), CVD (chemical vapor deposition) or Sol-Gel (Sol-Gel method).
14. The method of claim 12, wherein: in step (ii), the second fine array porous material is configured with a pore size larger than the pore size of the fine array porous material, and the second fine array porous material is configured with a hydrophilic surface.
15. The method of claim 14, wherein: in step (ii), the second fine array porous material is composed of a hydrophilic conductive polymer.
16. The method of claim 14, wherein: in step (ii), the second fine array porous material is surface-treated to form hydrophilicity.
17. The method of claim 16, wherein: in step (ii), the second fine array porous material is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt and zinc, and a surface of the second fine array porous material is treated by an oxidation reaction.
18. The method of claim 16, wherein: in step (ii), the second fine array porous material is coated with a hydrophilic material.
19. The method for producing a fuel cell electrode material according to claim 12, further comprising a step performed immediately after step (i):
(iv) dispersing the plurality of particles of the catalyst carrier carrying the plurality of particles of the catalyst into the surface or the plurality of pores of the fine array porous material.
20. The method of manufacturing a fuel cell electrode material according to claim 19, characterized in that: the catalyst carrier is selected from at least one of carbon nano-tube or carbon nano-sphere.
21. The method of claim 20, further comprising, immediately after step (iv), the step of:
(iii) combining the particles as the catalyst with the fine array porous material in the fuel cell electrode material.
22. The method of claim 21, wherein: this step (iii) is accomplished by heating.
23. The method of claim 12, further comprising, immediately after step (i), the step of:
(v) applying an etching resist to the fine array porous material.
24. The method of claim 23, wherein: (ii) in step (i) the fine array porous material is composed of a metal selected from the group consisting of zinc, titanium and nickel; and in step (v) the etching resist is an oxidation process.
25. The method of claim 23, wherein: (ii) in step (i) the fine array porous material is composed of a metal selected from the group consisting of zinc, titanium and nickel; and in step (v) the resist is surface coated with a resist material.
CN201580078974.4A 2015-10-22 2015-10-22 Fuel cell device and method for manufacturing electrode material for fuel cell Active CN109618561B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/092499 WO2017066949A1 (en) 2015-10-22 2015-10-22 Fuel cell electrode material and apparatuses

Publications (2)

Publication Number Publication Date
CN109618561A CN109618561A (en) 2019-04-12
CN109618561B true CN109618561B (en) 2022-03-04

Family

ID=58556483

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580078974.4A Active CN109618561B (en) 2015-10-22 2015-10-22 Fuel cell device and method for manufacturing electrode material for fuel cell

Country Status (5)

Country Link
JP (1) JP6726210B2 (en)
KR (1) KR102039536B1 (en)
CN (1) CN109618561B (en)
TW (1) TWI650897B (en)
WO (1) WO2017066949A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101988567B1 (en) * 2017-06-01 2019-06-12 전남대학교산학협력단 Three-dimensional membrane electrode assembly, fuel cell provided with the same and fabrication method thereof
CN109037699B (en) * 2017-06-09 2021-10-12 清华大学 Fuel cell electrode and fuel cell
CN108745308A (en) * 2018-05-07 2018-11-06 江苏大学 A kind of conductive traces Ag@PANI/CoFe2O4The preparation method and applications of/C
CN108993470A (en) * 2018-08-02 2018-12-14 福州大学 A kind of preparation and application of the double array structure catalysis materials of titanium dioxide/graphene/zinc oxide
CN108956730B (en) * 2018-08-08 2020-06-16 甘肃省食品检验研究院 Electrochemical sensor for direct alcohol fuel cell and preparation method and application thereof
JP2020064784A (en) * 2018-10-18 2020-04-23 株式会社グラヴィトン Electrode and electrode manufacturing method
JP7235284B2 (en) * 2018-11-29 2023-03-08 グローバル・リンク株式会社 polymer electrolyte fuel cell
JP7262739B2 (en) * 2018-11-29 2023-04-24 グローバル・リンク株式会社 Manufacturing method for anode and cathode of electrolyzer
KR102387596B1 (en) * 2018-12-26 2022-04-18 코오롱인더스트리 주식회사 Catalyst, method for manufacturing the same, electrode comprising the same, membrane-electrode assembly comprising the same, and fuel cell comprising the same
JP2020167064A (en) * 2019-03-29 2020-10-08 正己 奥山 Solid polymer fuel cell
JP2020167041A (en) * 2019-03-29 2020-10-08 正己 奥山 Electrode and manufacturing method thereof
JP7127603B2 (en) * 2019-04-15 2022-08-30 トヨタ自動車株式会社 METHOD FOR MANUFACTURING ELECTRODE CATALYST LAYER FOR FUEL CELL
CN112206799A (en) * 2019-07-12 2021-01-12 丰田自动车株式会社 Silicon-nitrogen co-doped graphene material, and preparation method and application thereof
CN110846690B (en) * 2019-10-14 2021-01-01 中南大学 Manganese oxide-FeSiMnTi intermetallic compound based composite porous electrode material and preparation method thereof
CN116435560A (en) * 2023-06-14 2023-07-14 清氢(北京)科技有限公司 Batch preparation process of polymer electrolyte ordered large-area membrane electrode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005183263A (en) * 2003-12-22 2005-07-07 Nissan Motor Co Ltd Porous structure
CN102059114A (en) * 2010-12-02 2011-05-18 华南师范大学 Anode porous array catalyst Pt-HxMoO3 for direct methanol fuel cell and preparation method thereof
WO2015151828A1 (en) * 2014-03-31 2015-10-08 住友電気工業株式会社 Collector for fuel cells, and fuel cell

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437525A (en) * 1964-01-20 1969-04-08 Engelhard Ind Inc Fuel cell with titanium-containing electrode and process of use thereof
JPH05283094A (en) * 1992-03-31 1993-10-29 Toshiba Corp Fuel cell
JPH10167855A (en) * 1996-12-05 1998-06-23 Toho Rayon Co Ltd Porous carbon material
US6284114B1 (en) * 1997-09-29 2001-09-04 Rodel Holdings Inc. Method of fabricating a porous polymeric material by electrophoretic deposition
JP2004186046A (en) * 2002-12-04 2004-07-02 Honda Motor Co Ltd Electrode structure for solid polymer fuel cell
DE10345261A1 (en) * 2003-09-29 2005-04-21 Ballard Power Systems Polymer electrolyte membrane fuel cell comprises membrane-electrode arrangement having gas diffusion electrode with hydrophilic nano-porous catalytic layer and first hydrophobic nano-porous gas diffusion layer
JP2007184204A (en) * 2006-01-10 2007-07-19 Canon Inc Fuel cell membrane electrode assembly and method for fabrication thereof
JP2008041467A (en) * 2006-08-08 2008-02-21 Toshiba Corp Device and method of manufacturing electrode for fuel cell
JP2008147031A (en) * 2006-12-11 2008-06-26 Sharp Corp Manufacturing method of membrane-electrode assembly
JP4683021B2 (en) * 2007-08-02 2011-05-11 トヨタ自動車株式会社 Catalyst support for forming fuel cell electrode and method for producing polymer electrolyte fuel cell
KR100982326B1 (en) * 2008-05-13 2010-09-15 삼성에스디아이 주식회사 Membrane electrode assembly for fuel cell, and fuel cell system comprising the same
US20120251926A1 (en) * 2010-04-29 2012-10-04 Ford Global Technologies, Llc Thin Film Catalyst With Heat-Extendable Wires
US20150263366A1 (en) * 2012-08-01 2015-09-17 Kyushu University, National University Corporation Paper-structured catalyst, paper-structured catalyst array body, and solid oxide fuel cell provided with paper-structured catalyst or paper-structured catalyst array body
KR20140065283A (en) * 2012-11-21 2014-05-29 삼성전자주식회사 Electrode for fuel cell, method for preparing the same, membrane electrode assembly for fuel cell the electrode and fuel cell including the membrane electrode assembly
CN103606687B (en) * 2013-11-26 2015-08-26 华南师范大学 A kind of anode catalyst porous array Pt-p-H for direct methanol fuel cell xmoO 3and preparation method thereof
CN103887518B (en) * 2014-03-26 2016-08-17 清华大学 A kind of ordered polymer membrane electrode from humidification
CN104393318B (en) * 2014-09-30 2016-06-29 成都新柯力化工科技有限公司 A kind of fuel cell ceramics PEM and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005183263A (en) * 2003-12-22 2005-07-07 Nissan Motor Co Ltd Porous structure
CN102059114A (en) * 2010-12-02 2011-05-18 华南师范大学 Anode porous array catalyst Pt-HxMoO3 for direct methanol fuel cell and preparation method thereof
WO2015151828A1 (en) * 2014-03-31 2015-10-08 住友電気工業株式会社 Collector for fuel cells, and fuel cell

Also Published As

Publication number Publication date
KR102039536B1 (en) 2019-11-01
TWI650897B (en) 2019-02-11
JP6726210B2 (en) 2020-07-22
WO2017066949A1 (en) 2017-04-27
CN109618561A (en) 2019-04-12
JP2018522365A (en) 2018-08-09
TW201715778A (en) 2017-05-01
KR20180003536A (en) 2018-01-09

Similar Documents

Publication Publication Date Title
CN109618561B (en) Fuel cell device and method for manufacturing electrode material for fuel cell
US8211593B2 (en) Low platinum fuel cells, catalysts, and method for preparing the same
JP5055788B2 (en) Electrocatalyst
EP1873849B1 (en) Catalyst for a fuel cell, method of preparing the same, and membrane-electrode assembly and fuel cell system including the same
US20090311578A1 (en) Water repellent catalyst layer for polymer electrolyte fuel cell and manufacturing method for the same
CN107785588B (en) Fuel cell redox reaction catalyst
KR100722093B1 (en) Membrane-electrode assembly for fuel cell, method for manufacturing the same, and fuel cell system comprising the same
JP2006339124A (en) Membrane-electrode assembly for fuel cell, and solid polymer fuel cell using this
US20090023032A1 (en) Electrode for fuel cell, electrolyte-dispersed solution for forming electrode, method of producing the solution, and polymer electrolyte fuel cell
JP2013215701A (en) Method for manufacturing core-shell catalyst and method for manufacturing membrane electrode assembly
JP2007250210A (en) Electrode catalyst layer for fuel cell and its manufacturing method
US20110159403A1 (en) Layered Catalyst Assembly and Electrode Assembly Employing the Same
JP2007073291A (en) Electrode catalyst particles for fuel cell and fuel cell using it
US11145873B2 (en) Membrane electrode assembly and fuel cell comprising core-shell catalyst
JP2005197195A (en) Solid polymer fuel cell
JP2006012449A (en) Membrane electrode junction body and solid polymer fuel cell using above
JP2009129667A (en) Fuel cell
JP2020068148A (en) Electrode catalyst layer, membrane electrode assembly, and solid polymer fuel cell
KR102544711B1 (en) Electrode for fuel cell using Two types of carbon with different shapes and membrane electrode assembly including same
JP2005190887A (en) Electrode catalyst having surface constitution to structure catalyst layer having high performance and durability, and its manufacturing method
US20160104895A1 (en) Templated non-carbon metal oxide catalyst support
JP2007213947A (en) Manufacturing method of catalyst support powder for polymer electrolyte fuel cell, and polymer electrolyte fuel cell having catalyst support powder provided by same
CN117702155A (en) Membrane electrode assembly
KR20210126218A (en) A membrane-electrode assembly for fuel cell and preparation method thereof
CN117254056A (en) Electrochemical cell with dual layer electrocatalyst structure comprising graphene-based materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant