EP4214780A1 - Procédé de production de membrane revêtue de catalyseur - Google Patents
Procédé de production de membrane revêtue de catalyseurInfo
- Publication number
- EP4214780A1 EP4214780A1 EP21770268.7A EP21770268A EP4214780A1 EP 4214780 A1 EP4214780 A1 EP 4214780A1 EP 21770268 A EP21770268 A EP 21770268A EP 4214780 A1 EP4214780 A1 EP 4214780A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ink
- catalyst
- membrane material
- layer
- coated
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229920000554 ionomer Polymers 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 9
- 238000010410 dusting Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000004876 x-ray fluorescence Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 abstract description 5
- 239000000976 ink Substances 0.000 description 77
- 239000000446 fuel Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036647 reaction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010152 pollination Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
- H01M4/8642—Gradient in composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—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
- H01M4/8663—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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- 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
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- 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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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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- 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
Definitions
- the invention relates to a method for producing a catalyst-coated membrane (CCM for “catalyst-coated membrane”).
- Fuel cell devices are used for the chemical conversion of a fuel with oxygen into water in order to generate electrical energy.
- fuel cells contain a proton-conductive (electrolyte) membrane as a core component, to which electrodes are assigned.
- the fuel in particular hydrogen (H2) or a hydrogen-containing gas mixture
- H2 hydrogen
- a hydrogen-containing gas mixture this is first reformed and hydrogen is thus made available.
- An electrochemical oxidation of H2 to H + takes place at the anode with the release of electrons.
- the electrons provided at the anode are fed to the cathode via an electrical line.
- Oxygen or an oxygen-containing gas mixture is fed to the cathode, so that a reduction of O2 to O2' takes place , with the electrons being absorbed.
- WO 2008 106 504 A2 WO 2016 149 168 A1 and WO 2002 043 171 A2 describe the industrial production of catalyst-coated membranes, the membrane being provided in web form in order to be subsequently coated with electrode material.
- WO 2008 106 504 A2 in particular proposes coating the membrane material from one roll to the next, with different ink compositions being used for coating the substrate.
- the greatest accumulation of moisture or liquid occurs precisely on the cathode side of the membrane electrode arrangement, so that efficient water management through a suitable composition of the catalyst layer is required.
- the method according to the invention comprises in particular the following steps:
- first ink preparing and/or providing a first ink with a first ink composition
- a first ink composition comprising supported catalyst particles, proton conductive ionomer and dispersant, in which the proportion of the supported catalyst particles lags behind the proportion of the proton conductive ionomer
- Sputtering of a catalyst powder consisting of or comprising catalyst particles onto a surface of the outermost ink layer facing away from the membrane material by means of a sputtering device is characterized by the fact that a multi-stage process with different densities of catalyst loadings is used, with the layer that has direct contact with the membrane having a larger proportion of the ionomer and thus a lower proportion of catalyst particles than the layer at the edge of the membrane Catalyst Coated Membrane Electrode.
- the final - particularly porous and therefore only partially closed - layer of catalyst particles on the outermost layer of ink causes the greatest amount of catalyst to be found at the point of the CCM that is furthest away from the proton-conducting (core) membrane, which also promotes the fuel cell reaction.
- core proton-conducting
- This is particularly advantageous since a large number of such membrane electrode arrangements are required for use, for example in motor vehicles, in order to provide the desired performance.
- the catalyst material which is usually very expensive, can be saved as a result of the stepwise increase in the catalyst density which can be achieved with the method according to the invention and which increases with increasing distance from the membrane.
- Ink compositions close to the membrane can also be dimensioned in such a way that they have a lower proportion of components that are harmful to the membrane adjacent to them than ink compositions that are further away.
- At least one second ink can be prepared and/or provided that comprises the supported catalyst particles, the proton conductive ionomer and the dispersant, with the proportion of the proton conductive ionomer lagging behind the proportion of the supported catalyst particles.
- at least one layer of the second ink is then applied to an outermost layer of the first ink before the catalyst powder is dusted on.
- a gradual increase in the density of catalyst particles can thus also be implemented.
- a plurality of three or more inks can also be used and therefore the present invention is not limited to two inks and two ink compositions.
- the dusting with catalyst powder is preferably always carried out after the application of the outermost layer of ink. In principle, however, there is also the possibility of sputtering on intermediate layers of catalyst powder.
- the first ink is applied to both sides of the membrane material with the first application tool, if subsequently the second ink is applied with the second application tool on both sides to the outermost , applied to the membrane material, layer of the first ink is applied, and when the catalyst particle powder is dusted on both sides of the respective outermost ink layer following the application of the second ink.
- the membrane material coated with the first ink is conveyed to an intermediate drying unit in which the first ink is dried before the second ink is applied. In this way, mixing of the individual ink coatings can be avoided, so that there is a defined—in particular gradually increasing—distribution of the catalyst particles in each ink coating up to the edge of the electrode.
- the catalyst powder is dusted onto the outermost ink layer which is still in a moist or wet state.
- the individual catalyst particles can partially penetrate into the outermost layer during dusting, whereby they are reliably bound into the composite of the final catalyst-coated membrane (CCM).
- the catalyst particles are dusted onto the outermost layer of ink if this is only partially dried, This is because the increased viscosity of the outermost layer of ink due to partial drying ensures that the sprayed catalyst particles do not penetrate too deeply into the outermost layer of ink.
- the atomized catalyst powder can in turn consist of supported, in particular carbon-supported, catalyst particles. However, there is also the possibility of using unsupported catalyst particles for the catalyst dusting.
- the production process can be accelerated in that the intermediate drying unit is exclusively set up in such a way to exclusively partially dry the first ink, so that only a dry edge film of the first ink results, on which the second ink is applied. In this way, the process time is shortened, since only part of the first ink is dried, onto which the second ink can be applied, without the two inks being mixed.
- a layer thickness measurement of the layer of the first ink is carried out after the application of the first ink.
- This layer thickness measurement can be carried out dry or wet, for example.
- the information about the layer thickness of the first ink on the membrane material can be used to regulate various parameters that influence the subsequent electrochemical reaction. For example, overly thick application of the first ink may cause the first ink to be applied to subsequent portions of the membrane material in a lesser manner to reduce the layer thickness of subsequent first ink portions of membrane material. It is thus possible in this way for the first ink to be applied to subsequent sections of the membrane material as a function of the measured layer thickness of preceding sections of the membrane material.
- a final (limit) electrode thickness can also be specified, so that it has proven to be advantageous if the second ink to be applied afterwards and/or the catalyst powder then sprayed on in Depending on the measured layer thickness of the first ink is applied to limit an electrode thickness.
- a layer thickness measurement of the electrode thickness is carried out after the catalyst powder has been sprayed on, and that the first ink and/or the second ink and/or the catalyst powder is applied to subsequent sections of the membrane material depending on the measured electrode thickness. It is also possible in this way to maintain a predetermined limit electrode thickness.
- the membrane material coated with the at least one ink and dusted with the catalyst powder is conveyed to a drying unit in which the coating is completely dried.
- a catalyst particle loading of the membrane material coated with the at least one ink and dusted with the catalyst powder is determined by means of an X-ray fluorescence analysis, and if the proportion of catalyst particles in the inks is adjusted as a function of the measured catalyst particle loading. In this way, it is possible to react early on to an excess or to a residue of the catalyst particles in the inks or the sprayed catalyst particle powder layer, which means that the proportion of rejects, i.e. poorly manufactured catalyst-coated membranes, can be reduced.
- the membrane material coated with the at least one ink and dusted with the catalyst powder is cut up into individual catalyst-coated membranes (CCM).
- FIG. 2 shows a detailed view II, shown only schematically, of an electrode from FIG. 1, and
- FIG. 3 shows a schematic representation of a device for producing a catalyst-coated membrane in a side view.
- a fuel cell 1 is shown in FIG.
- a semipermeable electrolyte membrane 2 is covered on a first side 3 with a first electrode 4, in this case the anode, and on a second side 5 with a second electrode 6, in this case the cathode.
- the first electrode 4 and the second electrode 6 comprise carrier particles 14 on which catalyst particles 13 made of noble metals or mixtures comprising noble metals such as platinum, palladium, ruthenium or the like are arranged or supported. These catalyst particles 13 serve as a reaction accelerator in the electrochemical reaction of the fuel cell 1.
- the carrier particles 14 can contain carbon. However, carrier particles 14 made of a metal oxide or carbon with a corresponding coating also come into consideration.
- the electrolyte membrane 2 In such a polymer electrolyte membrane fuel cell (PEM fuel cell) are at the first electrode 5 (anode) or fuel Fuel molecules, especially hydrogen, split into protons and electrons.
- the electrolyte membrane 2 lets the protons (eg H + ) through, but is impermeable to the electrons (e-).
- the electrolyte membrane 2 is formed from an ionomer, preferably a sulfonated tetrafluoroethylene polymer (PTFE) or a polymer of perfluorinated sulfonic acid (PFSA). The following reaction takes place at the anode:
- a cathode gas in particular oxygen or air containing oxygen, is provided at the cathode, so that the following reaction takes place here: O2 + 4H++
- the electrodes 4, 6 are each assigned a gas diffusion layer 7, 8, of which one gas diffusion layer 7 is assigned to the anode and the other gas diffusion layer 8 to the cathode.
- the anode-side gas diffusion layer 7 is assigned a flow field plate designed as a bipolar plate 9 for supplying the fuel gas, which has a fuel flow field 11 .
- the fuel is supplied to the electrode 4 through the gas diffusion layer 7 by means of the fuel flow field 11 .
- the gas diffusion layer 8 is assigned a flow field plate, which includes a cathode gas flow field 12 and is also designed as a bipolar plate 10 , for supplying the cathode gas to the electrode 6 .
- the electrodes 4, 6 are formed with a plurality of catalyst particles 13, which can be formed as nanoparticles, for example as core-shell nanoparticles (“core-shell-nanoparticles”). They have the advantage of a large surface area, with the noble metal or noble metal alloy being arranged only on the surface, while a lower-grade metal, for example nickel or copper, forms the core of the nanoparticle.
- the catalyst particles 13 are on a plurality of electrically conductive Carrier particles 14 arranged or supported.
- an ionomer binder 15 which is preferably formed from the same material as the membrane 2 .
- This ionomer binder 15 is preferably formed as a polymer or ionomer containing a perfluorinated sulfonic acid.
- the ionomer binder 15 is present in a porous form having a porosity greater than 30 percent. This ensures, particularly on the cathode side, that the oxygen diffusion resistance is not increased, thereby enabling a lower loading of the catalyst particle 13 with noble metal or a lower loading of the carrier particles 14 with catalyst particles 13 (FIG. 2).
- a first ink 16 is prepared and/or provided which comprises a first ink composition comprising supported catalyst particles 13, proton conductive ionomer 15 and dispersant.
- the ionomer 15 is preferably formed from the same material as the membrane 2 .
- suitable dispersants are isopropanol or acetone.
- a second ink 18 is prepared or provided which has an ink composition comprising the supported catalyst particles 13, the proton conductive ionomer 15 and the dispersant.
- the proportion of the proton-conductive ionomer 15 lags behind the proportion of the supported catalyst particles 13.
- a “lagging behind” preferably means a difference of at least 10 percent, more preferably at least 30 percent and most preferably at least 50 percent in the proportions.
- a catalyst powder coating 30 made of supported catalyst particles 13 is dusted onto the outermost layer of ink, which represents the final edge of the respective electrode 4, 6, which is adjacent to the respective adjacent gas diffusion layer 7, 8.
- a web-shaped, on a roll 22 provided, proton-conductive membrane material unrolled and first out in a conveying direction 21 to a film cleaning unit 25, in which the membrane material 20 is cleaned dust-free and free of deposits.
- the membrane material 20 is then transported further in the conveying direction 21 to a first application tool 17, with which the first ink 16 is applied to at least one section, preferably completely to the membrane material 20.
- a first application tool 17 in the conveying direction 21 the layer thickness of the layer of the first ink 16 is measured by means of a layer thickness measuring device 27.
- an intermediate drying unit 23 is provided in order to dry the first ink 16 before it is mixed with another ink is printed.
- the intermediate drying unit 23 shown here is designed to only partially dry the first ink 16 in order to form a dry edge film there from the first ink 16 before the second ink 18 is subsequently applied in the conveying direction 21 with a second application tool 19 to an outermost layer applied to the membrane material 20 , Layer of the first ink 16 is applied. Downstream of the second application tool 19 in the conveying direction 21 there is again a layer thickness measuring device 27 in order to measure the coating formed from the first ink 16 and the second ink 18 . This layer thickness measuring device 27 can be used to measure the prevailing wet film cover.
- a dusting device 29 Downstream of the second application tool 19 in the conveying direction 21 is a dusting device 29 with which a powder consisting of or comprising catalyst particles 13 is dusted onto a surface of the outermost ink layer facing away from the membrane material 20 .
- This catalyst powder can be dusted onto the outermost layer of ink, which is still in a moist or wet state, whereby it partially penetrates into the outermost layer of ink and thus completes the electrode 4, 6.
- the density of the catalyst particles 13 increases step by step with the distance from the membrane 2 .
- the dusting device 29 is followed in the conveying direction 21 by a drying unit 24 which is designed to completely dry the membrane material 20 coated with the inks 16, 18 and dusted with the catalyst powder.
- a further layer thickness measuring device 27 is located downstream of the drying unit 24 in the conveying direction 21 downstream, which can measure the dried electrode film, for example by means of an optical layer thickness measuring head.
- an X-ray fluorescence analysis unit 26 which determines the catalyst particle loading of the membrane material 20 coated with the inks 16, 18 and dusted with the catalyst powder, the proportion of supported catalyst particles 13 in the inks 16, 18 and the catalyst powder coating 30 then being determined as a function of the measured catalyst particle loading can be adjusted.
- the coated membrane material 20 Before the coated membrane material 20 is rolled up again on the further roll 22, it is guided past a unit for error marking 28, with which any holes present in the electrode layers or the like can be marked, so that when the membrane material 20 is subsequently cut to size into individual catalyst-coated membranes (CCM) it is excluded that these have a defective coating.
- CCM catalyst-coated membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Abstract
L'invention concerne un procédé de production d'une membrane revêtue de catalyseur (CCM), comprenant les étapes consistant à : produire et/ou fournir au moins une première encre (16) avec une première composition d'encre, comprenant des particules de catalyseur supportées (13), un ionomère conducteur de protons (15), et un agent de dispersion, la teneur en particules de catalyseur supportées (13) dans la composition restant en dessous de la teneur en ionomère conducteur de protons (15) ; le déroulement d'un matériau de membrane conducteur de protons en forme de bande (20) qui est disposé sur un rouleau (22) ; appliquer au moins une couche de la première encre (16) sur au moins une section du matériau de membrane (20) à l'aide d'un premier outil d'application (17) ; et la pulvérisation d'une poudre de catalyseur constituée de ou comprenant des particules de catalyseur (13) sur la couche d'encre la plus à l'extérieur opposée au matériau de membrane (20) à l'aide d'un dispositif de pulvérisation (29).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102020124217.4A DE102020124217A1 (de) | 2020-09-17 | 2020-09-17 | Verfahren zur Herstellung einer katalysatorbeschichteten Membran |
PCT/EP2021/075034 WO2022058260A1 (fr) | 2020-09-17 | 2021-09-13 | Procédé de production de membrane revêtue de catalyseur |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4214780A1 true EP4214780A1 (fr) | 2023-07-26 |
Family
ID=77774932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21770268.7A Pending EP4214780A1 (fr) | 2020-09-17 | 2021-09-13 | Procédé de production de membrane revêtue de catalyseur |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230238543A1 (fr) |
EP (1) | EP4214780A1 (fr) |
JP (1) | JP7470816B2 (fr) |
KR (1) | KR20230002803A (fr) |
CN (1) | CN115668552A (fr) |
DE (1) | DE102020124217A1 (fr) |
WO (1) | WO2022058260A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102021214489A1 (de) | 2021-12-16 | 2023-06-22 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren zum Herstellen einer elektrochemischen Zelle |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6967038B2 (en) | 2000-10-27 | 2005-11-22 | E.I. Du Pont Demours And Company | Production of catalyst coated membranes |
US20020068213A1 (en) * | 2000-12-01 | 2002-06-06 | Honeywell International, Inc. Law Dept. Ab2 | Multiple layer electrode for improved performance |
JP5002874B2 (ja) | 2001-01-25 | 2012-08-15 | トヨタ自動車株式会社 | 燃料電池の電極触媒層形成方法 |
CA2525565C (fr) * | 2003-05-14 | 2011-11-29 | Toray Industries Inc. | Complexe electrode-membrane et pile a combustible polymere solide l'utilisant |
JP4576813B2 (ja) | 2003-09-05 | 2010-11-10 | 株式会社豊田中央研究所 | 高分子電解質膜及び膜電極接合体 |
US20050098101A1 (en) | 2003-11-04 | 2005-05-12 | Palcan Power Systems Inc. | Apparatus for manufacturing fuel cell membrane electrode assembly |
KR100721640B1 (ko) | 2004-01-26 | 2007-05-23 | 마쯔시다덴기산교 가부시키가이샤 | 막촉매층 접합체, 막전극 접합체 및 고분자 전해질형연료전지 |
JP2008027799A (ja) * | 2006-07-24 | 2008-02-07 | Toyota Motor Corp | 燃料電池用接合体、燃料電池、及び燃料電池の製造方法 |
US20080206616A1 (en) | 2007-02-27 | 2008-08-28 | Cabot Corporation | Catalyst coated membranes and sprayable inks and processes for forming same |
US8735023B2 (en) * | 2009-12-14 | 2014-05-27 | GM Global Technology Operations LLC | Fuel cell with layered electrode |
JP5899522B2 (ja) | 2012-02-08 | 2016-04-06 | パナソニックIpマネジメント株式会社 | 燃料電池用膜電極接合体の製造方法および製造装置 |
JP2016167452A (ja) | 2015-03-03 | 2016-09-15 | 株式会社フジクラ | ダイレクトメタノール型燃料電池用膜電極接合体及びその製造方法並びにダイレクトメタノール型燃料電池及びその製造方法並びに膜電極接合体及びその製造方法並びに燃料電池及びその製造方法 |
US11322765B2 (en) | 2015-03-13 | 2022-05-03 | UMM Rainforest Innovations | Smart-MEAs for high power fuel cells |
-
2020
- 2020-09-17 DE DE102020124217.4A patent/DE102020124217A1/de active Pending
-
2021
- 2021-09-13 CN CN202180042753.7A patent/CN115668552A/zh active Pending
- 2021-09-13 WO PCT/EP2021/075034 patent/WO2022058260A1/fr unknown
- 2021-09-13 JP JP2022567117A patent/JP7470816B2/ja active Active
- 2021-09-13 EP EP21770268.7A patent/EP4214780A1/fr active Pending
- 2021-09-13 US US18/001,852 patent/US20230238543A1/en active Pending
- 2021-09-13 KR KR1020227040113A patent/KR20230002803A/ko unknown
Also Published As
Publication number | Publication date |
---|---|
JP7470816B2 (ja) | 2024-04-18 |
US20230238543A1 (en) | 2023-07-27 |
WO2022058260A1 (fr) | 2022-03-24 |
CN115668552A (zh) | 2023-01-31 |
DE102020124217A1 (de) | 2022-03-17 |
KR20230002803A (ko) | 2023-01-05 |
JP2023524741A (ja) | 2023-06-13 |
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