EP4285426A1 - Système de revêtement multicouche notamment destiné à être appliqué sur une pile à combustible et pile à combustible comportant un tel système de revêtement - Google Patents

Système de revêtement multicouche notamment destiné à être appliqué sur une pile à combustible et pile à combustible comportant un tel système de revêtement

Info

Publication number
EP4285426A1
EP4285426A1 EP21844012.1A EP21844012A EP4285426A1 EP 4285426 A1 EP4285426 A1 EP 4285426A1 EP 21844012 A EP21844012 A EP 21844012A EP 4285426 A1 EP4285426 A1 EP 4285426A1
Authority
EP
European Patent Office
Prior art keywords
layer
coating system
hydrogen
hydrogen carrier
fuel cell
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
Application number
EP21844012.1A
Other languages
German (de)
English (en)
Inventor
Peter Wasserscheid
Patrick PREUSTER
Simon Thiele
Gabriel Sievi
Karsten Müller
Andreas BÖSMANN
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.)
Hydrogenious Technologies GmbH
Original Assignee
Hydrogenious LOHC Technologies GmbH
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 Hydrogenious LOHC Technologies GmbH filed Critical Hydrogenious LOHC Technologies GmbH
Publication of EP4285426A1 publication Critical patent/EP4285426A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637—Direct internal reforming at the anode of the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C01B2203/067—Integration with other chemical processes with fuel cells the reforming process taking place in the fuel cell
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • 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
    • 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

Definitions

  • Multi-layer coating system in particular for attachment to a fuel cell, and fuel cell with such a coating system
  • the invention relates to a multi-layer coating system, in particular for attachment to a fuel cell, and to a fuel cell with such a coating system.
  • Fuel cells are used to generate electricity from hydrogen gas.
  • DE 10 2017 209 891 A1 discloses advantageous operation of a so-called direct fuel cell with a secondary alcohol which can be converted into a ketone with the release of hydrogen gas and the hydrogen gas can be converted into electricity in the direct fuel cell.
  • the object of the invention is to improve the design and operation of a fuel cell, in particular a direct fuel cell.
  • the core of the invention is that a multi-layer coating system is provided that can be attached in particular to a fuel cell.
  • the multi-layer coating system includes a first cata- lysator layer with a first catalyst material for dehydrogenating a hydrogen carrier material.
  • the dehydration of the hydrogen carrier material releases hydrogen which is chemically bound to the hydrogen carrier material.
  • the dehydrogenation converts the hydrogen carrier material from a hydrogen-rich form into a hydrogen-poor form.
  • the hydrogen carrier material in the hydrogen-rich form is a secondary alcohol in the general representation with organyl radicals XI, X2, which are in particular alkyl radicals, alkenyl radicals, aryl radicals and/or benzyl radicals.
  • the hydrogen carrier material of the hydrogen-poor form is a ketone with the organyl radicals XI, X2, which are in particular alkyl radicals, alkenyl radicals, aryl radicals and/or benzyl radicals. The ketone can be broken down into the structural formula represent.
  • the hydrogen carrier material can be liquid and/or gaseous.
  • the multilayer coating system includes a barrier layer that is impervious to the hydrogen carrier material.
  • the barrier layer is non-wetting to the hydrogen carrier material.
  • the barrier layer is impermeable to the hydrogen carrier material.
  • the barrier layer is permeable to the hydrogen gas released during the dehydrogenation, ie permeable.
  • the first catalyst layer for the dehydrogenation of the hydrogen carrier material is dehydrogenated at the first catalyst layer but cannot penetrate the barrier layer. Due to the fact that the barrier layer has a selective permeability, the released hydrogen gas passes, in particular exclusively, through the barrier layer and can advantageously be converted into electricity in the fuel cell arranged behind the barrier layer. In particular, the hydrogen gas is available at an interface of the barrier layer. It is possible that at least small proportions of the hydrogenated and/or dehydrogenated hydrogen carrier material can reach the interface of the barrier layer.
  • the proportions of the hydrogenated and/or dehydrogenated hydrogen carrier material at the interface of the barrier layer are at most 30% by volume based on the material at the interface of the barrier layer, in particular at most 25% by volume, in particular at most 20% by volume, in particular at most 15% by volume , in particular at most 12% by volume, in particular at most 10% by volume, in particular at most 8% by volume and in particular at most 5% by volume.
  • the first catalyst layer is separated from the fuel cell and in particular from a fuel cell membrane by the barrier layer.
  • the first catalyst layer is arranged facing away from the fuel cell and in particular the fuel cell membrane.
  • the first catalyst layer and/or the barrier layer each have a layer thickness between 10 nm and 500 ⁇ m, in particular between 20 nm and 400 ⁇ m, in particular between 40 nm and 300 ⁇ m, in particular between 50 nm and 200 ⁇ m, in particular between 75 nm and 150 pm, in particular between 100 nm and 100 pm, in particular between 200 nm and 50 pm, in particular between 500 nm and 10 pm, in particular between 1 pm and 5 pm.
  • the first catalyst layer and/or the barrier layer can have the same or different layer thicknesses.
  • the ratio of the smaller layer thickness to the larger layer thickness is between 0.001 and 0.9, in particular between 0.002 and 0.8, in particular between 0.005 and 0.7, in particular between 0.01 and 0.5, in particular between 0.03 and 0.3, in particular between 0.05 and 0.2, in particular between 0.1 and 0.15.
  • the coating system according to the invention can advantageously be constructed and manufactured by additive manufacturing processes.
  • Additive manufacturing methods that can process ink are particularly suitable, in particular methods of spray coating, slot nozzle coating, 3D printing, aerosol printing, laser and/or electron beam sintering, screen printing methods, flexographic printing methods, sputtering and/or gravure methods.
  • a gravure method is understood to mean a gravure printing method, in particular a rotogravure printing method, in which an image is engraved on an image carrier. Using intaglio, the image is engraved on a cylinder used as in offset printing.
  • additive manufacturing processes are suitable for layer production.
  • the properties of the individual layers, in particular the barrier layer and/or the first catalyst layer in a targeted manner and in particular to set a gradient within the respective layer in order in particular to improve and in particular promote gas transport through the layers.
  • the properties of the individual layers can be set to be variable along the layer thickness direction and/or in a plane transverse and in particular perpendicular to the layer thickness direction and in particular have a gradient.
  • a gradient is understood to mean, in particular, a property change along a direction of change, it being possible for the direction of change to be oriented transversely and in particular perpendicularly along the layer thickness direction.
  • the respective gradient results in particular from the fact that the property changes from a maximum value to a minimum value or vice versa.
  • the course of the gradient between the minimum and maximum value can be linear or non-linear, in particular curved and in particular progressive or degressive.
  • the value range which is limited at the bottom by the minimum value and at the top by the maximum value, is for the porosity between 20% and 80%, in particular between 10% and 90%, in particular between 5% and 95% and in particular between 1% and 99%.
  • the range of values for the pore size is between 100 nm and 10 ⁇ m, in particular between 10 nm and 100 ⁇ m, in particular between 1 nm and 500 ⁇ m and in particular between 0.1 nm and 1 mm.
  • the range of values for the particle size is between 100 nm and 10 ⁇ m, in particular between 10 nm and 100 ⁇ m, in particular between 1 nm and 500 ⁇ m and in particular between 0.1 nm and 1 mm.
  • the range of values for the amount of particles is between 0.1 and 1 g/cm 2 .
  • the range of values for the wetting angle is between 45° and 135°, in particular between 30° and 150°, in particular between 15° and 165°, in particular between 5° and 175° and in particular between 0° and 180°.
  • the gradient profiles have at least one local minimum and/or at least one local maximum. It is for example, it is conceivable that along the layer thickness direction the property value has values at the surface of the layer thickness that are smaller than a local maximum value within the layer.
  • a polymer electrolyte membrane (PEM) fuel cell known from the prior art can advantageously be retrofitted with the coating system according to the invention.
  • a PEM fuel cell has improved functionality and is particularly suitable for use with secondary alcohols or other hydrogen carrier materials.
  • a coating system according to claim 2 is designed to be particularly compact and robust.
  • the barrier layer is formed immediately adjacent to the first catalyst layer.
  • the first catalyst layer and the barrier layer form a two-layer but one-piece combination layer.
  • a first catalyst material according to claim 3 has proven to be particularly advantageous for the dehydrogenation of the hydrogen carrier material.
  • the first catalyst material can have platinum, iridium, osmium, ruthenium, rhodium and/or palladium.
  • the first catalyst material can include metals such as copper, cobalt, nickel, silver, gold and/or phosphorus.
  • the first catalyst material can have nitrogen-based materials such as, for example, iron-nitrogen complexes, in which, for example, graphene can be embedded.
  • Catalyst materials of this type are, for example, Fe-NC compounds. Phosphorus and/or sulfur dopings are also possible.
  • a porous barrier layer according to claim 4 ensures advantageous transport of the hydrogen gas through the barrier layer.
  • the hydrogen carrier material is prevented from passing through the barrier layer.
  • the porous barrier material allows retention of the hydrogen carrier material as a result of interaction with the pore walls through optimal bonding properties between the hydrogen carrier material and the pore walls.
  • the porous barrier layer comprises one or more materials such as carbon, metals, polytetrafluoroethylene, zeolites, i.e. crystalline aluminosilicates, metal-organic framework compounds, i.e. metal-organic frameworks (MOFs), polybenzimidazoles (PBI), polyetheretherketone (PEEK) and/or ionomers, in particular a perfluorinated copolymer comprising a sulfo group as an ionic group, and/or alkaline ionomers, and/or perfluorosulfonic acids (PFSA), in particular derivatives thereof.
  • materials such as carbon, metals, polytetrafluoroethylene, zeolites, i.e. crystalline aluminosilicates, metal-organic framework compounds, i.e. metal-organic frameworks (MOFs), polybenzimidazoles (PBI), polyetheretherketone (PEEK) and/or ionomers,
  • a porosity of the barrier layer according to claim 5 has proven to be advantageous for the hydrogen transport on the one hand and the retention of the hydrogen carrier material on the other hand.
  • the barrier layer according to claim 6 can be made non-porous, ie impervious.
  • the hydrogen gas is then transported through the barrier layer by means of diffusion.
  • the barrier layer has a hydrogen diffusion coefficient that is greater than a hydrogen carrier material diffusion coefficient.
  • the hydrogen carrier material diffusion coefficient is at most 10' 15 m 2 / s, in particular at most 10' 14 m 2 / s, in particular at most 10' 13 m 2 / s, in particular at most 10' 12 m 2 / s, in particular at most 10' 11 m 2 /s, in particular at most 10' 10 m 2 /s.
  • Plastics in particular polymers, in particular a perfluorinated copolymer containing a sulfo group as an ionic group, or polytetrafluoroethylene (PTFE) are suitable for a non-porous, ie impermeable, embodiment of the barrier layer.
  • PTFE polytetrafluoroethylene
  • a gas diffusion layer according to claim 7 represents an additional barrier for the hydrogen carrier material.
  • the proportion of the hydrogen carrier material which reaches the fuel cell is additionally reduced.
  • the gas diffusion layer is arranged on a side opposite the first catalyst layer with respect to the barrier layer.
  • the gas diffusion layer is formed in particular from porous carbon fibers.
  • the gas diffusion layer comprises carbon fiber nonwovens and in particular a layer of carbon black.
  • the gas diffusion layer can additionally or alternatively have carbon, titanium and/or stainless steel.
  • the porous carbon fibers of the gas diffusion layer are connected to the barrier layer in particular by the contact pressure via the cell plates and/or by means of a thermal pressure process.
  • the gas diffusion layer has a layer thickness between 10 ⁇ m and 10 mm, in particular between 100 ⁇ m and 1 mm.
  • a further barrier layer according to claim 8 additionally reduces the risk that the hydrogen carrier material reaches the fuel cell.
  • the further barrier layer is identical to the barrier layer arranged on the first catalyst layer.
  • the further barrier layer can have a different layer thickness and/or a different ches material such as the barrier layer arranged on the first catalyst layer.
  • the embodiment of the coating system according to claim 9 is particularly suitable for the direct and in particular one-piece attachment of the coating system to an already existing fuel cell. Due to the fact that the coating system is designed over a large area and in particular over the entire surface, that is to say without interruption, a robust and long-lasting connection of the coating system to the fuel cell is made possible.
  • a coating system has at least one hydrogen carrier flow channel in which the hydrogen carrier material can flow.
  • the hydrogen carrier flow channel has a closed flow channel wall in a circumferential direction, viewed with respect to the direction of flow, so that an unintentional escape of the hydrogen carrier material from the hydrogen carrier flow channel is prevented.
  • the flow channel wall has the barrier layer at least in regions. In these areas, hydrogen gas released by dehydrogenation of the hydrogen carrier material in the hydrogen carrier flow channel may leak out of the hydrogen carrier flow channel. Due to the size of the areas in which the barrier layer is arranged and the arrangement of the areas in which the barrier layer is arranged, the hydrogen gas can be released from the hydrogen carrier flow channel in a targeted manner.
  • Such a coating system enables liquid water and/or other liquids to be transported away better.
  • the transport port of liquid is possible in particular in a plane perpendicular to the direction of gas flow through the coating system. Gas transport perpendicular to the coating system is essentially unhindered.
  • the dehydrogenation is ensured in the hydrogen carrier flow channel.
  • a hydrogen carrier transport layer according to claim 12 improves the transport of the hydrogen carrier material.
  • the hydrogen carrier transport layer can be embodied as a separate layer and is in particular embodied adjacent to the first catalyst layer and in particular surrounded by the first catalyst layer.
  • the hydrogen carrier transport layer can be mixed with the first catalyst layer and in particular can be embodied as a mixed layer in which the material for the hydrogen carrier transport layer and the first catalyst material are mixed.
  • the hydrogen carrier transport layer includes metal, carbon, plastics and/or composite materials.
  • Composite materials are understood to be composite materials which consist of one or more transport layer elements, in particular of different transport layer elements, which are in particular graded in different ways, ie have different property gradients.
  • the transport layer elements form a self-contained hydrogen carrier transport layer.
  • the hydrogen carrier flow channel can be designed without a hydrogen carrier transport layer.
  • a hollow space can be provided in the hydrogen carrier flow channel.
  • the water hydrogen carrier material are also transported through the first catalyst layer.
  • a coating system according to claim 13 has improved flow characteristics for the gas flows perpendicular to the coating system and liquid in a plane parallel to the coating system.
  • the coating system has a plurality of hydrogen carrier flow channels, with a fluid flow channel being arranged between two adjacent hydrogen carrier flow channels.
  • the coating system does not have a full-surface, ie not an uninterrupted, structure, but rather an interrupted structure.
  • a fuel cell according to claim 14 with the multi-layer coating system essentially has the advantages of the coating system itself, to which reference is hereby made.
  • the multilayer coating system with the first catalyst layer is arranged at a distance from a second catalyst layer.
  • the second catalyst layer comprises a second catalyst material for hydrogen oxidation of the hydrogen gas released from the hydrogen carrier material.
  • the second catalyst material is, in particular, a metal-containing electrocatalyst which, in particular, has platinum. Additionally or alternatively, the second catalyst material can have ruthenium, palladium, iridium, gold, silver, rhenium, rhodium, copper, nickel, cobalt, iron, manganese, chromium, molybdenum and/or vanadium.
  • the metals of the second catalyst material are present in particular as elemental metals, metal oxides and/or metal hydroxides. Mixed catalysts containing platinum and ruthenium have proven particularly advantageous nium, in particular in elemental form and/or in oxidic form.
  • the first catalyst layer is spatially separated from the second catalyst layer at least by the barrier layer. Further layers can be arranged between the first catalyst layer and the second catalyst layer.
  • the coating system is directly and robustly attached to and connected to the fuel cell.
  • the coating system can be materially bonded to the second catalyst layer. Additionally or alternatively, the coating system can be bonded to an intermediate layer, with the intermediate layer itself being bonded to the second catalyst layer.
  • the multi-layer coating system is materially connected to the fuel cell.
  • the intermediate layer itself can have one or more layers, in particular a gas diffusion layer and/or a further barrier layer.
  • the coating system is connected indirectly to the second catalyst layer through the intermediate layer.
  • a fuel cell of this type can be produced advantageously and robustly, in particular by additive manufacturing methods, by applying the multi-layer coating system directly to an existing fuel cell.
  • the multi-layer coating system according to claim 16 can be held on a carrier element.
  • the carrier element can be detachably connected to an already existing fuel cell.
  • the carrier element is designed in particular in the form of a plate.
  • the carrier element can be attached to the second catalyst layer in particular in a detachable manner.
  • the carrier element can be designed so that it can be attached to an intermediate layer that is integrally bonded to the second catalyst layer.
  • the detachable attachment of the carrier element is particularly advantageous if the coating system has a plurality of hydrogen carrier flow channels and fluid flow channels arranged between them.
  • the multi-layer coating system can be placed on an already existing fuel cell by means of the carrier element and assembled and disassembled on it.
  • FIG. 1 shows a schematic sectional view of a fuel cell with a multilayer coating system according to the invention according to a first exemplary embodiment
  • FIG. 2 shows an enlarged sectional view of the attachment of the multi-layer coating system to the fuel cell according to FIG. 1, 3 shows a representation corresponding to FIG. 2 of a coating system according to a second exemplary embodiment,
  • FIG. 4 shows a representation of a fuel cell corresponding to FIG. 2 with a coating system held on a carrier element according to a third exemplary embodiment
  • FIG. 5 shows a schematic diagram to explain the fluid flows in the fuel cell according to FIG. 4,
  • FIG. 6 shows a representation corresponding to FIG. 4 of a multi-layer coating system with a carrier element according to a fourth exemplary embodiment.
  • a fuel cell denoted as a whole by 1 in FIG. 1 is a polymer electrolyte membrane (PEM) fuel cell which is designed with a multilayer coating system 2 according to the invention.
  • PEM fuel cell is composed of Qi, Z; Kaufmann A.: “Permormance of 2-Propanol in Direct-Oxidation Fuel Celis", Journal of Power Sources 112 (2002) 121-129, which is expressly referred to with regard to the basic structure and the function of the PEM fuel cell 1 .
  • the coating system 2 is shown in a purely schematic and simplified manner in FIG. The specific configuration of the coating system 2 is explained in detail in the following figures.
  • the coating system 2 is provided on the fuel cell 1, a bipolar plate and/or a gas diffusion position, which are provided in a standard fuel cell, dispensable.
  • the structure of the fuel cell 1 is simplified as a result. However, it is also possible to provide the bipolar plate and/or the gas diffusion layer.
  • the fuel cell 1 has an anode 3 and a cathode 4 .
  • a proton-conducting membrane 5 Directly connected to the anode 3 is a proton-conducting membrane 5, which is made in particular of a perfluorinated copolymer containing a sulpho group as the ionic group.
  • the membrane 5 is arranged between the anode 3 and the cathode 4 .
  • the anode 3 has a catalyst layer 6 for hydrogen oxidation of hydrogen gas.
  • the catalyst layer 6 has a catalyst material suitable for this purpose.
  • the coating system 2 is attached directly to the anode 3, in particular to the catalyst layer 6, and is directly connected to it.
  • an educt collecting tank 7 with an educt inflow opening 8 and an educt outflow opening 9 is provided on the anode side.
  • a hydrogen carrier material in a hydrogen-rich form in particular as a secondary alcohol, is provided as starting material.
  • the coating system 2 is shown in more detail in FIG.
  • the coating system 2 comprises a further catalyst layer 15 comprising a catalyst material for dehydrogenating a hydrogen carrier material.
  • the catalyst layer 15 is also referred to as the first catalyst layer.
  • the catalyst layer 6 is correspondingly referred to as the second catalyst layer.
  • the first catalyst layer 15 is spatially separated from the second catalyst layer 6 by a barrier layer 16 .
  • the barrier layer 16 is formed by a microporous layer of polytetrafluoroethylene (PTFE) mixed with carbon particles.
  • the barrier layer 16 prevents hydrogen carrier material from being able to reach the anode 3 and in particular the second catalyst layer 6 .
  • the barrier layer 16 is permeable to hydrogen gas.
  • the first catalyst layer 15 is arranged on the outside. Along a thickness direction 17, the barrier layer 16, the anode 3 with the second catalyst layer 6 and the membrane 5 connect.
  • the anode 3 is represented with the second catalyst layer 6 as a homogeneous, continuous layer. It is also conceivable that the second catalyst layer 6 is arranged on the outside of the anode 3 , in particular facing the coating system 2 .
  • the first catalyst layer 15 is arranged facing away from the barrier layer 16 of the fuel cell 1, in particular the anode 3 and/or the membrane 5.
  • the first catalyst layer 15 is arranged facing the educt collection container 7 so that the hydrogen carrier material can come into direct contact with the first catalyst layer 15 .
  • a hydrogen-rich form of a hydrogen carrier material in particular a secondary alcohol, in particular isopropanol, which is also known as 2-propanol, is fed to the fuel cell 1 in an educt collection container 7 .
  • the hydrogen carrier material can be gaseous and/or liquid.
  • the hydrogen-rich form of the hydrogen carrier material is dehydrogenated at the first catalyst layer 15, that is to say it is converted into a hydrogen-poor form, in particular into a ketone, in particular into acetone, with the release of hydrogen gas.
  • the low-hydrogen form of the hydrogen carrier material is discharged from the educt collection tank 7 via the educt outflow opening 9 .
  • the low-hydrogen form of the hydrogen carrier material can then be hydrogenated again, ie enriched with hydrogen, and made available again as hydrogen carrier material for the fuel cell 1 .
  • hydrogen transfer hydrogenation by means of a hydrogen storage material in particular a liquid organic hydrogen storage material (LOHC)
  • LOHC liquid organic hydrogen storage material
  • the transfer hydrogenation of the hydrogen carrier material by means of the hydrogen storage material mentioned reference is made to DE 10 2017 209 891 A1. Because the barrier layer 16 is impermeable to the hydrogen carrier material, only the released hydrogen gas passes through the barrier layer 16 to the anode 3 with the second catalyst layer 6. The hydrogen gas can flow in the direction of thickness 17 through the coating system 2 to the anode 3.
  • the hydrogen gas is provided at an interface of the barrier layer 16 adjoining the anode 3 , in particular the second catalyst layer 6 .
  • the hydrogen gas dissociates on the anode side and is oxidized to two protons H + each, giving off two electrons e'. These protons diffuse through the membrane 5.
  • oxygen is reduced by the electrons e', which could perform electrical work in an external circuit.
  • Water is formed together with the protons H + transported through the membrane 5 .
  • anode 3 and cathode 4 are connected to electrical consumer 18 .
  • An electric motor serves as the electrical load 18 .
  • a second exemplary embodiment of the invention is described below with reference to FIG. 3 .
  • Structurally identical parts are given the same reference numbers as in the first exemplary embodiment, to the description of which reference is hereby made.
  • Structurally different, but functionally similar parts are given the same reference numbers with a suffix a.
  • the coating system 2 according to the second exemplary embodiment additionally has a further barrier layer 19, with a gas diffusion layer 20 made of porous carbon fiber between the barrier layers 16, 19. sem is arranged.
  • the coating system 2 according to the first exemplary embodiment can be expanded by the gas diffusion layer 20 and the further barrier layer 19 and then attached to the fuel cell 1 as shown in FIG. 2 .
  • the coating system 2 comprises the first catalyst layer 15 lying on the outside, with the barrier layer 16 , the gas diffusion layer 20 and the further barrier layer 19 adjoining it along the direction of thickness 17 .
  • the coating system 2--as in the first exemplary embodiment--only has the first catalyst layer 15 and the barrier layer 16, with the gas diffusion layer 20 and the further barrier layer 19 already being provided on the fuel cell 1 before the coating system 2 is applied.
  • Such a structure is common, for example, in a standard PEM fuel cell.
  • FIGS. A third exemplary embodiment of the invention is described below with reference to FIGS. Structurally identical parts are given the same reference numbers as in the first exemplary embodiments, the description of which is hereby referred to. Structurally different but functionally similar parts are given the same reference numbers with a suffix b.
  • the coating system 2b is not attached directly to the anode 3 of the fuel cell 1 as a continuous layer.
  • the coating system 2b has a carrier plate 21 on the underside 22 of which a plurality of hydrogen carrier flow channels 23 are arranged.
  • the carrier plate 21 can be attached directly to the fuel cell, for example, so rest against it and / or with it, in particular directly to be connected.
  • the carrier plate 21 can in particular rest directly on the second catalyst layer 6, on the further barrier layer 19 or on the gas diffusion layer 20 and/or be connected thereto.
  • a fluid flow channel 24 which is formed by the intermediate space between two hydrogen carrier flow channels 23 , is arranged between two adjacent hydrogen carrier flow channels 23 .
  • the hydrogen carrier flow channels 23 each specify a flow direction 25, in particular for the hydrogen carrier material. According to FIG. 4, the direction of flow 25 is oriented perpendicularly to the plane of the drawing.
  • the hydrogen carrier flow channel 23 has a closed flow channel wall in the circumferential direction, which wall is essentially rectangular.
  • the flow channel wall is formed by a U-profile shape of the barrier layer 16b, the open U of the barrier layer 16b being closed by the carrier plate 21.
  • the flow channel wall can also have another closed contour, in particular triangular, pentagonal, hexagonal, octagonal or in another polygonal shape.
  • the contour of the flow channel wall can also be curved at least in sections, in particular round or oval.
  • the support plate 21 and each of the U-shaped barrier layers 16b enclose an internal cavity in which a hydrogen carrier transport layer 26 surrounded by the first catalyst layer 15 is arranged.
  • the coating system 2b with the hydrogen carrier flow channels 23, which are also referred to as webs, and the fluid flow channels 24 can be used as a dehydrogenation attachment on a standard PEM fuel cell a membrane 5, an anode 3 with a second catalyst layer 6, a further barrier layer 19 and a gas diffusion layer 20 are attached.
  • the coating system 2b can be attached in a detachably connectable manner.
  • the hydrogen carrier material is supplied to the hydrogen carrier flow channels 23 in its hydrogen-rich form.
  • the hydrogen carrier material flows through the hydrogen carrier flow channels 23 along the direction of flow 25. Due to the hydrogen carrier transport layer 26, the flow of the hydrogen carrier material is promoted. Because the hydrogen carrier material comes into contact with the first catalyst layer 15 while flowing along the flow direction 25, hydrogen gas is released and the hydrogen carrier material is converted into the hydrogen-poor form.
  • the hydrogen gas can leak out of the hydrogen carrier flow channel 23 in the areas in which the flow channel wall is formed by the barrier layer 16b.
  • the barrier layer 16b prevents the hydrogen carrier material from escaping from the hydrogen carrier flow channel 23.
  • side walls 27 are fastened in one piece to the carrier plate 21 and define the hydrogen carrier flow channels 23 .
  • the side walls 27 are milled from a plate.
  • a hydrogen carrier flow channel 23 and a fluid flow channel 24 are formed between two adjacent side walls 27, in particular alternately.
  • the hydrogen carrier transport layer 26, the first catalyst layer 15, and the barrier layer 16 are sequentially arranged.
  • the coating system 2c in particular the carrier plate 21 with the side walls 27, can be produced in a particularly uncomplicated and cost-efficient manner.
  • the production of the coating system 2c is simplified.
  • the coating system 2c can be made available as a compact unit for upgrading an already existing PEM fuel cell.
  • the carrier plate 21 is made in particular from metal, in particular high-grade steel and/or noble metal.
  • the carrier plate 21 is made in particular from titanium and/or carbon. It is conceivable to use metal foils to produce the carrier plate 21 .
  • the carrier plate 21 can also have plastic material.
  • the wall thickness of the side walls 27 is between 10 gm and 5 mm, in particular between 50 gm and 3 mm, in particular between 100 gm and 2 mm, in particular between 500 gm and 1 mm.
  • the widths of the webs and channels are between 100 gm and 5 mm, in particular between 500 gm and 1 mm.
  • the ratio of the widths of the webs and the channels in relation to the wall thickness of the side walls 27 can be between 5:1 and 1:5, in particular between 3:1 and 1:3, in particular between 2:1 and 1:2 and in particular 1:1 be.
  • an electrolytic capacitor with a coating system according to the invention, the coating system having a catalytically active layer in order to convert the hydrogen carrier material from the hydrogen-poor form into the hydrogen-rich form, ie to hydrogenate it.
  • the PEM fuel cell which can be operated in the reverse direction, can serve as the electrolyzer.

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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un système de revêtement multicouche (2) notamment destiné à être appliqué sur une pile à combustible (1) et comprenant une première couche de catalyseur contenant un premier matériau catalyseur pour la déshydrogénation d'un matériau support d'hydrogène et une couche barrière imperméable au matériau support d'hydrogène.
EP21844012.1A 2021-01-29 2021-12-23 Système de revêtement multicouche notamment destiné à être appliqué sur une pile à combustible et pile à combustible comportant un tel système de revêtement Pending EP4285426A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021200837.2A DE102021200837A1 (de) 2021-01-29 2021-01-29 Mehrlagiges Beschichtungssystem, insbesondere zur Anbringung an einer Brennstoffzelle, sowie Brennstoffzelle mit einem derartigen Beschichtungssystem
PCT/EP2021/087450 WO2022161722A1 (fr) 2021-01-29 2021-12-23 Système de revêtement multicouche notamment destiné à être appliqué sur une pile à combustible et pile à combustible comportant un tel système de revêtement

Publications (1)

Publication Number Publication Date
EP4285426A1 true EP4285426A1 (fr) 2023-12-06

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Application Number Title Priority Date Filing Date
EP21844012.1A Pending EP4285426A1 (fr) 2021-01-29 2021-12-23 Système de revêtement multicouche notamment destiné à être appliqué sur une pile à combustible et pile à combustible comportant un tel système de revêtement

Country Status (4)

Country Link
EP (1) EP4285426A1 (fr)
KR (1) KR20230141810A (fr)
DE (1) DE102021200837A1 (fr)
WO (1) WO2022161722A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19734634C1 (de) * 1997-08-11 1999-01-07 Forschungszentrum Juelich Gmbh Brennstoffzelle zur direkten Verstromung von Methanol
JP4171978B2 (ja) 2002-05-27 2008-10-29 ソニー株式会社 燃料改質器及びその製造方法、並びに電気化学デバイス用電極及び電気化学デバイス
JP4356966B2 (ja) 2002-12-06 2009-11-04 勝 市川 燃料電池
CN101351268B (zh) 2005-12-28 2012-06-13 株式会社日立制作所 具有脱氢作用或加氢作用的催化剂及用该催化剂的燃料电池和氢贮藏、供给装置
US8288055B2 (en) 2009-01-20 2012-10-16 Adaptive Materials, Inc. Fuel cell system having a hydrogen separation member
DE102017209891A1 (de) 2017-06-12 2018-12-13 Forschungszentrum Jülich GmbH Vorrichtung und Verfahren zum Erzeugen von elektrischem Strom

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KR20230141810A (ko) 2023-10-10
DE102021200837A1 (de) 2022-08-04
WO2022161722A1 (fr) 2022-08-04

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