WO2020074165A1 - Demi-cellule pour un dispositif électrochimique - Google Patents

Demi-cellule pour un dispositif électrochimique Download PDF

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Publication number
WO2020074165A1
WO2020074165A1 PCT/EP2019/072497 EP2019072497W WO2020074165A1 WO 2020074165 A1 WO2020074165 A1 WO 2020074165A1 EP 2019072497 W EP2019072497 W EP 2019072497W WO 2020074165 A1 WO2020074165 A1 WO 2020074165A1
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WO
WIPO (PCT)
Prior art keywords
layer
fluid distribution
distribution layer
half cell
basic structure
Prior art date
Application number
PCT/EP2019/072497
Other languages
German (de)
English (en)
Inventor
Jan Hendrik OHS
Original Assignee
Robert Bosch 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 Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2020074165A1 publication Critical patent/WO2020074165A1/fr

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Classifications

    • 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]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • 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
    • H01M8/0234—Carbonaceous 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • 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

  • the present invention relates to the construction of a half cell for a
  • electrochemical device such as B. a PEM, SOFC, high temperature or low temperature fuel cell, an electrolyser or a redox flow battery.
  • Fuel cells or batteries as examples of electrochemical devices are typically used as electrical power sources for the supply of electric motors or machines. Electric drives are increasingly part of a vehicle drive for electric bicycles,
  • Electric cars Electric cars, hybrid vehicles and the like.
  • PEM proton exchange membrane fuel cell
  • Water management in the cathode half-cell is of particular importance, since if the water which is formed at the cathode is not adequately drained off, the catalyst layer is flooded with water in such a way that the performance of the fuel cell breaks down under high electrical currents.
  • Reaction gases together with the water ensures the gas diffusion layer, GDL, which is usually used, and a distribution of these gases even under the land areas of the channel-shaped fluid distributors.
  • GDL gas diffusion layer
  • open porous metal structures have also been used in the layer sequence of the construction of fuel cells in order to improve the distribution and the
  • DE 10 2015 226 753 A1 describes a method for producing a flow plate for a fuel cell with a multiplicity of gas guide webs and with at least one electrically conductive and porous layer unit arranged on the gas guide webs. It is proposed that a geometry and / or a structure of the layer unit be generated during the application of material to the gas guide webs.
  • a half-cell for an electrochemical device is specified according to the features of independent claim 1, which at least partially solves the stated problems.
  • Advantageous embodiments are the subject of the dependent claims and the following
  • the invention is based on the knowledge that a conventional
  • Gas diffusion layer in the structure of a half cell which provides a fluid distribution layer with an open porous basic structure for process fluid supply, with corresponding adjustments in the structure, can be omitted.
  • the present invention provides a half cell for an electrochemical device that includes a catalyst layer for contacting an ion conducting membrane, a fluid distribution layer, and a microporous functional layer.
  • a half cell defines itself as consisting of two or more electrically conductive phases connected in series, between which
  • Load carriers can be exchanged.
  • One of the final stages is a
  • Electron conductor d. H. one electrode, the other an electrolyte.
  • the proton exchange membrane corresponds to the electrolyte and a bipolar plate that can be electrically contacted with an electrically conductive fluid distribution layer represents the electrically conductive phase.
  • the fluid distribution layer is arranged in the half cell such that the fluid distribution layer carries the complete fluid flow of the half cell of the electrochemical device.
  • the gas flow of the process gases is transported together with the process water, which arises during the electrochemical reaction or is also supplied to the process gases, completely within the fluid distribution layer.
  • the half cell of the electrochemical device therefore does not provide any additional channel structure for the fluid flow.
  • the good electrical conductivity of the fluid distribution layer is ensured by a suitable choice of materials for the openly porous ones
  • the basic structure achieves and ensures the electrical current transport from the catalyst layer to a bipolar plate, which is the electrode for the half cell.
  • This fluid distribution structure has an openly porous basic structure and consists of exactly one material. This means that exactly one material is used to build up the structure, which defines the spatial structure of the layer. This basic structure is then optionally coated using additional materials, or materials are introduced into the basic structure in order, for. B. to protect the basic structure against corrosion or to
  • the basic structure has a shape-like morphology over the entire fluid distribution layer. This means that the openly permeable pores which are formed by the openly porous basic structure have only one type of pores which are similar in their three-dimensional shape.
  • the term “pore” includes any shape-defining cavity of the open porous basic structure.
  • An open porous structure has a large number of pores d. H. Cavities, which are connected to one another and / or to an environment in particular in terms of fluid technology.
  • the shape similarity of the morphology therefore does not relate to the size of the pores or the size distributions of the pores, which are different
  • Regions of the layer can have different sizes or size distributions, but rather size-independent morphological criteria such as the type of cells, the arrangement and shape of the cell webs and cell walls.
  • size-independent morphological criteria such as the type of cells, the arrangement and shape of the cell webs and cell walls.
  • Such a shape-like morphology can e.g. B. can be achieved in that the
  • Basic structure is produced using only one production process.
  • the microporous functional layer of the half cell for an electrochemical device is designed such that it directly contacts both the catalyst layer and the side of the fluid distribution layer facing the membrane.
  • This contact is made both electrically and mechanically.
  • the microporous functional layer is primarily defined by its properties, namely good electron transport from the
  • a gas diffusion layer is typically formed from hydrophobized carbon fibers and has a typical thickness of less than 1 mm, more precisely from 0.1 mm to 0.3 mm. Consequently, the half cell without this Gas diffusion layer is built up, be built accordingly smaller and thus with the same performance, for. B. of the entire fuel cell, have a higher volumetric power density.
  • the microporous functional layer be completely between the catalyst layer and the
  • a typical microporous functional layer is made by hydrophobized
  • MPL Carbon particles formed and usually as a microporous layer
  • the microporous functional layer thus collects the electrical current in order to pass it on to the fluid distribution layer, which has a lower specific electrical resistance.
  • microporous functional layer at least partially within the microporous functional layer
  • the microporous functional layer be arranged entirely within the fluid distribution layer. Areas close to the surface of the fluid distribution layer on the side facing the membrane are covered with components of the microporous functional layer within the open pores without any
  • the higher specific electrical conductivity of the fluid distribution structure can also interact particularly advantageously with the microporous functional layer in order to achieve a low total electrical resistance of the half cell and thus low electrical losses.
  • the openly porous basic structure of the fluid distribution layer (6, 8) have a uniform distribution of the size of pores over the entire fluid distribution layer (6, 8).
  • the porosity of the basic structure must be large, which can only be achieved with large pores or cavities.
  • the openly porous basic structure of the fluid distribution layer in the direction of the membrane has a distribution of the size of pores that is uniform over the thickness of the
  • Fluid distribution layer is shifted towards smaller pores.
  • a fluid distribution layer with pores will always have a certain distribution of the size of the pores.
  • the fluid distribution layer is set up in such a way that the distribution of the size of the pores becomes smaller pores in one
  • the openly porous basic structure of the fluid distribution layer in the direction of the membrane has a distribution of the size of pores, which is shifted in steps in the direction of the thickness of the membrane towards smaller pores.
  • This can e.g. B. can be achieved by manufacturing thin layers with shape-like morphology, which have different pore sizes and z. B. are connected to each other via a sintering process.
  • the material of the porous basic structure is electrically conductive. This is already with the
  • the basic structure can also be non-electrically conductive and can be made electrically conductive by coating it with electrically conductive material.
  • the material of the porous basic structure comprises stainless steel or titanium or nitrided titanium or carbon. These materials are for the function as Fluid distribution layer particularly suitable due to its corrosion resistance. The corrosion resistance of the fluid distribution layer can be increased even further by coating the basic structure with suitable materials.
  • the open porous basic structure of the fluid distribution layer can also be realized by means of expanded metals, nets and wire meshes of the materials already mentioned.
  • the fluid distribution layer by means of a coating with a suitable material, for. B. on the basis of PTFE and similar materials, hydrophobic.
  • a suitable material for. B. on the basis of PTFE and similar materials, hydrophobic.
  • the water repellency can also be only in parts of the
  • Fluid distribution layer can be provided.
  • a partial layer of the fluid distribution layer facing the membrane can be made hydrophobic in order to, for. B. at least partially similar to the microporous layer.
  • FIGS. 1 c) and 1 d) Exemplary embodiments of the invention are shown in FIGS. 1 c) and 1 d) and are explained in more detail below.
  • Figures 1 a) and 1 b) serve in comparison with conventional electrochemical devices for a better understanding of the invention. It shows:
  • Figure lb shows a conventional half cell of a PEM fuel cell with a
  • Figure lc a half cell of a PEM fuel cell with a microporous
  • Figures 1 a) to 1 d) show different layer sequences of the construction of half cells of electrochemical devices.
  • the figure la) shows a conventional structure of z. B. a cathode half-cell 9 of a PEM fuel cell, in which the process gases are supplied via a channel structure 5 to the gas diffusion layer 3, 4 in order to be distributed uniformly over the active fuel cell area.
  • the gas diffusion layer would have no reaction gas under the webs of the channel structure and the reaction gas distribution within the catalyst layer would be inhomogeneous.
  • FIG. 1 a it is compressed in FIG. 1 a) parallel to the contact surface between the gas diffusion layer 4 and the channel-web structure 5.
  • the webs of the channel-web structure 5 are typically 0.7 mm to 1 mm extended in the contact surface direction, the backbone of the gas diffusion layer is typically 0.15 mm to 0.3 mm thick.
  • Such a gas diffusion layer 3, 4 typically has two layers.
  • the first layer here referred to as backbone 4
  • backbone 4 is very roughly porous and serves both as a carrier layer for the second layer and that above
  • the second layer is the microporous functional layer 3.
  • the microporous functional layer 3 is typically hydrophobic and regulates, among other things, the water management of the half-cell arrangement. On the one hand, it retains sufficient water in the catalyst layer 2 and the membrane 1, so that they cannot dry out. Secondly, it ensures that at high current densities, the product water is transported away sufficiently quickly and the catalyst layer 2 does not flood. When flooding, the pores in the catalyst layer 2 are full of water, so that the diffusive transport of
  • Oxygen to z. B. platinum catalyst 2 is severely hampered and the cell performance drops.
  • FIG. 1b shows a variation of a conventional cathode half-cell 10 of a PEM fuel cell, in which the process gases are supplied via an open porous basic structure 6, which, for. B. as a net, foam,
  • Wire mesh or expanded metal can be made of stainless steel, titanium or carbon. There are none in such a layer structure of the half cell
  • Channel structures are provided for the supply of process gases. Instead, the reaction gases flow through the open porous structure.
  • Figure lc shows an example of the layer structure according to the invention of a half cell of an electrochemical device, such as. B. a fuel cell or more specifically a PEM fuel cell.
  • the catalyst layer 2 is in direct contact with the ion-conductive membrane 1 on a first side and in direct contact with the microporous functional layer on the second side.
  • Process gases take place in and on the catalyst layer 2, which for this purpose receives the process gases from the microporous layer 3.
  • the water formed on the catalyst layer 2 must be from the microporous
  • microporous functional layer 3, 7 is corresponding to another
  • Embodiment applied directly to the fluid distribution layer 6 and is thus in direct contact with it.
  • Functional layer 3 applied to the fluid distribution layer 6 so that it does not overlap, i. that is, the components of the microporous functional layer 3 do not penetrate into the fluid distribution layer 6.
  • the direct application of the microporous functional layer 3 to the fluid distribution layer 6 achieves the advantageous effect that it is eliminated the gas distribution layer 3, 4 the structure of the half cell becomes smaller and also the costs for a half cell 11, 12 constructed in this way are reduced accordingly, ie without a backbone layer.
  • the fluid distribution layer 6 has a basic structure which is openly porous and electrically conductive.
  • This basic structure can e.g. B. be designed as a metal foam.
  • Open-pore metal foams are produced by casting or powder coating a placeholder structure. After casting, the placeholder is removed using a special process, leaving almost no residue.
  • Metal foams then have a distribution corresponding to the distribution in the placeholder structure.
  • the pore size and thus the porosity of the metal foam can be changed in accordance with the required parameters of the electrochemical device, such as. B. a fuel cell, adjust.
  • Pore distributions can be set by appropriate boundary conditions for foam formation. If the pores have a distribution towards smaller pore sizes, this results in a correspondingly lower porosity and vice versa.
  • Basic structure can be coated with other materials. Furthermore, the partially porous basic structure can be made hydrophobic to a desired extent by a partial or complete coating with hydrophobic materials in accordance with the requirements for the electrochemical device. This can particularly affect partial layers that face the membrane.
  • the microporous functional layers 3, 7 and the fluid distribution layer 6 overlap one another in a partial layer 7. In this exemplary embodiment, too, this means that the microporous functional layer 3, 7 and the fluid distribution layer 6 are in direct contact. Components of the microporous functional layer 3,
  • Fluid distribution layer 6 a gradient in the course of the size distribution of the
  • the part of the fluid distribution layer 6 which is closer to the membrane will have a lower porosity in order to be able to support water management through capillary action and to improve the electrical conductivity of the combination of microporous functional layer 3, 7 and fluid distribution layer 6, because the lower porosity requires a higher density on electrically conductive
  • Structural webs that can absorb the current of the catalyst layer 2.
  • the side of the fluid distribution layer 6 facing away from the membrane 1 should advantageously have a higher porosity in order to allow the flow through the
  • This gradient can be set up in a step-like manner, as indicated in FIG. 8d) with the layer elements 8a, 8b and 8c, or it can have a uniform course from the side near the membrane to the side facing away from the membrane.

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une demi-cellule (11, 12) pour un dispositif électro-chimique, présentant : une couche de catalyseur (2) à mettre en contact avec une membrane conductrice d'ions (1) ; une couche de distributeur de fluide (6, 8), qui est disposée dans la demi-cellule (11, 12), de sorte que la couche de distributeur de fluide (6, 8) porte l'intégralité du flux de fluide de la demi-cellule (11, 12) du dispositif électro-chimique, et qui présente une structure de base à pores ouverts, la structure de base à pores ouverts étant constituée d'un seul matériau, et présentant sur toute la couche de distributeur de fluide (6, 8) une seule morphologie de forme similaire ; et une couche fonctionnelle microporeuse (3, 7), qui est directement en contact aussi bien avec la couche de catalyseur (2) qu'avec la face, tournée vers la membrane (1), de la couche de distributeur de fluide (6, 8).
PCT/EP2019/072497 2018-10-10 2019-08-22 Demi-cellule pour un dispositif électrochimique WO2020074165A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018217258.7A DE102018217258A1 (de) 2018-10-10 2018-10-10 Halbzelle für eine elektrochemische Vorrichtung
DE102018217258.7 2018-10-10

Publications (1)

Publication Number Publication Date
WO2020074165A1 true WO2020074165A1 (fr) 2020-04-16

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WO (1) WO2020074165A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100040926A1 (en) * 2008-06-23 2010-02-18 Nuvera Fuel Cells, Inc. Consolidated fuel cell electrode
DE102015111918A1 (de) * 2015-07-17 2017-01-19 Deutsches Zentrum für Luft- und Raumfahrt e.V. Stromkollektor, Membraneinheit, elektrochemische Zelle, Verfahren zur Herstellung eines Stromkollektor, einer Membraneinheit und einer elektrochemischen Zelle
DE102015226753A1 (de) 2015-12-28 2017-06-29 Robert Bosch Gmbh Verfahren zur Herstellung einer Strömungsplatte für eine Brennstoffzelle

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641586A (en) * 1995-12-06 1997-06-24 The Regents Of The University Of California Office Of Technology Transfer Fuel cell with interdigitated porous flow-field
DE102015213950A1 (de) * 2015-07-23 2017-01-26 Volkswagen Ag Brennstoffzelle und Brennstoffzellenstapel
KR101886492B1 (ko) * 2016-04-26 2018-08-07 현대자동차주식회사 연료전지 스택 및 연료전지 스택 제조 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100040926A1 (en) * 2008-06-23 2010-02-18 Nuvera Fuel Cells, Inc. Consolidated fuel cell electrode
DE102015111918A1 (de) * 2015-07-17 2017-01-19 Deutsches Zentrum für Luft- und Raumfahrt e.V. Stromkollektor, Membraneinheit, elektrochemische Zelle, Verfahren zur Herstellung eines Stromkollektor, einer Membraneinheit und einer elektrochemischen Zelle
DE102015226753A1 (de) 2015-12-28 2017-06-29 Robert Bosch Gmbh Verfahren zur Herstellung einer Strömungsplatte für eine Brennstoffzelle

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