WO2023208279A2 - Cellule électrochimique et procédé de production d'un composant d'une cellule électrochimique - Google Patents

Cellule électrochimique et procédé de production d'un composant d'une cellule électrochimique Download PDF

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Publication number
WO2023208279A2
WO2023208279A2 PCT/DE2023/100289 DE2023100289W WO2023208279A2 WO 2023208279 A2 WO2023208279 A2 WO 2023208279A2 DE 2023100289 W DE2023100289 W DE 2023100289W WO 2023208279 A2 WO2023208279 A2 WO 2023208279A2
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WO
WIPO (PCT)
Prior art keywords
sintered body
electrochemical cell
channels
component
electrode plate
Prior art date
Application number
PCT/DE2023/100289
Other languages
German (de)
English (en)
Other versions
WO2023208279A3 (fr
Inventor
Sander Ten Hoopen
Paul TEN HOOPEN
Original Assignee
Schaeffler Technologies AG & Co. KG
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 Schaeffler Technologies AG & Co. KG filed Critical Schaeffler Technologies AG & Co. KG
Publication of WO2023208279A2 publication Critical patent/WO2023208279A2/fr
Publication of WO2023208279A3 publication Critical patent/WO2023208279A3/fr

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Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/60—Constructional parts of cells
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0236—Glass; Ceramics; Cermets
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth

Definitions

  • the invention relates to a method for producing a component of an electrochemical cell, in particular an electrolysis cell for producing hydrogen from water.
  • the invention further relates to an electrochemical cell which has flow-conducting contours.
  • Electrochemical cells which include elements for conducting fluids
  • a patent family which includes the documents US 6,232,010 B1, US 6,991,869 B2 and EP 1 214 749 B1. Structures that enable the distribution of gases can then be made, for example, from metal foam or sintered material. Plate-shaped electrodes which are made of a porous material and at the same time provide flow channels of defined geometry are also assumed to be known in principle.
  • a paste can be applied to such a layer, for example, which is dried in the further manufacturing process.
  • Conductive carbon fiber is proposed as a component of a gas diffusion matrix.
  • a current collector in the form of a network made of a metallic material can be located within a gas diffusion layer.
  • DE 10 2016221 395 A1 discloses a biopolar plate and a porous transport layer for an electrolyzer.
  • a comb-like structuring of the bipolar plate in cross section is provided.
  • the bipolar plate has a layer which contains a component selected from Ir, Ru, Rh, Os, their oxides or mixtures thereof.
  • the same components are also mentioned in DE 102016 221 395 A1 as components of the porous transport layer.
  • the use of electrically conductive nanofibers for polymer membrane-based electrolysis is known from EP 3 748 039 A1.
  • the nanofibers are part of a layer system and can be catalytically active.
  • the layer system according to EP 3 748 039 A1 can also comprise several transport layers in addition to a polymer membrane.
  • KR 20200127077 A Another electrolyzer for water electrolysis, which has structures for conducting fluids, is disclosed, for example, in KR 20200127077 A. In this case too, gas diffusion layers and a polymer membrane are present. In addition, sealing structures are described in KR 20200127077 A.
  • the invention is based on the object of achieving progress over the stated prior art in the electrolytic production of hydrogen, taking into account flow and electrical engineering aspects as well as manufacturing engineering aspects.
  • the manufacturing process includes the following steps:
  • Geometric inaccuracies in each individual electrochemical cell and its individual components can add up when assembling a stack, so that in the worst case scenario there is a risk that specified tolerance ranges will be exceeded.
  • a particular role is played here by matching the height of the inner cell components to the height of the frame surrounding these components. This coordination is particularly relevant with regard to the sealing and functionality of the electrochemical cells.
  • specified dimensions in particular the height of the sintered body, must be adhered to exactly. The same applies to the surface quality of the sintered body.
  • the simultaneous fulfillment of both requirements i.e. both the external dimensions including a width and a length as well as the production of surfaces with precisely defined features, is achieved in the present cases by forming processes in the calibration step.
  • the sintered material from which the open-porous transport layer is formed is per se a material which, due to open porosity, provides flow cross sections of a geometrically undefined or irregular shape.
  • the finished electrochemical cell there is therefore in all cases an interaction of geometrically defined, at least partially calibrated contours with geometrically undefined contours.
  • the sintered body is an open-porous body through which fluid can flow.
  • the sintered body preferably has an open porosity in the range of at least 25% by volume, in particular in the range from 25 to 55% by volume, particularly preferably in the range from 27 to 33% by volume.
  • the pore size is preferably predominantly in the macroporous range at > 35 nm.
  • the open-porous sintered body is already designed with contours of at least one channel for the directed passage of a fluid, that is, the operating medium of the electrochemical cell.
  • contours of at least one channel are formed for the directed passage or guidance of a fluid, that is to say the operating medium of the electrochemical cell.
  • the calibration can in principle be carried out in a discontinuous process, in particular by means of a press, and/or in a continuous process, in particular by means of calibration rollers.
  • the electrochemical cell according to the invention has at least one component with flow-conducting channels, the component comprising an open-porous sintered body provided as an open-porous transport layer, which has a contact surface designed as a calibrated surface of a geometrically defined macroscopic shape, which each channel for conducting a in the Fluid located in the electrochemical cell is limited and has an electrode plate.
  • the electrode plate is formed in contact with the contact surface of the sintered body and covers it, so that the electrode plate covers the existing fluid-carrying channels and closes it off on its open side facing away from the sintered body.
  • a fluid-carrying channel is introduced mechanically and designed to be geometrically defined using the tool used for this purpose.
  • Channel cross sections can be arcuate, in particular semicircular, or trapezoidal.
  • Such a channel is preferably designed with a square geometric cross-section, in particular with a geometric cross-section in the form of an isosceles symmetrical trapezoid.
  • the cross section defined at least one channel is therefore formed on that side of the generally flat or plate-shaped sintered body which faces an electrode plate, in particular a monopolar or bipolar plate.
  • Elongated channels are preferably introduced into the surface of the sintered body that is arranged in contact with the electrode plate.
  • Such a channel with a defined geometric cross-section preferably has a depth in the range of 0.2 to 1 mm, in particular in the range of 0.2 to 0.5 mm. Furthermore, a channel of defined cross-section preferably has a width in the range of 0.5 to 1.5 mm, preferably in the range of 0.8 to 1.2 mm.
  • the side walls of a channel with a defined cross section preferably open starting from the channel base as a reference line, with a channel with a trapezoidal cross section having the side walls opening preferably at an angle of 90 ⁇ 15 degrees starting from the channel base as a reference line.
  • a channel with a defined geometric cross-section for the directed guidance of fluid and its arrangement can therefore be seen with the naked eye on the sintered body.
  • a membrane-electrode arrangement containing a preferably polymeric ion exchange membrane and a microporous electrode on each side of the membrane, facing the electrochemical cell, in particular on the membrane-electrode arrangement, there are none in an advantageous embodiment Channels of defined geometry available.
  • the electrodes applied to both sides of the membrane are each at least mesoporous with a pore size ⁇ 50 nm, in particular microporous with a pore size ⁇ 2 nm.
  • the electrodes in particular have a catalytic property.
  • the geometrically structured, calibrated surface of the sintered body in a precisely defined manner can, for example, rest directly on an electrode plate, in particular a monopolar or bipolar plate. In this case, a reduced contact area compared to the membrane side is not a problem due to the much more stable design of the electrode plate compared to the membrane-electrode unit.
  • an electrically conductive grid between the sintered body and the electrode plate, for example in the form of a braid, knitted fabric, fabric, fiber structure, in particular made of metal, or in the form of expanded metal.
  • the sintered body ensures a distance between the electrode plate and the membrane-electrode arrangement of the electrochemical cell, so that damage to the membrane-electrode arrangement caused by the grid is fundamentally excluded.
  • the grid which delimits flow channels together with at least partially calibrated outer contours of the sintered body, provides generously dimensioned free cross sections for liquid and/or gaseous fluids to be passed through.
  • the flow channels of a geometrically defined shape are formed by the sintered body, there are, for example, a plurality of channels connected parallel to one another in terms of flow technology.
  • the individual channels are, for example, open along their entire length to the grid, which contacts the electrode plate.
  • the flow channels can each have a cross section which is delimited on one side directly by the electrode plate.
  • the sintered body can, for example, be made of alloyed or unalloyed titanium, in particular Ti Gr1 (material number 3.7025) or Ti Gr2 (material number 3.7035). This is particularly preferred for the oxygen side, i.e. the anode side.
  • a sintered body made of stainless steel can also be used inexpensively for the cathode side.
  • inlet and outlet openings are able to be formed in the sintered body in such a way that the inflow and outflow directions each enclose a right angle with the longitudinal direction of the channels.
  • all channels can have the same height or channels of different heights can be present.
  • the individual channels do not necessarily run straight. Rather, at least some of the channels can describe kinks or bends, for example, in order to specifically adjust the pressure drop resulting from the flow of fluid.
  • the advantage of the invention lies in particular in the fact that, through a clever combination of geometrically defined structures (fluid-carrying channels) and geometrically undefined structures (pore space that can be flowed through), forces that act in a cell stack, flowing media and electrical currents in such a way in an electrochemical cell as well as in
  • the entire cell stack is distributed so that different components of each cell, in particular its membrane-electrode arrangement and an electrode plate, are exposed to different loads depending on the design of the respective component, taking into account the different electrical and mechanical load capacities. At the same time, there is good flow through the cell in relation to the cell height.
  • FIG. 1 shows a first exemplary embodiment of an electrochemical cell, namely an electrolysis cell, in a sectional view, 2 components of a known embodiment of an electrochemical cell,
  • FIG. 5 in a perspective view of another design option
  • FIG. 7 and 8 are a schematic representation of various plate-shaped sintered bodies, each of which has channels that extend from one end face to the opposite end face of the sintered body,
  • a stack 1 of electrochemical cells 2 shown only in part in the figures, is a stack of no further Electrolysis plant shown for hydrogen production.
  • a stack 1 of electrochemical cells 2 shown only in part in the figures, is a stack of no further Electrolysis plant shown for hydrogen production.
  • the electrolysis stack 1 comprises a plurality of electrode plates 3, which are arranged in mutually parallel planes and separate a half cell of a first electrochemical cell 2, that is, an electrolysis cell, from a half cell 5 of a further cell 2.
  • a membrane-electrode arrangement 6 that separates its half-cells 4, 5 from each other.
  • Components of the membrane-electrode arrangement 6 are an electrode 7 with open microporosity, a membrane 8 in the form of a polymeric ion exchange membrane, and an electrode 9 with open microporosity.
  • the membrane-electrode arrangement 6 is contacted on both sides by a porous transport layer 10, which in the present cases is designed as a sintered body 10.
  • Figure 2 shows a known embodiment of an electrochemical cell 2, in which there are no geometrically defined channels between a sintered body 10 and the electrode plate 3.
  • a grid 12 is inserted between the sintered body 10 and the electrode plate 3.
  • FIG. 3 shows an embodiment according to the invention in which geometrically defined channels 11 are present between the sintered body 10 and the electrode plate 3.
  • the sintered bodies 10, i.e. macroporous bodies, can be designed differently on the anode side and cathode side, with Ti 1 (material number 3.7025) and Ti 2 (material number 3.7035) being particularly suitable for producing the sintered body 10 in both cases.
  • the sintered body 10 delimits fluid-conducting channels 11, which have a geometrically defined shape and enable the flow of a fluid containing gaseous and/or liquid components through the electrochemical cell 2.
  • opening cross sections can be provided through the porous transport layer 10 and/or through the grid 12.
  • the grid 12 which is present, for example, in the form of expanded metal
  • flow cross sections of a geometrically defined shape are in any case given.
  • the transport layer 10 a combination of openings of a geometrically undefined shape, due to the open porosity, with geometrically defined opening cross sections due to channels 11 is possible.
  • the channels 11 shown in cross section have a groove shape, which is given by the structuring of the porous transport layer 10.
  • the adjacent channels 11 are covered by an electrode plate 3.
  • the height of the sintered body 10 is indicated by H.
  • the cell height of the electrochemical cell 2, indicated by HZ, results from twice the height H, the thickness of the electrode plate 3 and the thickness of the membrane-electrode arrangement 6.
  • the views chosen in the figures do not contain any information about the orientation of the cells 2 in space.
  • the electrode plates 3 as well as the channels 11 can be aligned vertically.
  • Geometric inaccuracies of each individual electrochemical cell 2 and its individual components can add up when assembling the stack 1, so that in the worst case scenario there is a risk that predetermined tolerance ranges will be exceeded.
  • a particular role is played here by matching the height of the inner cell components to the height of the frame surrounding these components. This coordination is particularly relevant with regard to the sealing and functionality of the cells 2.
  • the sintered body 10 lies against the membrane-electrode arrangement 6 almost over its entire surface, without recesses of a geometrically defined shape. In this way, both a high current-carrying capacity and the mechanical stress on the membrane-electrode arrangement 6 are minimized.
  • the electrode plate 3 On the opposite side of the sintered body 10 is the electrode plate 3, which is comparatively strong mechanically, so that flat contact at this point is of minor importance as long as there is sufficient electrical conductivity.
  • particularly large free flow cross sections are present, since these are due, on the one hand, to the groove structure of the sintered body 10 and, on the other hand, to the electrically conductive, here metallic grid 12, which is arranged in a sandwich-like manner between the sintered body 10 and the electrode plate 3. are formed.
  • each channel 11 is generally designated y.
  • a web of width x remains between two adjacent channels 11.
  • the height of the channels 11 is indicated by h, with different channel heights h1, h2 of different channels 11, 13 running parallel to one another being given in the case of FIG. 6.
  • the channel cross sections specified by the sintered body 10 can be arcuate, in particular semicircular, or trapezoidal (FIG. 4). In the latter case, the angle between flanks of channel walls is given as a. The angle a in this case is 90° ⁇ 15°.
  • all channels 11 extend from one end face of the overall cuboid sintered body 10 to the opposite end face of the sintered body 10.
  • the channels 11 can have a straight shape, as in Figure 7 sketched.
  • channels 11 with kinks 14 may be present.
  • FIGS. 9 to 11 A further group of exemplary embodiments, which is illustrated in FIGS. 9 to 11, enables the inflow and/or outflow of a medium perpendicular to the orientation of the channels 11, 13.
  • openings 15 are present, which, based on the arrangement according to Figures 9 to 11, on the top and/or bottom of the plate-shaped sintered body 10. In these cases there are no front openings. Instead, as indicated in Figures 10 and 11, cross-connections can be present between the channels 11, which run essentially parallel to one another.
  • 3 electrode plate especially monopolar plate or bipolar plate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention concerne un procédé pour produire un composant d'une cellule électrochimique (2) et une cellule électrochimique (2), en particulier une cellule d'électrolyse, comprenant au moins un composant comportant des canaux (11, 13) de guidage d'écoulement, ce composant comprenant un corps fritté (10) à pores ouverts conçu sous la forme d'une couche de transport à pores ouverts, présentant une surface de contact conçue sous la forme d'une surface calibrée, qui délimite chaque canal (11, 13) pour guider un fluide, ainsi qu'une plaque d'électrode (3).
PCT/DE2023/100289 2022-04-27 2023-04-21 Cellule électrochimique et procédé de production d'un composant d'une cellule électrochimique WO2023208279A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022110126.6A DE102022110126A1 (de) 2022-04-27 2022-04-27 Elektrochemische Zelle und Verfahren zur Herstellung eines Bauteils einer elektrochemischen Zelle
DE102022110126.6 2022-04-27

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WO2023208279A2 true WO2023208279A2 (fr) 2023-11-02
WO2023208279A3 WO2023208279A3 (fr) 2024-04-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6232010B1 (en) 1999-05-08 2001-05-15 Lynn Tech Power Systems, Ltd. Unitized barrier and flow control device for electrochemical reactors
DE102016221395A1 (de) 2016-10-31 2018-05-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Bipolarplatte und poröse Transportschicht für einen Elektrolyseur
KR20200127077A (ko) 2019-04-30 2020-11-10 아크로랩스 주식회사 액체흐름 구조 고효율 수전해스택
EP3748039A1 (fr) 2019-06-07 2020-12-09 Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. Nano-fibres électro-conductrices pour une électrolyse à base de membrane polymère

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3564135D1 (en) * 1984-01-26 1988-09-08 Bbc Brown Boveri & Cie Bipolar plate for an apparatus made of a stack of electrochemical cells with solid electrolyte, and its manufacturing process
JP7133171B2 (ja) * 2018-07-27 2022-09-08 国立大学法人東京工業大学 電気化学セル、電気化学セル用の支持体及び電気化学セルの製造方法
CN112838232B (zh) * 2019-11-22 2023-03-31 西部金属材料股份有限公司 一种全通孔金属纤维烧结体燃料电池双极板及燃料电池堆

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6232010B1 (en) 1999-05-08 2001-05-15 Lynn Tech Power Systems, Ltd. Unitized barrier and flow control device for electrochemical reactors
EP1214749B1 (fr) 1999-05-08 2005-03-30 Lynntech, Inc. Dispositif a fonctions de barriere et de regulation du flux unifiees, pour reacteurs electrochimiques
US6991869B2 (en) 1999-05-08 2006-01-31 Lynntech Power Systems, Ltd. Unitized barrier and flow control device for electrochemical reactors
DE102016221395A1 (de) 2016-10-31 2018-05-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Bipolarplatte und poröse Transportschicht für einen Elektrolyseur
KR20200127077A (ko) 2019-04-30 2020-11-10 아크로랩스 주식회사 액체흐름 구조 고효율 수전해스택
EP3748039A1 (fr) 2019-06-07 2020-12-09 Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. Nano-fibres électro-conductrices pour une électrolyse à base de membrane polymère

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DE102022110126A1 (de) 2023-11-02

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