WO2022122080A1 - Tôle formant électrode destinée à une batterie redox et batterie redox - Google Patents

Tôle formant électrode destinée à une batterie redox et batterie redox Download PDF

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Publication number
WO2022122080A1
WO2022122080A1 PCT/DE2021/100978 DE2021100978W WO2022122080A1 WO 2022122080 A1 WO2022122080 A1 WO 2022122080A1 DE 2021100978 W DE2021100978 W DE 2021100978W WO 2022122080 A1 WO2022122080 A1 WO 2022122080A1
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WO
WIPO (PCT)
Prior art keywords
electrode sheet
redox flow
embossed elements
electrode
embossed
Prior art date
Application number
PCT/DE2021/100978
Other languages
German (de)
English (en)
Inventor
Wente ZENG
Pia SUESS
Thomas Motz
Richard Baier
Hanna WINTER
Günter Schmitt
Ladislaus Dobrenizki
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 WO2022122080A1 publication Critical patent/WO2022122080A1/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
    • H01M8/02—Details
    • 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 invention relates to an electrode sheet suitable for use in a redox flow cell and to a redox flow cell.
  • a redox flow cell uses chemically stored energy to generate electrical energy via redox reactions, where electrolyte solutions used for energy storage flow through the redox flow cell.
  • the electrolytes which each flow through a half-cell of the redox flow cell, are also referred to as catholyte and anolyte.
  • the catholyte also referred to as posolyte
  • the anolyte also referred to as negolyte
  • a redox flow battery can be constructed from a large number of redox flow cells in a manner that is in principle comparable to an accumulator.
  • a fundamental advantage of a redox flow battery compared to an accumulator is that the capacity and electrical output of a redox flow battery can be scaled independently of one another, since the electrolyte solutions are kept ready in tanks in the case of a redox flow battery, whose size is independent of the geometry and number of redox flow cells.
  • a common feature of an electrochemical cell, as used in accumulators, and a redox flow cell is a membrane or ion exchange membrane, which is permeable in a defined way for certain ions or molecules, but impermeable to electrons. Ions or molecules that penetrate the membrane of a redox flow cell, i.e. migrate from one half-cell to the other half-cell, can give off or take up electrons at electrodes located in the half-cells, which represents an oxidation or reduction.
  • the electrodes can be designed in particular as walls of the half-cells.
  • electrode sheets can be used which have a half cell of the first type, that of a first ten redox flow cell is attributable, delimited by a half-cell of the second type, which is attributable to a further redox flow cell.
  • each electrode sheet with the exception of the sheets located on the two outer sides of the stack, is therefore on one side of the catholyte and on the opposite side of the anolyte when the redox flow battery is in operation flows around. Different reactions therefore take place on the two sides of each electrode sheet. Accordingly, in this case one speaks of bipolar plates. Only the two electrode plates, which delimit the stack to the outside, represent monopolar plates.
  • WO 2018/146282 A1 discloses an electrode which is intended for use in a redox flow battery and delimits a flow channel. In this case, individual flow cross sections are separated from one another by barriers formed by the electrode.
  • Electrode 2009 018 028 B3 Another electrode for redox batteries is disclosed in DE 10 2009 018 028 B3.
  • the electrode consists of a metallic carrier, a porous sintered metal layer and a thin electrically conductive graphite layer.
  • a total of four pumps are provided in the redox battery according to DE 10 2009 018 028 B3 for pumping around an oxidizing and a reducing electrolyte.
  • a redox flow battery described in DE 10 2018 119 930 A1 works with only two pumps, with the two pumps being able to be driven via a common drive motor.
  • An electrode sheet known from DE 84 13 919 U1 for use in electrolytic liquids has a core sheet, in particular copper sheet, to which cover layers are applied by roll cladding.
  • the electrode sheet should, for example, be deformable in such a way that it can be used in a multiple kinked form as an insert for a liquid-tight pan.
  • Various redox-active components for redox flow cells are known from DE 10 2015 010 083 A1.
  • the redox-active components can be dissolved or dispersed in an electrolyte solvent, in which case conducting salts and other additives can also be dissolved.
  • a possible mechanical structure of a redox flow battery is described in WO 2020/127207 A1.
  • aluminum profiles can be provided as sealing elements or clamping tubes.
  • JP 2005 166 380 A2 discloses a method for producing an oxide-ceramic solid electrolyte film having dome-shaped bulges for use in a fuel cell or an electrolyzer, the solid electrolyte film having fluid-permeable electrode layers applied to both sides, which are electrically connected to flat Current collector plates are connected.
  • the invention is based on the object of further developing an electrode sheet suitable for use in a redox flow cell compared to the prior art mentioned, in particular with regard to manufacturing aspects, while at the same time aspects of flow technology should be sufficiently taken into account.
  • an electrode sheet having the features of claim 1 .
  • the electrode sheet intended for use in a redox flow cell has an embossed structure which comprises a multiplicity of individual embossed elements spaced apart from one another, which are raised embossed elements and recessed embossed elements of a uniform basic shape.
  • the design of the elevations and depressions as embossing elements enables rational shaping without cutting.
  • the same flow conditions can be created on both sides of the electrode sheet, which allow electrolyte solution to flow around a surface that is large compared to the base area of the electrode sheet.
  • An electrode sheet is a self-supporting, fluid-impermeable structure made of metal or a metal alloy, in particular steel, in particular high-grade steel, preferably of the type 1.4404, titanium, a titanium alloy or bronze, in particular the composition CuSn6.
  • the embossed elements also have a mechanically stabilizing function in numerous embodiments.
  • the embossing elements can be arranged in such a way that there is no straight line lying in the plane of the electrode sheet which runs exclusively through non-formed areas of the electrode sheet. Such a straight line would represent a line along which the electrode sheet can be easily bent or bent.
  • the elevations and depressions are distributed on the electrode sheet in such a way that the electrode sheet cannot be unrolled geometrically in any way, not even partially.
  • the various embossed elements are arranged, for example, alternately in a longitudinal direction of the electrode sheet.
  • the longitudinal direction is understood to mean the direction of flow of the electrolytes within the fully assembled redox flow cell.
  • Each bipolar plate which includes precisely one electrode sheet, can be equipped with means for sealing the fluid spaces, ie the cavities of the half-cells through which the electrolyte can flow. Furthermore, even before the individual redox flow cells are assembled to form a redox flow battery, each electrode sheet can be mechanically connected to a membrane as part of a bipolar plate. The same applies to electrode sheets that are part of a monopolar plate.
  • embossed elements of the same type can each be arranged in rows, with mutually parallel rows of embossed elements forming an acute angle with respect to the longitudinal direction mentioned. Irrespective of the shape and arrangement of the individual embossed elements, in a preferred embodiment these merge into the flat base surface of the electrode sheet without kinks. This avoids both mechanical stress peaks within the electrode sheet and dead spaces in which the flow of the electrolyte solution is impeded. Rather, the embossed elements ensure a comprehensive, turbulent flow of the electrolyte.
  • the embossed structure is in particular such that the height of the embossed elements is greater than the sheet thickness of the electrode sheet. A particularly favorable ratio between mass and stability of the electrode sheet can thus be achieved with a very pronounced flow-guiding effect at the same time.
  • the height of each embossed element is at least three times the thickness of the electrode sheet.
  • the various embossed elements each describe a convex or concave dome shape, that is to say at least approximately a spherical shape.
  • the embossed elements are each designed in the form of a three-armed star.
  • each embossing element can have a cylindrical section as the first arm and a torus section which extends from this section and through which the two further arms are formed.
  • a preferred direction is given by the cylindrically shaped arm, which corresponds in particular to the direction of flow of the electrolyte solution.
  • the arm which is cylindrical in shape at least in sections, can be the longest of the three arms.
  • the individual, star-shaped embossed elements can be placed on the electrode sheet in such a way that there are overlaps between the embossed elements both in the longitudinal direction and in the transverse direction of the electrode sheet, which gives the electrode sheet overall particularly high mechanical stability and at the same time an aerodynamically optimized design of the redox flow cell favored.
  • Another possible configuration of the electrode sheet includes embossing elements that form a hexagonal pattern.
  • embossing elements that form a hexagonal pattern.
  • such a pattern can be produced with relatively simple embossing tools, whereby rounded transitions between the individual embossed elements and the base area of the electrode sheet can also be formed in this case.
  • a redox flow cell comprising at least one electrode sheet according to the invention.
  • a redox flow battery is formed comprising a plurality of redox flow cells.
  • the redox flow cell comprises at least two electrode plates, a first reaction space and a second reaction space, each reaction space being in contact with one of the electrode plates and the reaction spaces being separated from one another by an ion exchange membrane.
  • a three-dimensional deformation of this membrane itself is neither intended nor necessary. Rather, the membrane that separates the first reaction space from the second reaction space is of planar design, so that the surfaces of the membrane that are in contact with the electrolyte(s) (posolyte, negolyte) form parallel surfaces.
  • two redox flow cells which are delimited by one and the same electrode sheet, can be electrically connected in parallel. All in all, the electrode sheet enables a wide variety of variants of series and parallel connections of redox flow cells.
  • FIG. 1 shows a first exemplary embodiment of an electrode sheet for a redox flow cell
  • FIG. 2 shows a second exemplary embodiment of an electrode sheet for a redox flow cell
  • FIG. 3 shows a third exemplary embodiment of an electrode sheet for a redox flow cell
  • FIG. 4 shows the electrode sheet according to FIG. 1 in a sectional view
  • FIG. 7 shows a detail of the electrode sheet according to FIG. 3,
  • FIG. 9 shows a single embossed element of the electrode sheet according to FIG. 3, 10 shows an exploded view of a stack of a redox flow battery made up of a large number of flow plates, each of which has an electrode sheet,
  • FIG. 11 shows a detail of the arrangement according to FIG. 10,
  • FIG. 12 shows the distribution of dome-shaped embossed elements on the base area of an electrode sheet of the redox flow battery according to FIG. 11 in a symbolized representation
  • FIG. 13 shows a redox flow cell or a redox flow battery with a redox flow cell in a schematic representation.
  • An electrode plate marked 1 is provided for use in a redox flow cell (compare FIG. 13) which is not shown in more detail in FIGS.
  • the electrode sheet 1 is made of sheet steel and can be connected to a single-layer or multi-layer coating in a manner that is not shown. Electrode sheet 1 is surrounded by electrolyte within the redox flow cell.
  • the electrode sheet 1 is part of a flow plate 15, a multiplicity of flow plates 15 together with two end plates 22 forming a stack 20 of a redox flow battery.
  • Each flux plate 15 has a flux frame 16 and a cover plate 17 for holding a single electrode sheet 1 .
  • opening cross sections 21 are formed through flow plates 15 , which are arranged such that the electrolyte solution flows in a defined manner through the cavities formed between electrode plates 1 and membranes 19 .
  • the electrolyte flowing around the electrode sheet 1 is influenced by an embossed structure 2 of the electrode sheet 1 .
  • the embossed structure 2 is formed by a multiplicity of individual embossed elements 3, 4 spaced apart from one another.
  • the embossed elements 3, 4 are raised embossed elements 3 and recessed embossed elements 4 of the same shape.
  • the terms "raised” and “recessed” depend on the point of view of the viewer and are used without limitation of generality.
  • Viewed from each side of the electrode sheet 1, the embossed structure 2 has the same shape.
  • the embossed structure 2 not only plays a role with regard to the flow dynamics, but also with regard to the mechanical stability of the electrode sheet 1 . As the name embossed structure already expresses, this is created by embossing, i.e. a transforming process.
  • the entire electrode sheet 1 has an approximately uniform thickness t.
  • the height of each embossed element 3, 4 is denoted by h and is at least 3 times and at most 20 times the thickness t.
  • the overall thickness D of the electrode sheet 1, including the embossed elements 3, 4, is at least 7 times and at most 41 times the sheet thickness t.
  • the proportion of the surface of the electrode sheet 1, which is occupied by the embossing elements 3, 4, accounts for more than 30% in all exemplary embodiments, and even more than 80% in the exemplary embodiments according to FIGS.
  • the embossed elements 3, 4 are in the form of dome-shaped elevations or depressions. Each embossed element 3, 4 approximately represents a hemisphere.
  • FIG. 1 a plan view of the electrode sheet 1
  • several V-shaped arrangements are formed by the raised embossed elements 3.
  • FIG. The same applies to the deepened embossed elements 4.
  • each type of embossed elements 3, 4, several V-shaped arrangements of embossed elements 3, 4 are put together, so that overall zigzag-shaped arrangements of similar embossed elements 3, 4 result. If you look at each V-structure formed by similar embossed elements 3, 4 as an arrow, the electrolyte flows in the direction of the arrow or against the direction of the arrow.
  • the direction of flow of the electrolyte is denoted by FE and should be understood as the main direction of flow.
  • FE The direction of flow of the electrolyte
  • VS designates a V structure formed by the embossed structure 2 . This also applies to the exemplary embodiment according to FIG.
  • the exemplary embodiment according to FIG. 2 differs from the exemplary embodiments according to FIGS. 1 and 3, among other things, in that a line structure LS is formed by the embossed elements 3, 4.
  • embossed elements 3, 4 of the first type are arranged in a straight row, which runs through the entire electrode sheet 1 and is arranged at an angle to the direction of flow FE of the electrolyte.
  • a row of embossing elements 4, 3 of the other type is arranged parallel to this row.
  • Each individual embossed element 3, 4 of the electrode sheet 1 according to FIG. 2 has a shape referred to as a crowfoot, which is aligned in the direction of flow FE.
  • the so-called crowfoot which is formed by the embossing element 3, 4, describes the shape of a three-armed star.
  • This has a first arm 6, to which two further arms 7, 8 connect.
  • the main component of the first arm 6 is a cylindrical section 9.
  • the cylindrical section 9 includes a if there is still a spherical transition section 10 to be attributed to the first arm 6 , which merges into the base surface 5 at the end of the arm 6 . All transitions of the arms 6, 7, 8 in the base 5 are rounded.
  • the two arms 7, 8 of the embossing element 3, 4 together form a torus section 11.
  • the center point of the torus described by the arms 7, 8 lies outside the embossing element 3, 4.
  • the torus section 11 also ends in the form of spherical transition sections 12 which close off the arms 7, 8.
  • the various crowfoot-like embossed elements 3, 4 are, as can be seen in particular from FIG. Because any such straight line that could represent a buckling line is avoided, the electrode sheet 1 according to FIG. 2 has a particularly high mechanical stability. At the same time, this ensures that electrolyte cannot pass through the electrode sheet 1 on a flat surface of the electrode sheet 1 in the direction of flow FE, which contributes significantly to the turbulent flow of the electrolyte solution.
  • a raised embossed element 3 always alternates with a recessed embossed element 4 in the direction of flow FE.
  • embossed elements 3, 4 are designed as hexagonal elements, resulting in an overall visual impression pronounced of a honeycomb structure.
  • Each embossed element 3 , 4 has six side surfaces 13 which are inclined relative to the base surface 5 of the electrode sheet 1 and which adjoin a central end surface of the embossed element 3 , 4 which is designated 14 .
  • the width of the end surface 14 is denoted by a.
  • the overall width of the embossed element 3, 4 is twice this, ie 2a, and deviates from the overall thickness D of the electrode sheet 1 by no more than 40%.
  • the overall width 2a of each embossing element 3, 4 is less than the overall thickness D of the electrode sheet 1.
  • this exemplary embodiment is characterized in that the base area 5 takes up only a particularly small part of the electrode sheet 1 .
  • An angle a is enclosed between two opposing side surfaces 13 of the embossing element 3, 4, which is 60° in the exemplary embodiment.
  • a side surface 13 of a raised embossed element 3 and a side surface 13 of an adjacent recessed embossed element 4 lie, as can be seen from FIG. 8, in parallel spaced apart planes.
  • the individual embossed elements 3, 4 have a spherical basic shape, just as in the exemplary embodiment according to FIG. In contrast to the exemplary embodiment according to FIG. 1, however, the embossed elements 3, 4 are arranged in the form of rows and columns, as shown in abstract form in FIG . The centers of the individual embossed elements 3, 4 lie on the crossing points of a grid which is formed by equidistant lines crossing at right angles. As far as the integration of the electrode sheet 1 in the flow plate 15 and the design of the entire stack 20 of the redox flow battery is concerned, the exemplary embodiment according to FIGS.
  • FIG. 13 shows a redox flow cell 80 or a redox flow battery with a redox flow cell 80 in a schematic representation.
  • the redox flow cell 80 here comprises two electrode plates 1a, 1b, a first reaction space 90a and a second reaction space 90b, each reaction space 90a, 90b being in contact with one of the electrode plates 1a, 1b.
  • the electrode sheets 1a, 1b are integrated into a flux plate, not shown.
  • the reaction spaces 90a, 90b are separated from one another by an ion exchange membrane 19.
  • a liquid anolyte 91a is pumped from a tank 93a via a pump 92a into the first reaction space 90a and passed between the electrode plate 1a and the membrane 19 .
  • a liquid catholyte 91b is pumped from a tank 93b via a pump 92b into the second reaction chamber 90b and passed between the electrode plate 1b and the membrane 19. An ion exchange takes place across the membrane 19 away, electrical energy being released due to the redox reaction at the electrode sheets 1a, 1b.
  • FIG. 13 is only intended to show how a redox flow cell with a membrane 19 works. However, structures with at least 10 or more membranes 19 are possible.
  • Embossed structure raised embossed element, recessed embossed element, base area

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une tôle formant électrode (1, 1a, 1 b) pour batterie redox (80), qui présente une structure estampée (2), laquelle comprend une pluralité d'éléments estampés (3, 4) individuels mutuellement espacés, notamment d'éléments estampés (3) haut et d'éléments estampés (4) bas de forme de base uniforme. L'invention concerne également une batterie redox (80).
PCT/DE2021/100978 2020-12-11 2021-12-07 Tôle formant électrode destinée à une batterie redox et batterie redox WO2022122080A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020133090.1 2020-12-11
DE102020133090.1A DE102020133090A1 (de) 2020-12-11 2020-12-11 Elektrodenblech für eine Redox-Flow-Zelle und Redox-Flow-Zelle

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WO2022122080A1 true WO2022122080A1 (fr) 2022-06-16

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022119436A1 (de) 2022-08-03 2024-02-08 Schaeffler Technologies AG & Co. KG Elektrodenmodul für eine Redox-Flusszelle und Redox-Flusszelle

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8413919U1 (de) 1984-05-08 1984-09-27 Fr. Kammerer GmbH, 7530 Pforzheim Elektrodenblech zur verwendung in elektrolytischen fluessigkeiten
JP2005166380A (ja) 2003-12-02 2005-06-23 Mitsubishi Heavy Ind Ltd 固体電解質膜の製造方法
JP2007142071A (ja) 2005-11-17 2007-06-07 Casio Comput Co Ltd フレキシブル配線基板の熱圧着装置
DE102009018028B3 (de) 2009-04-18 2010-11-18 Horst Hager Elektrode für elektrolytische Prozesse und Redoxbatterien mit dieser
WO2012034042A2 (fr) * 2010-09-09 2012-03-15 California Institute Of Technology Systèmes et procédés de stockage d'énergie électrochimique
JP2017027847A (ja) * 2015-07-24 2017-02-02 三菱電機株式会社 電力貯蔵デバイス
DE102015010083A1 (de) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
DE102015224181A1 (de) 2015-12-03 2017-06-08 Bayerische Motoren Werke Aktiengesellschaft Regenerator eines Redox-Brennstoffzellensystems
WO2018146282A1 (fr) 2017-02-10 2018-08-16 Cmblu Projekt Ag Unité d'électrode à flux et son utilisation, système de batterie à flux redox et son utilisation, procédé de fabrication d'une unité d'électrode à flux, procédé de fonctionnement d'un système de batterie à flux redox
DE102018119930A1 (de) 2018-08-16 2020-02-20 Schaeffler Technologies AG & Co. KG Redox-Flow-Batterie
WO2020127207A1 (fr) 2018-12-18 2020-06-25 Spiraltec Gmbh Batterie enroulée à flux d'oxydoréduction

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8413919U1 (de) 1984-05-08 1984-09-27 Fr. Kammerer GmbH, 7530 Pforzheim Elektrodenblech zur verwendung in elektrolytischen fluessigkeiten
JP2005166380A (ja) 2003-12-02 2005-06-23 Mitsubishi Heavy Ind Ltd 固体電解質膜の製造方法
JP2007142071A (ja) 2005-11-17 2007-06-07 Casio Comput Co Ltd フレキシブル配線基板の熱圧着装置
DE102009018028B3 (de) 2009-04-18 2010-11-18 Horst Hager Elektrode für elektrolytische Prozesse und Redoxbatterien mit dieser
WO2012034042A2 (fr) * 2010-09-09 2012-03-15 California Institute Of Technology Systèmes et procédés de stockage d'énergie électrochimique
JP2017027847A (ja) * 2015-07-24 2017-02-02 三菱電機株式会社 電力貯蔵デバイス
DE102015010083A1 (de) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
DE102015224181A1 (de) 2015-12-03 2017-06-08 Bayerische Motoren Werke Aktiengesellschaft Regenerator eines Redox-Brennstoffzellensystems
WO2018146282A1 (fr) 2017-02-10 2018-08-16 Cmblu Projekt Ag Unité d'électrode à flux et son utilisation, système de batterie à flux redox et son utilisation, procédé de fabrication d'une unité d'électrode à flux, procédé de fonctionnement d'un système de batterie à flux redox
DE102018119930A1 (de) 2018-08-16 2020-02-20 Schaeffler Technologies AG & Co. KG Redox-Flow-Batterie
WO2020127207A1 (fr) 2018-12-18 2020-06-25 Spiraltec Gmbh Batterie enroulée à flux d'oxydoréduction

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