WO2014000984A1 - Dispositif de stockage d'énergie électrique - Google Patents

Dispositif de stockage d'énergie électrique Download PDF

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Publication number
WO2014000984A1
WO2014000984A1 PCT/EP2013/060482 EP2013060482W WO2014000984A1 WO 2014000984 A1 WO2014000984 A1 WO 2014000984A1 EP 2013060482 W EP2013060482 W EP 2013060482W WO 2014000984 A1 WO2014000984 A1 WO 2014000984A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage
contact pins
electrode
air
interconnector plate
Prior art date
Application number
PCT/EP2013/060482
Other languages
German (de)
English (en)
Inventor
Harald Landes
Carsten Schuh
Thomas Soller
Original Assignee
Siemens Aktiengesellschaft
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 Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2014000984A1 publication Critical patent/WO2014000984A1/fr

Links

Classifications

    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid 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
    • Y02E60/10—Energy storage using batteries
    • 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 electrical energy store according to claim 1.
  • ROB Rechargeable Oxide Battery
  • ROBs are usually operated at temperatures between 600 ° C and 900 ° C.
  • oxygen which is supplied to a (positive) air electrode of the electric cell is converted into oxygen ions, transported by a solid electrolyte and brought to the opposite negative electrode (discharge) or transported from the negative electrode via the solid electrolyte to the air side (charging).
  • a reduction or oxidation reaction takes place with a gaseous redox couple, whereby the oxygen taken up or released by the gaseous redox couple is converted by diffusion of the components of the redox couple to a porous redox couple , So gas-permeable and also oxidizable and reducible storage medium is transferred. Due to the high temperatures required for the transport of oxygen in the ceramic electrolyte for this process, the choice of materials for the cell materials used and the construction of the cell parts and the arrangement of the storage medium is very complex. In particular, the individual components suffer after several redox cycles, which are operated at the said operating temperatures.
  • the solution of the problem consists in an electrical energy storage device with a memory cell having the features of claim 1.
  • the memory cell of the electrical energy storage on an air electrode which is in communication with air channels of an air supply device and it further comprises a storage electrode, wherein the two electrodes usually separated from each other by a solid electrolyte.
  • a memory structure adjoins the storage electrode, electrical contacts being applied to the storage electrode.
  • the invention is characterized in that the contacts are designed in the form of a field of separate contact pins. This array of separate pins reduces the total surface area of contactors while increasing the volume available to the active storage material, and thus the ratio of the volume of active storage material to the total volume of the electrical energy storage.
  • the energy density ie the amount of energy per unit volume of the electrical energy storage is increased.
  • This also increases the power density per unit volume of the energy storage, which at the same time leads to a reduction in the cost per stored amount of energy or per stored power.
  • the memory structure per memory cell is designed as a coherent component, which in turn has recesses through which the contact pins extend.
  • the memory structure is inserted with their recesses on the pins.
  • self-service Of course, smaller units of the memory structure can be cut in such a way that they can be arranged around the individual contacts, which would, however, mean a higher assembly outlay.
  • an additional contact network between the contact pins and the storage electrode by means of which a better outflow of the electrons onto the contact pins can take place and by the deformability of which a mechanical relief of local pressure peaks is provided.
  • the diameter of the contact pins is advantageously between 2 mm and 7 mm, more preferably between 3 mm and 4 mm.
  • the cross-section of the contact pins can assume different expedient geometries.
  • a circular, but also an oval or rectangular or polygonal cross-section is expedient.
  • the cross section of the contact pins is particularly relevant for the production of the contact pins per se and the recess of the memory structure.
  • the distance between the contact pins is preferably between 10 mm and 30 mm, more preferably between 17 mm and 21 mm. This distance of the pins is small enough that an undisturbed flow of electrons can be made through the contacts, but at the same time it is large enough to provide as much volume for the memory structure available.
  • the contact pins on rounded heads which rest on the storage electrode.
  • Such a rivet shape similar design may be useful to reduce the mechanical pressure load of the stack structure or the pressure load on the substantially consisting of a ceramic material electrode structure.
  • the memory structure or the other stack components are compensated.
  • a metal net located between the contact pins and the storage electrode eg of nickel helps to limit local pressure forces.
  • the electrical energy store from a plurality of different memory cells, which are combined in total in a stack.
  • the current path in an energy store with a stack which in turn has interconnector plates preferably takes place as follows: First, the current passes through a volume material of a first interconnector plate, continues to flow via contact webs between the air channels of the first interconnector plate to which the air electrode abuts another station is the solid state electrolyte followed by the storage electrode. From here, the electrons flow along the current path into the contact pins of a second interconnector plate and finally into the bulk material of the second interconnector plate. Depending on how many stacks follow each other, the described current path is repeated several times to outer electrodes, the electrons are derived or introduced.
  • FIG. 1 shows a schematic representation of a cell of a rechargeable oxide battery
  • FIG. 2 is an exploded view of a stack viewed from above
  • FIG. 3 is an exploded view of the stack from FIG. 2 viewed from below
  • FIG. 5 shows a plan view of an interconnector plate on the memory side
  • FIG. 6 shows a cross section of the interconnector plate from FIG. 5,
  • Figure 7 is a plan view of a memory structure
  • FIG. 8 shows a cross section through the storage structure according to FIG. 7.
  • a common structure of a ROB is that at a positive electrode 6, which is also referred to as an air electrode, a process gas, in particular air, is blown through a gas supply 20, wherein the
  • Electrode 10 This is connected via a gaseous redox pair, for example a hydrogen-steam mixture, to the porous storage medium in the channel structure.
  • a gaseous redox pair for example a hydrogen-steam mixture
  • a storage structure 9 of porous material on the negative electrode 10 as the energy storage medium, which contains a functionally effective oxidizable material as an active storage material, preferably in the form of iron and / or iron oxide.
  • a gaseous redox couple for example H 2 / H 2 O
  • the oxygen ions transported by the solid electrolyte 7, after being discharged at the negative electrode in the form of water vapor through pore channels of the porous storage structure 9, which is the active Storage material includes transported.
  • the metal or the metal oxide (iron / iron oxide) is oxidized or reduced and the oxygen required for this is supplied by the gaseous redox couple H 2 / H 2 O or transported back to the solid electrolyte.
  • Oxygen transport via a redox couple is referred to as a shuttle mechanism.
  • the advantage of the iron as an oxidizable material, ie as an active storage material in the storage structure 9, is that it has approximately the same rest voltage of approximately 1 V in its oxidation process, such as the redox couple H 2 / H 2 O at a partial pressure ratio of 1, otherwise, there is an increased resistance to oxygen transport through the diffusing components of this redox couple.
  • the diffusion of the oxygen ions through the solid electrolyte 7 requires a high operating temperature of 600 to 900 ° C of the described ROB, but also for the optimal composition of the redox pair H 2 / H 2 0 in equilibrium with the storage material, this temperature range is advantageous.
  • this temperature range is advantageous.
  • the structure of the electrodes 6 and 10 and the electrolyte 7 a high thermal load out but also the memory structure 9, which comprises the active storage material.
  • ROB Reliable and Low-power
  • FIG. 2 shows the structure of a stack, which is viewed from above and is assembled in the order from bottom to top.
  • the stack 2 initially comprises a bottom plate 24, which is optionally composed of a plurality of individual plates, which in turn have functional structures and depressions, for example, for air guidance. This composition of individual plates, which is not described here in detail, to the bottom plate 24, for example, by a brazing process.
  • the base plate 24 has an air supply 20 and an air discharge 22. As already described, 24 non-visible channels for the supply of air are integrated here by the composition of individual plates in the bottom plate. Furthermore, the bottom plate 24 centering pin 29, through which now more
  • an electrode-electrolyte unit 25 which comprises, in particular, the already described positive electrode 6, the solid state electrolyte 7 and the storage electrode 10.
  • This is a self-supporting ceramic structure, to which the individual functional areas such as the electrodes or the solid electrolyte are applied in a thin-film process.
  • a seal 26 which consists for example of a slightly above the operating temperature melting glass frit, which then seals the individual plates of the stack 2 at the operating temperatures of the battery.
  • the next following plate is a so-called inner connector plate 27, which has two functionally effective sides. On its lower side 34, which is visible in FIG. 3, the air supply channels (air ducts 18) (not shown here in detail) are located on the positive electrode 6 of FIG. 3,
  • Memory cell 4 boundaries.
  • On the upper side (memory side 32) has the interconnector plate 27 (not shown in FIG. 2) contact pins 12 which penetrate the memory structure 9 and are introduced into this.
  • the upper side of the interconnector plate 27 in FIG. 2 has the same
  • the contact pins 12 are provided for insertion into the storage medium 9. This side with the contact pins 12 is in each case facing the storage electrode 10 of the storage cell 4.
  • FIG. 2 shows a further level of the sequence of electrode-electrolyte unit 25, seal 26 under a cover plate 28 for the overall construction of the stack 2.
  • a number of further levels of these components can follow, so that a stack usually has between 10 and more layers of memory cells 4.
  • FIG. 3 the same stack 2, which is described in FIG. 2, is shown in the opposite direction.
  • the interconnector plate 27 is now also visible from below, in which case the view is directed to the air side 34, the Air electrode faces (air side 34).
  • the memory cell 4 is thus composed in this example of a quarter of the surface of the respective interconnector plate 27 and the base plate 24 and the cover plate 28 together. Furthermore, the respective cell 4 is formed by a sequence of the respective air side 34, seal 26, electrode-electrolyte unit 25 and again a quarter of the memory side 32 of the base plate 24 and the interconnector plate 27.
  • the air side 34 is supplied with air by the process gas by means of a stack-internal air distribution device (also called a manifold), which is not shown in more detail here, and which encompasses several levels of the stack.
  • a stack-internal air distribution device also called a manifold
  • the supply of the memory side with the gaseous redox couple takes place in this example in that the memory pages of the interconnector plates are open to the environment and the stack is in a container which is filled with water vapor / hydrogen mixture.
  • FIG. 4 shows a cross-section through a memory cell 4, by means of which a current path 14 of the current flowing through the stack is exemplarily illustrated by the dashed line 14.
  • the cell 4 viewed from the top to the bottom, begins with an interconnector plate 27, which has contact webs 19 on its air side, through which in turn the air channels 18 are formed.
  • the electrode-electrolyte unit 25 On the surfaces of the contact webs 19 is applied to the electrode-electrolyte unit 25, the positive electrode (air electrode 6) the solid electrolyte 7 and the negative
  • Electrode called storage electrode 10 includes. On the storage electrode 10 are in turn contact pins 12, through which the current is derived and further led to the bulk material 36 of the interconnector plate 27.
  • FIG. 5 shows the plan view of an interconnector plate 27, with the memory page 32 being looked at.
  • the memory page 32 has the contact pins 12, the protrude from the interconnector plate 27, on.
  • the contact pins 12 can be produced, for example, by milling out the material from the surface of the interconnector plate 27. In principle, however, it is also possible to achieve this by a method, for example by welding,
  • FIG. 6 shows a cross section through the interconnector plate from FIG. 5.
  • FIG. 7 shows a memory structure 9 with recesses 16.
  • the recesses 16 are designed such that the memory structure 9 can be inserted directly into the memory side 32 of the interconnector plate 27 from FIG. 5 and the contact pins 12 run in the recesses 16.
  • the contact pins 12 rest closely against the material of the memory structure 9, but there is a certain amount of play, so that the memory structure 9 can be pushed onto the contact pins 12 without tilting. It may be appropriate that the contact pins are slightly longer than the thickness of the storage disk, so that between the storage electrode and the storage disk or between the storage electrode and the
  • FIG. 8 shows a cross section through the storage structure 9 from FIG.
  • a production of the storage structure can be effected, for example, by a uniaxial or isostatic pressing process of the storage material.
  • a film casting process and an optional lamination of several films one above the other may also be expedient.
  • the recesses 16 are introduced by drilling, punching, erosion, milling and laser, water or particle beam cutting.
  • it may be appropriate to the memory structure by near-net shape manufacturing such as by an extrusion process or by a
  • the diameter of the contact pins between 2 mm and 7 mm, preferably between see 2 mm and 4 mm.
  • the distance between the pins should be between 10 mm and 30 mm.
  • the distance should be between 17 mm and 21 mm.
  • the arrangement of the contact pins 12 need not necessarily take place in regular Cartesian form, as shown by way of example in FIG. In this case, other arrangement patterns may be expedient.
  • the distance and the diameter of the contact pins 12 essentially result from the specific resistances which are to be found in the cell 4 along the current path 14 on the memory side.
  • D is the diameter of the contact surface
  • L is the diameter of the electrode area supplied by this contact. 2. The effective resistance contribution caused by the voltage drop along the contact pin:
  • R 2 p P h (L / D) 2
  • h means the length of the pin.
  • R means the effective sheet resistance of the storage electrode, which, when the contact network rests only on the contact surfaces of the contact pins is given by p / d where

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

Abstract

L'invention concerne un dispositif de stockage d'énergie électrique comprenant un élément accumulateur (4) lequel comporte une électrode à oxygène (6) reliée à des canaux d'air d'un dispositif d'alimentation en air (20), et une électrode de stockage (10), l'électrode de stockage (10) jouxtant une structure de stockage (9), et des contacts électriques étant disposés sur l'électrode de stockage (10), ledit dispositif étant caractérisé en ce que les contacts se présentent sous forme d'un champ de broches de contact séparées (12).
PCT/EP2013/060482 2012-06-29 2013-05-22 Dispositif de stockage d'énergie électrique WO2014000984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012211322.3 2012-06-29
DE102012211322.3A DE102012211322A1 (de) 2012-06-29 2012-06-29 Elektrischer Energiespeicher

Publications (1)

Publication Number Publication Date
WO2014000984A1 true WO2014000984A1 (fr) 2014-01-03

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PCT/EP2013/060482 WO2014000984A1 (fr) 2012-06-29 2013-05-22 Dispositif de stockage d'énergie électrique

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WO (1) WO2014000984A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2894124A1 (fr) * 2014-01-08 2015-07-15 Siemens Aktiengesellschaft Accumulateur d'énergie électrochimique doté d'un matériau d'accumulation chimique externe

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005117192A1 (fr) * 2004-05-28 2005-12-08 Siemens Aktiengesellschaft Cellule de pile a combustible a electrolyte solide a haute temperature et pile a combustible comportant ladite cellule
WO2011070006A1 (fr) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie et procédé d'utilisation d'une batterie
WO2013110506A1 (fr) * 2012-01-25 2013-08-01 Siemens Aktiengesellschaft Empilement pour accumulateur d'énergie électrique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3644385B2 (ja) * 1998-07-10 2005-04-27 株式会社豊田中央研究所 燃料電池用セパレータ及びその製造方法
DE19958405B4 (de) * 1999-12-03 2006-08-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Elektrochemische Zelle
DE102010041019A1 (de) * 2010-09-20 2012-03-22 Siemens Aktiengesellschaft Wiederaufladbare Energiespeichereinheit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005117192A1 (fr) * 2004-05-28 2005-12-08 Siemens Aktiengesellschaft Cellule de pile a combustible a electrolyte solide a haute temperature et pile a combustible comportant ladite cellule
WO2011070006A1 (fr) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie et procédé d'utilisation d'une batterie
WO2013110506A1 (fr) * 2012-01-25 2013-08-01 Siemens Aktiengesellschaft Empilement pour accumulateur d'énergie électrique

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Publication number Publication date
DE102012211322A1 (de) 2014-01-02

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