WO2013110509A2 - Accumulateur d'énergie électrique - Google Patents

Accumulateur d'énergie électrique Download PDF

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Publication number
WO2013110509A2
WO2013110509A2 PCT/EP2013/050476 EP2013050476W WO2013110509A2 WO 2013110509 A2 WO2013110509 A2 WO 2013110509A2 EP 2013050476 W EP2013050476 W EP 2013050476W WO 2013110509 A2 WO2013110509 A2 WO 2013110509A2
Authority
WO
WIPO (PCT)
Prior art keywords
electrical energy
plate
air
energy store
electrode
Prior art date
Application number
PCT/EP2013/050476
Other languages
German (de)
English (en)
Other versions
WO2013110509A3 (fr
Inventor
Horst Greiner
Wolfgang Drenckhahn
Johann Rothfischer
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 WO2013110509A2 publication Critical patent/WO2013110509A2/fr
Publication of WO2013110509A3 publication Critical patent/WO2013110509A3/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
    • 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
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • ROB Rechargeable Battery oxides
  • ROBs are usually operated at temperatures between 600 ° C and 800 ° C, in this case oxygen, which is supplied to an air ⁇ electrode of the electric cell, converted into oxygen erstoffionen, transported by a solid electrolyte and brought to the opposite storage electrode. There, a redox reaction takes place, which receives or generates electrical current depending on the charging or discharging process.
  • the object of the invention is therefore to provide an electrical energy storage based on a ROB, which ensures over the prior art, a cost-effective, easy to assemble mounting and temperature-resistant structure of a stack or a memory cell.
  • the solution of the problem consists in an electrical energy storage according to the preamble of claim 1.
  • the electrical energy storage device according to claim 1 comprises a stack, so a stack of a plurality of memory cells, each memory cell having at least two housing plates.
  • a first housing plate comprises a memory cell an air feed.
  • a second housing plate of the memory cell ⁇ comprises a receptacle for a storage medium.
  • the energy store is characterized in that the second hous ⁇ plate of a first memory cell, so the housing plate with the receptacle for the storage medium, as well as the first Ge ⁇ housing plate (with the air supply) of a second memory cell in the form of a single integrated component are shown ,
  • the representation of two different housing plates of two adjacent cells in an integrated component which is thus designed in one piece, will cause the cell h ⁇ len are virtually back to back, the installation effort is thereby significantly reduced.
  • the integrated component is designed plate-shaped and one side of the integrated component ⁇ the first housing plate with the Heilzu ⁇ management (hereinafter called air supply side) of the second memory cell.
  • the other side of the integrated component is designed plate-shaped and one side of the integrated component ⁇ the first housing plate with the Heilzu ⁇ management (hereinafter called air supply side) of the second memory cell.
  • the other side of the integrated component is designed plate-shaped and one side of the integrated component ⁇ the first housing plate with the Heilzu ⁇ management (hereinafter called air supply side) of the second memory cell.
  • Component (the side in which the storage medium is deposited, hereinafter referred to as the memory side) in turn forms the second housing plate of the first memory cell.
  • the memory side the side in which the storage medium is deposited, hereinafter referred to as the memory side
  • the embodiment of the receptacle for the storage medium in the form of depressions which are at least 2 mm deep, offers an advantage over alternative Ausgestal ⁇ tion forms, as a larger storage medium can be introduced into the recess which these wells for the Storage medium is covered by an electrode support structure, which is also sealed from the environment.
  • At least one channel is introduced in the form of a recess which is connected via a bore with an air supply device of the stack.
  • the entire stack is thus supplied via a separate air supply with air, which is passed through fine holes in the channels, which leads the air as a process gas to the corresponding Elekt ⁇ rode, namely an air electrode or a positive Elekt ⁇ rode.
  • an electrode structure is provided, the recording of the storage medium preferably planar covering Compared to the wells of the storage side of the cell are beauts, wherein intended oxygen ions can migrate through the electrode structure for storage of the cell.
  • the water vapor present in the storage side should ideally remain there, however.
  • the electrode structure in this case has a positive electrode (air electrode), a solid electrolyte and a ne gative ⁇ electrode (storage electrode), which are preferably planar are stacked on top of each other and carried over a likewise planar substrate or a substrate structure.
  • the substrate structure on the side of the negative electrode that is the storage electrode is mounted and is in planar connection with this.
  • the at least one channel on the Lucaszu ⁇ driving side in direct contact with the positive electrode, ie the air electrode.
  • a further embodiment of the invention consists in an electrical energy store according to claim 12, wherein in this case a stack, that is to say a stack of individual cells, is configured in a layered manner with a following sequence.
  • First be ⁇ is a base plate with an air supply for the first memory cell.
  • This base plate thus forms the Luftzugot ⁇ side of the first memory cell.
  • Base plate, the electrode structure and the memory side of the integrated component thus form the essential components of the first memory cell. This is followed by a second one
  • Memory cell which is placed on the Lucaszu Bigseite by the remindsei ⁇ te of the integrated component, it follows in turn an electrode structure and a cover plate, which forms the memory side of the second cell.
  • the electrode structure is inserted so that each of the positive electrodes faces the air supply side and the negative electrode faces the storage side.
  • FIG. 1 shows a schematic representation of the mode of operation of an ROB
  • FIG. 2 shows an exploded view for constructing a stack in an ROB
  • FIG. 3 the exploded view from FIG. 2 with opposite viewing direction, FIG.
  • FIG. 4 shows a layer structure for a detailed illustration of a memory cell
  • FIG. 5 shows an integrated component with a view of the air supply side
  • Figure 6 is an integrated component with a view of the memory ⁇ page 7 shows a cross-sectional view of the integrated component
  • FIG. 8 is a plan view of a base plate with air and water supply device
  • FIG. 9 shows an alternative embodiment of the base plate according to FIG. 8,
  • Figure 10 is a cover plate
  • FIGS 11-16 different flow directions of the air supply.
  • a common structure of the ROB is that via a positive electrode, a process gas, in particular air is introduced via a gas supply 28, wherein oxygen is extracted from the air.
  • the positive electrode is hereinafter referred to as an air electrode.
  • the oxygen passes in the form of oxygen ions (0 2 ⁇ ) through a, applied to the positive electrode solid electrolyte 36 to a negative
  • Electrode 38 At the negative electrode is a Speicherme ⁇ dium in the form of a porous material, which was according to Charzu ⁇ (charging / discharging) is present in elemental form or in oxide form, arranged, which is a functional res acting oxidizable material, particularly a Metal, for example iron, contains.
  • the negative electrode is also referred to as a storage electrode, which term will be used hereinafter.
  • a gaseous redox couple for example H 2 / H 2 O
  • the oxygen ions transported through the solid electrolyte are transported or withdrawn through pore channels of a porous body, which serves as storage medium, to the oxidizable material, ie the metal .
  • the metal or metal oxide is oxidized or redu ⁇ sheet and required for this oxygen through the gasför ⁇ -shaped redox couple H 2 -H 2 O supplied, or to the solid state electric ⁇ LYTEN transported back (this mechanism is referred to as shutter mechanism).
  • the visible with respect to the base plate 42 side of the electric storage cell 4 is referred to as the air guide side 18.
  • the base plate 42 has a flat surface 50 on which a seal 46 is placed.
  • the seal 46 consists for example of a glass sheet having the required sealing properties at the ent ⁇ speaking temperatures between 600 ° C and 800 ° C.
  • an electrode structure 22 is placed, in which case the positive electrode 34 points down to the channels 24.
  • An integrated component 16 also referred to as interconnector plate, this term being used hereinafter
  • the interconnector plate 16 again has an air supply side 18 on the rear side, which is analogous to the air supply side
  • the air distribution plate 48 has recesses 56 or 56 ', which serve for the inlet (56) or outlet (56') of the air serving as process gas. Further, the partition plate 48 shipsver ⁇ recesses 58 and 58 ', the What can be ⁇ serdampf conducted into the stack 2, and through which the steam is distributed in the stack. Both the depressions 56, 56 'and the depressions 58, 58' have bores 60 and 62, respectively, which serve to supply the operating medium. The operating medium used in particular the air or the water ⁇ steam or a purge gas.
  • the air which is introduced adjusted via the recesses 56 in the stack thus flows through the recesses 64 in Randbe ⁇ reaching the bottom plate 44 upward.
  • These recesses 64 for air supply have bores 26, which can be seen in the perspective view of Figure 2 and in more detail in Figures 5 and 7. These bores 26 serve to bring the air into channels 24 which are in communication with the air electrode 34.
  • the air is thus diverted from the recesses 64 in the holes 26 and are thus supplied to the corresponding air electrode 34.
  • the described flow direction of the air is merely an exemplary example. Basically, the air can also be directed in the opposite direction. It is also possible through the described air distribution ⁇ plate without considerable technical effort and while maintaining the fundamentally advantageous stack structure with its relatively simple installation to generate a different Luftvertei ⁇ ment, if this should be necessary for thermal reasons.
  • This crossflow can, for example, as shown in Figures 11 to 13, run.
  • one speaks of a direct current when the recesses 13 and the channels 24 as shown in Figure 14, would run parallel on the interconnector plate 16.
  • Figures 15 and 16 a meandering course of the air flow is described, which may be performed in cocurrent or countercurrent.
  • the different flow patterns presuppose corresponding adaptations of the components of the steam supply device and the air supply device 28, which are not explicitly shown in FIGS. 11 to 16.
  • the interconnector plate 16 (or the integrated component 16) is applied, which also from ⁇ savings 64, 64 'which form an air channel with the recesses 64 of the bottom plate 44. Since the air duct according to FIGS.
  • This air duct continues through the interconnector plate also passes through a seal 46, which as well as the bottom plate 44 and the interconnector plate 16 which each have con ⁇ congruent recesses 47 through which the air or water vapor can flow and which also with the air duct form.
  • FIGS. 2 and 3 only one interconnector plate 16 is shown, onto which a so-called cover plate 42 now follows.
  • the cover plate 42 in turn has recesses 66 for the air supply device.
  • the depressions 66 in the cover plate 42 likewise have bores 26 which lead into channels 24, which likewise communicate with the air electrode 34 of an electrical energy storage cell 4, 4 '.
  • the air channel of the stack 2 is thus constructed in such a way that the air flows past the individual memory cells 4 and is branched off through the bores 26 to the respective air electrodes 34 of the individual cells 4.
  • the air is redirected accordingly and by depressions 64 ', which are arranged in this embodiment in the middle of the respective plate so the bottom plate 44, the cover plate 42 or the interconnector plate 16, and in turn form an air ⁇ channel, back directed to the air distribution plate 48.
  • these depressions and this air channel are in connection with the recess 56 'in the air distribution plate and the air is discharged from the stack again via the bore 60'.
  • the depressions 56 therefore serve to supply the air which is introduced into the stack to the individual air ducts and furthermore to the individual storage cells, of which there can be several per stack level (according to the example in FIG. 3 and FIG. 4, there are four storage cells per level).
  • the depression 56 ' serves to collect the air which has been returned from the air ducts and, if appropriate, to discharge it again from the stack.
  • the air from the depression 56 ' can also be recirculated at least partially to the circulation.
  • the entire system for air supply therefore comprises the holes 60, 60 ', the recesses 56, 56', the bores 26 to the channels 24, the recesses 64, 64 'and the recesses 66, 66' together the unnamed air ducts form.
  • This entire system is referred to as air supply device 28.
  • manifold is also used here.
  • Analogous to the just described air supply device 28 will now be discussed on the water vapor supply device 70.
  • Figure 3 should be noted, which in turn is based on the air distribution plate 48, which also has recesses 60, through the stanchions 62, 62 'water vapor or a purge gas can be introduced into the stack.
  • This steam is passed through the recesses 60 in recesses 65 of the bottom plate 44 and the interconnector plate 16. These recesses 65 in turn form an unspecified channel to the water vapor line, a steam channel.
  • the What ⁇ serdampf does not flow as the air in the air passage but the ⁇ What serdampf is preferably stationary front with a pressure of for example 20 mbar relative to ambient pressure.
  • the task of the water vapor channel or of the entire water vapor supply device 70 is, in particular, to keep the water vapor pressure for the storage medium 14 as constant as possible. If the water vapor pressure drops, it can be readjusted from the outside by the steam supply device. be liert.
  • the water vapor channels are in particular in direct communication with the recesses 13 on the memory side 20 of the interconnector plate 16 and with the Speicherme ⁇ dium fourteenth
  • the depressions 58, 58 'in the air distribution plate 48 also serve for distribution onto the steam passages of the stack, which supply each individual storage cell 4 with steam.
  • the special feature of the air distribution plate 48 is that in its ne ⁇ ben the air distribution and the water vapor distribution is integrated, which makes the entire structure of the stack less compli ⁇ edy and simplifies installation.
  • the air distribution plate 48 need not necessarily comprise two or three recesses for the air supply device 28 and water vapor supply device 70, respectively.
  • the air removal from the stack 2 can also take place via a further plate, not shown here, on the opposite side of the air distribution plate 48.
  • the structure described here is very convenient, space-saving and component-saving and very inexpensive to install.
  • FIGS. 8 and 9 the air distribution plate 48 is shown once more in an enlarged view, this being two alternative embodiments of the air distribution plate 48 with the same effect.
  • FIG. 10 shows an enlarged view of the cover plate 42.
  • the water vapor supply device 70 here comprises, in particular, the non-designated water vapor channels formed from the recesses 65 in the bottom plate 44 and the interconnector plate 16 and the depressions 58 and 58 'in the air distribution plate 48 and the holes 62 in the air distribution plate 48th
  • the interconnector plate 16 thus represents in an efficient manner in each case a housing plate of a cell 4 and a second cell 4 '. It has on each side flat surfaces 50 which are suitable for integrally integrated component or by this enclosed cells 4 in a simple and efficiently sealed.
  • each layer of a stack 2 may comprise a plurality of cells 4.
  • the structures for each four memory cells 4 are applied to the bottom plate 42 or the interconnector plate 16 and the cover plate 44.
  • Each layer sequence 54 of bottom plate 44, gasket 46, electrode structure 22 and the interconnector plate 16 thus provides four individual ⁇ ne memory cells 4, 4 '.
  • the stack 2 may of course advantageously include multiple layer sequences 54, 54 'of cells 4 and 4' using a higher number of interconnector plates 16.
  • a number of ten layer sequences 54 of cells 4, 4 'with in each case two to eight cells 4 per layer sequence 54 may be expedient here, taking into account the process-related costs of the distribution of air.
  • FIG. 4 shows a cross-sectional view of a section of a stack 2 in the assembled state, with the individual layers of the electrode structure 22 being shown in more detail here.
  • FIG. 4 shows a highly schematic representation, which is in no way to be considered as true to scale.
  • Broken lines 52 are drawn across the layer structure according to FIG. 4, which are provided on the outside by a curly bracket with the reference symbols 4 and 4 ', these two dashed lines 52, 52' representing the termination of a cell 4 or a layer success 54 ,
  • the dashed lines 50 in this case run transversely through the interconnector plate 16, which, as described, is in each case a component of two successive cells 4, 4 '.
  • the description will now begin from the dashed line 52, it describes a plane which runs parallel to the flat surface 50 through the Intercon ⁇ nectorplatte 16.
  • the channels 24, which are connected via bores 26 with the air supply device 28, not shown in FIG. The air flowing through the passages 24 the air is in direct ⁇ th contact with the air electrode 34 are ionized at the oxygen atoms to oxygen ions, which oxygen ions 0 2 ⁇ migrate through a solid electrolyte 36 to the storage electrode 38.
  • the storage electrode 38 for example of nickel is mixed with the yttrium-reinforced zirconia is placed on a substrate structure 40, which has substantially the same chemical composition as having the storage electrode 38, but with respect ih ⁇ rer porosity and their microstructure from that differs.
  • the substrate structure 40 serves to carry the electrodes 34, 38 or the solid-state electrolyte 36, which have a very thin extension of a few ym. In principle, the substrate structure 40 can also be applied to the air electrode side.
  • the oxygen ions are combined at the porous negative electrode 38 with molecular hydrogen, and oxidized to water.
  • the water diffuses through the pores of the substrate structure 40 for receiving 12 for the storage medium 14.
  • the receptacle 12 for the storage medium 14 is, as shown in more detail in Figure 6, in the form of channel-shaped recesses 13 designed. These recesses 13 have in particular ⁇ a depth of more than 2 mm, preferably about 6-10 mm.
  • pressed pins made of iron or iron oxide are inserted. This iron or iron oxide (depending on the operating state charging or discharging is the oxidized or reduced state before) serves as a storage medium 14.
  • These pressed pins are designed porous, so that the water vapor in all pores and thus reach all surfaces of the storage medium 14 can. Thus prevails in the wells 13 before a steam atmosphere.
  • FIGS. 5-7 show a detailed representation of the interconnector plate 16.
  • the figure 5 shows ei ⁇ NEN view of the air supply side 18 of the interconnector plate 16 which in this embodiment, the air supply is applied for each of four individual memory cells on a plate of the interconnector plate sixteenth
  • the air supply side 18 of the interconnector plate 16 has the individual channels 24, wherein it can be seen that the channels 24 communicate via bores 26 with the entire air supply device 28 of the stack 2.
  • ⁇ form is a single straight running Kanä ⁇ le 24, each having a bore 26 in the entrance and, not shown here, a further bore to the air outlet in have the generally designated air supply device 28.
  • the memory page is to see 20 of the interconnector plate 16, which is disposed on the rear side of the air supply side 18 ge ⁇ Mäss FIG. 4
  • the memory page also has channel-shaped recesses 13, which serve as a receptacle 12 for the storage medium 14, not shown here.
  • the flat sealing surfaces 50 can be seen on the seals 46 are placed and thus seal each side, the air supply side 18 and the Spei ⁇ cherseite 20 against the environment.
  • it is pos ⁇ lich to achieve a high degree of tightness in the wells 13 and thus to ensure a constant content of water vapor in the storage medium.
  • the thermal expansion coefficient of the integrated component ⁇ part is preferably in the vicinity of the expansion coefficient of the substrate structure 40.
  • the coefficient of expansion should te between 12 x 10 ⁇ 6 K -1 - 14 x 10 ⁇ 6 K -1 in particular at

Abstract

L'invention concerne un accumulateur d'énergie électrique comportant un empilement (2) qui comprend plusieurs éléments d'accumulation (4), chaque élément d'accumulation (4) présentant au moins deux plaques de boîtier (6, 8), une première plaque de boîtier (6) comprenant une entrée d'air (10) et une seconde plaque de boîtier (8) présentant une cavité (12) pour recevoir un milieu d'accumulation (14). Ledit accumulateur d'énergie se caractérise en ce que la seconde plaque de boîtier (8) d'un premier élément d'accumulation (4) et la première plaque de boîtier (6) d'un second élément d'accumulation (4' ) sont représentées sous forme d'élément structural intégré (16).
PCT/EP2013/050476 2012-01-25 2013-01-11 Accumulateur d'énergie électrique WO2013110509A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012201066.1 2012-01-25
DE102012201066A DE102012201066A1 (de) 2012-01-25 2012-01-25 Elektrischer Energiespeicher

Publications (2)

Publication Number Publication Date
WO2013110509A2 true WO2013110509A2 (fr) 2013-08-01
WO2013110509A3 WO2013110509A3 (fr) 2013-10-17

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DE (1) DE102012201066A1 (fr)
WO (1) WO2013110509A2 (fr)

Cited By (3)

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WO2014005773A1 (fr) * 2012-07-03 2014-01-09 Siemens Aktiengesellschaft Structure accumulatrice d'un élément d'accumulation d'énergie électrique
WO2014048724A1 (fr) * 2012-09-25 2014-04-03 Siemens Aktiengesellschaft Accumulateur d'énergie électrique
CN111430849A (zh) * 2020-04-09 2020-07-17 蜂巢能源科技有限公司 锂空气电池

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DE102009057720A1 (de) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie und Verfahren zum Betreiben einer Batterie
US8637198B2 (en) * 2009-12-24 2014-01-28 Konica Minolta Holdings, Inc. Reaction container and fuel cell system equipped with same
EP2528150A4 (fr) * 2010-01-22 2013-10-23 Konica Minolta Holdings Inc Système de pile à combustible
WO2012008266A1 (fr) * 2010-07-15 2012-01-19 コニカミノルタホールディングス株式会社 Pile à combustible
DE102010041019A1 (de) * 2010-09-20 2012-03-22 Siemens Aktiengesellschaft Wiederaufladbare Energiespeichereinheit
DE102011005599B4 (de) * 2011-03-16 2012-12-13 Siemens Aktiengesellschaft Elektrischer Energiespeicher und Verfahren zum Betreiben eines elektrischen Energiespeichers
US8894722B2 (en) * 2011-06-24 2014-11-25 Siemens Aktiengesellschaft Construction of planar rechargeable oxide-ion battery cells and stacks using stainless steel housing structures
DE102011078116A1 (de) * 2011-06-27 2012-12-27 Siemens Ag Energiespeicher und Verfahren zum Laden oder Entladen eines Energiespeichers

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014005773A1 (fr) * 2012-07-03 2014-01-09 Siemens Aktiengesellschaft Structure accumulatrice d'un élément d'accumulation d'énergie électrique
US10211453B2 (en) 2012-07-03 2019-02-19 Siemens Aktiengesellschaft Storage structure of an electrical energy storage cell
WO2014048724A1 (fr) * 2012-09-25 2014-04-03 Siemens Aktiengesellschaft Accumulateur d'énergie électrique
US9583804B2 (en) 2012-09-25 2017-02-28 Siemens Aktiengesellschaft Electrical energy store
CN111430849A (zh) * 2020-04-09 2020-07-17 蜂巢能源科技有限公司 锂空气电池
CN111430849B (zh) * 2020-04-09 2022-05-27 蜂巢能源科技有限公司 锂空气电池

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WO2013110509A3 (fr) 2013-10-17

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