WO2013127593A1 - Procédé de réalisation de la structure d'accumulateur d'un accumulateur d'énergie électrique - Google Patents

Procédé de réalisation de la structure d'accumulateur d'un accumulateur d'énergie électrique Download PDF

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Publication number
WO2013127593A1
WO2013127593A1 PCT/EP2013/051936 EP2013051936W WO2013127593A1 WO 2013127593 A1 WO2013127593 A1 WO 2013127593A1 EP 2013051936 W EP2013051936 W EP 2013051936W WO 2013127593 A1 WO2013127593 A1 WO 2013127593A1
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WO
WIPO (PCT)
Prior art keywords
layer
functional layer
functional
pore
energy store
Prior art date
Application number
PCT/EP2013/051936
Other languages
German (de)
English (en)
Inventor
Christiane Bauer
Ines Becker
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 WO2013127593A1 publication Critical patent/WO2013127593A1/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
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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

Definitions

  • the invention relates to a method for fabricating a memory structure of an electric energy storage device according to claim 1, a memory structure of a memory cell of an electric energy storage device according to claim 1 and a memory cell of an electric energy storage device according to ⁇ demanding. 13
  • this medium tends in anlie- constricting comparatively high operating temperatures of such a battery, which lie ⁇ gen usually between 600 and 800 ° C, to the fact that the required Microstructure in particular the pore structure of the storage medium is destroyed by sintering ⁇ zer. This leads to aging and eventually failure of the battery.
  • the object of the invention is to provide a storage structure of an energy store, a method for producing an energy store.
  • a memory structure and a memory cell of an electrical energy storage device to provide that over the prior art has a higher long-term stability and a higher number of cycles of charging and discharging withstand.
  • the object is achieved in a method for producing a memory structure of an electrical energy store having the features of patent claim 11 and in a memory structure having the features of claim 1 and in a memory cell for an electrical energy store having the features of patent claim 13.
  • the method according to the invention for producing a memory structure of an electrical energy store initially comprises the production of a carrier layer with a refractory material.
  • a functional layer is prepared which comprises an active Speichermateri ⁇ al as well as a pore former. Both layers are then placed on each other so that they form a layer composite ⁇ , again then the pore former is removed from the functional layer.
  • the described carrier layer which consists of a refraktä- ren material or it comprises a high Tem ⁇ peraturbeparix the entire memory structure is ensured.
  • the carrier layer serves to carry the one or more functional layers, which comprises an active storage material, and to design them thermally and mechanically stably in a layer composite.
  • the pore former which is stored in the functional layer, whereby before Trains t ⁇ open porosity remains from the function ⁇ layer, in particular by a thermal process, ent ⁇ removed in the finished functional layer a. This open porosity serves to transport a gaseous medium which must be conducted as a reactant to the active storage material.
  • the memory structure thus produced is therefore mechanically and thermally stable and has a reaching porosity in the area of the active storage material, so that a gaseous reactant can reach all surfaces of the active storage material. In this way, a high capacity of the electrical energy store is ensured, wherein the storage structure is designed mechanically much more stable compared to the prior art.
  • the layers can also be produced by screen printing or by an extrusion process.
  • Both the film casting and film drawing process and the extrusion process are endless processes in which arbitrarily long green bodies of the individual layers can be produced.
  • Such an endless green body of the carrier layer can serve to apply thereto a further layer in the same film casting or film-drawing process of the functional layer.
  • any number of alternating layers, carrier layers and functional layers of an arbitrarily thick layer composite can be represented. It is advantageous that a total of a horizontal layer composite is shown with cohesive layers. This can be provided by the endless processes described or by the stacking of individual layers produced separately, which are produced, for example, by a screen-printing process or by a pressing process.
  • the material for the support layer is a refractory material based on yttriumver prisonem zirconia (YSZ), scandiumver prisonem zirconia (ScSZ), silicon carbide and / or alumina be ⁇ stands.
  • YSZ yttriumver prisonem zirconia
  • ScSZ scandiumver prisonem zirconia
  • silicon carbide and / or alumina ⁇ stands.
  • Such material can in principle be extended to other groups of materials such as borides and Carbi- de of titanium, is divetemperaturbe ⁇ constantly and mechanically stable. Therefore it meets very special ⁇ DERS well the requirements that are imposed on the carrier layer.
  • the functional layer comprises the other hand, as an active Speicherma ⁇ TERIAL preferably iron, particularly in chemically bound form, for example as iron oxide.
  • the iron is also elekt ⁇ Roche mix reasons advantageous for use in a Rechargeable Battery oxides.
  • the pore-forming agent which is preferably based on an organic material or carbon, is preferably removed thermally from the functional layer, thereby leaving it exposed since, in particular, carbon dioxide is present during a thermal conversion, which in turn leads to an open pore channel being formed in the functional layer becomes.
  • a concentration gradient of the pore-forming agent may be applied in the functional layer, which reaches from one edge of the functional layer to a center of the functional layer.
  • the edge is a hö ⁇ here concentration of the pore former in front than in the center.
  • Another component of the invention is a storage structure of a memory cell of an electric Energyspei ⁇ Chers having an alternating layer sequence of at least two, a refractory material comprising the support layer as well as three, iron in elementary or in chemically bound form comprehensive functional layers.
  • the functional layers in this case have an open porosity, and the carrier ⁇ layer as well as the other functional layers are to be ⁇ least partly materially connected.
  • Such a memory structure has a high thermal and mechanical stability, through the pores in the functional layer, a process gas can advantageously flow far into the functional ⁇ layer and passes in an advantageous manner always to the active surface of the active storage material.
  • a part of the invention is a Speicherzel- le an electrical energy storage, a memory or ⁇ structure comprises according to one of claims 12 or 13 which is produced by a process according to any one of claims 1-11.
  • Figure 1 is a schematic representation of the structure of a SpeI ⁇ cherzelle an electrical energy store, in particular a Rechargeable Battery oxides, Figure 2, in steps a to c show a schematic depicting ⁇ development of fabricating a memory structure by a tape casting process,
  • FIG. 3 shows an enlarged view of the layer composite of a memory structure
  • FIG. 4 shows a memory structure in macroscopic representation.
  • a common structure of a ROB is that at a positive electrode 24, which is also referred to as Heilelekt ⁇ rode, a process gas, in particular air, is blown through a gas supply 18, wherein oxygen is withdrawn from the air.
  • the oxygen passes in the form of Sau ⁇ erstoffionen (0 2 ⁇ ) through a voltage applied to the positive electrode solid electrolyte 25 to a negative electrode 26, which is also referred to as a storage electrode.
  • a dense layer of the active storage material were present at the negative electrode 26, ie at the storage electrode, the charge capacity of the battery would quickly be exhausted.
  • a memory structure 2 made of porous material which thus contains a functionally acting oxy dierbares material an active storage material 6 before ⁇ Trains t in the form of iron.
  • a gaseous redox couple for example H 2 / H 2 O
  • the oxygen ions transported through the solid-state electrolyte 25 are vaporized by pore oxygen.
  • channels of a porous storage structure comprising the active storage material 6, transported.
  • the metal or the metal oxide iron / iron oxide
  • This mechanism is called a shuttle mechanism.
  • iron as an oxidizable material, ie as an active storage material, is that in its oxidation process it has somewhat the same quiescent voltage of about 1 V as the redox couple H 2 / H 2 O.
  • Solid electrolyte 25 requires a high operating temperature ⁇ ture of 600 to 800 ° C, the ROB described.
  • the storage structure 2 which contains the active Speicherma ⁇ TERIAL. 6
  • the individual grains are increasingly merging together by diffusion processes until the reactive tive surface is very small and is the pore structure ge ⁇ closed. With a closed pore structure, the redox couple H 2 / H 2 O can no longer reach the active surface of the active storage ⁇ material, so that the capacity of the battery is exhausted very quickly.
  • a ceramic mass 33 is poured, which is stored in a container 32.
  • the ceramic mass 33 is in the form of a Schli ⁇ ckers having the necessary for the film casting corresponding rheological properties.
  • the ceramic mass 33 is on a belt of the sheet drawing device 30th further and smoothed by a squeegee 34.
  • a band-shaped green body 36 is produced.
  • This base body 36 comprises, as the base material of the ceramic mass 33, a refractory material based on yttrium-reinforced zirconium oxide.
  • other ceramic refractory materials for example based on ScSZ, silicon carbide or aluminum oxide are useful.
  • mixtures of different ceramics may also be present for the production of particular mechanical and thermal properties.
  • the green body 36 is then passed a further time onto a film-drawing apparatus 30 ', and a further mass 38 is applied to this band-shaped green body 36, which mass is passed via a storage container 32' onto the band of the film drawing apparatus 30 '.
  • This mass 38 comprises the base material of the active storage material, advantageously this is iron oxide (Fe 2 O 3).
  • the mass 38 is also configured in the form of a rheologically suitable slip and it is also smoothed by a doctor blade 34 'on the green body 36, so that a
  • Layer composite 8 is formed, which is initially constructed of two layers.
  • the one layer thereof is referred to as carrier layer 4 and comprises the refractory material
  • the second layer is referred to as function view 6, this comprises the active storage material.
  • Any number of further of these layers 4 and 6 can now follow, if this is technically feasible. In principle, several of these layers can be cut out and placed one above the other so that a layer composite 8 is formed.
  • This layer composite 8 is now subjected to a heat treatment, which is illustrated in Figure 2c by the roller furnace 42 shown schematically.
  • the layer composite 8 is in turn driven through a belt through the roller furnace 42, wherein it is heated to a temperature at which, depending on the used material of the individual components of the functional layer 6 and the carrier layer 4, a sintering process. provides. It is ensured that no full sintering of the individual components takes place, but rather it is desirable that by diffusion processes take place stoffschlüs ⁇ SiGe connections between the individual particles of the components are formed so-called sintering necks, by which the stability of the green body 36 or the layer composite 8 is significantly increased, also improves its thermal stability.
  • a sintering process which is achieved in FIG.
  • the pore-forming agent which is contained in the mass 38, that is to say in the matrix for the functional layer 6, is burnt out.
  • the pore former is be ⁇ vorzugt an organic filler material, for example based on polyethylene or carbon, which decompose to form carbon dioxide atmosphere.
  • the per ⁇ which forms gaseous reaction product (including CO 2) stays awhile rolls through the material of the functional layer 4 channels that remain ty exist as open Porosi- after burnout of the pore former.
  • the pore-forming agent which burns out of the functional layer 4 is illustrated by the curved lines 44 of the layer composite 8 in FIG. 2c.
  • Theticianbe ⁇ treatment for the pre-sintering process and the heat treatment to burn out the pore former is exemplified in egg nem process step here. Basically, it can also be useful, especially if have applied for both processes under ⁇ Kunststoffliche temperatures, which split in two process steps.
  • the described film casting method according to FIG. 2 is merely an exemplary description of an advantageous production method of the memory structure 2. In principle, other endless processes, such as
  • FIG. 3 shows a finished memory structure 2 with its horizontal layer composite 8 of the functional layer 4 to 6 and the carrier layer in cross section.
  • a typical layer thickness of the porous functional layer 6 is usually between 200 ym and 1000 ym, preferably between 400 ym and 600 ym.
  • the functional layer 6 can be designed so that it has a higher porosity on an edge portion 10 as 12 in the center This is achieved that the mass 38, the example ⁇ example in the edge area 10 of the functional layer 6 in the Folieng discernwhitening according to Figure 2b is applied is, has a higher concentration of pore formers, as the mass 38, which is applied in the center 12 of the layer.
  • process gas H 2 / H 2 O can flow faster in the edge region and penetrate more easily into the comparatively thin functional layer 6, and thus also reaches the central regions of the functional layer 6 and the active storage material present there in a short time.
  • the pores created by the pore former also serve to compensate for volume differences that occur during the oxidation process or reduction process of the iron or iron oxide.
  • the storage structure 2 which is prepared by the method described in accordance with Figure 2, typically has Dimensio ⁇ NEN, which are of their flat expansion between 10 and 30 cm. In order to insert the memory structure 2 in the receptacles 28 of the cell 26, this is finally cut to the required geometry, which is illustrated in Figure 4 by the block shown there, which also represents the memory structure 2, as inserted into the memory cell 16 becomes.

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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)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Fuel Cell (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne une structure d'accumulateur d'un accumulateur d'énergie électrique, comprenant une série de couches alternées comportant au moins deux couches de support (4) qui présentent un matériau réfractaire, et trois couches fonctionnelles qui présentent du fer sous forme élémentaire ou chimiquement liée, les couches fonctionnelles (6) présentant des pores ouverts et les couches de support (4) étant reliées au moins partiellement par liaison de matière aux couches fonctionnelles (6) adjacentes.
PCT/EP2013/051936 2012-02-28 2013-01-31 Procédé de réalisation de la structure d'accumulateur d'un accumulateur d'énergie électrique WO2013127593A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012202978.8 2012-02-28
DE102012202978A DE102012202978A1 (de) 2012-02-28 2012-02-28 Verfahren zur Herstellung einer Speicherstruktur eines elektrischen Energiespeichers

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WO2013127593A1 true WO2013127593A1 (fr) 2013-09-06

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WO (1) WO2013127593A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013207576A1 (de) * 2013-04-25 2014-10-30 Siemens Aktiengesellschaft Wiederaufladbarer elektrischer Energiespeicher

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060113034A1 (en) * 2004-10-29 2006-06-01 Seabaugh Matthew M Electrochemical cell architecture and method of making same via controlled powder morphology
US20100143824A1 (en) * 2007-07-25 2010-06-10 The Regents Of The University Of California Interlocking structure for high temperature electrochemical device and method for making the same
DE102009057720A1 (de) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie und Verfahren zum Betreiben einer Batterie
US20110200891A1 (en) * 2008-10-30 2011-08-18 Toyota Jidosha Kabushiki Kaisha Metal-air battery and method for manufacturing the metal-air battery
US20120034520A1 (en) * 2010-08-09 2012-02-09 Chun Lu Self-sealed metal electrode for rechargeable oxide-ion battery cells

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10223182A1 (de) * 2002-05-24 2003-12-04 Zsw Verfahren zur Herstellung auf einem Schichtaufbau basierender galvanischer Elemente mit funktionalen Schichten und so hergestellte galvanische Elemente

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060113034A1 (en) * 2004-10-29 2006-06-01 Seabaugh Matthew M Electrochemical cell architecture and method of making same via controlled powder morphology
US20100143824A1 (en) * 2007-07-25 2010-06-10 The Regents Of The University Of California Interlocking structure for high temperature electrochemical device and method for making the same
US20110200891A1 (en) * 2008-10-30 2011-08-18 Toyota Jidosha Kabushiki Kaisha Metal-air battery and method for manufacturing the metal-air battery
DE102009057720A1 (de) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie und Verfahren zum Betreiben einer Batterie
US20120034520A1 (en) * 2010-08-09 2012-02-09 Chun Lu Self-sealed metal electrode for rechargeable oxide-ion battery cells

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