DE102012217309A1 - Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer - Google Patents

Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer

Info

Publication number
DE102012217309A1
DE102012217309A1 DE102012217309A DE102012217309A DE102012217309A1 DE 102012217309 A1 DE102012217309 A1 DE 102012217309A1 DE 102012217309 A DE102012217309 A DE 102012217309A DE 102012217309 A DE102012217309 A DE 102012217309A DE 102012217309 A1 DE102012217309 A1 DE 102012217309A1
Authority
DE
Germany
Prior art keywords
layer
battery cell
storage electrode
solid electrolyte
structure
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
DE102012217309A
Other languages
German (de)
Inventor
Carsten Schuh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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
Priority to DE102011083658 priority Critical
Priority to DE102011083658.6 priority
Priority to DE102011083732.9 priority
Priority to DE102011083732 priority
Application filed by Siemens AG filed Critical Siemens AG
Priority to DE102012217309A priority patent/DE102012217309A1/en
Publication of DE102012217309A1 publication Critical patent/DE102012217309A1/en
Application status is Pending legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/664Ceramic materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/08Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/128Hybrid cells composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type

Abstract

The invention relates to a layer composite (1) for a battery cell comprising a layer of oxygen ion conductive solid electrolyte (2) and a structure of OTM ceramic (oxygen ions and electron-conductive transfer layer) (3), wherein the needle-like or hill-like Structure of OTM ceramic (3) is on the layer of oxygen ion conductive solid electrolyte (2) and wherein a layer of storage electrode (4) covers the structure of OTM ceramic (3).

Description

  • The invention relates to a layer composite for a battery cell with a storage electrode, an oxygen ion-conducting solid electrolyte and an OTM ceramic (OTM = Oxygen Transfer Membrane) and a battery cell comprising the layer composite according to the invention.
  • Oxide ceramic high temperature fuel cells are known in the art. At temperatures above about 500 ° C, they convert chemical energy into electrical energy. The high temperature is required to make the solid electrolyte sufficiently conductive.
  • The solid oxide oxide fuel cell (SOFC) is a high-temperature fuel cell operated at a temperature of 650-1000 ° C. The electrolyte of this cell type consists of a solid ceramic material capable of conducting oxygen ions but insulating them for electrons. In general, yttrium-stabilized zirconia (YSZ) is used. The cathode is also made of a ceramic material (e.g., strontium-doped lanthanum manganate) that is conductive to ions and to electrons. The anode is made of nickel with yttrium-doped zirconia, a so-called cermet, which also conducts ions and electrons. The real innovation of a SOFC is in the ceramic material. Some of the constraints are: Cathode and anode must be gas permeable and conduct the current well. The layer thickness of the oxygen-conducting membrane must be as thin as possible in order to be able to transport the oxygen ions through the membrane with low energy. There must be no defects (cracks, pore channels) in the membrane through which gas molecules can pass. The high temperature makes the development of the systems expensive. The SOFC uses metal / ceramic fuel electrodes, and porous ceramic air electrodes, because pure metal electrodes can not withstand the high temperatures.
  • The operation of a SOFC is known. This function requires air and a gaseous fuel such as natural gas.
  • For SOFCs a variety of fuel cell designs are described ( NQ Minh, in Ceramic Fuel Cells, J. Am. Ceramic Soc, 76 [3] 563-588, 1993 ).
  • Hybrid vehicles today use NiMH technology. The lithium-ion battery is the preferred source of energy for rechargeable electronic devices.
  • Batteries serve not only to generate energy but also to store energy. The storage of electrical energy in electrical energy storage is a prerequisite for many modern technologies, such as the wider use of renewable energy. The current electrochemical energy storage systems are too expensive, do not provide enough power, use too many environmentally harmful materials and have too short a lifetime.
  • WO 2011/19455 discloses a battery cell having a storage electrode in combination with an oxygen ion conductive solid electrolyte and an air electrode, which cell may be operated in a charge and a discharge mode to store electrical energy in the storage electrode. The discharge mode of the battery cell is yMe + x / 2O2 = MeyOx and the charging mode is MeyOx = x / 2O2 + yMe, and it is x / y = 0.5 to 3.0 and Me = metal. The storage electrode is made of a single-phase metallic material selected from the group consisting of Sc, Y, La, Ti, Zr, Hf, Ce, Cr, Mn, Fe, Co, Ni, Cu, Nb, Ta, V, Mo, Pd and W, and a biphasic material selected from the group consisting of Sc-Sc 2 O 3, Y-Y 2 O 3, La-La 2 O 3, Ti-TiO 2, Zr-ZrO 2, Hf-HfO 2, Ce-CeO 2, Cr-Cr 2 O 3, Mn-Mn 2 O 3, Mn Mn3O4, Mn-MnO, Fe-FeO, Fe-Fe3O4, Fe-Fe2O3, Co-CoO, Co-Co3O4, Co-Co2O3, Ni-NiO, Cu-Cu2O, Cu-CuO, Nb-NbO, Nb-NbO2, Nb-Nb2O5, Ta-Ta2O5, V-V2O5, V-VO2, V-V2O3, V-VO, Mo-MoO2, Mo-MoO3, Pd-PdO and W-WO3. The ratio of metal to metal oxide in the biphasic composition is in the range of 0: 100 to 100: 0. The in the WO 2011/19455 disclosed battery cell does not use gaseous fuels such as natural gas.
  • The object of the present invention is to further improve the energy storage capacity of the battery cell.
  • The invention relates to a composite layer for a battery cell comprising a layer of oxygen ion conductive solid electrolyte and a structure of OTM ceramic (oxide transfer membrane stands for an oxygen ion and electron conductive transfer layer), wherein the needle or hill-like Structure of OTM ceramic is on the layer of oxygen ion conductive solid electrolyte and wherein a layer of storage electrode covers the structure of OTM ceramic.
  • A particular embodiment of the invention relates to a laminate for a battery cell, wherein the structure of OTM ceramic and also the free surface of the oxygen ion conductive solid electrolyte is coated with a layer of storage electrode.
  • In a particular embodiment of the invention, the OTM ceramic ( 3 ) have a needle or hill-like structure.
  • The invention also provides a layer composite for a battery cell obtainable by coating the surface of a needle or hill-like structure of OTM ceramic with a layer of storage electrode, wherein the needle or hill-like structure of OTM ceramic on a layer of oxygen ions conductive solid electrolyte is located.
  • An embodiment of the invention relates to a layer assembly for a battery cell obtainable by coating the surface of a needle or hill-like structure of OTM ceramic with a layer of storage electrode and wherein the layer of storage electrode with one of the methods selected from the methods Infiltration with particulate Schlickern , Infiltration with organometallic precursors, deposition from solutions, in particular deposition from salt solutions, PVD processes or CVD processes is applied to the surface of a needle or hill-like structure of OTM ceramic, which is located on a layer of oxygen ion conductive solid electrolyte.
  • The invention also provides a layer composite for a battery cell obtainable by forming a needle or hill-like structure of OTM ceramic on a layer of oxygen ion conductive solid electrolyte with one of the methods selected from the methods rapid prototyping, screen printing, inkjet, selective laser sintering , Slip infiltration or lost-mold process and subsequent coating of the surface thus obtained with a layer of storage electrode, wherein the layer of storage electrode with one of the methods selected from the methods infiltration with particulate Schlickern, infiltration with organometallic precursors, deposition from solutions, in particular deposition from salt solutions, PVD processes or CVD processes.
  • The layer of OTM ceramic (OTM = Oxygen Transfer Membrane) conducts oxygen ions and therefore facilitates and improves the transport of oxygen ions. At the same time, the layer of OTM ceramic has a high electronic conductivity. Therefore, the OTM ceramic layer also facilitates and improves the transfer of oxygen ions and electrons from the oxygen ion conductive solid electrolyte to the storage electrode and vice versa.
  • For example, the OTM ceramic has a total conductivity for oxygen ions and electrons of 0.1-10 Ωcm, preferably 0.2-5 Ωcm, more preferably 0.5-2 Ωcm. The OTM ceramic, for example, has a thickness of 1-200 μm, preferably 2-50 μm, more preferably 5-30 μm. The material from which the OTM ceramic is made is preferably selected from the group of materials comprising SExEAyMEzO3-δ, where SE = rare earths, EA = alkaline earth, ME = Fe, Cr, Ti, Mn and their mixture and x = 0.2-0.5, y = 0.5-0.8, z = 1.0 and δ = 0-0.05.
  • Due to the special geometric shape of the OTM ceramic, the mechanical stresses which arise with the expansion of the storage electrode during oxidation (expansion) can be kept low or completely prevented. Therefore, there is no bending of the layer composite or cracking. At the same time, the needle or hill-like structure of the OTM ceramic on the oxygen ion-conductive solid electrolyte causes optimum transfer of the oxygen ions and electrons from the electrolyte layer to the storage electrode and back. The needle or hill-like structure of the OTM ceramic also takes over the electrical contact (counter electrode) on the surface of the oxygen ion-conducting solid electrolyte. As a result, a constant good contacting of the oxygen ion-conducting solid electrolyte is ensured and the energy storage capability is improved.
  • The needle-like structures have for example an average height of 1 to 2000 .mu.m, preferably from 5 to 500 .mu.m, particularly preferably 100 .mu.m. The needle-like structures have for example an average diameter of 1 to 500 .mu.m, preferably from 5 to 100 .mu.m, particularly preferably 50 .mu.m. Hill-like structures have for example a height of 5 to 2000 microns, preferably from 10 to 1000 microns, more preferably 200 microns. Hill-like structures have for example a mean diameter of 5 to 5000 .mu.m, preferably from 10 to 1000 .mu.m, particularly preferably 200 .mu.m.
  • The structure of the OTM ceramic, the arrangement, geometric shape, thickness and height of the needles on the layer of oxygen ion conductive solid electrolyte and the proportion of surface covered with needles or hills of OTM ceramic, may be chosen that at maximum energy storage capacity, the negative effects such as bending and cracking are avoided in the composite layer. These structures are obtained, for example, when using said production processes.
  • Preferably, the OTM ceramic has a dense structure. A dense structure means that the OTM ceramic has a relative density of> 80%. In a particularly preferred embodiment of the invention, the OTM ceramic has a closed porosity, for example, the proportion of closed porosity is 80% or more compared to the total porosity.
  • A particular embodiment of the invention relates to a laminate for a battery cell, wherein the layer of storage electrode is 0.1 to 20 microns, preferably 1 to 10 microns, more preferably 5 microns thick.
  • The 3-dimensional configuration of the layer composite leads to a maximization of the upper and thus passage area for O 2- ions and also the active surface of the storage electrode per cell volume. The thickness of the storage electrode may be, for example, 2-15 microns. Preferably, the storage electrode has a small thickness, for example 3-9 microns, preferably 4-8 microns, more preferably 6 or 7 microns. The loading or unloading speed can also be influenced via the layer thickness of the storage electrode, and thus also the frequency with which the charging and discharging process can alternate when the battery cell is used as the energy store.
  • In a further particularly preferred embodiment of the invention, the storage electrode has a porous structure, for example a porosity of 30% to 50%, preferably 35% to 45%, particularly preferably 40%. The storage electrode may have an open or closed porosity. In a particularly preferred embodiment of the invention, the storage electrode has an open porosity in the structure, i. communicating with each other pore channels, which allow the passage of gases. By a porous structure of the storage electrode is additionally a cracking, which can be caused by the change in volume in the redox reaction avoided.
  • Another particular embodiment of the invention relates to a laminate for a battery cell, wherein the storage electrode comprises two layers, and wherein the first layer is disposed on the side facing away from the OTM ceramic and contains a single-phase metallic material and wherein the second layer on the OTM ceramic side facing and contains the two-phase material.
  • The storage electrode serves as a reservoir for oxygen. The storage electrode should have a suitable melting point with the appropriate melting point above the operating temperature of the battery cell. For example, a melting point of 800 ° C or more. The storage electrode must have a suitable thermodynamic emf (electromotive force), a suitable theoretical energy density (mJoule / kg metal), a suitable thermodynamic electrical efficiency, practicable costs ($ / k watt electrical hours eh; e = current, h = hour), a suitable maximum current density (determines the power) and charge (amp hours / cm 2 ) have. Considering these criteria, the material of the single-phase layer of the storage electrode can be selected from the materials Sc, Y, La, Ti, Zr, Hf, Ce, Cr, Mn, Fe, Co, Ni, Cu, Nb, Ta, V, Mo Based on these considerations, the material of the biphasic layer of the storage electrode can be selected, for example, from the materials comprising Sc-Sc 2 O 3, Y-Y 2 O 3, La-La 2 O 3, Ti-TiO 2, Zr-ZrO 2, Hf-HfO 2, Ce. CeO2, Cr-Cr2O3, Mn-Mn2O3, Mn-Mn3O4, Mn-MnO, Fe-FeO, Fe-Fe3O4, Fe-Fe2O3, Co-CoO, Co-Co3O4, Co-Co2O3, Ni-NiO, Cu-Cu2O, Cu-CuO, Nb-NbO, Nb-NbO2, Nb-Nb2O5, Ta-Ta2O5, V-V2O5, V-VO2, V-V2O3, V-VO, Mo-MoO2, Mo-MoO3, Pd-PdO and W- WO3.
  • In the biphasic layer of the storage electrode, the metal to metal oxide ratio is in the range of 0 to 100 to 100 to 0.
  • The second layer is also referred to as the redox layer, since the redox processes take place there. The inventive arrangement of the layers in the preferred embodiment, the lowest possible specific electrical resistance of the storage electrode is achieved while ensuring a particularly good volume-diffusivity for oxygen ions between the oxygen ion-conducting solid electrolyte and the metallic redox layer. By this arrangement, moreover, the diffusion distance between the oxygen ion conductive solid electrolyte and the redox layer is minimal.
  • The materials of the biphasic layer were further investigated ( WO2011 / 019455 ). Some materials have proven to be particularly suitable. The systems Ti / TiO2, Cr / Cr2O3, Mn / Mn2O3, Mo / MoO2, Fe / FeO and W / WO3 have particularly high EMF values. High specific energy densities are exhibited by the Ti / TiO2, Cr / Cr2O3, Mn / Mn2O3, Mo / MoO2 and Fe / FeO systems. A high thermodynamic electrical efficiency in the temperature range of interest (about 600-800 ° C) have the systems Ti / TiO2, Cr / Cr2O3, Fe / FeO and Mn / Mn2O3. Outstandingly low material costs have the systems W / W03, Fe / FeO, Mn / Mn2O3, Cu / Cu2O, Ti / TiO2 and Cr / Cr2O3. A high maximum current density can be achieved in the systems W / WO3, Fe / FeO, MnMn2O3 and Co / CoO. A high maximum storage capacity have the systems W / WO3, Fe / FeO and Mn / Mn2O3.
  • Based on the properties mentioned, preferred storage electrodes comprise at least one single-phase metallic material selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo and W and at least one biphasic material selected from the group comprising Ti-TiO 2, Cr-Cr 2 O 3, Mn-Mn 2 O 3, Fe-FeO, Co-CoO, Ni-NiO, Cu-Cu 2 O, Mo-MoO 2 and W-WO 3. Particularly preferred are materials containing at least one material selected from the group consisting of Fe / FeO, Mn / Mn2O3, W / WO3 and Mo / MoO2. Another particular embodiment of the invention relates to a battery cell, wherein the storage electrode comprises Fe / FexOy or Ni / NiO.
  • A further embodiment of the invention relates to a laminate for a battery cell, wherein the needle-shaped or hill-shaped structure of OTM ceramic on the entire free surface with a thin 1 to 10 microns, preferably 2 to 9 microns thin, more preferably 3 to 7 Micrometer thin layer of FexOy is coated.
  • A particularly preferred embodiment of the invention relates to a layer composite for a battery cell, which additionally comprises an air electrode. For example, the air electrode has a layer thickness of about 10 microns to 100 microns. In a further embodiment of the layer composite, the air electrode comprises a doped or undoped oxide or mixed oxide selected from the group of perovskites, for example La1-x Srx MnO3 or La1-x Srx Co1y FeO3, or the air electrode comprises mixed oxides of rare earths and / or oxides of Co, Ni, Cu , Fe, Cr, Mn and their combinations.
  • The invention also relates to a battery cell comprising at least one layer composite according to the invention.
  • A particular embodiment of the invention relates to a battery cell according to the invention, wherein the battery cell can be operated in a charge and a discharge mode to store electrical energy in the storage electrode, and wherein the discharge reaction yMe + x / 2O2 = MeyOx and the charging reaction MeyOx = x / 2O2 + yMe are and
    where x and y are stoichiometric numbers, with x / y = 0.5 to 3.0 and O = oxygen and Me = metal.
  • The invention also relates to the use of a battery cell according to the invention or a layer composite according to the invention for power supply, as an energy converter or as energy storage.
  • The energy storage capability of the battery cell or the layer composite can also be optimized by selecting the layer thickness of the storage electrode. That is, the energy storage ability can be influenced and optimized by the arrangement of the needles or mounds of OTM ceramics covered with storage electrode and the layer thickness of the storage electrode.
  • The invention also provides a device or a device comprising at least one layer composite according to the invention and / or at least one battery cell according to the invention.
  • The invention also provides a process for producing a layer composite according to the invention for a battery cell, wherein a needle-shaped or hill-like structure made of OTM ceramic is applied to a layer of oxygen ions conducting solid electrolyte, and where appropriate, first the second layer of the storage electrode is applied , which mainly comprises a two-phase material and then the first layer of the storage electrode is applied, which predominantly comprises a single-phase metallic material.
  • In a particular embodiment of the method according to the invention, the needle or hill-like structure is made of OTM ceramic with one of the methods selected from the methods rapid prototyping, screen printing, inkjet, selective laser sintering, silt infiltration or with the method of lost form on the layer of oxygen ions formed conductive solid electrolyte.
  • Another embodiment of the invention may include a battery cell ( 10 ) with a storage electrode ( 12 ) in combination with an oxygen ion-conducting solid electrolyte ( 14 ), an OTM layer (oxygen ion and electron transfer layer) ( 13 ) and an air electrode ( 15 ), the battery cell ( 10 ) can be operated in a charging and discharging mode in order to store electrical energy in the storage electrode ( 12 ), and wherein the discharge reaction yMe + x / 2O2 = MeyOx and the charging reaction MeyOx = x / 2O2 + yMe are and
    where x and y are stoichiometric numbers, with x / y = 0.5 to 3.0 and O = oxygen and Me = metal
    and wherein the OTM layer ( 13 ) between the oxygen ion-conducting solid electrolyte ( 14 ) and the storage electrode ( 12 ) is arranged.
  • In a further embodiment according to the invention, the battery cell ( 10 ) a storage electrode ( 12 ) with at least one single-phase metallic material ( 17 ) and at least one biphasic material ( 16 ).
  • In an additional aspect of the invention, the battery cell ( 10 ) a storage electrode ( 12 ), wherein the storage electrode ( 12 ) comprises two layers, and wherein the first layer ( 17 ) on the OTM layer ( 13 ) side facing away and contains a single-phase metallic material and wherein the second layer ( 16 ) on the OTM layer ( 13 ) side facing and containing the biphasic material.
  • In a further preferred embodiment, the battery cell ( 10 ) have a special structure, wherein on a planar or corrugated layer of oxygen ions conductive solid electrolyte ( 14 ) at least one OTM layer ( 13 ) and on the OTM layer ( 13 ) a layer of storage electrode ( 12 ) and wherein the storage electrode ( 2 ) the OTM layer ( 13 ) completely or partially covered.
  • Furthermore, in a preferred embodiment of the invention, the battery cell ( 10 ) a storage electrode ( 12 ), wherein the storage electrode ( 12 ) 55-45% of the surface of the OTM layer ( 13 ), preferably 52-48%, more preferably 50%.
  • In an additional aspect of the invention, the battery cell ( 10 ) have a special structure, wherein on the surface of the OTM layer ( 13 ) Alternate areas of the storage electrode ( 12 ) and areas that are not covered by the storage electrode ( 12 ) are covered so that the storage electrode ( 12 ) as a flat distribution of discrete islands or intermittently on the OTM layer ( 13 ) is arranged.
  • The subject of a further, preferred embodiment is also a battery cell ( 10 ) comprising a layer composite, wherein the layer composite in the cell has a geometry selected from the group of geometries comprising a linear arrangement of the planar or wavy layer composite ( 18 ), a tubular arrangement ( 19 ) or a fractal arrangement of the planar or wavy layer composite ( 20 ).
  • In an additional embodiment of the invention, the battery cell ( 10 ) are used for power supply, as an energy converter or energy storage.
  • In a further aspect of the invention, a method for producing a battery cell ( 10 ), wherein a planar or corrugated layer of oxygen ions conducting solid electrolyte ( 14 ) flat an OTM layer ( 13 ) is applied, and where appropriate, first the second layer of the storage electrode ( 16 ), which predominantly comprises a biphasic material, and then the first layer of the storage electrode ( 17 ), which predominantly comprises a single-phase metallic material.
  • In a further preferred embodiment, a method for producing a battery cell ( 10 ), wherein the application of the OTM layer ( 13 ) and / or the layers of the storage electrode ( 12 ) with one of the methods selected from the methods screen printing, lamination of metallic or ceramic green sheets, slip casting, spray processes or by electrophoretic deposition takes place.
  • The invention also provides a process for producing a battery cell according to the invention, wherein a needle-shaped or hill-like structure made of OTM ceramic is applied to a layer of oxygen ions conducting solid electrolyte, and optionally first the second layer of the storage electrode is applied, which predominantly comprises a two-phase material and then the first layer of the storage electrode is applied, which predominantly comprises a single-phase metallic material and wherein the layer composite obtained is provided with an air electrode.
  • The storage electrode and / or the individual layers of the storage electrode can be applied, for example, with a method selected from the methods infiltration with particle-containing slip or organometallic precursors, (hydrothermal) deposition from (salt) solutions, PVD or CVD processes with or without thermal aftertreatment become. PVD means "physical vapor deposition" (e.g., sputtering or vapor deposition), whereas the chemical vapor deposition (CVD) process involves a chemical vapor / gas phase or interfacial reaction.
  • The invention also provides processes for producing the layer composite according to the invention, in which the layer composite is thermally treated at temperatures of up to 1500 ° C. or a common debindering / sintering ( Cofiring) of the layer composite after layer structure and structuring in the green state.
  • The invention also provides a composite of battery cells comprising at least two battery cells according to the invention and wherein the battery cells are electrically connected to one another.
  • The invention also provides an electrical storage device comprising at least one battery cell according to the invention.
  • The invention also provides a method of storing electrical energy using an electrical memory according to the invention and storing the electrical energy by ion transfer between the electrodes on both sides of the oxygen ion conductive solid electrolyte and wherein one electrode is a reservoir for ions (storage electrode ) and the ions are transferred back and forth between the electrodes.
  • The layer composite according to the invention for a battery cell can be configured geometrically differently, for example, the layer composite can be planar or wavy.
  • This geometrical configuration maximizes the surface area of the laminar structure in a given battery cell and thus maximizes the energy storage capacity of the battery cell. The layer composite according to the invention ensures a continuous good contact of the oxygen ion-conducting solid electrolyte with the storage electrode and the inventive design ensures maximization of the contact surface, so that the transport of O 2- ions and electrons per unit time is maximized. As a result, the achievable energy density is greatly increased and brought close to the theoretical limit. The theoretical limit is given by the complete conversion of the reactants of the redox couple yMe + x / 2O2 = MeyOx.
  • The subject matter of the invention is also a battery cell which comprises a layer composite according to the invention. The layer composite can be arranged in the battery cell in such a way that the greatest possible storage capacity is achieved, for example by the fact that the planar or wavy layer composite is unfolded in the battery cell. The invention also relates to a battery cell, wherein the layer composite in the cell has an arrangement selected from the group of arrangements comprising a linear or planar arrangement, a tubular arrangement, or a cauliflower-like or fractal arrangement.
  • The invention also relates to a composite of battery cells. Such a composite comprises two or more battery cells according to the invention. In the composite, the battery cells are electrically connected together. The invention also relates to an electrical storage with at least one battery cell according to the invention.
  • The invention also relates to a method for storing electrical energy, wherein one or more electrical memories according to the invention are used, and the electrical energy is stored by transferring the oxygen ions between the electrodes on both sides of the oxygen ion-conducting solid electrolyte and wherein one electrode is a reservoir for Is oxygen ions.
  • Further advantages and advantageous embodiments of the subject invention are illustrated by the drawings and explained in the following description. It should be noted that the drawings are only descriptive and are not intended to limit the invention in any way. It shows:
  • 1 a layer composite according to the invention 1 for a battery cell with storage electrode 4 , hill-like structure made of OTM ceramic 3 and layer of oxygen ion conductive solid electrolyte 4 ,
  • 2 the layer composite 1 with storage electrode 4 , hill-like structure made of OTM ceramic 3 , Oxygen ion conductive solid electrolyte 2 and air electrode 5 ,
  • 3 the planar layer composite of a battery cell according to the invention 10 with storage electrode 12 that the OTM layer 13 completely covered. The OTM layer 13 covers the entire surface of the oxygen ion-conducting solid electrolyte 14 that is on the planar air electrode 15 located.
  • 4 the planar layer composite of a battery cell according to the invention 10 with the two layers 16 . 17 the storage electrode, which is the OTM layer 13 completely covered. This in turn completely covers the oxygen ion-conducting solid electrolyte 14 that is on the planar air electrode 15 located. Shown is the single-phase layer 17 and the biphasic layer 16 the storage electrode, wherein the biphasic layer 16 on the side of the storage electrode 10 located on the OTM layer 13 facing side is located.
  • 5 the planar layer composite of a battery cell according to the invention 10 , wherein the storage electrode 12 intermittently on the OTM layer 13 is designed and the storage electrode 12 the OTM layer 13 partially covered.
  • 6 the corrugated layer composite of a battery cell according to the invention 10 with a corrugated layer of storage electrode 12 which is a corrugated OTM layer 13 completely covered. The corrugated OTM layer 13 covers the corrugated layer of oxygen ions conductive solid electrolyte over its entire surface 14 which is located on the corrugated layer of air electrode 15 located.
  • 7 the geometry of the laminate in a battery cell 10 , which has a corrugated but flat laminate 18 includes.
  • 8th the geometry of the laminate in a battery cell 10 , which has a corrugated, tubular layer composite 19 includes.
  • 9 the geometry of the laminate in a battery cell 10 that have a cauliflower-like or fractal structure 20 Has.
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
  • Cited patent literature
    • WO 2011/19455 [0008, 0008]
    • WO 2011/019455 [0029]
  • Cited non-patent literature
    • NQ Minh, in Ceramic Fuel Cells, J. Am. Ceramic Soc, 76 [3] 563-588, 1993 [0005]

Claims (19)

  1. Layer composite ( 1 ) for a battery cell comprising a layer of oxygen ion conductive solid electrolyte ( 2 ) and a needle or hill-like structure of OTM ceramic (oxygen ion and electron conductive transfer layer) ( 3 ), wherein the structure of OTM ceramic ( 3 ) on the layer of oxygen ion conductive solid electrolyte ( 2 ) and wherein a layer of storage electrode ( 4 ) the structure of OTM ceramic ( 3 ) covers.
  2. Layer composite ( 1 ) for a battery cell according to claim 1, wherein also the free surface of the oxygen ion conducting solid electrolyte ( 2 ) with a layer of storage electrode ( 4 ) is coated.
  3. Layer composite ( 1 ) for a battery cell obtainable by coating the surface of a structure, which is preferably needle-shaped or hill-like, of OTM ceramic ( 3 ) with a layer of storage electrode ( 4 ), wherein the needle or hill-like structure of OTM ceramic ( 3 ) on a layer of oxygen ion conductive solid electrolyte ( 2 ) is located.
  4. Layer composite ( 1 ) for a battery cell according to claim 3, wherein the layer of storage electrode ( 4 ) is applied by one of the methods selected from the methods of infiltration with particulate-containing slip, infiltration with organometallic precursors, deposition from solutions, in particular deposition from salt solutions, PVD processes or CVD processes on the surface of a structure, which preferably needle-like or hill-like is made of OTM ceramic ( 3 ) deposited on a layer of oxygen ion conductive solid electrolyte ( 2 ) is located.
  5. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, wherein the layer of storage electrode ( 4 ) 0.1 to 20 microns, preferably 1 to 10 microns, more preferably 5 microns thick.
  6. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, wherein the storage electrode ( 4 ) comprises two layers, and wherein the first layer on the OTM ceramic ( 3 ) and containing a single-phase metallic material and wherein the second layer is on the OTM ceramic ( 3 ) side facing and containing the biphasic material.
  7. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, wherein the single-phase metallic material is selected from the group of chemical elements comprising Sc, Y, La, Ti, Zr, Hf, Ce, Cr, Mn, Fe, Co, Ni, Cu, Nb, Ta, V, Mo, Pd and W.
  8. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, wherein the biphasic material is selected from the group of metal / ceramic composites comprising Sc-Sc2O3, Y-Y2O3, La-La2O3, Ti-TiO2, Zr-ZrO2, Hf -HfO2, Ce-CeO2, Cr-Cr2O3, Mn-Mn2O3, Mn-Mn3O4, Mn-MnO, Fe-FeO, Fe-Fe3O4, Fe-Fe2O3, Co-CoO, Co-Co3O4, Co-Co2O3, Ni-NiO , Cu-Cu2O, Cu-CuO, Nb-NbO, Nb-NbO2, Nb-Nb2O5, Ta-Ta2O5, V-V2O5, V-VO2, V-V2O3, V-VO, Mo-MoO2, Mo-MoO3, Pd -PdO and W-WO3.
  9. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, wherein the structure, preferably needle-shaped or hill-shaped, made of OTM ceramic ( 3 ) is coated on the entire free surface with a layer of FexOy thin, preferably 2 to 9 microns thin, more preferably 3 to 7 microns thick, thin 1 to 10 microns thick.
  10. Layer composite ( 1 ) for a battery cell according to one of the preceding claims, comprising an air electrode ( 5 ).
  11. Battery cell comprising at least one layer composite according to one of claims 1 to 10.
  12. A battery cell according to claim 11, wherein the battery cell is operable in a charging and discharging mode to supply electrical energy in the storage electrode (10). 4 ), and wherein the discharge reaction yMe + x / 2O2 = MeyOx and the charging reaction MeyOx = x / 2O2 + yMe and wherein x and y are stoichiometric numbers, with x / y = 0.5 to 3.0 and O = oxygen and Me = metal.
  13. Use of a battery cell according to one of claims 11 or 12 for the power supply, as energy converter or energy storage.
  14. Device or device comprising at least one layer composite ( 1 ) according to one of claims 1 to 10 or at least one battery cell according to one of claims 11 or 12.
  15. Process for producing a composite layer ( 1 ) for a battery cell according to one of claims 1 to 10, wherein a layer of oxygen ions conducting solid electrolyte ( 2 ) one Structure, preferably needle-shaped or hill-like, of OTM ceramic ( 3 ) is applied, and where appropriate, first the second layer of the storage electrode is applied, which mainly comprises a two-phase material and then the first layer of the storage electrode is applied, which predominantly comprises a single-phase metallic material.
  16. Process according to claim 15, wherein the structure, preferably needle-shaped or hill-like, is made of OTM ceramic ( 3 ) with one of the methods selected from the methods rapid prototyping, screen printing, inkjet, selective laser sintering, slip infiltration or with the method of the lost form on the layer of oxygen ions conducting solid electrolyte ( 2 ) are formed.
  17. A composite of battery cells comprising at least two battery cells according to one of claims 11 or 12 and wherein the battery cells are electrically connected together.
  18. Electrical storage comprising at least one battery cell according to one of claims 11 or 12.
  19. A method of storing electrical energy using an electrical memory according to claim 18 and the electrical energy by ion transfer between the electrodes on both sides of the oxygen ion conductive solid electrolyte ( 2 ) and wherein one electrode is a reservoir for ions (storage electrode ( 4 )) and where the ions between the electrodes ( 4 . 5 ) are transmitted back and forth.
DE102012217309A 2011-09-28 2012-09-25 Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer Pending DE102012217309A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE102011083658 2011-09-28
DE102011083658.6 2011-09-28
DE102011083732.9 2011-09-29
DE102011083732 2011-09-29
DE102012217309A DE102012217309A1 (en) 2011-09-28 2012-09-25 Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102012217309A DE102012217309A1 (en) 2011-09-28 2012-09-25 Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer

Publications (1)

Publication Number Publication Date
DE102012217309A1 true DE102012217309A1 (en) 2013-03-28

Family

ID=47828169

Family Applications (1)

Application Number Title Priority Date Filing Date
DE102012217309A Pending DE102012217309A1 (en) 2011-09-28 2012-09-25 Laminate used for battery cell, has oxygen-ion conductive solid electrolyte layer, oxygen ion and electron conducting transfer layer having needle- or hill-like structure and storage electrode layer

Country Status (1)

Country Link
DE (1) DE102012217309A1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011019455A1 (en) 2009-08-10 2011-02-17 Siemens Energy, Inc. Electrical storage device including oxide-ion battery cell bank and module configurations

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011019455A1 (en) 2009-08-10 2011-02-17 Siemens Energy, Inc. Electrical storage device including oxide-ion battery cell bank and module configurations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NQ Minh, in Ceramic Fuel Cells, J. Am. Ceramic Soc, 76 [3] 563-588, 1993

Similar Documents

Publication Publication Date Title
Singhal Solid oxide fuel cells for stationary, mobile, and military applications
Weber et al. Materials and concepts for solid oxide fuel cells (SOFCs) in stationary and mobile applications
US7351488B2 (en) Structures and fabrication techniques for solid state electrochemical devices
Minh Solid oxide fuel cell technology—features and applications
US7740966B2 (en) Electrochemical cell stack assembly
US5942349A (en) Fuel cell interconnect device
ES2363799T3 (en) Fuel cells.
US7901837B2 (en) Structures for dense, crack free thin films
Doshi et al. Development of solid‐oxide fuel cells that operate at 500° C
Maric et al. Solid Oxide Fuel Cells with Doped Lanthanum Gallate Electrolyte and LaSrCoO3 Cathode, and Ni‐Samaria‐Doped Ceria Cermet Anode
US20040115503A1 (en) Planar electrochemical device assembly
AU2003248623B2 (en) Ceramic anodes and method of producing the same
Wen et al. Material research for planar SOFC stack
Gauckler et al. Solid oxide fuel cells: systems and materials
US7553573B2 (en) Solid state electrochemical composite
US20030077504A1 (en) Unit cell for fuel cell and solid oxide fuel cell
US6887361B1 (en) Method for making thin-film ceramic membrane on non-shrinking continuous or porous substrates by electrophoretic deposition
US6767662B2 (en) Electrochemical device and process of making
US6479178B2 (en) Direct hydrocarbon fuel cells
Howe et al. Micro-tubular solid oxide fuel cells and stacks
JP2011507161A (en) High performance multilayer electrode for use in oxygen-containing gases
Tucker Progress in metal-supported solid oxide fuel cells: A review
CN102473987B (en) An electrical storage device comprising an oxide ion battery module and a battery pack arranged
EP2595230B1 (en) Fuel cell structural body
Stöver et al. Processing and properties of the ceramic conductive multilayer device solid oxide fuel cell (SOFC)

Legal Events

Date Code Title Description
R012 Request for examination validly filed