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WO2011070056A1 - Batterie et son procédé de fonctionnement - Google Patents

Batterie et son procédé de fonctionnement Download PDF

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Publication number
WO2011070056A1
WO2011070056A1 PCT/EP2010/069141 EP2010069141W WO2011070056A1 WO 2011070056 A1 WO2011070056 A1 WO 2011070056A1 EP 2010069141 W EP2010069141 W EP 2010069141W WO 2011070056 A1 WO2011070056 A1 WO 2011070056A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
phase
battery
battery according
electrically conductive
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.)
Ceased
Application number
PCT/EP2010/069141
Other languages
German (de)
English (en)
Inventor
Horst Greiner
Harald Landes
Alessandro Zampieri
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
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 AG, Siemens Corp filed Critical Siemens AG
Publication of WO2011070056A1 publication Critical patent/WO2011070056A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • 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 battery according to the preamble of patent claim 1 and to a method for operating a battery according to claim 10.
  • Rechargeable batteries such as lithium ion on base, have in the mobile world gained a steadily increasing Be ⁇ importance. It involves, in particular, the Ener ⁇ gie Why that are capable of storing to increase steadily.
  • the object of the invention is to present a battery with a possible high energy density, which has a high process reliability.
  • the solution of the problem consists in a battery having the features of patent claim 1 and in a method for operating a battery having the features of patent claim 10.
  • the battery according to the invention according to claim 1 comprises a first electrode and a second electrode, between which a solid electrolyte is arranged. Furthermore, it comprises a process gas feed, which is arranged on the first electrode, which serves to introduce a process gas into the battery.
  • the invention is characterized in that the material of the second electrode, comprising, in a state of the power output of the battery, ie during the Entladungsvor ⁇ gear operates as an anode, at least two phases, a first phase of an electrically conductive material and a second phase of an electrolytically conductive mate rial is ⁇ .
  • an electrically conductive material is understood to be a material in which electrons are moved in the material, as in the case of a metallic line for an electric current flow.
  • an electrolytic line is a line in which charged ions are transported through a material, ie an ionic line. The solid electrolyte between the electrodes thus conducts ions which are conducted from the first electrode, in the discharge case of the battery the cathode, to the anode. It must be gas-tight, ie in particular non-porous, and must not have any significant electrical conductivity, since otherwise it would short the cell internally.
  • An anode means the electrode at which negative charges from the ions of the electrolyte in the form of electrons pass into the electron conductor, with either negative ions moving towards the anode or positive ions moving away from it. It is therefore clear that the technical direction of current in the wire is directed towards the anode, but points away from it in the electrolyte. Anode and cathode thus exchange the place when changing the current direction. By contrast, the sign of the potential position of the electrodes of an electrochemical cell is fixed and does not change when the current direction is reversed, unless the cell is symmetrical, ie the two electrodes are made of the same material, so that their no-load voltage disappears.
  • oxidation processes take place at the anode, ie the anions coming from the electrolyte (negatively charged ions) are discharged or neutral atoms become cations.
  • the anode and cathode now connected to a circuit flowing through these external connecting electrons to the cathode, in this external circuit, the anode acts as a negative terminal (this effect occurs as in the following be ⁇ written in batteries or fuel cells on).
  • the same electrode can operate alternately as an anode or a cathode, depending on whether the battery is charged or discharged.
  • the state of discharge of the battery is described, and the handle of the first electrode is equated with the term cathode and the term second electrode is used with the term anode.
  • the advantage of the invention is that z.
  • negatively charged ions that strike the anode through the solid electrolyte may react with an electrically conductive anode material, thereby releasing electrons that are dissipated as a current flow.
  • the anode material usually reacts with the ions directly at the contact surface to the solid electrolyte. If the electrically conductive anode mate rial ⁇ is consumed at the contact surface, the discharge takes process of the battery to a standstill. The battery is therefore empty.
  • the anode material is constructed such that it also comprises electrolytically conductive phases, through which the charged ions can migrate further into the anode material and can react with the electrically conductive material in the inner volume region of the anode material.
  • electrolytically conductive phases through which the charged ions can migrate further into the anode material and can react with the electrically conductive material in the inner volume region of the anode material.
  • more electrically conductive material remains in contact with the ions for the reaction and more and longer electrons could flow away as a current flow.
  • Such electronic and ionic conduction pathways are typical of high current density and capacitance electrodes found in rechargeable memory cells.
  • the anode material is such built on ⁇ that the electrolytically conductive phase of the Ano ⁇ denmaterials runs through this in the form of continuous strands, because the ions can be transported well with the oxidized electrically conductive phase along this strands. In contrast to the electrolyte layer between the electrodes, it does not interfere with the electrolyte material in ⁇ nerrenz the anode if this also is not electronically conductive.
  • the electrically conductive phase is preferably a tall Me ⁇ consisting again preferably based on lithium, manganese, iron or titanium.
  • the electrolytically conductive phase is again preferably a metal oxide, for example a scandium-doped zirconium oxide or cerium oxide.
  • the material of the anode has a phase composition, after which the electrically conductive phase between 25 vol .-% and
  • the electrolytically conductive phase is also between 25% and 45%, whereby between these two The phases each have an internal porosity of the anode material, which compensates for a volume expansion of the electrically conductive phase in the oxidation.
  • a process gas is supplied by a first electrode disposed on the process gas distributor.
  • the process gas is in an advantageous embodiment of air or the oxygen contained in the air.
  • Another object of the invention is a method for operating a battery according to claim 10.
  • an electronegative gas is fed to a first Elek ⁇ trode, the gas is reduced and the reduced gas in ionic form by a arranged on the first electrode solid state electrolyte layer passed to a second electrode.
  • the discharging process of the battery involves the cathode at the first electrode and the anode at the second electrode.
  • width ⁇ ren the terms cathode and anode used in accordance with this definition.
  • the ionized gas is then introduced into the volume of the anode via electrolytically conductive phase components of the anode.
  • the anode comprises electrically conductive, metallic phase constituents to which the ionized gas is passed via the electrolytically conductive phase and these constituents are oxidized onto electrically and ionically conductive phase constituents.
  • the Bat ⁇ terie invention has the advantage that the anode material is not consumed immediately and a larger reservoir of metallic Pha ⁇ sen personally tone for oxidation with the ionized process gas is available.
  • Figure 1 is a schematic representation of a corresponding
  • FIG. 2 shows a schematic representation of the individual layers arranged in the battery, which form the electrodes and the electrolyte.
  • Figure 3 shows a schematic section, in which a solid-state perelektrolyt and deGrama ⁇ material including an electrically conductive phase and an electrolytically conductive phase in a unloading is shown and
  • FIG. 4 shows the same representation as in FIG. 3 during a charging process of the battery.
  • FIG. 1 schematically shows the construction of a rechargeable battery 2 with an electrolyte transporting oxide ions.
  • This comprises a first electrode, the charging process in the decision forms the cathode, wherein the cathode, a kon ⁇ tinuier Anlagen air stream is fed, which is the so-called process gas.
  • the battery comprises a second electrode, which forms the anode in the discharge process of the battery, which is separated from the cathode by a solid electrolyte.
  • an ionic transport of negatively charged oxygen ions (0 2 ⁇ ) takes place between the cathode and the anode.
  • This oxygen ion flux takes place in the discharge process from the positive electrode (process gas electrode) to the negative electrode, in charge processes, however, this transport takes place in the reverse direction, but the polarity of the electrodes is maintained.
  • the operating temperature of this battery is between 500 ° C and 800 ° C, especially at about 600 ° C. This temperature is particularly useful for the ionic transport in Fest redesignelek- trolyte and for the chemical reactions at the electrodes.
  • the battery 2 according to FIG. 2 has a process gas feed 8, which comprises a process gas distributor 18, which in turn includes webs 22 which form so-called process gas channels 20 through which the process gas, which as a rule is air, flows is directed to a first electrode 4.
  • the first electrode 4 is, as already mentioned be ⁇ , in the discharge process, the cathode.
  • the process gas in the process gas or air ent ⁇ holding oxygen (0 2) to oxygen ions (0 ⁇ 2) is reduced at the Ka ⁇ Thode. 4
  • the oxygen ions 0 2 ⁇ migrate through a solid electrolyte 7, through which the ionic oxygen 0 2 ⁇ in the form of electrolytic conduction to a second electrode, here in the discharge state, the anode, can migrate.
  • the ionic oxygen (0 2 ⁇ ) reacts with the electrically conductive, preferably metallic anode material present there.
  • the electrically conductive Anodenmateri ⁇ al is oxidized and there is a metal oxide.
  • the anode material is designed in the form that it contains ionically conductive phases 12, preferably in the form of strands 14, as shown in FIG. 3, which are present side by side with electrically conductive phases 10.
  • the electrolytically leit ⁇ capable phases 12 contact preferably with the electrically conductive phase 10 and at the same time include pores 16.
  • the oxygen ions can be transported away from the electrolyte surface 24, which is indicated by the arrows in FIG.
  • the oxygen ions react with the electrically conductive phase 10, usually a metal, for example based on lithium, manganese, iron or titanium.
  • the oxide with corresponding metal is formed according to the following equation: x Me + y O 2 " -> Me x O y + 2y e- ( G 1. 1)
  • the electrons released in this case are removed via an anode contact, not shown here.
  • an increase in volume occurs due to the transition of the metallic to the oxidic solid, which is compensated by the pores 16.
  • the oxidizing metal can thus grow into the pores 16. When all the metal is oxidized with oxygen, the battery is discharged.
  • the battery can be recharged by electrical energy is introduced from the outside.
  • the second electrode 6 which acts as an anode during the discharge of the battery, serves as the cathode, the introduced electrons reduce the metal oxide according to the following equation:
  • it can serve to absorb excess energy from energy networks, for example, when in strong sunshine or in strong wind large amounts of energy are available through renewable energy sources that can not be used up at the time of origin. These energies can be introduced into the described battery and stored there. The battery can be used to return the stored energy back to the mains in peak times.
  • FIGS. 2 and 3 are in each case cells of batteries which can be stacked on one another, wherein the cells have, for example, a base area of
  • the channels 20 of the Vietnamese chips 20 of the Vietnamese heartsvertei ⁇ coupler 18 may have a height of 1 mm.
  • the above arrival parent first electrode 4 has a thickness in the sizes ⁇ order of about 30 to 100 ym.
  • the solid electrolyte 7 is applied, which usually has a layer thickness between 30 .mu.m and 50 .mu.m, preferably about 40 .mu.m.
  • the solid electrolyte 7 may preferably consist of a metalldotier ⁇ th metal oxide.
  • the doping metal which consists of scandium in an advantageous form, serves to generate oxygen vacancies in the solid electrolyte, which in turn make it possible to transport the oxygen ions.
  • the second electrode 6 On the solid-state electrolyte 7 follows the second electrode 6, which has a layer thickness between 40 ym and 1000 ym, preferably zugt 100 ym, has.
  • the second electrode 6 is preferably made of a metal-ceramic composite material, a so-called cermet.
  • cermet a metal-ceramic composite material
  • the structure already described can be formed by respectively connecting webs of the electronically conductive metallic phase and the ionically conductive ceramic phase.
  • the material of the second electrode 6 can crack macroscopically, which can lead to destruction of the battery.
  • the metallic mate rial ⁇ a phase content of 25 vol .-% to 45 vol .-% on.
  • the volume fraction is also the proportion of the ceramic phase, which forms the electrolytically conductive phase 12.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une batterie présentant une première électrode et une seconde électrode ainsi qu'une amenée de gaz de processus disposée sur la première électrode, un électrolyte solide étant disposé entre lesdites électrodes. L'invention est caractérisée en ce que le matériau de la seconde électrode comporte au moins deux phases, une première phase étant un matériau électroconducteur et une seconde phase étant un matériau électrolytiquement conducteur ou électroniquement et ioniquement conducteur.
PCT/EP2010/069141 2009-12-10 2010-12-08 Batterie et son procédé de fonctionnement Ceased WO2011070056A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009057718A DE102009057718A1 (de) 2009-12-10 2009-12-10 Batterie und Verfahren zum Betreiben einer Batterie
DE102009057718.1 2009-12-10

Publications (1)

Publication Number Publication Date
WO2011070056A1 true WO2011070056A1 (fr) 2011-06-16

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ID=43622626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/069141 Ceased WO2011070056A1 (fr) 2009-12-10 2010-12-08 Batterie et son procédé de fonctionnement

Country Status (2)

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DE (1) DE102009057718A1 (fr)
WO (1) WO2011070056A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107482283A (zh) * 2017-04-25 2017-12-15 浙江地坤键新能源科技有限公司 一种高性能金属空气电池及其应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011083501A1 (de) * 2011-09-27 2013-03-28 Siemens Aktiengesellschaft Komposit-Anode für Batterie-Zelle
DE102012223794A1 (de) * 2012-12-19 2014-06-26 Siemens Aktiengesellschaft Wiederaufladbarer elektrischer Energiespeicher, insbesondere in Form eines Metalloxid-Luft-Energiespeichers, mit wenigstens einem wenigstens ein Speichermaterial zur Speicherung elektrischer Energie umfassenden Speicherelement
DE102013200759A1 (de) * 2013-01-18 2014-07-24 Siemens Aktiengesellschaft Wiederaufladbarer elektrischer Energiespeicher
DE102013207576A1 (de) * 2013-04-25 2014-10-30 Siemens Aktiengesellschaft Wiederaufladbarer elektrischer Energiespeicher

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4803134A (en) * 1987-06-24 1989-02-07 Eltron Research, Inc. High energy density lithium-oxygen secondary battery
US20050175894A1 (en) * 2004-02-06 2005-08-11 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US20060063051A1 (en) * 2004-09-20 2006-03-23 Jang Bor Z Metal-air battery with ion-conducting inorganic glass electrolyte
US20080182147A1 (en) * 2003-06-10 2008-07-31 Celltech Power Llc Electrochemical device configurations

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FR2279230A1 (fr) * 1974-07-19 1976-02-13 Alsthom Cgee Procede de production d'electricite par transit de pate metal-electrolyte et dispositif pour la mise en oeuvre de ce procede
DE19630210A1 (de) * 1996-07-26 1998-01-29 Dornier Gmbh Brenngaselektrode für elektrochemische Zellen
DE10317361A1 (de) * 2003-04-15 2004-11-04 Bayerische Motoren Werke Ag Brennstoffzelle und/oder Elektrolyseur sowie Verfahren zu deren/dessen Herstellung
DE102005039442A1 (de) * 2005-08-18 2007-02-22 Forschungszentrum Jülich GmbH Schutz anodengestützter Hochtemperaturbrennstoffzellen gegen Reoxidation der Anode
DE102006030393A1 (de) * 2006-07-01 2008-01-03 Forschungszentrum Jülich GmbH Keramische Werkstoffkombination für eine Anode für eine Hochtemperatur-Brennstoffzelle

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4803134A (en) * 1987-06-24 1989-02-07 Eltron Research, Inc. High energy density lithium-oxygen secondary battery
US20080182147A1 (en) * 2003-06-10 2008-07-31 Celltech Power Llc Electrochemical device configurations
US20050175894A1 (en) * 2004-02-06 2005-08-11 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US20060063051A1 (en) * 2004-09-20 2006-03-23 Jang Bor Z Metal-air battery with ion-conducting inorganic glass electrolyte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
COSTAMAGNA P ET AL: "Effect of composition on the performance of cermet electrodes. Experimental and theoretical approach", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 47, no. 7, 11 January 2002 (2002-01-11), pages 1079 - 1089, XP004332202, ISSN: 0013-4686, DOI: DOI:10.1016/S0013-4686(01)00830-1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107482283A (zh) * 2017-04-25 2017-12-15 浙江地坤键新能源科技有限公司 一种高性能金属空气电池及其应用

Also Published As

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