WO2014040790A1 - Élément d'accumulateur lithium-ion doté d'un échangeur d'ions inorganique - Google Patents

Élément d'accumulateur lithium-ion doté d'un échangeur d'ions inorganique Download PDF

Info

Publication number
WO2014040790A1
WO2014040790A1 PCT/EP2013/065964 EP2013065964W WO2014040790A1 WO 2014040790 A1 WO2014040790 A1 WO 2014040790A1 EP 2013065964 W EP2013065964 W EP 2013065964W WO 2014040790 A1 WO2014040790 A1 WO 2014040790A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion exchange
lithium
exchange material
ion
cell
Prior art date
Application number
PCT/EP2013/065964
Other languages
German (de)
English (en)
Inventor
Ingo Zeitler
Original Assignee
Robert Bosch Gmbh
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 Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2014040790A1 publication Critical patent/WO2014040790A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/14—Base exchange silicates, e.g. zeolites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an alkali cell, a separator, an anode, a cathode, processes for their preparation and an energy storage system.
  • the subject of the present invention is an alkali cell comprising an anode, a cathode and a separator disposed between the anode and the cathode.
  • an alkali cell can be understood in particular to be an electrochemical cell or a galvanic element whose electrochemical reaction is based on a redox reaction of an alkali metal.
  • the alkaline cell may comprise an alkali intercalation anode, that is, an anode comprising an intercalation material, such as graphite, into which
  • Alkali metal atoms reversibly incorporated (intercalated) and again outsourced (deintercalated) can be, as well as an alkali metal anode, which is a metallic alkali metal or an alkali metal alloy or with a
  • Metal alloy comprises.
  • the alkaline cell may be a lithium cell.
  • a lithium cell may, in particular, be understood to mean an electrochemical cell or a galvanic element whose electrochemical reaction is based on a redox reaction of lithium.
  • at least one layer disposed between the anode and the cathode includes at least one inorganic ion exchange material loaded with alkali ions.
  • the life-prolonging effect of the ion exchange material is based on the fact that when using high-energy alkaline batteries, in particular high-energy lithium-ion batteries, at the cathode often a resolution of divalent and / or polyvalent metal ions, such as manganese, Nickel and cobalt ions from which the active material of the cathode occurs in the electrolyte. In addition, especially on the cathode side, an oxidation of the electrolyte may occur in which protic degradation products may arise.
  • the degradation products or aging products formed on the cathode side can diffuse through the separator to the anode in conventional cells and be deposited there and / or poisoning of the anode, for example by a, in particular catalytic, degradation of the protective film formed on the anode so-called SEI (English: Solid Electrolyte Interface), and thus lead to accelerated cell aging.
  • SEI Solid Electrolyte Interface
  • at least one layer arranged between the anode and the cathode comprises the alkali-ion-loaded, inorganic ion exchange material
  • degradation products formed on the cathode side must first contain the alkali-ion-charged, inorganic ion exchange material happen.
  • both divalent and polyvalent metal ions such as manganese, nickel and cobalt ions, as well as protons displace the charged alkali ions and release with release of
  • Passing the ion exchange material can therefore only diffuse alkali ions to the anode.
  • a diffusion of both divalent and polyvalent metal ions, such as manganese, nickel and cobalt ions, as well as protons to the anode can be at least significantly reduced or even completely prevented, in particular without the diffusion of
  • a deposition of divalent and polyvalent metals, such as manganese, nickel and cobalt, at the anode and / or poisoning of the anode by the degradation products formed on the cathode side and in particular a degradation of the SEI protective film and a cell aging associated therewith can be advantageously avoided and thus the Life of the cell can be significantly extended.
  • the alkali ions liberated by the ion exchange additionally contribute to an extension of the service life, since this loss of alkali ions which are continuously consumed in the cell to build up the SEI protective film or to repair aging cracks in the SEI protective film on the anode , compensated and so on
  • the ion exchange material-containing layer also has the function of increasing the safety of the cell
  • Safety layer a so-called safety function layer, fulfilled, in which it takes over a mechanically stabilizing and possibly also separating function.
  • a polymeric separator material for example a polyethylene (PE) separator, which contains particles of the inorganic ion exchange material and / or coated with these and otherwise, for example, already at temperatures of> 100 ° C. irreversible shrinkages and deformations could be thermally stabilized and by the inorganic ion exchange material, for example, even in a defect of the polymeric separator layer still a anode and cathode separating layer can be maintained.
  • PE polyethylene
  • a layer of the inorganic ion-loaded, inorganic ion exchange material itself may also function as a separator, so that it may be possible to dispense with the use of temperature-sensitive, polymeric separator materials.
  • the stabilizing and optionally separating action of the inorganic ion exchange material can advantageously a thermal runaway of the cell (English: Thermal Runaway) avoided and thus the safety of the cell can be increased.
  • the inorganic ion exchange material can also be dispensed with the use of chemically non-functional, exclusively for increasing the mechanical stability serving inorganic particles, which advantageously weight and cost and the energy density can be optimized.
  • the ion exchange material It is possible to charge the ion exchange material with ions of an alkali metal which is different from the alkali metal on which the electrochemical (redox) reaction of the cell is based or which is different from the alkali metal of the cathode and / or the anode and / or the electrolyte is.
  • Alkali metals in contrast to divalent and polyvalent metal ions hardly tend to a catalytic effect, which is why by loading with different types of alkali ions, a positive effect can be achieved.
  • Lonen handlingmatenal loaded with ions of the alkali metal on which (also) the electrochemical (redox) reaction of the cell is based.
  • the cell may in particular be a lithium
  • the anode of the cell can be intercalatable and / or alloyable or lithium intercalatable and / or lithium alloyable / lithium alloy capable, for example.
  • the cell may be a lithium-ion cell, in particular with a
  • Lithiuminterkalationsanode for example with graphite as intercalation material, or a lithium metal cell, in particular with a lithium metal anode comprising metallic lithium or a lithium alloy, or with a lithium alloy anode having a lithium alloyable metal / metalloid, for example silicon, or with a Lithium alloyable (semi) metal alloy, for example a silicon alloy, comprises or is formed from, be.
  • the cell may be a (rechargeable bare) secondary cell.
  • the cell is a lithium cell and the at least one ion exchange material loaded with lithium ions.
  • the anode is a
  • Lithium intercalation anode for example based on graphite, or a lithium alloy anode, for example based on silicon.
  • the cell is a lithium-ion
  • the cell in particular with a lithium intercalation anode.
  • the cell may be a lithium-ion cell and the at least one
  • the at least one ion exchange material comprises a silicate and / or aluminate, in particular charged with alkali ions, for example lithium ions.
  • the at least one ion exchange material may be selected from the group of silicates and / or aluminates, in particular charged with alkali ions, for example lithium ions.
  • the at least one ion exchange material may comprise a, in particular alkali ion-loaded, for example, lithium ion-loaded,
  • the ion exchange material may be selected from the group of zeolites, in particular charged with alkali ions, for example lithium ions.
  • the at least one ion exchange material may be a zeolite, especially alkali ion loaded, for example, lithium ion loaded.
  • Zeolites have proven to be particularly advantageous as an ion exchange material, since both a drying effect and an acid-capturing effect can be achieved by these.
  • the use of a dried zeolite therefore advantageously also in the electrolyte located or emerging water and electrolytes or resulting hydrogen fluoride (H F) can be absorbed and thereby rendered harmless to the cell and its environment.
  • the absorption of water and hydrogen fluoride continues to have an advantageous effect on increasing the service life.
  • the at least one ion exchange material may comprise an alkali metal
  • Zeolites for example a lithium zeolite and / or a sodium zeolite.
  • the at least one ion exchange material selected from the group of alkali metal zeolites, for example, the zeolites of lithium and / or sodium.
  • the at least one ion exchange material may be an alkali zeolite, for example, a lithium zeolite and / or a sodium zeolite.
  • the at least one ion exchange material comprises a lithium zeolite.
  • the at least one ion exchange material may be selected from the group of
  • Lithium zeolites Lithium zeolites.
  • ion exchange material may be a lithium zeolite.
  • Lithium zeolites have been found to be particularly advantageous for lithium cells because they can trap and neutralize both divalent and polyvalent metal ions such as manganese, nickel, and cobalt ions, as well as protons, and thereby lithium ions release, which cause no undesirable side reactions at the anode and also advantageously can build up or repair the SEI protective film.
  • the separator comprises the at least one ion exchange material.
  • the separator may advantageously act as a selective ion sieve and filter harmful substances, such as divalent and polyvalent metal ions, for example manganese ions, from the electrolyte.
  • the separator may comprise a layer comprising the at least one ion exchange material.
  • the separator may be a polymer separator, for example a polyolefin separator, for example a polyethylene and / or polypropylene separator, in whose matrix particles of the at least one
  • ion exchange material are introduced and / or, in particular on one or both sides, be provided with a coating containing at least one ion exchange material or formed therefrom, or be formed from the at least one ion exchange material separator.
  • the at least one ion exchange material in particular particles of the at least one ion exchange material, is introduced into a, in particular polymeric, matrix material of the separator.
  • a matrix material for example, polyolefins such as polyethylene (PE) and / or polypropylene (PP) can be used.
  • the separator may comprise a layer of a, in particular polymeric, matrix material, in the matrix of which the at least one ion exchange material, in particular particles of the at least one ion exchange material, is / are introduced.
  • the separator has at least one coating, which the at least one ion exchange material comprises or is formed therefrom.
  • the separator in particular on one or both sides, may have a coating which comprises or is formed from the at least one ion exchange material.
  • the separator may comprise a layer of a, in particular polymeric, material, which, in particular on one or both sides, is provided with a coating which comprises or is formed from the at least one ion exchange material.
  • the layer provided with the coating (s) may both contain and at least be filled with the at least one ion exchange material, for example
  • polystyrene resin such as polyethylene (PE) and / or polypropylene (PP) can be used as the polymeric material for the layer provided with the coating (s).
  • PE polyethylene
  • PP polypropylene
  • other organic materials or inorganic materials may be used for the layer provided with the coating (s).
  • the separator has a layer, in particular an ion exchange material layer, which is formed from the at least one ion exchange material.
  • the separator may only comprise or consist of this (ion exchange material layer), in other words, the (ion exchange material) layer may serve as a separator or be the separator.
  • Layer / coating substantially, for example, more than 90 wt .-%, based on the total weight of the layer, which consists of at least one ion exchange material and only small amounts of other substances, for example to binders comprises.
  • a layer / coating formed of the at least one ion exchange material may be greater than or equal to 95% by weight, optionally even greater than or equal to
  • Binder which may comprise, for example, polyvinylidene fluoride (PVDF), polyolefins such as polyethylene (PE) and / or polypropylene (PP), polyimides, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR) and / or polyacrylates.
  • PVDF polyvinylidene fluoride
  • PE polyethylene
  • PP polypropylene
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • the anode and / or the cathode has a coating which comprises or is formed from the at least one ion exchange material.
  • the side of the anode facing the cathode and / or the side of the cathode facing the anode may have a coating which comprises or is formed from the at least one ion exchange material.
  • the coating can be both in addition to a
  • Separator for example ion exchange material filled and / or
  • coated or formed therefrom be provided as well as itself, for example, serve as the sole separator.
  • the cell may in particular comprise an electrolyte.
  • the electrolyte may in particular comprise at least one electrolyte solvent and at least one conductive salt.
  • the at least one electrolyte solvent may, for example, be selected from the group of organic carbonates, such as ethylene carbonate and / or dimethyl carbonate, ethers and mixtures thereof.
  • the at least one conductive salt may be, for example, a lithium-containing conductive salt, for example lithium hexafluorophosphate (LiPF 6 ).
  • the cathode may be, for example, one or more metal oxides, for example nickel and / or as, in particular electrochemically active, cathode material
  • Cobalt and / or manganese oxide for example, nickel cobalt manganese oxide (NMC).
  • NMC nickel cobalt manganese oxide
  • a cell according to the invention can be produced, for example, by the process according to the invention explained below.
  • the separator according to the invention the cathode according to the invention and / or anode, the inventive method, the inventive
  • Another object of the present invention is a separator for an alkaline cell, such as a lithium cell, for example a lithium-ion cell or a lithium-metal cell, in particular a lithium-ion cell, which at least one with alkali ions loaded or loadable,
  • a lithium cell for example a lithium-ion cell or a lithium-metal cell, in particular a lithium-ion cell, which at least one with alkali ions loaded or loadable
  • the separator may comprise at least one lithium ion-loaded or loadable inorganic ion exchange material.
  • An ion exchange material which can be charged with alkali ions or lithium ions can, in particular, be understood as meaning an ion exchange material which is loaded with ions, for example ammonium ions, which can be exchanged for alkali ions or lithium ions.
  • this includes at least one
  • alkali ion-loaded or alkali ion-loadable for example lithium-ion loaded or
  • the at least one ion exchange material may be selected from the group of,
  • the at least one ion exchange material may be a silicate and / or aluminate, in particular charged with alkali ions or loaded with alkali ions, for example, charged with lithium ions or loaded with lithium ions.
  • the at least one ion exchange material may comprise a zeolite, in particular charged with alkali ions or charged with alkali ions, for example, charged with lithium ions or loaded with lithium ions.
  • the at least one ion exchange material can be selected from the group of, in particular alkali ion-loaded or
  • alkali ion-loadable for example, lithium-ion loaded or
  • Lithium ion-loading, zeolites Lithium ion-loading, zeolites.
  • the at least one ion exchange material may be, in particular, alkali ion loaded or alkali ion loaded, for example, lithium ion loaded or
  • the at least one ion exchange material may comprise an alkali metal zeolite, for example a lithium zeolite and / or a sodium
  • the at least one ion exchange material can be selected from the group of alkali metal zeolites, for example the zeolites of lithium, sodium and / or ammonium.
  • the at least one ion exchange material may be an alkali zeolite, for example a lithium zeolite and / or sodium zeolite and / or ammonium zeolite.
  • Ammonium zeolites can be selected from the group of alkali metal zeolites, for example the zeolites of lithium, sodium and / or ammonium.
  • lithium ions and / or sodium ions in particular lithium ions, loaded and converted into lithium zeolites or sodium zeolites.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • Lonen storagematenal be selected from the group of lithium zeolites.
  • at least one ion exchange material may be a lithium zeolite.
  • the separator may comprise at least one layer comprising or formed from the at least one ion exchange material.
  • ion exchange material in particular particles of the at least one
  • ion exchange material introduced into a, in particular polymeric, matrix material of the separator.
  • a matrix material for example, polyolefins such as polyethylene (PE) and / or polypropylene (PP) can be used.
  • the separator may comprise a layer of a, in particular polymeric, matrix material, in the matrix of which the at least one ion exchange material, in particular particles of the at least one ion exchange material, is introduced.
  • the separator has at least one coating which comprises or is formed from the at least one ion exchange material.
  • the separator in particular on one or both sides, may have a coating which comprises or is formed from the at least one ion exchange material.
  • the separator may comprise a layer of a, in particular polymeric, material, which, in particular on one or both sides, is provided with a coating which comprises or is formed from the at least one ion exchange material.
  • the layer provided with the coating (s) may both contain and at least be filled with the at least one ion exchange material, as well as be free of ion exchange material.
  • the separator has a layer, in particular an ion exchange material layer, which is formed from the at least one ion exchange material.
  • the separator may comprise only this (ion exchange material) layer or consist thereof.
  • (Ion exchange material) layer may serve as a separator or be the separator.
  • the separator may be a polymer separator, for example a polyolefin separator, such as a polyethylene and / or polypropylene separator, in the matrix of which particles of the at least one ion exchange material are introduced and / or which, in particular on one or both sides, with a at least one ion exchange material containing or formed coating is provided, or be formed from the at least one ion exchange material separator.
  • a polyolefin separator such as a polyethylene and / or polypropylene separator
  • a separator according to the invention can be produced, for example, by the method according to the invention explained below.
  • Another object of the present invention is an anode or cathode for an alkali cell, for example a lithium cell, for example a lithium-ion cell or a lithium-metal cell, in particular a
  • a lithium-ion cell having a coating comprising or formed of at least one alkali ion-loaded or loadable inorganic ion exchange material.
  • the anode or cathode may have a coating which has at least one lithium ion-loaded one or loadable, inorganic ion exchange material comprises or is formed therefrom.
  • this includes at least one
  • alkali ion-loaded or alkali ion-loadable for example lithium-ion loaded or
  • the at least one ion exchange material may be selected from the group of silicates and / or aluminates, in particular charged with alkali ions or loaded with alkali ions, for example lithium ion-loaded or lithium-ion-loadable.
  • alkali ion-loaded or alkali ion-loadable for example lithium-ion loaded or
  • lithium ion loadable, silicate and / or aluminate be lithium ion loadable, silicate and / or aluminate.
  • the at least one ion exchange material may comprise a zeolite, in particular charged with alkali ions or charged with alkali ions, for example, charged with lithium ions or charged with lithium ions.
  • the at least one ion exchange material may be selected from the group of, in particular alkali ion-loaded or
  • alkali ion-loadable for example, lithium-ion loaded or
  • the at least one ion exchange material may be a, in particular, alkali ion loaded or alkali ion loadable, for example, lithium ion loaded or
  • the at least one ion exchange material may comprise an alkaline zeolite, for example a lithium zeolite and / or a sodium zeolite and / or an ammonium zeolite.
  • the at least one ion exchange material may be selected from the group of alkali zeolites, for example the zeolites of lithium, sodium and / or ammonium.
  • the at least one ion exchange material may be an alkali zeolite, for example a lithium zeolite and / or sodium zeolite and / or ammonium zeolite.
  • Ammonium zeolites can be used to provide ammonium zeolites.
  • lithium ions and / or Sodium ions in particular lithium ions, loaded and converted into lithium zeolites or sodium zeolites.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • ion exchange material selected from the group of lithium zeolites.
  • at least one ion exchange material may be a lithium zeolite.
  • one side of the anode or cathode can be provided with the coating, or the anode or cathode can be coated on one side with the at least one ion exchange material.
  • that side of the anode, which faces the cathode in the cell structure, and / or the side of the cathode, which faces the anode in the cell structure may have the coating.
  • An anode and / or cathode according to the invention can be produced, for example, by the process according to the invention explained below.
  • Anode or cathode layer for example a conventional one A separator, anode or cathode comprising a coating component comprising at least one alkali ion-loaded or loadable inorganic ion exchange material.
  • the coating can be done, for example, by spraying, dipping and / or
  • the coating component may comprise at least one binder and optionally at least one solvent.
  • the at least one binder may be selected, for example, from the group consisting of polyvinylidene fluoride (PVDF), polyolefins, such as polyethylene (PE) and / or
  • Polypropylene PP
  • polyimides polyimides
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • the at least one binder can on the one hand for binding of individual (powder) particles of the at least one
  • ion exchange material with each other (cohesion) as well as for the connection of the thus formed layer to the separator, anode or cathode layer (adhesion) serve.
  • a method for producing a separator according to the invention may comprise the method steps: mixing a separator
  • a raw material comprising at least one alkali ion-loaded or loadable inorganic ion exchange material and forming a separator layer of the separator-raw-mass ion exchange material mixture.
  • the at least one ion exchange material can advantageously be dispersed into the separator raw material, for example directly in the preparation of the separator, for example in the form of a powder. Separators made in this manner may then advantageously include very finely divided ion exchange material.
  • the at least one ion exchange material may comprise, for example, a silicate and / or aluminate loaded in particular with alkali ions or with alkali ions, for example lithium ion-loaded or lithium-ion-loadable.
  • the at least one ion exchange material may be selected from the group of, in particular, alkali ion-laden or alkali ion-loadable, for example, lithium ion-loaded or lithium ion loadable, silicates and / or aluminates.
  • the at least one ion exchange material may be a silicate and / or aluminate, especially alkali ion loaded or alkali ion loaded, for example, lithium ion loaded or lithium ion loaded.
  • the at least one ion exchange material may comprise a zeolite, in particular charged with alkali ions or charged with alkali ions, for example, charged with lithium ions or charged with lithium ions.
  • the at least one ion exchange material may be selected from the group of, in particular alkali ion-loaded or
  • alkali ion-loadable for example, lithium-ion loaded or
  • Lithium ion-loading, zeolites Lithium ion-loading, zeolites.
  • the at least one ion exchange material may be one, in particular alkali ion loaded or
  • alkali ion loadable for example, lithium ion loaded or
  • the at least one ion exchange material may comprise an alkaline zeolite, for example a lithium zeolite and / or a sodium zeolite and / or an ammonium zeolite.
  • the at least one ion exchange material may be selected from the group of alkali zeolites, for example the zeolites of lithium, sodium and / or ammonium.
  • the at least one ion exchange material may be an alkali zeolite, for example a lithium zeolite and / or sodium zeolite and / or ammonium zeolite.
  • Ammonium zeolites can advantageously be charged by ion exchange with lithium ions and / or sodium ions, in particular lithium ions, and converted into lithium zeolites or sodium zeolites.
  • the process for producing a separator according to the invention, an anode according to the invention or a cathode according to the invention, for example before or after the coating and / or mixing step, can comprise the process step of loading the at least one, in particular alkali ion-loading, inorganic ion exchange material with alkali ions by means of ion exchange , For example, you can do that Ammonium ions are exchanged for lithium ions and / or sodium ions, in particular lithium ions.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • the at least one ion exchange material may comprise a lithium zeolite.
  • a method for producing a cell according to the invention can in particular comprise the method step of assembling an anode layer, a cathode layer and optionally a separator layer into a galvanic cell, wherein the anode layer, the cathode layer and / or the separator layer comprises at least one alkali ion-loaded inorganic ion exchange material.
  • the anode layer, the cathode layer and / or the separator layer can be replaced by an above-described
  • the invention relates to the use of an alkali ion-laden or loadable, in particular charged or charged with lithium ions, inorganic ion exchange material, for example an alkali metal zeolite, in particular lithium zeolite, for the production of an alkali metal.
  • Cell in particular lithium cell, for example lithium-ion cell, for example for producing a separator and / or an anode and / or a cathode of such a cell.
  • lithium cell for example lithium-ion cell
  • separator for example lithium-ion cell
  • cathode for example for producing a separator and / or an anode and / or a cathode of such a cell.
  • the present invention relates to a battery or an energy storage system, in particular for a vehicle, for example a
  • Electric vehicle or hybrid vehicle or for stationary operation,
  • the battery can be any suitable battery according to the invention, a separator according to the invention, an anode according to the invention and / or a cathode according to the invention.
  • the battery can be any suitable battery according to the invention.
  • FIG. 1 shows an enlarged detail of FIG. 1
  • Fig. 3 is a schematic cross-section to illustrate further
  • FIG. 4 shows a schematic cross section to illustrate yet another embodiment of a cell according to the invention.
  • FIG. 1 shows an alkali cell, in particular a lithium-ion cell, which has two electrodes 1, 2, namely an anode 1 and a cathode 2.
  • FIG. 1 shows that the anode 1 and the cathode 2 are spatially separated from one another by a membrane permeable to alkali ions, the so-called separator 3, and have no direct electrical contact with one another.
  • FIG. 1 shows that the anode 1 and the cathode 2 are spatially separated from one another by a membrane permeable to alkali ions, the so-called separator 3, and have no direct electrical contact with one another.
  • the cell additionally has an anode current collector 4, for example of copper, for example in the form of a copper foil, and a cathode current collector 5, for example made of aluminum, for example in the form of an aluminum foil, which in each case on the outside, in particular of the Separator 3 and the counter electrode 1, 2 facing away, side of the anode 1 and the cathode 2 abut.
  • anode current collector 4 for example of copper, for example in the form of a copper foil
  • a cathode current collector 5 for example made of aluminum, for example in the form of an aluminum foil, which in each case on the outside, in particular of the Separator 3 and the counter electrode 1, 2 facing away, side of the anode 1 and the cathode 2 abut.
  • FIG. 2 shows an enlarged detail of FIG. 1 and illustrates that the cell further comprises solvated alkali ions A + in an electrolyte (not shown), which are lithium ions (Li + ) in the case of a lithium cell the separator 3 from the cathode 2 to the anode 1 and back can permeate.
  • solvated alkali ions A + in an electrolyte which are lithium ions (Li + ) in the case of a lithium cell the separator 3 from the cathode 2 to the anode 1 and back can permeate.
  • sodium ions (Na + ) or potassium ions (K + ) can be used instead of lithium ions.
  • FIGS. 1 and 2 show that in the case of a lithium-ion cell, the anode 1 comprises an intercalation material 10, 1, for example graphite, which may initially be lithium-free during the assembly of the cell and only in the first charge cycle with lithium atoms.
  • Li) A can be intercalated.
  • FIG. 2 illustrates that, during the first charging cycle, a protective film 12 is also deposited on the anode 1 from the lithium-ion-containing electrolyte Said SEI, which 12 is formed from degradation products of various chemical composition, is only a few nanometers thick and protects the anode 1 from intercalating electrolyte solvent molecules into the intercalation material 10.1, for example into the graphite, which otherwise results in exfoliation and Destruction of Interkalationsmaterials 10.1 1 could lead.
  • FIGS. 1 and 2 further show that the cathode 2 comprises a cathode material 20, which in the case of a lithium-ion cell is, in particular, an oxide of divalent and / or polyvalent metals, for example a nickel,
  • Manganese and / or cobalt oxide for example nickel manganese cobalt oxide (NMC).
  • NMC nickel manganese cobalt oxide
  • FIG. 2 illustrates that in the case of such cathode materials 20 during operation divalent and / or polyvalent metal ions Y x + , such as
  • Manganese ions (Mn 2+ ), nickel ions (Ni 2+ ) and / or cobalt ions (Co 2+ ) can dissolve from the active material 20 of the cathode 2 in the electrolyte.
  • an oxidation of the electrolyte may occur in the protic degradation products (not shown) may arise.
  • the degradation products Y x + formed on the cathode side can be used in conventional
  • FIG. 2 illustrates that diffusion of the cathode-side decomposition products Y x + through the separator 3 to the anode is achieved by means of an inventive method
  • alkali ion loaded A + especially lithium ion loaded (Li + ),
  • inorganic ion exchange material 40 can be prevented, which is shown schematically in Figure 2 and in the following Figures 3 and 4 by pentagons.
  • Figure 2 shows that the cathode-side degradation products, in particular metal ion, Y x + in the cell of the invention, first the alkali ion A + loaded, in particular lithium ion loaded (Li +), inorganic ion exchange material must pass 40th At the alkali ion-loaded A + , in particular lithium ion-loaded (Li + ), inorganic However, ion exchange material 40 displace both divalent and
  • polyvalent metal ions Y x + such as manganese ions (Mn 2+ ), nickel ions (Ni 2+ ) and / or cobalt ions (Co 2+ ), Y x + and protons, the charged alkali ions A + , in particular lithium ions (Li + ), and are Release of alkali ions A + , in particular lithium ions (Li + ), bound to the ion exchange material 40.
  • the cathode-side degradation products Y x + are trapped before reaching the anode 1 and made harmless.
  • FIG. 2 shows that in this way after passing through the
  • Ion exchange material 40 only alkali ions A + , in particular lithium ions (Li + ), diffuse to the anode 1 and thus prevents deposition of divalent and polyvalent metals, such as manganese, nickel and cobalt, at the anode 1 and / or poisoning of the anode 1 and thus the life of the cell can be significantly extended. Since the separator 3 is in a cell between the cathode 2 and anode 1, this spatially separates and
  • the separator 3 acts as a kind of sieve or filter for the degradation products Y x + .
  • the separator 3 essentially prevents the diffusion of aging products Y x + , ie by its pore size or mesh size, but chemically, namely by the ion exchange and can thus advantageously lead to the desired diffusion of alkali ions A + , in particular Provide lithium ions (Li + ), sufficiently large pore size or mesh size.
  • the liberated by the ion exchange alkali ions A + in particular lithium ions (Li + ), can also advantageously contribute in addition to a structure or a repair of the SEI protective film 12 and extend the life in this way.
  • the alkali ion-loaded A + inorganic ion exchange material 40 may be, for example, a chemically active, in particular
  • the ion exchange material 40 may be an alkali ion-loaded zeolite, in particular Lithium zeolite, be.
  • the mode of action of zeolites charged with alkali ions, in particular lithium zeolites, is similar to water softening in which calcium and magnesium ions dissolved in water are exchanged for sodium ions by addition of a zeolite A, but in the present case manganese is used instead of calcium and magnesium ions.
  • FIG. 2 illustrates that the ion exchange material 40 additionally contributes to the mechanical stabilization and possibly also the separating function of the separator 3 due to its inorganic nature.
  • Matrix material 30 introduced increased ion exchange material particles 40 and a thermal runaway of the cell can be prevented.
  • the embodiments shown in FIG. 3 differ essentially from the embodiment shown in FIG. 2 in that the alkali ion-loaded A + , inorganic ion exchange material 40 is not introduced into the matrix of the polymeric matrix material 30 of the separator 3, but in the form of a coating 3 or of two coatings 2a, 3a, la, 3b is provided.
  • the double reference designation indicates that it is both possible for the separator 3, in particular the matrix material layer 30 of the separator 30, to be coated on one or both sides with a coating 3a, 3b comprising the ion exchange material A + , 40 and also the side of the anode facing the cathode 2 1 or the side of the cathode 2 facing the anode 1 with a coating 1a, 2a comprising the ion exchange material A + , 40.
  • one of the coatings 2a, 3a, 1a, 3b shown is sufficient for protecting the anode 1.
  • the coating (s) 2a, 3a, 1a, 3b can in particular be formed from the alkali ion-loaded A + , inorganic ion exchange material 40 and, in particular, contain at most low amounts of binder.
  • the embodiment shown in FIG. 4 differs essentially from the embodiment shown in FIGS. 2 and 3 in that the cell does not comprise a polymeric matrix material layer 30, but only an ion-exchange layer formed from the alkali-ion-charged A + , inorganic ion exchange material 40 such acts as a separator 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un élément d'accumulateur alcalin, par exemple un élément lithium-ion, qui comprend une anode (1), une cathode (2) et un séparateur (3) disposé entre l'anode (1) et la cathode (2). Pour accroître la durée de vie et la sécurité de l'élément, au moins une couche (3, 3a, 3b, 1a, 2a) disposée entre l'anode (1) et la cathode (2) comprend au moins un matériau échangeur d'ions (40) inorganique chargé en ions alcalins (A+). L'invention concerne en outre un séparateur (3), une anode (1) et une cathode (2) qui comprend un matériau échangeur d'ions (40) inorganique chargé en ions alcalins (A+), ainsi que des procédés pour les fabriquer et un système accumulateur d'énergie équipé en conséquence.
PCT/EP2013/065964 2012-09-11 2013-07-30 Élément d'accumulateur lithium-ion doté d'un échangeur d'ions inorganique WO2014040790A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012216055.8 2012-09-11
DE102012216055.8A DE102012216055A1 (de) 2012-09-11 2012-09-11 Lithium-Ionen-Zelle mit anorganischem Ionenaustauscher

Publications (1)

Publication Number Publication Date
WO2014040790A1 true WO2014040790A1 (fr) 2014-03-20

Family

ID=48875683

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/065964 WO2014040790A1 (fr) 2012-09-11 2013-07-30 Élément d'accumulateur lithium-ion doté d'un échangeur d'ions inorganique

Country Status (2)

Country Link
DE (1) DE102012216055A1 (fr)
WO (1) WO2014040790A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110832673A (zh) * 2018-03-20 2020-02-21 株式会社Lg化学 包括含锂复合物的涂层的隔板、包括所述隔板的锂二次电池和用于制造所述二次电池的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018200978A1 (de) * 2018-01-23 2019-07-25 Robert Bosch Gmbh Separator für eine Batteriezelle und Batteriezelle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728489A (en) * 1996-12-12 1998-03-17 Valence Technology, Inc. Polymer electrolytes containing lithiated zeolite
US20020122986A1 (en) * 2001-03-02 2002-09-05 Labarge William J. Lithium battery with separator stored lithium
DE10347566A1 (de) * 2003-10-14 2005-05-12 Degussa Keramischer Separator für elektrochemische Zellen mit verbesserter Leitfähigkeit
DE102010026613A1 (de) * 2010-07-09 2012-01-12 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Neue Phosphat- und Silikat-basierte Elektrodenmaterialien, insbesondere für Lithiumionen-Batterien und Lithiumkondensatoren

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728489A (en) * 1996-12-12 1998-03-17 Valence Technology, Inc. Polymer electrolytes containing lithiated zeolite
US20020122986A1 (en) * 2001-03-02 2002-09-05 Labarge William J. Lithium battery with separator stored lithium
DE10347566A1 (de) * 2003-10-14 2005-05-12 Degussa Keramischer Separator für elektrochemische Zellen mit verbesserter Leitfähigkeit
DE102010026613A1 (de) * 2010-07-09 2012-01-12 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Neue Phosphat- und Silikat-basierte Elektrodenmaterialien, insbesondere für Lithiumionen-Batterien und Lithiumkondensatoren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110832673A (zh) * 2018-03-20 2020-02-21 株式会社Lg化学 包括含锂复合物的涂层的隔板、包括所述隔板的锂二次电池和用于制造所述二次电池的方法
CN110832673B (zh) * 2018-03-20 2022-04-19 株式会社Lg化学 包括涂层的隔板、包括该隔板的锂二次电池及其制法

Also Published As

Publication number Publication date
DE102012216055A1 (de) 2014-03-13

Similar Documents

Publication Publication Date Title
DE102018118730B4 (de) Konforme Beschichtung von Lithium-Anoden durch Dampfabscheidung für wiederaufladbare Lithium-Ionen-Batterien
WO2013135353A1 (fr) Séparateur contenant du graphène pour batteries lithium-ion
EP2573845B1 (fr) Matériau actif à structure stable pour électrodes de batterie
EP3050142A2 (fr) Élément de batterie électrochimique rechargeable
EP3167500B1 (fr) Cellule électrochimique secondaire
DE112011105969T5 (de) Lithiumsekundärbatterie
DE102011109137A1 (de) Lithiumionen-Batterie
WO2013017217A1 (fr) Batterie lithium-ion
EP3308418A1 (fr) Ncm à haute énergie dopé na et dopé nb, w et/ou mo
DE102016216267A1 (de) Chemische Lithiierung von Elektrodenaktivmaterial
DE102014226396A1 (de) Kompositkathode und diese umfassende Lithiumionenbatterie sowie Verfahren zur Herstellung der Kompositkathode
WO2013135351A1 (fr) Graphène dans des batteries lithium-ion
DE102010027950A1 (de) Kathodenzusammensetzung für Lithium-Schwefel-Zellen
EP2422390A1 (fr) Accumulateur électrochimique au titanate de lithium
WO2013020661A1 (fr) Accumulateur au lithium-ion et procédé de fabrication d'un accumulateur au lithium-ion
DE102014221279A1 (de) Kompositelektrode und diese umfassende Lithiumionenbatterie sowie Verwendung der Lithiumionenbatterie in einem Kraftfahrzeug
WO2014040790A1 (fr) Élément d'accumulateur lithium-ion doté d'un échangeur d'ions inorganique
EP3178125B1 (fr) Élément électrochimique secondaire à base de nickel / fer
DE102022107900A1 (de) Verbund-zwischenschicht für festkörperbatterien auf lithiummetallbasis und verfahren zu deren herstellung
WO2014206600A1 (fr) Électrode pour accumulateur d'énergie électrochimique
DE202007018823U1 (de) Separatoren für Lithium-Batterien
WO2011009620A1 (fr) Batterie au lithium-ion
DE102018203161A1 (de) Precursor-Elektrodenmischung für eine Festkörperzelle
DE102011003016A1 (de) Elektrode für Lithium-Ionen-Batterien und ihre Herstellung
DE102016217709A1 (de) Hybridsuperkondensator mit SEI-Additiven

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13742023

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 13742023

Country of ref document: EP

Kind code of ref document: A1