WO2013017216A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

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Publication number
WO2013017216A1
WO2013017216A1 PCT/EP2012/003121 EP2012003121W WO2013017216A1 WO 2013017216 A1 WO2013017216 A1 WO 2013017216A1 EP 2012003121 W EP2012003121 W EP 2012003121W WO 2013017216 A1 WO2013017216 A1 WO 2013017216A1
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WO
WIPO (PCT)
Prior art keywords
active material
electrochemical
electrochemical cell
electrochemical active
sei
Prior art date
Application number
PCT/EP2012/003121
Other languages
German (de)
English (en)
Inventor
Tim Schaefer
Original Assignee
Li-Tec Battery 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
Priority claimed from DE102011109137A external-priority patent/DE102011109137A1/de
Priority claimed from DE102011109134A external-priority patent/DE102011109134A1/de
Application filed by Li-Tec Battery Gmbh filed Critical Li-Tec Battery Gmbh
Publication of WO2013017216A1 publication Critical patent/WO2013017216A1/fr

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    • 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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to an electrochemical cell, wherein the electrochemical cell has at least one electrode which has electrochemical active material which has been treated, in particular regenerated, by predetermined external measures, in particular by renewal and / or reformation of the SEI layer.
  • the cell can preferably be used in batteries for the drive of vehicles with electric motor, preferably with hybrid drive or in "plug in" operation.
  • electrochemical cells in particular lithium secondary batteries
  • mobile information devices such as, for example, mobile telephones
  • electrochemical cells are used as energy stores in mobile information devices, such as, for example, mobile telephones, in tools or in electrically powered automobiles and in hybrid-powered automobiles.
  • all cells used, but especially those for driving automobiles have to fulfill high requirements: the highest possible electrical capacity and energy density, which remains stable over a large number of charging and discharging cycles, with the lowest possible weight.
  • the longevity of electrochemical cells is often dependent on the aging of the electrodes. During the aging process, the electrochemical cells lose in particular in capacity and performance.
  • SEI layer An example of such a chemical reaction is the formation of the so-called SEI layer.
  • the solid electrolyte interface (SEI) layer is formed at the interface between the active material of the cathode and / or the anode and the nonaqueous electrolyte during the first charge and discharge cycles, and consists essentially of reaction products of electrolyte and active material , Such reaction products may be, for example, Li 2 O, LiF, polymeric compounds or (semi) carbonates such as Li 2 C0 3 .
  • the initial formation of the SEI layer results in an initial irreversible capacity loss of the electrochemical cell.
  • This can lead to the formation of cracks within the SEI layer, as a result of which electrolyte can increasingly penetrate into the active material again and decompose it further, which can lead to a further irreversible loss of capacity and thus to a further progressive aging of the cell; the SEI layer is growing.
  • the invention has for its object to provide an electrochemical cell, which can be produced inexpensively and with low energy and material costs than corresponding electrochemical cells from the prior art.
  • an electrochemical cell comprising at least one negative electrode and at least one positive electrode, wherein the at least one negative electrode and / or the at least one positive electrode comprises electrochemical active material which is capable of producing a "solid electrolyte interface", that is, an SEI layer to be formed on at least parts of the surface of the at least one negative electrode and / or the at least one positive electrode, wherein the electrochemical active material has been treated at least partially by at least one predetermined measure other than charging or discharging an electrochemical cell , and which involves a renewal and / or re-education of the SEI layer.
  • One of the advantages of the present invention is that valuable resources, such as energy and raw materials, needed to re-synthesize electrochemical active material are saved, and costs for producing electrochemical cells are reduced.
  • the at least one predetermined measure is selected from: ⁇ at least partial rejuvenation of an SEI layer by mechanical action of force and / or
  • Electrochemical active material Treatment of the electrochemical active material with at least one SEI-layer-forming and / or SEI-layer-supporting substance, in particular with at least one electrolyte and / or at least one additive.
  • the at least one additive is selected from phenylene carbonate, fluorine-containing or non-fluorine-containing lithium organoborates, in particular lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, in particular lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP).
  • phenylene carbonate fluorine-containing or non-fluorine-containing lithium organoborates
  • LiDFOB lithium difluoro (oxalato) borate
  • LiBOB lithium bis (oxalato) borate
  • fluorine-containing or non-fluorine-containing lithium organophosphates in particular lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (
  • the mechanical force has at least one abrasive process, in particular scraping and / or removal and / or abrasion and / or abrasion.
  • the at least one solvent is selected from polar organic solvents, non-polar organic solvents, or ionic liquids.
  • the electrochemical cell is used for supplying energy to mobile information devices, tools, electrically powered automobiles, hybrid-powered automobiles and stationary energy storage devices.
  • the electrochemical active material is removed irreversibly from an electrochemical cell which has already been subjected to at least one charging and discharging cycle, wherein the at least one charging and discharging cycle was preferably not carried out for the purpose of conditioning the electrochemical cell.
  • the present invention further provides electrochemical active material which has already been subjected to at least one charge and discharge cycle, wherein the at least one charge and discharge cycle is preferably not performed for the purpose of conditioning the electrochemical cell obtainable by employing at least one predetermined measure with respect to the electrochemical active material wherein the at least one predetermined Measure is not a charging or discharging of an electrochemical cell and involves the renewal and / or re-education of the SEI layer.
  • the at least one predetermined measure is selected from:
  • Electrochemical active material Treatment of the electrochemical active material with at least one SEI-layer-forming and / or SEI-layer-supporting substance, in particular with at least one electrolyte and / or at least one additive.
  • the electrochemical active material according to the invention has preferably been removed irreversibly from an electrochemical cell which has been subjected to at least one charge and discharge cycle, wherein the at least one charge and discharge cycle was preferably not carried out for the purpose of conditioning the electrochemical cell.
  • the electrochemical active material according to the invention can preferably be used in electrodes of electrochemical cells.
  • a process for the treatment, in particular for the regeneration of electrochemical active material, by at least one predetermined measure is preferably selected from:
  • an electrochemical cell in the sense of the present invention means any type of device for the electrical storage of energy.
  • the term thus includes in particular electrochemical cells of the primary or secondary type, but also other forms of energy storage, such as capacitors.
  • an electrochemical cell is to be understood as a lithium-ion battery / cell.
  • the electrochemical cell has at least one positive electrode, at least one negative electrode, and at least one separator separating the positive from the negative electrode, wherein the electrodes and separator are at least partially surrounded by at least one sheath.
  • "Brand new" in the sense of the present invention is to be understood that the electrochemical active material used is an electrochemical active material which has not previously been used in an electrochemical cell and has not been subjected to a separation and grinding and / or classification process, that is has not already been applied once to a metallic substrate such as preferably aluminum or copper, or which does not come from a battery that has already been used as a power source at least once, so in the case of a secondary battery at least once charged and / or discharged.
  • the term “virgin” means that this material is used for the first time as an electrochemical active material in an electrode material for an electrode Further, “virgin” also means that in one embodiment, the surface of the electrochemical active material never, even partially a SEI layer was formed, which is formed during the first charging and / or discharging operations.
  • the at least one positive and / or the at least one negative electrode has electrochemical active material which is capable of forming on the surface of the electrochemical active material exposed to the electrolyte a "solid electolyte interface", also called an SEI layer
  • a positive and / or at least one negative electrode in the sense of the present invention contains at least partially treated, in particular regenerated, electrochemically active material
  • the treated electrochemical active material of the at least one positive and / or at least one negative electrode is added as a conductivity additive to the electrode material.
  • the treated electrochemical active material of the at least one positive and / or at least one negative electrode may be used as the sole conductivity additive or with at least one further conductivity additive.
  • a conductivity additive mixture of at least two conductivity additives up to 2%, preferably up to 5%, preferably up to 7%, preferably up to 10%, more preferably between 2.5% to 4.8% treated electrochemical active material as a conductivity additive.
  • An SEI layer according to the present invention is preferably formed during the first charge and / or discharge cycles at least partially on the surface of the electrochemical active material of the at least one positive and / or negative electrode.
  • the formation of the SEI layer can be carried out by reaction of a lithium ion-containing electrolyte with the surface of the active material exposed to the electrolyte. But it is also possible that the formation of the SEI layer by the reaction of an SEI layer-forming or SEI layer affecting additive such as LiBOB occurs.
  • an SEI layer is formed.
  • the SEI layer has electrically insulating and lithium ion conducting properties.
  • a newly formed or renewed SEI layer has an average thickness of greater than 0 nm up to 20 nm, preferably up to 30 nm, preferably up to 40 nm, preferably up to 50 nm.
  • a newly formed or renewed SEI layer on the electrochemical active material of a negative electrode has an average greater thickness than a newly formed or renewed SEI layer on the electrochemical active material of a positive electrode.
  • a newly formed or renewed SEI layer on the electrochemical active material of a negative electrode has an average smaller thickness than a newly formed or renewed SEI layer on the electrochemical active material of a positive electrode.
  • a newly formed or renewed SEI layer on the electrochemical active material of a negative electrode has an average same thickness as a newly formed or renewed SEI layer on the electrochemical active material of a positive electrode.
  • newly formed or “new formation” means that a new SEI layer is formed on the surface of electrochemical active material.
  • up to 70%, more preferably up to 100%, of the surface of the electrochemical active material comprises an SEI layer.
  • Raster or “renewal” in the sense of the present invention means that an already formed on the surface of the electrochemical active material SEI layer is treated and preferably changed in their chemical or physical properties.
  • the treatment of the SEI layer may preferably be carried out such that cracks or pores in the SEI layer are closed or the thickness of the SEI layer is reduced.
  • the at least partial renewal or reformation of the SEI layer has the advantage that electrochemical active material is treated in a simple manner and in particular regenerated, so that it can be reused in an electrode of an electrochemical cell. It has surprisingly been found that electrodes which at least partially comprise electrochemical active material which has already been used in electrodes of electrochemical cells have a conductivity which is up to 10%, preferably up to 15%, higher than electrodes which are used exclusively for the first time in An active material used for an electrochemical cell, ie "brand new" electrochemical active material.
  • the brand-new active material has hitherto only been subjected to at least one charge and / or discharge cycle for the purpose of conditioning.
  • Conditioning is to be understood as meaning that measures are carried out, in particular loading and unloading operations, in particular also at temperatures which are higher or lower than 25 ° C. Furthermore, conditioning may also include storage of charged cells at higher temperatures.
  • the conditioning of an electrochemical cell has the goal is to form a stable SEI layer on the surface of the electrochemical active material for the first time.
  • At least one positive and / or at least one negative electrode is removed from an already operated electrochemical cell, in particular if the at least one positive and / or the at least one negative electrode has a significantly reduced capacitance.
  • the removal of the damaged or no longer fully efficient electrode, and in particular the removal of the electrochemical active material to be treated with at least one predetermined measure from the electrochemical cell is preferably irreversible.
  • the electrochemical cell is at least partially destroyed, as now at least one electrode has been removed, and thus is missing. Destroying does not mean that the electrochemical cell in its entirety is destroyed. It is quite preferable that a damaged electrode is removed, and replaced by another functional electrode, which may have an electrochemical active material according to the invention, and is thus reusable.
  • the term "irreversible" here means that the application of the at least one predetermined measure can only be carried out if the electrode and in particular the electrochemical active material are removed from the electrochemical cell.
  • the remote electrode is first examined for damage, for example with the aid of microscope devices or radiographic methods.
  • predetermined measure means according to the invention that at least one measure is taken, which was preferably determined taking into account the present defect of the electrode electrochemical active material can again be used in an electrode of an electrochemical cell, ie it is preferably regenerated This is achieved according to the invention by an at least partial reformation and / or renewal of the SEI layer located on the surface of the electrochemical active material to be treated by at least one predetermined measure ,
  • the electrode has a mixture which, in addition to the electrochemical active material, also contains at least one further compound and / or at least one further substance, in particular at least one binder and / or at least one conductivity additive and / or electrolyte. It is advantageous, prior to application of the at least one predetermined measure, a possibly in addition to the electrochemical active material containing at least one compound and / or the at least one substance, in particular the at least one binder contained and / or the at least one additive, in particular conductivity additive and / or electrolyte to be separated from the electrochemical active material.
  • the advantage is that the at least one predetermined measure can essentially act completely on the electrochemical active material. The effectiveness of the treatment of the electrochemical active material by the at least one predetermined measure is thereby increased.
  • the methods for separating the electrochemical active material from the optional additional at least one compound and / or at least one substance should be selected depending on the chemical and / or physical properties of the compound to be separated from the electrochemical active material and / or the substance to be separated.
  • the at least one compound to be separated from the electrochemical active material and / or the substance to be separated is not damaged or destroyed in the separation or by the separation process, so that the at least one compound and / or the at least one substance also in an electrochemical cell, preferably after Application of cleaning and / or (up) concentration methods, can be used again.
  • the separation of the at least one compound and / or the at least one substance from the electrochemical active material is carried out using solvents.
  • organic and / or polymeric compounds and / or substances can be separated by the use of suitable solvents due to the ability to substantially completely dissolve in the appropriate solvent substantially insoluble constituents, such as the electrochemical active material, in particular by centrifugation and / or filtering methods.
  • suitable solvents, in particular for separating off binders, in particular polyvinylidene fluoride (PVdF) are dimethylformamide (DMF), dimethylacetamide (DMAC) or, more preferably, N-methylpyrrolidone (NMP) or mixtures thereof.
  • At least one predetermined measure comprises a tapering or at least partial, preferably complete removal of the SEI layer of the electrochemical active material, in particular by mechanical action of force and / or at least partial removal and / or dissolution of the SEI layer using at least one solvent and / or the treatment of the electrochemical active material with at least one SEI-layer-forming and / or SEI-layer-supporting substance, in particular at least one electrolyte or at least one additive.
  • the thickness of the SEI Layer at least partially changed, in particular diluted or the SEI layer can be at least partially completely removed.
  • the effectiveness of this measure can be increased if any other compounds or substances such as conductivity additives or binders are separated from the electrochemical active material before application of the mechanical force.
  • the at least one abrasive process can be applied at least partially to the SEI layer of the electrochemical active material, in particular by means of corresponding devices which preferably have a rough surface.
  • a washing-drum type device which rotates about an axis, which is preferably arranged orthogonal to the direction of gravity, whereby the electrochemical active material contained in the washing drum-like device is set in motion. At this time, the electrochemical active material grinds along the surface of the washing drum-like device, whereby the SEI layer contained on the surface of the electrochemical active material is at least partially subjected to abrasive processes.
  • the electrochemical active material is arranged on a belt-shaped device which performs movements, in particular shaking movements, whereby the SEI layer contained on the surface of the electrochemical active material is at least partially subjected to abrasive processes.
  • the electrochemical active material is arranged between two devices, wherein at least one of the devices has a rough surface facing the electrochemical active material.
  • the SEI layer on the surface of the electrochemical active material is at least partially in contact with the devices.
  • the devices perform abrasive operations by movements, in particular by opposite movements, preferably rubbing movements. It is conceivable to exert pressure on the electrochemical active material located between the devices in order to enhance the effect of the abrasive processes.
  • the at least one predetermined measure is followed by a cleaning of the treated electrochemical active material, and any residues of old electrolyte or old SEI layer to remove.
  • Suitable solvents for at least partial removal and / or dissolution of the SEI layer are polar organic solvents, nonpolar organic solvents, or ionic liquids.
  • ionic liquids are suitable for the at least partial removal and / or dissolution of constituents of the SEI layer which have salts, in particular lithium salts, in particular inorganic lithium salts.
  • the SEI layer is first treated with polar and / or non-polar organic solvents, and then with at least one ionic liquid.
  • the SEI layer is at least partially fluorinated by using at least one SEI layer-forming and / or SEI layer-supporting substance, in particular at least one electrolyte and / or at least one additive, which is preferably selected from phenylene carbonate or non-fluorine-containing lithium organoborates, in particular lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, in particular lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP).
  • the electrolyte and / or additive used are able to influence the formation of the SEI layer on the electrochemical active material, in particular to form the SEI layer on the electrochemical active material with the electrochemical active material.
  • highly pure electrolyte is applied to the electrochemical active material or to parts of the electrochemical active material on which at least partially the SEI layer is to be newly formed.
  • the order of the high-purity electrolyte is preferably carried out by pipetting, brushing, dripping or spraying or other measures appropriate to the electrolyte.
  • an excess of high purity electrolyte in particular up to 3%, preferably up to 4%, preferably up to 5%, preferably up to 6%, preferably up to 7%, excess of high purity Electrolyte used.
  • the term "excess” refers to the (theoretically) calculated amount of electrolyte which is required by the manufacturer of the electrolyte to fill a standard lithium-ion cell, ie using an excess of electrolyte, ie more, preferably up to 7% more Electrolyte as theoretically needed, this has the advantage that the cell has a longer life.
  • the electrolyte may additionally comprise an additive which is preferably selected from fluorine-containing or non-fluorine-containing lithium organoborates, in particular lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, in particular lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP) or mixtures thereof.
  • an additive which is preferably selected from fluorine-containing or non-fluorine-containing lithium organoborates, in particular lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, in particular lithium tetrafluoro (oxalato)
  • the at least partial reformation of the SEI layer on electrochemical active material then takes place during a first charging step. It is according to the invention to accompany the at least partially new formation of the SEI layer on the electrochemical active material by Anwalzmann.
  • the at least one predetermined measure is applied only to that part of the electrochemical active material which has a corresponding one Damage shows.
  • the at least one predetermined measure can also be applied to the entire electrochemical active material of the electrode.
  • a damaged portion of the electrochemical active material of an electrode is removed. This damaged part is, if possible, treated with at least one predetermined measure, in particular regenerated. It is also conceivable that the damaged part of the electrochemical active material of the electrode is irreversibly damaged, so that no predetermined measure can regenerate the electrochemical active material. In this case, the irreversibly damaged electrochemical active material must be disposed of in accordance with the applicable regulations.
  • an electrode pad is placed on the part of the electrode where the (irreversibly) damaged electrochemical active material has been removed. The placement of the electrode pad replaces the removed (irreversibly) damaged electrochemical active material.
  • An “electrode pad” in the sense of the present invention comprises at least partially electrochemical active material which has been treated, in particular regenerated, by at least one predetermined measure
  • virgin electrochemical active material can be used
  • the electrode pad it is also possible, however, for exclusively virgin electrochemical active material to be used in the electrode pad
  • the electrode pad it is possible for the electrode pad to comprise at least one further compound or at least one further substance which is contained in the non-removed electrochemical active material of the electrode
  • the composition of the electrochemical active material contained in the electrode pad substantially corresponds to the composition of the electrochemical active material of the electrode.
  • the electrode has a mixture which, in addition to the electrochemical active material, also has at least one further compound or at least one further substance, in particular at least one binder and / or at least one conductivity additive.
  • the electrode pad used also has a mixture which, in addition to the electrochemical active material, has at least one binder and / or at least one conductivity additive in quantitatively and / or qualitatively equal amounts.
  • the electrode mixture and the electrode pad mixture are preferably substantially identical quantitatively and / or qualitatively.
  • Substantially means that at least up to 50%, at least up to 70%, at least up to 90%, at least up to 99%, preferably 100% of the mixture of the electrode is identical to the mixture of the electrode pad.
  • the electrode pad at least partially at least one binder which is capable of crosslinking and / or at least one additive which is capable of forming an SEI layer, on.
  • this binder and / or the additive is located at the edges of the electrode pad.
  • the electrode pad can in particular be materially connected to the electrode material surrounding the electrode pad, so that the lithium ion migration between the electrochemical active material of the electrode pad and the electrochemical active material of the surrounding electrode material is not hindered.
  • the binder preferably has reactive groups which by activation, in particular by chemical, UV or thermal activation, are capable of crosslinking, preferably for crosslinking with the binder of the surrounding electrode material.
  • activation in particular by chemical, UV or thermal activation
  • the formation of an SEI layer at the interface between electrochemical active material of the electrode pad and electrochemical active material of the surrounding electrode material by the additive takes place during first charge and / or discharge cycles. As a result, the electrode pad "grows" on the surrounding electrode material and is connected to this materially bonded.
  • Cohesive means in this case that the connection is no longer destructive solvable.
  • the electrode pad can no longer be separated from the surrounding electrode material without destruction.
  • the at least one predetermined measure is performed in an atmosphere different from the normal breathable ambient air.
  • the atmosphere is preferably in the form of a protective gas atmosphere, which preferably has substantially, particularly preferably more than 90% to 100%, nitrogen gas or argon gas.
  • the protective gas atmosphere preferably has less than 1 ppm of oxygen and / or less than 1 ppm of water.
  • the electrochemical cell has at least one electrolyte.
  • the electrolyte used can be a nonaqueous electrolyte consisting of at least one organic solvent and at least one alkali metal-containing, preferably lithium ion-containing, inorganic or organic salt.
  • the organic solvent is selected from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB), ethyl acetate (EA), 1,2-dimethoxyethane, ⁇ -butyrolactone, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1 , 3-Dioxylane, sulfulane, ethylmethylsulfone (EMS), tetramethylene sulfone (TMS), butylsulfone (BS), ethylvinylsulfone (EVS), 1-fluoro-2- (methylsulfonyl) benzene (FS), acetonitrile or phosphoric acid esters, or mixtures of these solvents
  • the alkali ion-containing, preferably lithium-ion-containing salt has one or more counterions selected from AsF 6 - , PF 6 -, PF 3 (C 2 F 5 ) 3 - PF 3 (CF 3 ) 3 " BF - BF 2 (CF 3 ) 2 " , BF 3 (CF 3 r, [B (COOCOO) 2 r, [B (C 6 H 5 ) 4 r, Cr, Bf, AICU ', CF 3 S0 3 -, C 4 F 9 S0 3 -, [(CF 3 S0 2 ) 3 Cr, [(CF 3 S0 2 ) 2 NJ “ [(C 2 F 5 S0 2 ) N] " , [(CN) 2 Nr, CI0 4 ⁇ , SiF 6 ⁇ , or mixtures thereof.
  • counterions selected from AsF 6 - , PF 6 -, PF 3 (C 2 F 5 ) 3 - PF 3 (CF 3 ) 3 " BF -
  • ionic liquids may also be used as the solvent.
  • Such "ionic liquids” contain only ions.
  • Preferred cations which may in particular be alkylated are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiuronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations.
  • Examples of useful anions are halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions.
  • suitable ionic liquids are: N-methyl-N-propyl-piperidinium-bis (trifluoromethylsulfonyl) imide, N-methyl-N-butyl-pyrrolidinium-bis (trifluoromethyl-sulfonyl) -amide, N-butyl-N-trimethyl-ammonium bis (trifluoromethylsulfonyl) imide, triethylsulfonium bis (trifluoromethylsulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) -ammonium bis (trifluoromethylsulfonyl) -imide.
  • the separator of the electrochemical cell is impregnated with the electrolyte.
  • the electrolyte may have adjuvants that are commonly used in electrolytes for lithium-ion batteries.
  • radical scavengers such as biphenyl
  • flame retardant additives such as organic phosphoric acid esters or hexamethylphosphoramide
  • acid scavengers such as amines.
  • the electrolyte preferably contains additives preferably phenylene carbonate, fluorine-containing or non-fluorine-containing lithium organoborates, for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, for example lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP), which may affect the formation of the SEI layer on the electrodes.
  • additives preferably phenylene carbonate, fluorine-containing or non-fluorine-containing lithium organoborates, for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, for
  • the electrolyte is configured as a polymer electrolyte which, in addition to the abovementioned salts, solvents, auxiliaries and additives, has a polymer matrix.
  • the polymer or polymer blend for the polymer matrix may be selected from among the polymers that can be used for separators.
  • a polymer electrolyte of a lithium salt and polyethylene oxide is used.
  • Ionic liquids are ionic compounds which are in a liquid state at room temperature.
  • Ionic liquids consist of anions and cations, the size ratio between cations and anions being chosen so that they do not arrange in a crystal lattice at room temperature, whereby a, preferably liquid at room temperature salt can be obtained, which is referred to as ionic liquid.
  • the ionic liquid typically has "large" organic cations, such as the ethylmethylimidazolium cation, and relatively "small” anions, such as the tetrafluoroborate anion.
  • suitable Combination of cations and anions can also affect the properties of the ionic liquid. For example, if a basic anion such as the cyanato anion OCN "is used, the ionic liquid is also more basic in nature.
  • ionic liquids which have cationic imidazole-containing derivatives, in particular the cation ethyl-methyl-imidazolium.
  • Preferred anions can be selected from the group AICI 4 , AI 2 CI 7 , F, F x HF, NO 2 , NO 3 , BF 4 , AIF 4 , PF 6 , AsF 6 , SbF 6 , NbF 6 , TaF 6 , WF 7, CH3CO2, CF 3 C0 2, C 3 F 7 C0 2, CH3SO3, CF3SO3, C 4 F 9 S0 3, (CF 3 CO) (CF 3 S0 3) N, (CF 3 S0 2) 2 N, ( CF 3 S0 2 ) (C 2 F 5 S0 2 ) N, (C 2 F 5 S0 2 ) 2 N, (CF 3 S0 2 ) 3 C, (CN) 2 N, (CN) 3 C, CF 3 BF 3, C 2 F5BF 3, C3F 7 BF 3,
  • negative electrode means according to the invention that the electrode emits electrons when connected to a consumer, for example an electric motor.
  • the negative electrode is the anode.
  • the negative electrode has at least one electrochemical active material which is suitable for incorporation and / or removal of redox components, in particular of lithium ions.
  • the electrochemical active material of the negative electrode is selected from amorphous graphite, crystalline graphite, mesocarbon, doped carbon, fullerenes, graphene, carbonaceous materials, lithium metal, lithium metal alloys, titanates, silicates, silicon, silicon alloys, tin, tin alloys, Niobium pentoxide or mixtures thereof.
  • the negative electrode in addition to the electrochemical active material, also has at least one further additive, preferably an additive for increasing the conductivity, for example based on carbon, for example carbon black, and / or a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • an additive for increasing the conductivity for example based on carbon, for example carbon black
  • a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • the negative electrode has a metallic substrate.
  • this metallic substrate is at least partially coated with electrochemical active material.
  • the negative electrode comprises a binder capable of enhancing adhesion between electrochemical active material and a metallic substrate.
  • a binder comprises a polymer, preferably a fluorinated polymer, preferably polyvinylidene fluoride sold under the tradenames Kynar® or Dyneon®, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethylene (propylene diene monomer) copolymer ( EPDM) and mixtures and copolymers thereof.
  • positive electrode means that the electrode receives electrons when connected to a consumer, such as an electric motor.
  • the positive electrode is the cathode.
  • the positive electrode of the electrochemical cell preferably has at least one electrochemical active material which is suitable for incorporation and / or removal of redox components, in particular of lithium ions.
  • the positive electrode electrochemical material is selected from at least one oxide, preferably one Mixed oxide having one or more elements selected from nickel, manganese, cobalt, aluminum, phosphorus, iron or titanium.
  • the positive electrode comprises a compound having the formula LiMP0 4 , where M is at least one transition metal cation, preferably a transition metal cation of the first series of transition metals of the Periodic Table of the Elements.
  • the at least one transition metal cation is preferably selected from the group consisting of manganese, iron, nickel, cobalt or titanium or a combination of these elements.
  • the compound preferably has an olivine structure, preferably parent olivine, with iron or cobalt being particularly preferred, preferably LiFePO 4 or LiCoPO 4 .
  • the compound may also have a structure different from the olivine structure.
  • the positive electrode comprises an oxide, preferably a transition metal oxide, or a transition metal mixed oxide, preferably of the spinel type, preferably a lithium manganate, preferably LiMn 2 O 4 , a lithium cobaltate, preferably LiCoO 2 , or a lithium Nickelate, preferably LiNi0 2 , or a mixture of two or three of these oxides.
  • the oxides can also be different from the spinel type.
  • the positive electrode in addition to the aforementioned transition metal oxides or exclusively a lithium transition metal mixed oxide containing manganese, cobalt and nickel, preferably a lithium cobalt manganate, preferably LiCoMn0 4> preferably a lithium nickel manganate, preferably LiNio. 5 Mni, 5 0 4 , preferably a lithium-nickel-manganese-cobalt oxide, preferably LiNi 0 , 33 Mno, 33Coo, 33 0 2 , or a lithium-nickel-cobalt oxide, preferably LiNiCo0 2 , which is not in the spinel Type or spinel type.
  • the positive electrode in addition to the electrochemical active material, also has at least one further additive, preferably an additive for increasing the conductivity, for example based on carbon, for example carbon black, and / or a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • an additive for increasing the conductivity for example based on carbon, for example carbon black
  • a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • the positive electrode comprises a binder capable of enhancing adhesion between electrochemical active material and a metallic substrate.
  • a binder comprises a polymer, preferably a fluorinated polymer, preferably polyvinylidene fluoride sold under the tradenames Kynar® or Dyneon®, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethylene (propylene diene monomer) copolymer ( EPDM) and mixtures and copolymers thereof.
  • the positive electrode has a metallic substrate.
  • this metallic substrate is at least partially coated with electrochemical active material.
  • metallic substrate in the sense of the present invention preferably relates to that component of an electrochemical cell which is known as “electrode carrier” and "collector.”
  • the metallic substrate is presently suitable for applying electrochemical active composition and is essentially of a metallic nature, preferably completely metallic nature.
  • At least one electrode has at least partially a metallic substrate.
  • this metallic substrate is at least partially designed as a film or as a network structure or as a fabric, preferably comprising a metal.
  • a metallic substrate comprises copper or a copper-containing alloy.
  • a metallic substrate comprises aluminum.
  • the metallic substrate can be configured as a film, mesh structure or fabric, which preferably comprises at least partially plastics.
  • up to 30%, preferably up to 50%, preferably up to 70%, preferably up to 100%, of the total surface of a metallic substrate has at least one layer which has at least one electrochemical active material which is suitable for incorporation and / or removal of lithium ions suitable is.
  • a separator which separates the positive electrode from the negative electrode and is not or only poorly electron-conducting, and which consists of an at least partially permeable carrier.
  • the support is preferably coated on at least one side with an inorganic material.
  • at least partially permeable carrier is preferably an organic material is used, which is preferably designed as a non-woven fabric.
  • the organic material which preferably comprises a polymer, and more preferably one or more polymers selected from polyethylene terephthalate (PET), polyolefin or polyetherimide, is coated with an inorganic, preferably ion-conducting material, which is more preferably in a temperature range of -40 ° C is at least 200 ° C ion conducting, and preferably at least one compound selected from the group of oxides, phosphates, silicates, titanates, sulfates, aluminosilicates with at least one of zirconium, aluminum, lithium and more preferably zirconium oxide.
  • PET polyethylene terephthalate
  • polyolefin or polyetherimide is coated with an inorganic, preferably ion-conducting material, which is more preferably in a temperature range of -40 ° C is at least 200 ° C ion conducting, and preferably at least one compound selected from the group of oxides, phosphates, silicates, titanates, s
  • the inorganic, ion-conducting material of the separator particles with a size diameter below 100 nm, preferably from 0.5 to 7 pm, preferably from 1 to 5 ⁇ , preferably from 1, 5 to 3 ⁇ > on.
  • the separator has a porous inorganic coating on and in the nonwoven, the aluminum oxide particles having an average particle size of from 0.5 to 7 ⁇ m, preferably from 1 to 5 ⁇ m, and very particularly preferably from 1.5 to 3 ⁇ which are bonded with an oxide of the elements Zr or Si.
  • the maximum particle size is preferably 1/3 to 1/5 and more preferably less than or equal to 1/10 of the thickness of the nonwoven fabric used.
  • Suitable polyolefins are preferably polyethylene, polypropylene or polymethylpentene. Particularly preferred is polypropylene.
  • polyamides, polyacrylonitriles, polycarbonates, polysulfones, polyethersulfones, polyvinylidene fluorides, polystyrenes as organic carrier material is also conceivable. It is also possible to use mixtures of the polymers.
  • a separator with PET as carrier material is commercially available under the name Separion®. It can be prepared by methods as disclosed in EP 1 017 476.
  • nonwoven web means that the polymers are in the form of nonwoven fibers (non-woven fabric). Such nonwovens are known from the prior art and / or can be produced by the known methods, for example by a spunbonding process or a meltblowing process, as described for example in DE 195 01 271 A1.
  • the separator has a nonwoven, which has an average thickness of 5 to 30 ⁇ , preferably from 10 to 20 ⁇ .
  • the fleece is flexible.
  • the nonwoven fabric has a homogeneous pore radius distribution, preferably at least 50% of the pores have a pore radius of 75 to 100 pm.
  • the web has a porosity of 50%, preferably from 50 to 97%.
  • Porcity is defined as the volume of the web (100%) minus the volume of the fibers of the web (corresponds to the volume fraction of the web that is not filled by material.)
  • the volume of the web can be calculated from the dimensions of the web.
  • the volume of the fibers is determined by the measured weight of the fleece under consideration and the density of the polymer fibers.
  • the large porosity of the fleece also allows a higher porosity of the separator, which means that a higher absorption of electrolytes with the separator can be achieved.
  • the separator consists of a polyethylene glycol terephthalate, a polyolefin, a polyetherimide, a polyamide, a polyacrylonitrile, a polycarbonate, a polysulfone, a polyethersulfone, a polyvinylidene fluoride, a polystyrene, or mixtures thereof.
  • the separator consists of a polyolefin or of a mixture of polyolefins. Particularly preferred in this embodiment is then a separator which consists of a mixture of polyethylene and polypropylene.
  • such separators have a layer thickness of 3 to 14 ⁇ .
  • the polymers are preferably in the form of fiber webs, wherein the polymer fibers preferably have an average diameter of 0.1 to 10 ⁇ , preferably from 1 to 4 ⁇ .
  • the term "mixture” or “mixture” of the polymers in the context of the present invention means that the polymers are preferably in the form of their nonwovens, which are bonded together in layers. Such nonwovens or nonwoven composites are disclosed, for example, in EP 1 852 926.
  • this consists of an inorganic material.
  • the inorganic material used are oxides of magnesium, calcium, aluminum, silicon and titanium, as well as silicates and zeolites, borates and phosphates.
  • Such materials for separators as well as methods for producing the separators are disclosed in EP 1 783 852.
  • the separator consists of magnesium oxide.
  • separator 50 to 80 wt .-% of the magnesium oxide by calcium oxide, barium oxide, barium carbonate, lithium, sodium, potassium, magnesium, calcium, barium phosphate or by lithium, sodium, potassium borate, or Mixtures of these compounds, be replaced.
  • the separators of this embodiment have a layer thickness of 4 to 25 pm.
  • Also according to the invention is a method for the treatment, in particular for the regeneration of electrochemical active material by at least one predetermined measure.
  • At least one provided, damaged electrode is examined for damage, in particular with the aid of suitable methods or devices such as microscopes or X-ray methods.
  • the electrochemical active material of the electrode is at least partially of any existing ones - -
  • At least one predetermined measure is applied in particular to the electrochemical active material of the at least one electrode, which has the goal of at least partially treating the electrochemical active material in such a way that the electrochemical active material is again used in an electrode of an electrochemical cell can come, in particular so was regenerated.
  • This is achieved according to the invention by an at least partial reformation and / or renewal of the SEI layer located on the surface of the electrochemical active material to be treated by at least one predetermined measure.
  • the at least one predetermined measure is preferably selected from: ⁇ at least partial rejuvenation of the SEI layer by mechanical work
  • the renewed with at least one predetermined measure, especially regenerated electrochemical active material may be subjected to further treatments, in particular dried and / or with other compounds and / or substances, in particular binder and / or electrolyte and / or solvents and / or Conductive additive and / or optionally brand new electrochemical active material are mixed.
  • a method for assembling an electrochemical cell according to the invention is a method for assembling an electrochemical cell according to the invention.
  • a first, non-optional step provided by at least one predetermined measure, in particular renewed electrochemical active material is provided.
  • the electrochemical active material provided in the first step is mixed with further substances and / or compounds, in particular at least one binder and / or solvent and / or conductivity additive and / or electrolyte and / or optionally brand-new electrochemical active material.
  • the electrochemical active material which is possibly mixed with at least one further substance and / or at least one further compound is applied to a metallic substrate.
  • electrode material is already present on the metallic substrate, and an electrode pad to be applied has the, by at least a predetermined measure, treated, in particular regenerated electrochemical active material.
  • at least one electrode thus produced is joined together with at least one second electrode and an electrically insulating layer located therebetween, in particular a separator or a polymer electrolyte.
  • the second electrode also has, by at least one predetermined measure treated, in particular regenerated electrochemical active material.
  • the electrochemical cell according to the invention can be operated at ambient temperatures of -40 to + 100 ° C.
  • Preferred discharge currents of an electrochemical cell according to the invention are greater than 100 A, preferably greater than 200 A, preferably greater than 300 A, more preferably greater than 400 A.
  • the electrochemical cell according to the invention can be used for supplying energy to mobile information devices, tools, electrically powered automobiles, hybrid-powered automobiles and stationary energy storage devices.

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Abstract

L'invention concerne une cellule électrochimique présentant au moins une électrode négative et au moins une électrode positive, cette ou ces électrodes négatives et/ou cette ou ces électrodes positives présentant une matière active électrochimique capable de former une "interface électrolyte solide", c'est-à-dire une couche SEI sur au moins des parties de la surface de la ou des électrodes négatives et/ou de la ou des électrodes positives. L'invention se caractérise en ce qu'au moins une mesure prédéterminée est appliquée au moins partiellement à la matière active électrochimique, cette mesure n'étant ni un chargement ni un déchargement d'une cellule électrochimique et comprenant une rénovation et/ou une reformation de la couche SEI. L'invention concerne en outre une matière active électrochimique qui a déjà subi au moins un cycle de chargement et de déchargement, ce cycle de chargement et de déchargement n'ayant pas été effectué à des fins de conditionnement de la cellule électrochimique, laquelle matière active électrochimique peut être obtenue par application d'au moins une mesure prédéterminée relativement à la matière active électrochimique, cette ou ces mesures prédéterminées n'étant ni un chargement ni un déchargement d'une cellule électrochimique et comprenant la rénovation et/ou la reformation de la couche SEI.
PCT/EP2012/003121 2011-08-01 2012-07-24 Cellule électrochimique WO2013017216A1 (fr)

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