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WO2018033333A1 - Procédé de fabrication d'une électrode pour un élément d'accumulateur d'énergie électrochimique, élément d'accumulateur d'énergie électrochimique et véhicule - Google Patents

Procédé de fabrication d'une électrode pour un élément d'accumulateur d'énergie électrochimique, élément d'accumulateur d'énergie électrochimique et véhicule Download PDF

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Publication number
WO2018033333A1
WO2018033333A1 PCT/EP2017/068185 EP2017068185W WO2018033333A1 WO 2018033333 A1 WO2018033333 A1 WO 2018033333A1 EP 2017068185 W EP2017068185 W EP 2017068185W WO 2018033333 A1 WO2018033333 A1 WO 2018033333A1
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WO
WIPO (PCT)
Prior art keywords
composite
collector layer
carrier liquid
weight
binder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2017/068185
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German (de)
English (en)
Inventor
Ann-Christin GENTSCHEV
Isaac Lund
Simon LUX
Odysseas Paschos
Thomas Wöhrle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayerische Motoren Werke AG
Original Assignee
Bayerische Motoren Werke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayerische Motoren Werke AG filed Critical Bayerische Motoren Werke AG
Publication of WO2018033333A1 publication Critical patent/WO2018033333A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/133—Electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for producing an electrode for an electrochemical energy storage cell, in particular lithium-ion cell, an electrochemical energy storage cell and a vehicle having an electrochemical energy storage cell.
  • Such an electrochemical energy storage device essentially comprises two electrodes, which are separated by a separator, and an electrolyte for transporting lithium ions between the electrodes.
  • collector films are coated with so-called slurries (coating composition) in which an active material, conductive carbon black and electrode binder are suspended in a solvent, and then dried in a complicated process.
  • slurries coating composition
  • an active material, conductive carbon black and electrode binder are suspended in a solvent, and then dried in a complicated process.
  • this may be, for example, dissolved (e.g., PVdF in NMP) or suspended (e.g., SBR in water).
  • a method for producing an electrode for an electrochemical energy storage cell, in particular a lithium-ion cell comprises the following steps: producing a, in particular plastically deformable, composite comprising the following components: carboxymethyl cellulose (CMC), styrene-butadiene Rubber (SB), polytetrafluoroethylene (PTFE), active material and carrier liquid, wherein the proportion of the carrier liquid on the composite, ie based on the composite coating composition, at least 0.5% by weight and at most 20% by weight, applying the composite to a metallic collector layer and Remove the carrier liquid from the composite.
  • CMC carboxymethyl cellulose
  • SB styrene-butadiene Rubber
  • PTFE polytetrafluoroethylene
  • An electrochemical energy storage cell in particular a lithium-ion cell, according to another aspect of the invention has a metallic collector layer and a dry composite applied to the metallic collector layer, which is obtainable by mixing carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR ), Polytetrafluoroethylene (PTFE), active material and carrier liquid, wherein the proportion of the carrier liquid to the composite is at most 20% by weight, and removing the carrier liquid from the composite after the composite has been applied to the metallic collector layer.
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • PTFE Polytetrafluoroethylene
  • a vehicle according to the invention in particular a motor vehicle, has a large number of electrochemical energy storage cells according to the invention, in particular lithium-ion cells.
  • the invention therefore also relates to a mobile device, in particular for telecommunications, and / or a stationary storage for electrical energy with one or more such electrodes and / or energy storage cells.
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • PTFE polytetrafluoroethylene
  • the proportion of the carrier liquid in the total amount of of the composite is at most 20% by weight. Due to the small amount of carrier liquid in comparison to conventional methods of the prior art, the carrier liquid is to some extent an aid for uniform distribution of the materials in the composite.
  • the moist composite is applied to a metallic collector layer and then dried by removing the carrier liquid (eg by means of heat and / or vacuum).
  • one or more of the binders such as e.g. SBR and / or PTFE, already suspended in carrier liquid or dissolved (e.g., CMC) before mixing with the remainder of the recipe components.
  • carrier liquid or dissolved e.g., CMC
  • at least one binder such as e.g. CMC, in the dry state before and is first dissolved or dissolved in carrier liquid before it is mixed with the remaining components.
  • the invention enables a simple, cost-reduced, environmentally friendly and safe or more reliable production of electrodes for electrochemical energy storage cells.
  • the terms “lithium ion battery” and “lithium ion secondary battery” are used interchangeably.
  • the terms also include the terms “lithium battery”, “lithium ion secondary battery” and “lithium ion cell” and all lithium alloy batteries.
  • the term “lithium ion battery” is used as a generic term for the conventional terms used in the prior art.
  • a “battery” in the context of the present invention also includes a single “electrochemical cell”.
  • At least one of the binders i. CMC, SBR and / or PTFE, and / or the active material, optionally including electrical Leitadditive, dissolved in powder or in carrier liquid or before or when they are mixed together to form the composite.
  • CMC can be thickened with water.
  • CMC or PTFE can be applied as a suspension.
  • bindery or “powder” is meant a substantially dry granular solid of a plurality of particles. Depending on the size, size distribution, agglomeration and / or shape of the particles, a powder may optionally also be a powder or granules.
  • the carrier liquid preferably has at least one aprotic-polar solvent, in particular acetone, N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP), or a protic-polar solvent, in particular alcohol or water.
  • aprotic-polar solvent in particular acetone, N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP), or a protic-polar solvent, in particular alcohol or water.
  • a dispersant is added as a further component in the manufacture of the composite.
  • a particularly good homogeneous mixing of the other components is promoted and stabilized.
  • Polyvinylpyrrolidone (PVP) is preferably used as the dispersant.
  • the proportion of the carrier liquid in the composite is preferably at most 15% by weight, particularly preferably at most 10% by weight.
  • a composite with particularly high and consistent homogeneity is obtained nevertheless easy and safe to process, apply to the collector layer and allow to dry.
  • the proportion of the carrier fluid in the composite is preferably at least 1% by weight, more preferably at least 2% by weight, in particular at least 4% by weight.
  • the composite is made by mixing the components at a temperature which is above the glass transition temperature of one or more of the binders, i. CMC, SBR and PTFE.
  • glass transition temperature also referred to as softening temperature, is meant the temperature above which an amorphous or partially crystalline solid, e.g. powdered CMC or SBR, from a hard elastic state in a soft-elastic or liquid state passes and a gummy to viscous melt is obtained.
  • typical glass transition or softening temperatures are between about 60 and 130 ° C.
  • the Vicat softening temperature (VST) VST / A50, VST / A120, VST / B50 or VST / B120 according to DIN EN ISO 306.
  • the glass transition temperature or softening temperature of the binder or the binder can be reduced.
  • the mixing of the components is carried out at a temperature which is between the glass transition temperature and the melting temperature of one or more of the binders, ie CMC, SBR and PTFE. Above the melting temperature, crystalline or partially crystalline components change from the solid to the liquid state of aggregation.
  • the binder or the binders are converted into a, preferably viscous, melt, which can be processed particularly easily and safely (further). Due to the carrier liquid present in small amounts, such a viscous melt at lower Temperatures are obtained as in a mixture without carrier liquid.
  • the carrier liquid thus also has the function of a plasticizer or plasticizer in this case.
  • At least one of the binders is present at the beginning of the process as a solid or dissolved in carrier liquid or suspended and is softened by heating to a temperature above the glass transition temperature, in particular plastically deformable and correspondingly easy to process.
  • the handling, in particular the dosage, of the binder mixture or of the at least one component of the binder mixture becomes particularly simple.
  • the heating of the components, in particular of the at least one binder can take place at different times or in different time periods, for example even before mixing the at least one binder with the active material and / or the carrier liquid after an initial mixing of the not yet softened binder the active material and / or the carrier liquid, or during the mixing of the at least one binder with the active material and / or the carrier liquid.
  • the resulting composite can be processed in a particularly simple and secure manner or applied to the metallic collector layer.
  • the use of the electrodes obtained in this way significantly increases the lifetime of electrochemical energy storage cells.
  • the temperature between the glass transition temperature and the melting temperature depends on the molecular parameters of the at least one binder, in particular on the polymer used, its side groups and / or its chain length.
  • the temperature or at least the temperature range between the glass transition temperature and the melting temperature can be determined by means of differential scanning calorimetry on the at least one binder. This ensures that the at least one binder is heated on reaching the determined temperature such that the first solid, preferably potformige, at least one binder has been converted into a melt, the one easy and safe mixing with the active material and a simple and safe application of the composite allowed on the metallic collector layer.
  • the binder components are mixed in the presence of the carrier liquid with the active material by kneading, preferably in a kneader or extruder.
  • the kneader or extruder is heatable.
  • the kneader or extruder is heated during the mixing process.
  • the composite is kneaded such that shear forces caused substantially disappear or at least remain small, preferably at a shear gradient of less than 10 s -1 , particularly preferably less than 1 s -1 , in particular substantially 0.1 s -1 .
  • the binder components are mixed with the active material particularly gently, so that a homogeneous composite is obtained in which the polymers or molecular chains contained therein are not significantly impaired by the mixing.
  • the mixing container is preferably designed double-walled, so that it can be cooled and heated during the mixing process in order to keep the processing temperature in the range of the glass transition temperature as constant as possible.
  • At least two of the binder components may also be premixed prior to mixing with the active material and / or conductive carbon black, in particular by kneading, preferably in a pre-kneader or pre-extruder.
  • the premixed binder component mixture can then be mixed particularly well with the active material and optionally with at least one further binder component, so that the composite produced is particularly homogeneous.
  • carrier liquid can be added or present.
  • the mixer or kneader can be heated in order to bring or to hold the components to be mixed or the composite at the respectively required temperature.
  • metering and / or mixing preferably takes place in a closed container.
  • the temperature in the kneading region of the kneader or extruder is preferably adjustable such that the binder components to be mixed and / or the active material can be heated to a temperature above the glass transition temperature or softening temperature.
  • the kneader or extruder optionally also the pre-kneader or extruder, is double-walled, so that the set temperature in the kneading area remains substantially constant even when one or more binder components and / or the active material are refilled. This reliably ensures that a homogeneous and soft, in particular plastically deformable and processable composite is produced.
  • the application of the composite to the metallic collector layer takes place by lamination.
  • the composite and the collector layer preferably without auxiliary materials, materially and interfacially connected.
  • the composite adheres particularly reliably and permanently to the metallic collector layer.
  • the coating mass i. the composite
  • a carrier sheet e.g. of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the active material of the negative electrode contains a lithium-intercalating material, ie a material which can store lithium or lithium ions.
  • the lithium intercalating material preferably comprises carbon, in particular graphite, and / or silicon.
  • the active material additionally contains an electrically conductive material, in particular so-called conductive carbon black, conductive graphite, graphene, carbon nanotube (CNT) or a mixture of two or more of these materials.
  • an electrically conductive material in particular so-called conductive carbon black, conductive graphite, graphene, carbon nanotube (CNT) or a mixture of two or more of these materials.
  • the electrical conductivity of the composite is advantageously increased, so that electrons released during the oxidation are transported particularly well from the reaction site on the surface of the electrode to the metallic collector foil or for the reduction of electrons from the metallic collector foil to the reaction site on the surface of the electrode can be.
  • the use of carbon nanotubes in the composite electrode increases the electrical conductivity of the composite while at the same time reducing the volume fraction or proportion by weight of the carbon nanotubes in comparison with carbon black and / or graphite.
  • the proportion of binder components in the composite is between 1 and 15% by weight.
  • good adhesion properties, in particular on the metallic collector foil, for example a copper layer, and / or good mechanical film properties, in particular high flexibility, of the composite (composite electrode) are achieved, and on the other hand it is avoided that too high a Proportion of the binder mixture in the composite, the electrical conductivity of the electrode produced decreases.
  • the proportion of carboxymethylcellulose (CMC) in the entirety of the binder components is between 1 and 35% by weight and / or the proportion of styrene-butadiene rubber (SBR) in the entirety of the binder components between 1 and 70% by weight and / or the proportion of polytetrafluoroethylene (PTFE) in the total of binder components between 1 and 50% by weight.
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • PTFE polytetrafluoroethylene
  • a composite can be produced in which the combination of CMC and SBR causes a strong adhesion between the composite and the metallic collector layer.
  • the advantageous interaction of the binder mixture of CMC and SBR leads to a homogeneous distribution of the composite on the collector layer.
  • the proportion of PTFE means that the composite can be subjected to a high mechanical load without any brittleness and / or chip peeling in the further processing process, in particular during cutting, punching and / or winding, and / or during operation of the electrode ,
  • the ductile properties of PTFE result in a homogeneous, uniformly flat and smooth surface of the electrode produced, thereby avoiding the discharge of micro-, submicron- or nanoparticles from the electrode, in particular during their production, further processing or operation.
  • a homogeneous surface of the electrode produced leads to a more uniform pressure distribution in the electrochemical energy storage and thus increased reliability or life of the cell itself.
  • PTFE affects the wetting of the electrode produced by fluorinated organic electrolytes and polymer electrolytes advantageous.
  • the production process and / or the operation of the electrode on the one hand is thereby particularly reliably and simply increased and, on the other hand, the service life of the electrodes produced is advantageously increased.
  • the collector layer is heated before or during the application of the composite to a temperature which is above the glass transition temperature of at least one of the binder components in application. senheit the carrier liquid is located.
  • the collector layer is heated to a temperature which is between the glass transition temperature and the melting temperature of the at least one binder component in the presence of the carrier liquid. This reliably prevents the composite, when applied to the metallic collector layer, from cooling off by the release of heat to the metallic collector layer, before the composite reliably adheres to the metallic collector layer, in particular by lamination.
  • the collector layer is heated by passing it over at least one heated roller roller whose temperature is above the glass transition temperature of the at least one binder component in the presence of the carrier liquid.
  • the collector layer is heated particularly reliably.
  • the at least one heated roller is also adapted to introduce the collector layer to the composite, in particular to an outlet opening of a kneader or extruder, from which the mixed composite emerges, for example an outlet nozzle, and preferably for further processing, in particular for cutting, Punching and / or winding, to be transported away.
  • the manufacturing process is kept very simple.
  • the composite is applied to the metallic collector layer by means of a template, by means of which the composite is brought into a predetermined shape and / or layer thickness, and / or by applying a pressure, in particular a contact pressure, by pressing the composite onto the collector layer applied.
  • a pressure in particular a contact pressure
  • the composite adheres to the metallic collector layer under pressure (optionally by heat input) particularly reliable and durable.
  • the collector foil is etched and / or roughened before the application of the composite and / or coated, in particular with a bonding agent.
  • etching the surface of the collector foil is activated and / or roughened and thereby advantageously increases the adhesion forces between the composite and the collector foil.
  • Etching cleans and activates the surface of the collector; this improves in particular the adhesion between electrode and collector foil.
  • a coating, in particular with an adhesive mean, the adhesion between the composite and the collector foil particularly reliable. If an electrically conductive additive is added to the adhesion promoter, the contact resistance between electrode and collector can also be reduced.
  • the layer thickness, in particular of the adhesion promoter is preferably a fraction of the layer thickness of the collector layer, preferably 40%, particularly preferably 20%, in particular substantially 5-15%, of the layer thickness of the collector layer.
  • FIG. 1 shows an example of an apparatus for producing a composite and applying the composite to a collector foil in a highly schematic representation.
  • FIG. 1 shows an example of a device 1 with a mixer 2 for producing a composite 8, a first roller 3 for transporting a metallic collector layer 4 to the mixer 2 and a second roller 3 'for applying the composite 8 produced in the mixer 8 to the collector layer 4 ,
  • the mixer 2 is divided into several areas 5 to 7.
  • a binder mixture 9 an active material 10 and a carrier liquid 18 are metered and mixed in a mixing region 6 to the composite 8, which is finally applied to the metallic collector layer 4 in a discharge region 7.
  • the binder components of the binder mixture 9 and / or the active material 10 are preferably in the form of a powder, suspension or concentrated solution. This allows a simple dosage, for example by weighing or pipetting of the individual components, and mixing.
  • the binder mixture 9 is first prepared in a premixer 1 1.
  • the pre-mixer 1 1 is preferably heatable, so that in powder form, as Suspension or solution in the premixer 1 1 metered introduced binder components of the binder mixture 9 are heated to a temperature above their respective glass transition temperature.
  • the binder components of the binder mixture 9, which are carboxymethylcellulose 12 (CMC), styrene-butadiene rubber 13 (SBR) and polytetrafluoroethylene-14 (PTFE) change into a viscous melt or mass ,
  • the binder mixture 9 is then metered into the mixing region 6, where it is mixed with the active material 10 and the carrier liquid 18 to the, preferably plastically deformable, composite 8, in particular kneaded is.
  • the amount of carrier liquid 18 to be fed or contained in the composite 8 is comparatively small and is preferably at most 20% by weight of the composite 8.
  • the carrier liquid is e.g. acetone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), alcohol or water.
  • a dispersing agent e.g. Polyvinylpyrrolidone (PVP) can be added, through which a particularly good mixing of the components 9 and 12-14, 10 and 18 promoted and stabilized.
  • PVP Polyvinylpyrrolidone
  • an electrically conductive additive such as e.g. Leitruß or Leitgraphit be included.
  • an electrical conductive additive may also be supplied separately (not shown) to the mixing region 6.
  • the mixing region 6 is preferably heated, so that in the mixing region 6 there is a temperature which is above the glass transition temperature or softening temperature of the binder components or binder mixture 9 .
  • the glass transition or softening temperature is preferably reduced by the carrier liquid 18 added or mixed in the mixing region 6 with respect to the glass transition or softening temperature of the individual binder components 12-14 or of the binder mixture 9.
  • the composite 8 produced is applied to the metallic collector layer 4 in the discharge region 7.
  • the discharge area 7 has for this purpose an outlet nozzle 15, via which the composite 8 leaves the mixer 2.
  • the emerging composite 8 is laminated to the collector layer 4 by the second roller 3 ' , preferably under a predetermined pressure.
  • the discharge area 7, in particular the second roller 3 'and / or the discharge nozzle 15, is preferably likewise heatable, so that the composite 8 also passes through the discharge area 7 or the discharge nozzle 15, in particular when applied to the collector layer 4 by the second roller 3 ⁇ is kept at a temperature which is above the glass transition temperature of the binder components 12-14 or of the binder mixture 9.
  • this temperature is also sufficiently high to apply the composite 8 through the outlet nozzle 15 and / or the second roller 3 'to the collector layer 4.
  • the collector layer 4 is moved by the first roller 3 to the outlet nozzle 15 or past this.
  • the rotational speed of the first roller 3 and thus the transport speed of the collector layer 4 is adapted to the dosage of the composite 8 through the outlet nozzle 15, so that a desired amount of the composite 8 is applied to the collector layer 4.
  • the layer thickness of the composite 8 can be adjusted.
  • the second roller 3 ' is not part of the discharge area 7.
  • the second roller 3' together with the first roller 3 may be part of a transport system for the collector layer 4.
  • the first roller 3 is preferably likewise heatable, so that the collector layer 4 passing over the roller 3 is heated to a temperature which is above the glass transition temperature of the binder components 12-14 or of the binder mixture 9.
  • the temperature conditions for laminating the composite 8 to the collector layer 4 are met at the location of the outlet nozzle 15. In particular, this reliably prevents the composite 8 from cooling too much when hitting the collector layer 4 and can no longer be laminated to the collector layer 4.
  • the metallic collector layer 4 can be pretreated before the application of the composite 8.
  • a layer of an adhesion promoter 17, for example a thermoplastic film of a co-polyolefin, co-polyamide, co-polyester or polyurethane, PVdF, PVdF-HFP, acrylate polymer, is applied to the collector layer 4 with the aid of a pretreatment nozzle 16 .
  • the metering of the mediator 17 is adjusted by the pretreatment nozzle 16 to the rotational speed of the first roller 3, so that the layer thickness of the mediator 17 is a fraction of the subsequently determined by the outlet nozzle 15 and / or second roller 3 'layer thickness of the composite 8, for example 50%, 25% or 20% of the layer thickness of the composite 8.
  • the adhesion of the composite 8 on the collector layer 4 is advantageously increased.
  • the pretreatment nozzle 16 may also be designed to etch the metallic collector layer 4.
  • the adhesion of the composite 8 to the collector layer 4 is likewise advantageously increased.
  • the composite 8 contained in the carrier liquid is withdrawn. Due to the comparatively small proportion of the carrier liquid in the total mass of the composite 8, it is e.g. it is possible, by heating the first and / or second roller 3 or 3 'and / or the collector foil 4, to effect or promote evaporation or vaporization of the carrier fluid from the composite 8 even during application. Alternatively or additionally, after the application of the composite, the carrier liquid can also be removed by heating the collector-composite composite and / or generating a negative pressure.
  • a negative electrode with very good mechanical properties in further processing, for example by punching, cutting and winding, as well as in the Operation is obtained, for example, by using a composite 8 of 3% by weight of binder mixture 9 (CMC, SBR and PTFE), 87% by weight of active material 10 (thereof 86% by weight of lithium intercalating material and 1% by weight of electrically conductive material) and 10% by weight of demineralized water, preferably at a temperature above the glass transition temperature of the binder mixture 9 or the binder components 12-14, mixed and the resulting plastically deformable mass on a 12 pm thick copper foil coated with a 2 pm thick adhesion promoter is laminated.
  • CMC binder mixture 9
  • SBR and PTFE binder mixture 9
  • active material 10 thereof 86% by weight of lithium intercalating material and 1% by weight of electrically conductive material
  • demineralized water preferably at a temperature above the glass transition temperature of the binder mixture 9 or the binder components 12-14, mixed and the resulting plastically
  • CMC carboxymethylcellulose 12
  • SBR styrene-butadiene rubber
  • PTFE polytetrafluoroethylene 14
  • Super C45, Imerys 1% by weight of conductive black
  • CMC Carboxymethylcellulose
  • SBR Styrene butadiene rubber

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une électrode pour un élément d'accumulateur d'énergie électrochimique, en particulier un élément lithium-ion, un élément d'accumulateur d'énergie électrochimique et un véhicule. Selon le procédé de l'invention, un composite, en particulier plastiquement déformable, est fabriqué, lequel comprend les constituants suivants : la carboxyméthylcellulose, le caoutchouc styrène-butadiène, le polytétrafluoréthylène, un matériau actif et un liquide porteur, la proportion de liquide porteur sur le composite étant égale à 20 % en poids maximum. Le composite est appliqué sur une couche collectrice métallique et est séché par élimination du liquide porteur.
PCT/EP2017/068185 2016-08-17 2017-07-19 Procédé de fabrication d'une électrode pour un élément d'accumulateur d'énergie électrochimique, élément d'accumulateur d'énergie électrochimique et véhicule Ceased WO2018033333A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016215337.4 2016-08-17
DE102016215337.4A DE102016215337A1 (de) 2016-08-17 2016-08-17 Verfahren zur herstellung einer elektrode für eine elektrochemische energiespeicherzelle, elektrochemische energiespeicherzelle sowie fahrzeug

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WO2018033333A1 true WO2018033333A1 (fr) 2018-02-22

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DE102019130194A1 (de) * 2019-11-08 2021-05-12 Bayerische Motoren Werke Aktiengesellschaft Elektrode, galvanisches Element und Herstellungsverfahren dafür

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010053257A2 (fr) * 2008-11-04 2010-05-14 Energreen Co., Ltd. Procédé de fabrication d'électrode négative pour batterie secondaire nickel/zinc
CN101747571A (zh) * 2008-12-02 2010-06-23 北京有色金属研究总院 一种Ni-MH动力电池负极用的复合粘结剂
KR20150132710A (ko) * 2014-05-16 2015-11-26 파워카본테크놀로지 (주) 코크스를 원료로 하는 활성탄의 입도 조절을 통한 출력 특성 개선방법

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US20060109608A1 (en) * 2004-04-02 2006-05-25 Maxwell Technologies, Inc. Dry-particle based capacitor and methods of making same
US20100021807A1 (en) * 2008-07-24 2010-01-28 Lee Ha-Young Energy storage device
DE102011109813A1 (de) * 2011-08-09 2013-02-14 Li-Tec Battery Gmbh Lithiumionen-Batterie und Verfahren zur Herstellung einer Lithiumionen-Batterie
EP3125338B1 (fr) * 2014-03-26 2019-08-21 Mitsubishi Chemical Corporation Particules composites de graphite pour une électrode négative de batterie rechargeable non aqueuse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010053257A2 (fr) * 2008-11-04 2010-05-14 Energreen Co., Ltd. Procédé de fabrication d'électrode négative pour batterie secondaire nickel/zinc
CN101747571A (zh) * 2008-12-02 2010-06-23 北京有色金属研究总院 一种Ni-MH动力电池负极用的复合粘结剂
KR20150132710A (ko) * 2014-05-16 2015-11-26 파워카본테크놀로지 (주) 코크스를 원료로 하는 활성탄의 입도 조절을 통한 출력 특성 개선방법

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