EP3642894A1 - Procédé de fabrication d'une électrode par fibrillation de liant - Google Patents

Procédé de fabrication d'une électrode par fibrillation de liant

Info

Publication number
EP3642894A1
EP3642894A1 EP18756376.2A EP18756376A EP3642894A1 EP 3642894 A1 EP3642894 A1 EP 3642894A1 EP 18756376 A EP18756376 A EP 18756376A EP 3642894 A1 EP3642894 A1 EP 3642894A1
Authority
EP
European Patent Office
Prior art keywords
electrode component
electrode
binder
mixing process
average particle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18756376.2A
Other languages
German (de)
English (en)
Inventor
Harald Bauer
Bernd Reinsch
Wolfgang Weydanz
Leonore Glanz
Calin Iulius WURM
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.)
Robert Bosch GmbH
GS Yuasa International Ltd
Original Assignee
Robert Bosch GmbH
GS Yuasa International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH, GS Yuasa International Ltd filed Critical Robert Bosch GmbH
Publication of EP3642894A1 publication Critical patent/EP3642894A1/fr
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 present invention relates to a method for producing an electrode for an electrochemical cell, in particular for a battery cell, an electrode produced thereby and an electrochemical cell equipped with such an electrode.
  • Batteries for example based on lithium cells or sodium cells, such as lithium-ion cells or sodium-ion cells, offer for mobile and stationary applications a very high potential for energy saving and local avoidance of emissions.
  • Electrode components mixed with at least one solvent to a (viscous) liquid slurry or slurry, from which then, for example by means of a slot die, a doctor blade or a roller application, a layer or coating is formed.
  • the layers or coatings In order to remove the at least one solvent, the layers or coatings must be dried slowly and controlled in long drying tunnels. However, this leads to a long
  • Electrodes with a limited layer thickness for example of up to 100 ⁇ m, can be produced by wet coating methods. However, for large batteries, such as those needed in electric vehicles, thicker electrodes would be desirable.
  • US 3,898,099 and US 6,335,857 Bl relate to processes for making electrodes.
  • the present invention relates to a method for producing an electrode, for example an anode and / or a cathode, for an electrochemical cell.
  • the method can be used in particular for producing an electrode, for example an anode and / or a cathode, for a battery cell, in particular for a lithium cell or for a sodium cell or for a metal-air cell, for example for a lithium cell.
  • an anode and / or a cathode for a lithium cell, for example, for a lithium-ion cell and / or lithium-metal cell designed.
  • the mixture containing the fibrillated binder is (in particular)
  • Process step a) at least one further electrode component mixed by a mixing process with a low shear stress.
  • a shear stress By the mixing process with a high shear stress, in particular a shear stress can be realized, which is higher than that through the
  • Blending process with a low shear stress is realized shear stress and by which a fibrillation of the at least one binder can be achieved. Therefore, the mixing process with a high shear stress
  • the mixing process with a low shear stress in particular a shear stress can be realized, which is lower than the shear stress realized by the mixing process with a high shear stress. Therefore, the mixing process with a low shear stress can be referred to in particular as a mixing process with a lower shear stress.
  • a mixing process with a high shear stress can in particular be understood as a mixing process in which particles are moved relative to each other, in particular without lubricant, such as liquid, in particular high shear stresses at high velocity gradients of particles to each other and / or from particles to a wall of the mixer occur.
  • the particles can under high shear loads
  • a mixing process with a high shear stress can be done by
  • Blasting method in particular by a jet mill, and / or carried out by a three-roll chair and / or by a two-screw extruder.
  • a mixing process in which material flows are entangled with each other, in particular wherein between the particles to each other and / or of particles to a wall of the mixer only small
  • the particles can receive their shape under low shearing loads in particular and / or only rubbed off.
  • a low shear mixing process by a ploughshare and / or paddle mixer also called a paddle mixer, and / or by a static mixer, for example, based on expansive flows - zi -
  • Example by a sequence of extensions and constrictions in a channel system, and / or performed by a free-fall mixer.
  • the at least one binder By the mixing process with a high shear load, for example by a jet mill (Jet Mill), the at least one binder, for example by relative movement and / or impact / shooting on particles of at least one electrode component, be fibrillated.
  • the at least one binder in particular to long fibrils (binder threads) are formed.
  • the fibrils (binder threads) of the at least one fibrillated binder can then be applied to the surface of the at least one
  • Electrode component to be connected distributed. This allows an electrode to dry from the resulting mixture
  • Manufacturing process ie a manufacturing process, such as a
  • Coating process which / s uses no solvent, for example by dry coating, form. This allows electrodes with a
  • the at least one electrode component Due to the mixing process with a high shear stress, however, the at least one electrode component is heavily mechanically stressed.
  • Anode-active, brittle and / or brittle storage alloys such as silicon and / or tin alloys, and / or coated anode components serving as anode active material or cathode active material, for example in the form of particles having a particle core and a particle shell surrounding the particle core (core shell Particles), and / or in the form of
  • Gradient material particles are affected and / or changed by the mechanical forces acting on it.
  • Under gradient material particles can be understood in particular particles which are within the particle and / or from the surface
  • soft, brittle and / or brittle electrode components can be comminuted and / or ground, which results in a reduction of their average
  • Particle shape can result.
  • Graphite particles are converted properties such as the morphology of the electrode, for example, their porosity, and thus, among other things, for example, their wetting behavior, current carrying capacity and / or capacity and their surface structure and reactivity are adversely affected.
  • coated electrode components for example in the form of particles having a particle core and a particle shell surrounding the particle core (core
  • Shell particles and / or gradient material particles are destroyed. This can likewise lead to a reduction in their reversible storage capacity and / or to an increase in irreversible losses due to, in particular reinforced, surface layer formations, for example due to binding of lithium on their surface, during the first startup of the cell and a negative
  • Dividing into at least two separate mixing stages advantageously makes it possible for the individual in the individual mixing stages
  • Electrode components according to their properties and / or their functionality. For example, mechanically stable
  • Electrode components and / or serving as a conductive additive or conductive agent electrode components whose functionality even with small average particle sizes still given and may be particularly advantageous in the mixing process with a high shear stress and / or mechanically sensitive electrode components and / or as
  • Electrode active electrode components whose functionality may be affected by comminution, be used in the mixing process with low shear stress.
  • the fibrillation of the at least one binder can also advantageously be effected by a material which fulfills a function in the electrode to be produced, which can advantageously affect the specific energy density.
  • a homogeneous mixture can be produced, in particular in which of the at least one binder, for example all, particles of the at least one electrode component and the at least one other
  • Electrode component from which, for example, by a dry manufacturing process and / or by coating, for example by dry coating, for example a Stromableiters or a carrier substrate, an electrode, for example an anode or a cathode, with improved properties and / or (also) with a layer thickness of significantly more than 100 ⁇ m, for example for vehicle batteries,
  • the at least one electrode component and / or the at least one further electrode component may, for example, at least one conductive additive, in particular for improving the electrical conductivity, and / or at least one electrode active material, in particular for energy storage, for example for the storage of lithium, and / or surface-coated particles and / or gradient material particles include or be formed therefrom.
  • the at least one electrode component and / or the at least one further electrode component at least one
  • Conducting carbon for example Leitgraphit and / or at least one amorphous lead carbon, in particular in the form of non-porous carbon particles such as Leitruß, and / or carbon fibers (English: Carbon Fibers) and / or
  • Carbons and / or soft carbon, and / or at least one memory alloy for example at least one lithium memory alloy, for example a silicon and / or tin alloy, in particular as anode active material, and / or at least one metal oxide and / or phosphate, for example
  • Silica in particular for the formation of an anode active material or as
  • Cathode active material and / or at least one Leitzusatz- electrode active material composite, for example at least one Leitzusatz -
  • Anode active material composite or conductive additive cathode active material composite for example at least one carbon electrode active material composite, for example at least one carbon anode active material composite or at least one carbon cathode active material composite, for example at least one carbon metal phosphate composite, for example in the form of conductive coated, for example carbon coated,
  • Electrode active material particles in particular anode active material particles or cathode active material particles, for example in the form of
  • Surface-coated particles for example particles with a particle core and a particle shell surrounding the particle core, so-called core-shell particles, and / or gradient material particles comprise or be formed therefrom.
  • Expanded graphite may, in particular, be understood as meaning a material which is produced by expansion of graphite and serves to provide graphene and / or comprises graphene.
  • a recombination material may, in particular, be understood to mean an active material whose mode of action is based on a recombination and / or phase conversion reaction, such as, for example, Li + Al-> LiAl.
  • insertion and / or hard carbon can be used
  • intercalation capable, in particular more stable, amorphous carbons are understood, in particular which are non-graphitizable and as
  • Anode active material can be used.
  • intercalation capable, in particular more stable, amorphous carbons are understood, in particular which are graphitizable and can be used as anode active material.
  • Process step a in particular by a jet mill (English: Jet Mill) and / or by a three-roll chair and / or by a two-screw extruder and / or by a fluidized bed counter-jet mill and / or a ball mill and / or a Mortar mill and / or a rolling mill (so-called rolling) and / or a tablet press done
  • the high shear forces can be achieved, for example, by a relative movement of the at least one
  • Electrode component against the at least one fibril forming, in particular polymeric binder are formed.
  • the relative movement of the materials to each other can be realized by a rolling mill and / or a tablet press.
  • the at least one electrode component may have a larger average particle size than the at least one binder.
  • the mixing process takes place at a high shear rate, in particular in process step a), by a jet mill (English: Jet Mill) or is thereby carried out.
  • a jet mill can advantageously achieve a homogeneous distribution of the at least one binder on the at least one electrode component in a particularly simple and time-saving manner.
  • a jet mill in particular a gas, for example air, with a very high
  • the jet mill is preferably operated in such a way that the at least one electrode material is not or at least minimally or possibly only controlled damaged.
  • the jet mill can be operated with a minimum necessary speed and / or residence time for application of the at least one binder.
  • the operating conditions for the jet mill can be determined, for example, by test series.
  • the nature of the at least one electrode component can be investigated, for example, by means of scanning electron microscopy (SEM).
  • At least one electrode component for fibrillation of the at least one binder can be used, which, in particular in the mixing process with a high shear stress or under the conditions of
  • Shear load to be mixed, at least one further electrode component Shear load to be mixed, at least one further electrode component.
  • mechanical stressing or comminution of the at least one electrode component in the mixing process with a high shear stress can be tolerated in particular and / or the at least one electrode component can serve as sacrificial material.
  • Shear stress can then be at least one further electrode component, which - for example due to their mechanical stability and / or a sensitive coating - less mechanically stable or more sensitive / sensitive than those in the mixing process with a high
  • Shear stress mixed at least one electrode component is homogeneously incorporated with a lower mechanical stress in the mixture containing the fibrillated binder.
  • Electrode component especially in the mixing process with a high shear stress or under the conditions of the mixing process with a high shear stress, mechanically stable than the at least one further electrode component and / or the functionality of the at least one electrode component less, in particular by the mixing process with a high shear stress or under the conditions of the mixing process with a high shear stress and / or by a mechanical load, for example comminution, impaired as the functionality of the at least one further electrode component.
  • the individual electrode components can be advantageously used according to their properties and / or their functionality.
  • a higher mechanical stability and / or a smaller impairment of the functionality of the at least one electrode component with respect to the at least one further electrode component can be realized in various ways.
  • the at least one electrode component for example in the case of spherical particles, has an average particle size, in particular primary particle size, of
  • the at least one electrode component may have an average particle size, in particular primary particle size, of ⁇ 8 ⁇ m, in particular of ⁇ 6 ⁇ m, and / or an average particle length, for example average fiber length and / or tube length, of ⁇ 8 ⁇ m, in particular of ⁇ 6 ⁇ m. and / or an average particle diameter of ⁇ 8 ⁇ m, in particular of
  • Tube length, or particle diameter are in this range, thereby - in particular from the physical boundary conditions of the mixer, such as the mill, and the material properties - are not further crushed.
  • Particle length for example average fiber length and / or
  • Tube length or an average
  • Particle diameter of ⁇ 10 ⁇ for example, of ⁇ 8 ⁇ , in particular of ⁇ 6 ⁇
  • Particle diameter of ⁇ 10 ⁇ can be reduced by the mixing process with a high shear stress acting crushing effect, since the particles then usually only on an average particle size or on an average Particle length, for example, average fiber length and / or tube length, or to an average particle diameter, for example in a range of> 4 ⁇ to ⁇ 6 ⁇ , crushed.
  • Mixing process can be achieved with a high shear stress.
  • Electrode component has an average particle size in a range of> 0.01 ⁇ to ⁇ 6 ⁇ , for example in a range of> 4 ⁇ to ⁇ 6 ⁇ , and / or an average particle length, for example average fiber length and / or tube length, in a range of > 0.01 ⁇ to ⁇ 6 ⁇ , for example in a range of> 4 ⁇ to ⁇ 6 ⁇ , and / or an average particle diameter in a range of> 0.01 ⁇ to ⁇ 6 ⁇ , for example in a range of> 4 ⁇ to ⁇ 6 ⁇ , on or is used with a / such. So can the through the mixing process with a high shear stress acting on crushing effect minimized and high mechanical stability of the at least one electrode component can be achieved in the mixing process with a high shear stress.
  • the at least one further electrode component for example in the case of spherical particles, has a larger average particle size, in particular primary particle size, and / or, for example in the case of fibrous and / or tubular particles, a larger average particle length, for example a larger one average fiber length and / or tube length, and / or, for example, in the case of platelet-shaped particles, a larger average particle diameter than the at least one
  • the at least one electrode component has a smaller average particle size and / or a smaller average particle length, for example a smaller average fiber length and / or tube length, and / or a smaller average one
  • Electrode component, the at least one electrode component with respect to the at least one further electrode component may be mechanically stable in the mixing process with a high shear rate.
  • the at least one further electrode component may have an average particle size, in particular primary particle size, and / or an average particle length, for example an average fiber length and / or tube length, and / or an average particle size
  • the at least one further electrode component may have an average
  • the at least one further electrode component is used in the mixing process with a low shear stress
  • the at least one further electrode component for example against strong mechanical loads or comminution effects, in particular by the mixing process with a high shear stress, can be spared, which makes it possible even more sensitive or mechanically less stable materials, such as relatively soft, ply
  • Intercalation graphite and / or coated particles such as core-shell particles, and / or gradient material particles, as material-friendly process.
  • Electrode component based on their average particle size, particle length, such as fiber length and / or tube length, and / or particle diameter, the at least one electrode component in view of a smaller impairment of their functionality by the
  • Blending process can be selected with a high shear stress with respect to the at least one further electrode component.
  • the at least one electrode component comprises at least one conductive additive, in particular for improving the electrical conductivity, or is formed therefrom.
  • the at least one electrode component may comprise or be formed from at least one conductive carbon and / or at least one conductive metal.
  • conductive additives in particular for improving the electrical conductivity, for example of conductive carbon, for example Leitgraphit and / or amorphous Leitkohlenstoffen such Leitruß, and / or
  • Carbon fibers (English: Carbon Fibers) and / or carbon nanotubes (CNT) and / or graphene and / or expanded
  • Graphite, and / or lead metals is characterized by a high mechanical load and / or by comminution usually significantly less impaired than, for example, the functionality of electrode active materials,
  • energy storage for example for the storage of lithium, for example of anode active materials and / or
  • Cathode active materials for example intercalation and / or insertion and / or recombination materials, such as intercalated graphite and / or insertable and / or intercalatable amorphous carbons, such as hard carbon and / or soft carbon, and / or memory alloys.
  • intercalation and / or insertion and / or recombination materials such as intercalated graphite and / or insertable and / or intercalatable amorphous carbons, such as hard carbon and / or soft carbon, and / or memory alloys.
  • conductive additives such as conductive carbon, such as lead graphite and / or Leitruß
  • Fibrillation of at least one binder can be supported advantageously.
  • the at least one electrode component comprises conductive graphite or is formed therefrom.
  • Lead graphite has a smaller average particle size, for example, in one
  • the at least one electrode component used in the highly mechanically stressing process step, in particular in process step a) can be, for example, a lead graphite which is marketed under the trade name KS4 and / or KS6 by Imerys (Timcal) or under another name
  • the at least one electrode component comprises amorphous conductive carbon, in particular in the form of nonporous carbon particles, or is formed therefrom.
  • the at least one electrode component comprises amorphous conductive carbon, in particular in the form of nonporous carbon particles, or is formed therefrom.
  • Electrode component while Leitruß comprise or be formed therefrom.
  • the at least one electrode component comprises
  • Carbon fibers (English: carbon fibers) and / or carbon nanotubes
  • Carbon fibers and / or carbon nanotubes are advantageously particularly well suited for fibrillation of the at least one binder.
  • Carbon fibers and / or carbon nanotubes are advantageously particularly well suited for fibrillation of the at least one binder.
  • carbon fibers and / or carbon nanotubes in the mixing process with a high shear load carbon fibers and / or carbon nanotubes particularly well dispersed and - possibly occurring in other mixing processes, in particular with a low shear stress - problems in the dispersion or in the homogeneous mixing of Carbon fibers and / or carbon nanotubes are dissolved.
  • Carbon nanotubes are particularly easy mixed or dispersed.
  • Diameter of ⁇ 1 ⁇ usually of ⁇ 200 nm and / or with an average particle length, such as fiber length and / or
  • Tube length in a range of> 2 ⁇ to ⁇ 200 ⁇ , for example from> 2 ⁇ to ⁇ 20 ⁇ , and / or carbon nanotubes with a
  • average diameter of ⁇ 50 nm for example in a range of> 0.3 nm to ⁇ 50 nm, and / or with an average particle length, for example with an average fiber length and / or tube length, in a range of> 10 nm to ⁇ 50 cm, for example, from> 10 nm to ⁇ 20 ⁇ , include or be formed from.
  • Electrode component for example, carbon fibers with a
  • average particle length for example, with an average fiber length and / or tube length, in a range of> 2 ⁇ to ⁇ 10 ⁇ or ⁇ 8 ⁇ or ⁇ 6 ⁇ and / or carbon nanotubes with a
  • the at least one electrode component comprises graphene and / or expanded graphite or is formed therefrom.
  • the at least one electrode component comprises at least one Leitzusatz- electrode active material composite, for example, at least one Leitzusatz anode active material composite or at least one Leitzusatz- cathode active material composite, for example at least one carbon electrode active material composite, such as at least one
  • conductive coated anode active material particles or in the form of conductive coated cathode active material particles for example in the form of carbon coated electrode active material particles, in the form of carbon coated anode active material particles or in the form of carbon coated cathode active material particles, for example in the form of carbon coated metal phosphate particles, in particular with an average particle size of ⁇ 10 ⁇ m, for example ⁇ 8 pm or ⁇ 6 pm, for example ⁇ 4 pm or ⁇ 2 pm or ⁇ 1 pm.
  • Such composites can be processed as Leitzusatz, partially serve as active material and be mechanically stable.
  • the at least one electrode component comprises at least one conductive metal, for example silicon and / or tin and / or another metal and / or an alloy, for example in the form of a metallic powder, or is formed therefrom ,
  • the at least one further electrode component comprises at least one electrode active material, in particular for energy storage, for example for the storage of lithium.
  • the at least one more electrode active material in particular for energy storage, for example for the storage of lithium.
  • Electrode component at least one anode active material and / or Cathode-active material, for example at least one Interkalationsmaterial and / or insertion material and / or recombination material, for example, at least one lithium or sodium intercalation and / or -Insertions- and / or -Rekombinationsmaterial, include or be formed therefrom.
  • the at least one further electrode component comprises intercalation graphite and / or amorphous carbon capable of insertion and / or intercalation, for example hard carbon and / or soft carbon, in particular as anode active material, or is formed therefrom.
  • intercalation graphite and / or amorphous carbon capable of insertion and / or intercalation, for example hard carbon and / or soft carbon, in particular as anode active material, or is formed therefrom.
  • the at least one further electrode component comprises a memory alloy or is formed therefrom.
  • the at least one further electrode component may comprise or be formed from a lithium memory alloy, for example a silicon and / or tin alloy.
  • the at least one further electrode component comprises at least one metal oxide and / or phosphate or is formed therefrom.
  • the at least one further electrode component is configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured to be configured of the at least one further electrode component
  • Silica in particular for the formation of an anode active material or as
  • Anode-active material, and / or at least one metal oxide, in particular at least one layer oxide and / or at least one spinel, for example at least one nickel and / or cobalt and / or manganese oxide, for example lithium-nickel and / or cobalt and / or manganese oxide, and / or at least one metal phosphate, for example at least one iron and / or manganese and / or cobalt phosphate, for example at least one lithium iron and / or manganese and / or cobalt phosphate, for example based on the formula: L1MPO4 with M Fe, Mn and / or Co, in particular as
  • Cathode active material include or be formed from.
  • the at least one electrode component and / or the at least one further electrode component can be spherical and / or
  • Aspherical particles include or be formed from.
  • Particle shape can be adjusted.
  • the at least one electrode component comprises spherical particles or is formed therefrom.
  • the at least one electrode component can comprise or be formed from stable and / or compact, spherical particles.
  • Spherical particles such as MCMB (English: MesoCarbon MicroBeads)
  • aspheric particles such as platelet-shaped graphites, such as intercalated graphites.
  • the at least one further electrode component accordingly comprises, for example, insofar as aspheric particles are to be used in the method - in particular due to the lower one already explained
  • the at least one electrode component is therefore free of
  • the at least one electrode component may be free of particles having a particle core and a particle shell surrounding the particle core, so-called core-shell particles, and / or free of gradient material particles. This can be applied in particular if the
  • Gradient material particles are known to have lower mechanical stability.
  • Gradient material particles are damaged and / or destroyed. Therefore, it may be advantageous to mix them in the mixing process with a low shear stress.
  • the at least one further electrode component comprises
  • surface-coated particles for example particles having a particle core and a particle shell surrounding the particle core, so-called core-shell particles, and / or gradient material particles.
  • the at least one electrode component is free of electrode active materials, in particular for energy storage, for example for the storage of lithium, for example free of anode active materials and / or free of
  • Functional impairment of electrode active materials may, however, optionally - as already explained - by a small average particle size and / or a small average particle length,
  • conductive additive electrode active material composites for example, a small average fiber length and / or tube length, and / or a low average particle diameter, in particular of ⁇ 10 pm, for example of ⁇ 8 pm, for example of ⁇ 6 pm, counteracted.
  • conductive additive electrode active material composites in particular in the form of
  • Carbon-metal phosphate composites for example in the form of
  • carbon-coated metal phosphate particles with an average particle size of ⁇ 10 pm, for example of ⁇ 6 pm, in particular of ⁇ 4 pm or ⁇ 2 pm or ⁇ 1 pm, to be mechanically stable in high-shear mixing processes.
  • Functionality impairment of the at least one electrode component with respect to the at least one further electrode component by means of average particle size and / or average particle length, for example average fiber length and / or tube length, and / or average particle diameter and / or function as Leitzusatz or as electrode active material and / or by
  • Particle shape and / or by means of particle structure can - especially in
  • Electrode components which have one or more of the above
  • Electrode components can be difficult and can, for example, in particular only, on the basis of series of experiments with the graded electrode components and with the respective types of mixer to be used with a high shear load, for example with a jet mill or other mixer with a high shear stress, and by examining under comparable Mixing conditions produced mixtures,
  • SEM scanning electron microscopy
  • the at least one, in particular polymeric, binder may for example be at least one polymer which conducts lithium ions or conducts lithium ions, for example at least one polyalkylene oxide, for example polyethylene oxide (PEO), and / or at least one polyester and / or at least one
  • Polyacrylate and / or at least one polymethacrylate for example Polymethyl methacrylate (PMMA), and / or at least one polyacrylonitrile and / or at least one fluorinated and / or unfluorinated polyolefin, for example polyvinylidene difluoride (PvdF) and / or polytetrafluoroethylene (PTFE, Teflon) and / or polyethylene (PE) and / or polypropylene (PP ), and / or a copolymer thereof, for example polyethylene oxide-polystyrene copolymer (PEO-PS)
  • PMMA Polymethyl methacrylate
  • PEO-PS polyacrylonitrile
  • fluorinated and / or unfluorinated polyolefin for example polyvinylidene difluoride (PvdF) and / or polytetrafluoroethylene (PTFE, Teflon) and / or polyethylene (PE) and / or poly
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the at least one, in particular polymeric, binder comprises at least one polymer which conducts lithium ions or conducts lithium ions and / or a polymer
  • the at least one binder at least one polyalkylene oxide, for example polyethylene oxide, and / or at least one polyester and / or at least one polyacrylate and / or at least one polymethacrylate, for example polymethyl methacrylate, and / or at least one polyacrylonitrile and / or a Copolymer thereof, for example polyethylene oxide-polystyrene (PEO-PS copolymer) and / or acrylonitrile-butadiene
  • PEO-PS copolymer polyethylene oxide-polystyrene
  • Styrene copolymer include or be formed from.
  • the at least one, in particular polymeric, binder may comprise or be formed from at least one polyalkylene oxide, in particular polyethylene oxide, and / or a copolymer thereof.
  • the at least one binder can be used in particular in an amount which ensures that the at least one binder can bind to all particles of the at least one electrode component and the at least one further electrode component equally. In particular, a complete covering of the surface of the particles of the at least one electrode component and the at least one further electrode component can be avoided. Preferably, only point contacts between the at least one binder and particles of the at least one electrode component and the at least one further electrode component are formed. Thus, the largest possible surface active for the actual storage reaction can be achieved.
  • ⁇ 30 wt .-% for example> 0.25 wt .-% to ⁇ 20 wt .-%, for example> 0.5 wt .-% to ⁇ 15 wt .-% or ⁇ 10 wt .-% or ⁇ 5 wt .-%, of the at least one electrode component used.
  • ⁇ 90% by weight for example> 0.1% by weight to ⁇ 80% by weight, of the at least one further electrode component used.
  • the at least one binder In the process, for example, the at least one binder,
  • first a first binder and then one or more further binders are added and mixed with the at least one electrode component and / or to the at least one binder first, a first electrode component of the at least one electrode component and then a second electrode component are added and mixed by the at least one electrode component.
  • a first mixing process with a high
  • Shear stress at least a second binder and (the) at least one electrode component which may be, for example, equal to or different from the at least one electrode component used in the first mixing process, mixed to at least a second mixture containing fibrillated binder. This may be beneficial to the binder fibrillation and / or the
  • Binder electrode component mixing effect
  • step a) by a first mixing process with a high shear stress, at least one binder, optionally at least one first binder, and a first electrode component from the at least one electrode component to a first , fibrillated binder-containing mixture and by at least one second mixing process with a high shear stress (der) at least one binder which, for example, equal to or different from the at least one used in the first mixing process
  • Binder for example, at least a second binder, and a second electrode component of the at least one electrode component to at least a second, fibrillated binder-containing mixture mixed. This can have an advantageous effect on binder-electrode component mixing and / or binder fibrillation.
  • the first and second mixture containing fibrillated binder can then be used, in particular
  • Process step b) are mixed with (the) at least one further electrode component by the mixing process with a low shear stress.
  • the method for producing an anode is designed. It can be at least one more
  • Electrode component in particular at least one anode active material, such as intercalation graphite and / or insertion and / or
  • Intercalation capable, amorphous carbon, for example hard carbon and / or soft carbon, and / or a memory alloy, for example a lithium memory alloy, for example a silicon and / or tin alloy, and / or a metal oxide, in particular silicon oxide, include or be formed from. Based on the total weight of
  • Electrode components of the anode for example,> 80 wt .-%, optionally> 90 wt .-%, of the at least one anode active material can be used.
  • the total weight of the electrode components of the anode in particular in the form of the at least one electrode component,> 5% by weight to ⁇ 10% by weight of the at least one conducting carbon, for example amorphous
  • Guide carbon in particular Leitruß, and / or Leitgraphit and / or
  • the at least one binder and the at least one conducting carbon may contain a first fibrillated binder mixture and in a second mixing process with a high shear stress the at least one binder and the at least one Lead metal are mixed to a second mixture containing fibrillated binder.
  • the first fibrillated binder-containing mixture and the second fibrillated binder-containing mixture may then be blended by the low shear mixing process with the at least one anode active material, for example, intercalated graphite and / or insertable and / or intercalatable amorphous carbon, for example, hard carbon and / or soft carbon, and / or with a storage alloy, for example with a lithium storage alloy, for example with a silicon and / or - tin alloy, and / or with a metal oxide, in particular silicon oxide.
  • the method for producing a cathode is designed.
  • Cathode active material used.
  • Electrode component in particular the at least one
  • Cathode active material for example, an average
  • Particle size for example, primary particle size, in a range of> 10 ⁇ to ⁇ 20 ⁇ have.
  • the at least one electrode component may comprise or be at least one conductive carbon, for example conductive graphite and / or conductive carbon black.
  • wt .-% based on the total weight of the electrode components of the cathode,> 0.25 wt .-% to ⁇ 20 wt .-%, for example> 0.5 wt .-% to ⁇ 10 wt .-%, in particular
  • the at least one electrode component for example of the at least one lead carbon, for example
  • Lead graphite and / or Leitruß used.
  • the at least one further electrode component in particular the at least one cathode active material, comprises at least one metal oxide
  • At least one layer oxide and / or at least one spinel for example at least one nickel and / or cobalt and / or manganese oxide, for example lithium-nickel and / or cobalt and / or manganese oxide, or is formed out of it.
  • this can be at least one more
  • Electrode component in particular the at least one
  • Cathode active material for example, an average particle size, for example, primary particle size, in a range of> 10 ⁇ to ⁇ 20 ⁇ have. Based on the total weight of the electrode components of
  • Cathode for example,> 50 wt .-%, for example> 70 wt .-% or> 80 wt .-% or> 85 wt .-%, optionally> 90 wt .-%, of the at least one further electrode component, for example of which at least one metal oxide is used.
  • Electrode component at least one Leitzusatz, for example, at least one lead carbon, for example Leitgraphit and / or Leitruß, and / or at least one metal phosphate, for example at least one iron and / or
  • Leitzusatz- cathode active material composite for example at least one carbon cathode active material composite, for example at least one carbon-metal phosphate composite, for example in the form of conductive coated, for example carbon-coated, cathode active material particles, to the
  • Example in the form of carbon-coated metal phosphate particles for example, with an average particle size of ⁇ 10 ⁇ or
  • ⁇ 8 ⁇ or ⁇ 6 ⁇ for example, of ⁇ 4 ⁇ or ⁇ 2 ⁇ or ⁇ 1 ⁇ , or be formed therefrom.
  • the at least one electrode component for example of the at least one conductive additive, for example conductive carbon, for example Leitgraphit and / or Leitruß and / or of the at least one metal phosphate and / or from the combination thereof, in particular from the at least one
  • Conductive additive cathode active material composite for example of the at least one carbon cathode active material composite, for example of the at least one carbon metal phosphate composite, for example in the form of conductive coating, for example carbon-coated,
  • Cathode active material particles for example in the form of
  • carbon-coated metal phosphate particles for example with an average particle size of ⁇ 10 ⁇ m or ⁇ 8 ⁇ m or ⁇ 6 ⁇ m, for example of ⁇ 4 ⁇ m, in particular of ⁇ 2 ⁇ m or ⁇ 1 ⁇ m.
  • the premixing process can be carried out in particular in a method step aO) preceding process step a).
  • the mixing process takes place with a low shear load and / or the premixing process with a low shear load by a free-fall mixer and / or by a mixer based on the principle of turbulence, for example by expansion flows and / or pipe extensions. or by a kneader and / or by an extruder and / or by a ploughshare and / or paddle mixer (paddle mixer) and / or by a drum mixer or is carried out with it.
  • Such mixing units can advantageously have a low shear load, for example a lower shear load than a jet mill and / or a three-roller chair and / or a two-screw extruder, in particular a smaller one
  • Contact Mixing takes place.
  • Dry coating such as a current collector or a
  • an electrode in particular an anode and / or cathode formed. From this mixture, for example, an electrode, for example in the form of a film, for example, with a defined porosity and / or thickness defined, are formed.
  • the current collector may be, for example, a metallic arrester foil or other type of current arrester, for example an expanded metal, a mesh, a metal braid, a metallized fabric and / or a perforated or pierced or otherwise suitably prepared foil.
  • Another object of the invention is an electrode, for example an anode and / or cathode, which is produced by a method according to the invention.
  • An electrode produced by the method according to the invention for example anode and / or cathode, can be, for example, by means of
  • SEM Scanning electron microscopy
  • the invention relates to an electrochemical cell, in particular a battery cell, for example a lithium cell or a sodium cell or a metal-air cell, for example a lithium-ion cell and / or lithium-metal
  • Cell or a sodium-ion cell in particular a lithium cell, for example a lithium-ion cell and / or lithium-metal cell, which comprises at least one electrode according to the invention or produced according to the invention.
  • a lithium cell for example a lithium-ion cell and / or lithium-metal cell, which comprises at least one electrode according to the invention or produced according to the invention.
  • FIG. 1 is a schematic flowchart for illustrating a
  • FIG. 1 illustrates an embodiment of the invention
  • FIG. 1 shows that optionally in an optional upstream process step aO) in a premixing process with a small amount
  • Electrode component E1 are mixed to a premix B + E1.
  • the at least one binder B may, for example, at least one lithium ion conductive or lithium ion conductive polymer, such as polyethylene oxide (PEO) and / or polymethyl methacrylate (PMMA), and / or at least one fluorinated and / or unfluorinated polyolefin, such as polyvinylidene difluoride (PVDF) and / or polytetrafluoroethylene (PTFE ) and / or polyethylene (PE) and / or
  • PVDF polyvinylidene difluoride
  • PTFE polytetrafluoroethylene
  • PE polyethylene
  • Polypropylene (PP), and / or a copolymer thereof are examples of polypropylene (PP), and / or a copolymer thereof.
  • FIG. 1 further shows that in a process step a) the at least one binder B and the at least one electrode component E1, optionally in the form of the premix from the optional upstream process step aO), in a mixing process with a high shear stress to a mixture containing fibrillated binder fB + E1 are mixed.
  • the mixing process with a high shear rate can be done for example by a jet mill.
  • FIG. 1 shows that, in a method step b), at least one further electrode component E2 is admixed to the mixture fB + E1 comprising the fibrillated binder from method step a) by a mixing process with a low shear load.
  • the at least one electrode component E1 can, in particular in the
  • Functionality of the at least one electrode component El can be achieved by the mixing process with a high shear load and / or by a
  • the at least one electrode component E1 may have an average particle size or an average particle size
  • Particle diameter of ⁇ 10 ⁇ for example in a range of> 4 ⁇ to ⁇ 6 ⁇ have. It has been found that such small particles in a mixing process with a high shear stress, for example, in a jet mill, little or no further comminuted and thus are virtually mechanically stable in this.
  • electrode component E2 can have a larger average Particle size or a larger average particle length or a larger average particle diameter, for example, of> 10 ⁇ , for example in a range of> 10 ⁇ to ⁇ 20 ⁇ , and thus in a mixing process with a high
  • the at least one electrode component E1 may comprise at least one conductive additive, for example at least one conductive carbon, such as conductive graphite and / or amorphous conductive carbon, such as conductive carbon black, and / or
  • the functionality of conductive additives is reduced by comminution in a mixing process with a high
  • Electrode active materials such as anode active materials or cathode active materials, for example intercalation materials and / or
  • Insertion materials and / or recombination materials are Insertion materials and / or recombination materials.
  • the at least one electrode component E1 can be free of surface-coated particles and / or free of gradient material particles, for example, whereas the at least one further electrode component E2 can comprise surface-coated particles and / or gradient material particles.
  • Surface coating of surface-coated particles may be damaged and / or destroyed, which may affect their functionality.
  • FIG. 1 shows that in a method step c) from the mixture fB + E1 + E2 from method step b), which contains the at least one fibrillated binder fB, which contains at least one electrode component E1 and the at least one further electrode component E2, for example by a dry manufacturing process and / or by coating, for example by dry coating, an electrode E is formed.

Landscapes

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

Abstract

L'invention concerne un procédé de fabrication d'une électrode (E) pour une cellule électrochimique, en particulier une cellule de batterie, par exemple une cellule au lithium. Afin de produire un mélange homogène, permettant de fabriquer, par exemple par revêtement à sec, une électrode (E) présentant des propriétés améliorées et/ou une épaisseur de couche nettement supérieure à 100 μm, par exemple pour des batteries de véhicules, par exemple pour des véhicules électriques et/ou hybrides, de manière économique en temps et en coûts, au moins un liant (B) et au moins un composant d'électrode (E1) sont mélangés par un processus de mélange avec une contrainte de cisaillement élevée pour former un mélange (fB+E1) contenant un liant fibrillé, et au moins un autre composant d'électrode (E2) est ensuite mélangé au mélange (fB+E1) contenant le liant fibrillé par un processus de mélange avec une contrainte de cisaillement faible. L'invention concerne en outre une électrode (E) ainsi fabriquée et une cellule équipée d'une telle électrode (E).
EP18756376.2A 2017-08-02 2018-07-30 Procédé de fabrication d'une électrode par fibrillation de liant Pending EP3642894A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017213403.8A DE102017213403A1 (de) 2017-08-02 2017-08-02 Elektrodenherstellungsverfahren mittels Binderfibrillierung
PCT/EP2018/070536 WO2019025336A1 (fr) 2017-08-02 2018-07-30 Procédé de fabrication d'une électrode par fibrillation de liant

Publications (1)

Publication Number Publication Date
EP3642894A1 true EP3642894A1 (fr) 2020-04-29

Family

ID=63259485

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18756376.2A Pending EP3642894A1 (fr) 2017-08-02 2018-07-30 Procédé de fabrication d'une électrode par fibrillation de liant

Country Status (4)

Country Link
EP (1) EP3642894A1 (fr)
CN (1) CN111033813B (fr)
DE (1) DE102017213403A1 (fr)
WO (1) WO2019025336A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038579A (zh) * 2020-09-28 2020-12-04 合肥国轩高科动力能源有限公司 金属锂复合电极及其制备方法和电化学储能装置

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020210614A1 (de) 2020-08-20 2022-02-24 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung einer Elektrode einer Batteriezelle, Batteriezelle und Verwendung derselben
CN112420975B (zh) * 2020-10-20 2022-02-22 浙江南都电源动力股份有限公司 一种电池中电极极片的生产方法
KR20220065124A (ko) * 2020-11-12 2022-05-20 에스케이온 주식회사 코어-쉘 복합체를 포함하는 음극 활물질 및 이의 제조방법
DE102022105656A1 (de) 2022-03-10 2023-09-14 Volkswagen Aktiengesellschaft Verfahren zur kontinuierlichen Herstellung einer Batterieelektrode

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898099A (en) 1974-03-18 1975-08-05 Energy Res Corp Hydrophilic electrode and method for making the same
US4379772A (en) 1980-10-31 1983-04-12 Diamond Shamrock Corporation Method for forming an electrode active layer or sheet
US4354958A (en) 1980-10-31 1982-10-19 Diamond Shamrock Corporation Fibrillated matrix active layer for an electrode
US4556618A (en) 1983-12-01 1985-12-03 Allied Corporation Battery electrode and method of making
US5393617A (en) * 1993-10-08 1995-02-28 Electro Energy, Inc. Bipolar electrochmeical battery of stacked wafer cells
US5707763A (en) * 1994-10-19 1998-01-13 Daikin Industries, Ltd. Binder for batteries, and electrode compositions and batteries incorporating same
JP2000049055A (ja) 1998-07-27 2000-02-18 Asahi Glass Co Ltd 電気二重層キャパシタ用電極及び電気二重層キャパシタ
JP2000149954A (ja) * 1998-11-11 2000-05-30 Sanyo Electric Co Ltd 非水電解液電池およびその製造方法
US20050266298A1 (en) 2003-07-09 2005-12-01 Maxwell Technologies, Inc. Dry particle based electro-chemical device and methods of making same
WO2005049700A1 (fr) 2003-11-20 2005-06-02 Bayerische Julius-Maximilians- Universität Würzburg Materiaux fonctionnels a liaison polymere
MX2016013413A (es) * 2014-04-18 2017-04-06 Maxwell Lab Electrodo de dispositivo para almacenamiento de energia en seco y metodos para elaborar el mismo.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038579A (zh) * 2020-09-28 2020-12-04 合肥国轩高科动力能源有限公司 金属锂复合电极及其制备方法和电化学储能装置

Also Published As

Publication number Publication date
CN111033813B (zh) 2023-10-24
CN111033813A (zh) 2020-04-17
WO2019025336A1 (fr) 2019-02-07
DE102017213403A1 (de) 2019-02-07

Similar Documents

Publication Publication Date Title
EP3642894A1 (fr) Procédé de fabrication d'une électrode par fibrillation de liant
EP2820699B1 (fr) Cathode de batterie lithium-soufre et procédé sans solvant pour la produire
WO2019025337A1 (fr) Procédé de fabrication d'une électrode par fibrillation de liant au moyen d'un auxiliaire de fibrillation particulaire
EP2950375B1 (fr) Carbone fibreux ultramince pour accumulateur à électrolyte non aqueux, agrégat de carbone fibreux ultramince, corps composite et couche de matériau actif d'électrode
EP2179464A1 (fr) Electrodes et cellules lithium-ion comprenant un nouveau type de liant d'électrode
DE102013213273A1 (de) Kohlenstoffnanoröhren-haltige Dispersion und ihre Verwendung in der Herstellung von Elektroden
DE2547491A1 (de) Luftelektrode
EP3900077A1 (fr) Unité cathodique et procédé pour la fabrication d'une unité cathodique
DE102018222142A1 (de) Verfahren zum Herstellen einer Festelektrolytmembran oder einer Anode und Festelektrolytmembran oder Anode
EP2460213A1 (fr) Procédé de revêtement pour la production d'électrodes pour l'accumulateur d'énergie électrique
DE102012213219A1 (de) Elektrode für einen elektrochemischen Energiespeicher und Verfahren zum Herstellen einer solchen
DE102018209416A1 (de) Verfahren zur Herstellung eines Kompositmaterials
JP6436472B2 (ja) 導電性カーボンの製造方法、導電性カーボンを含む電極材料の製造方法、及び、電極材料を用いた電極の製造方法
WO2013124408A1 (fr) Matériau d'électrode pour accumulateurs d'énergie électrochimiques à base de lithium
EP3008768B1 (fr) Pile lithium-ion pour batterie secondaire
DE102016217386A1 (de) Verfahren zur lösungsmittelfreien Herstellung einer Aktivmaterialzusammensetzung
WO2024022823A1 (fr) Cathode et batterie lithium-ion comprenant la cathode
DE102011057015A1 (de) Verfahren zur Herstellung von Cobaltoxid-Kohlenstoff-Komposit
DE102022105956A1 (de) Verfahren zur herstellung einer elektrodenaufschlämmung für eine sekundärbatterie und elektrode, die diese enthält
EP2983236B1 (fr) Élément électrochimique secondaire à base de nickel / fer
DE102018205413A1 (de) Graphen- und Festelektrolyt-basierte Kathode für eine Lithium-Zelle
WO2015062985A1 (fr) Procédé permettant de produire une électrode pour une batterie lithium-ion
DE102014106002A1 (de) Elektrodenmaterial für Natrium-basierte elektrochemische Energiespeicher
DE102018200992A1 (de) Verfahren zum Herstellen einer Kathode einer Festkörper-Batterie und Festkörper-Batterie
DE102018205405A1 (de) Lithium-Vanadium-Phosphat- und Festelektrolyt-basierte Kathode für eine Lithium-Zelle

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200123

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)