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
  • H01M4/62—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
• • 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
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0433—Molding
• • 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
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0435—Rolling or calendering
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to VDF-based fluoropolymers with outstanding metal-adhesion properties for use as a binding agent for electrodes for batteries.
• the electrodes of a lithium secondary battery are mainly manufactured by a wet process that comprises preparing a slurry in which an electrode active material, additives and a binder are dispersed in a solvent or an aqueous medium, and processing the slurry in a way that forms an electrode film.
• VDF vinylidene fluoride
• TFE tetrafluoroethylene
• EP 0964464 discloses the use of VDF/TFE copolymers comprising at least 60% by moles of recurring units derived from VDF in the preparation of an electrode-forming slurry compositions comprising the active material and an organic solvent, such as NMP; said electrode-forming slurry compositions are coated onto a metal foil to prepare the electrodes.
• Typical dry processes use the fibrillation properties of certain polymers to provide a matrix for embedded conductive material.
• Some of the polymers in the family of fluoropolymers, such as polytetrafluoroethylene (PTFE), are particularly inert and stable in the common electrolyte solvents used in secondary batteries, even those using organic solvent at high working or storage temperatures.
• dry electrode preparation processes can include combining a PTFE binder with active electrode material in powder form, and calendering to form an electrode film.
• PTFE has good cohesion with the electrode active material and can form free-standing films of PTFE binder with active electrode material, it has difficulty in adhesiveness to the current collector.
• VDF-based fluoropolymers show improved adhesion to metals with respect to PTFE, having at the same time a good processability which make them suitable for the preparation of electrodes by dry processes or extrusion at low temperatures, thus providing electrodes by a very efficient process.
• binder composition for use in the preparation of electrodes for electrochemical devices, characterized by comprising a VDF-based copolymer [polymer (A)] that comprises:
• VDF vinylidene fluoride
• polymer (A) has at least two melting points, one melting point lower than 220 °C and one melting point higher than 250 °C.
• composition (C) for use in the preparation of electrodes for electrochemical devices, characterized by comprising: a) at least one electrode active material (AM); b) a binder (B) as above defined; and c) optionally, at least one conductive agent.
• the present invention thus provides a process for manufacturing an electrode [electrode (E)] for electrochemical cell, said process comprising:
• composition (C) dry mixing the at least one electrode active material (AM), the polymer (A) as above defined, and optionally, at least one conductive agent in the absence of solvent to provide a dry electrode forming composition [composition (C)];
• the present invention provides an electrode (E) for a secondary battery obtainable by the process as above defined.
• the present invention relates to an electrochemical device, such as a secondary battery or a capacitor, comprising at least one electrode (E) as defined above.
• weight percent indicates the content of a specific component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture.
• weight percent (wt %) indicates the ratio between the weight of the recurring units of such monomer over the total weight of the polymer/copolymer.
• weight percent (wt %) indicates the ratio between the weight of all non-volatile ingredients in the liquid.
• electrochemical device By the term “electrochemical device”, it is hereby intended to denote an electrochemical cell/assembly comprising a positive electrode, a negative electrode and a liquid electrolyte, wherein a monolayer or multilayer separator is in contact to at least one surface of one of the said electrodes.
• suitable electrochemical devices include, notably, secondary batteries, especially, alkaline or an alkaline- earth secondary batteries such as lithium ion batteries, lead-acid batteries, and capacitors, especially lithium ion-based capacitors and electric double layer capacitors (supercapacitors).
• electrochemical cells include, notably, batteries, preferably secondary batteries, and electric double layer capacitors.
• secondary battery it is intended to denote a rechargeable battery.
• Non-limitative examples of secondary batteries include, notably, alkaline or alkaline-earth secondary batteries.
• Each of the polymers (A) described herein has at least one melting temperature that is lower than 220°C, preferably lower than 180 °C and one melting temperature that is higher than 250 °C, even higher than 300 °C.
• the Applicant has surprisingly found that when at least one melting point of polymer (A) is below 220 °C, even if at least another higher melting point is present (higher than 250 °C, or even higher than 300 °C), the polymer shows high adhesion to metal, and thus it is suitable for use as binder for preparing electrodes having high adhesion to the metal current collector.
• the melting temperatures of polymer (A) may be determined from a DSC curve obtained by differential scanning calorimetry (hereinafter, also referred to as DSC).
• Polymer (A) is preferably a semi-crystalline fluororesin.
• polymer (A) comprising at least one crystallizable part and at least one amorphous part in the backbone and exhibiting at least a first-order reversible phase change temperature, such as a melting point (solid-liquid transition).
• Polymer (A) is preferably a semi-crystalline fluororesin having multiple endothermic peaks, the heat of fusion for the lower endothermic peak being of at least 1 J/g.
• the polymers (A) contain at least about 5 mol % VDF monomer.
• the polymers (A) may optionally contain at least one other monomer.
• Suitable comonomers that may be included in the polymer (A) include, but are not limited to, ethylene, propylene, isobutylene, fluorinated comonomers such as chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), fluorodioxoles, fluorodioxalanes, perfluoroalkyl ethylene monomers (e.g.
• PFBE perfluorobutylethylene
• PFHE perfluorohexylethylene
• PFOE perfluorooctylethylene
• PFEP perfluorobutylethylene
• PFHE perfluorohexylethylene
• PFOE perfluorooctylethylene
• a perfluoroalkyl vinyl ether monomer e.g., perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE)
• the optional comonomer(s) may be present in the polymers (A) in an amount from about 0.001 mol % to about 10 mol %, from about 0.01 mol % to about 7 mol %, or from about 0.1 mol % to about 5 mol %.
• polymer (A) consists essentially of recurring units derived from VDF and TFE.
• Determination of the amount of VDF and TFE monomer recurring units in polymer (A) can be performed by any suitable method. Mention can be notably made of NMR methods.
• Polymer (A) may still comprise other moieties such as defects, end-groups and the like, which do not affect nor impair its physico-chemical properties.
• the polymer (A) may be obtained by polymerization of a VDF monomer, TFE and optionally of an additional comonomer as above defined either in suspension in organic medium, or in aqueous emulsion, according to the procedures known in literature.
• the procedure for preparing the polymer (A) comprises polymerizing in an aqueous medium in the presence of a radical initiator the VDF, TFE and optionally of an additional comonomer as above defined, optionally in the presence of a chain transfer agent and of a dispersing agent in a reaction vessel.
• the process of the invention is carried out at a temperature of at least 40°C, preferably of at least 50°C, more preferably of at least 60°C.
• polymer (A) is typically provided in form of powder.
• polymer (A) is typically provided in the form of an aqueous dispersion (D), which may be used as directly obtained by the emulsion polymerization or after a concentration step.
• aqueous dispersion (D) preferably, the solid content of polymer (A) in dispersion (D) is in the range comprised between 10 and 50% by weight.
• Polymer (A) obtained by emulsion polymerization can be isolated from the aqueous dispersion (D) by concentration and/or coagulation of the dispersion and obtained in powder form by subsequent drying.
• the polymer (A) of the invention is preferably obtainable by emulsion polymerization in an aqueous polymerization medium, according to the procedures described, for example, in WO 2018/189090, in WO 2018/189091 and WO 2018/189092.
• polymer (A) is advantageously obtained by emulsion polymerization by a method being performed in the absence of any fluorosurfactant, for example according to the procedure described in WO 2019/076901.
• melting point As used herein, the terms “melting point”, “melt temperature”, and “melting temperature” are meant to define the peak of the melt endotherm as determined from a differential scanning calorimetry (hereinafter, also referred to as DSC). Where the DSC curve shows a plurality of melting peaks (endothermic peaks), the plurality of melting temperatures (Tm) is determined.
• DSC differential scanning calorimetry
• the amount of polymer (A) which may be used in step B) of the process of the invention is subject to various factors.
• One such factor is the surface area and amount of the active material, and the surface area and amount of any electroconductivity-imparting additive which are added to the electrode-forming composition. These factors are believed to be important because the binder particles provide bridges between the conductor particles and conductive material particles, keeping them in contact.
• the term “electrode active material” is intended to denote a compound that is able to incorporate or insert into its structure, and substantially release therefrom, alkaline or alkaline-earth metal ions during the charging phase and the discharging phase of an electrochemical cell.
• the electrode active material is preferably able to incorporate or insert and release lithium ions.
• the nature of the electrode active material in the electrode-forming composition (C) depends on whether said composition is used in the manufacture of a negative electrode (anode) or a positive electrode (cathode).
• the electrode active material may comprise a composite metal chalcogenide of formula LiMGh, wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V and Q is a chalcogen such as O or S.
• M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V
• Q is a chalcogen such as O or S.
• Preferred examples thereof may include LiCoC , LiNiC>2, LiNi x Coi- x O2 (0 ⁇ x ⁇ 1) and spinel-structured LiM ⁇ C .
• the electrode active material may comprise a lithiated or partially lithiated transition metal oxyanion-based electro-active material of formula MiM2(JO4)fEi.f, wherein Mi is lithium, which may be partially substituted by another alkali metal representing less than 20% of the Mi metals, M2 is a transition metal at the oxidation level of +2 selected from Fe, Mn, Ni or mixtures thereof, which may be partially substituted by one or more additional metals at oxidation levels between +1 and +5 and representing less than 35% of the M2 metals, including 0, JO4 is any oxyanion wherein J is either P, S, V, Si, Nb, Mo or a combination thereof, E is a fluoride, hydroxide or chloride anion, f is the molar fraction of the JO4 oxyanion, generally comprised between 0.75 and 1.
• the MiM2(JO4)fEi-f electro-active material as defined above is preferably phosphate-based and may have an ordered or modified olivine structure.
• the electrode active material (AM) in the case of forming a positive electrode has formula Li3-xM’ y M”2- y (JO4)3 wherein 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M’ and M” are the same or different metals, at least one of which being a transition metal, JO4 is preferably PO4 which may be partially substituted with another oxyanion, wherein J is either S, V, Si, Nb, Mo or a combination thereof.
• the electrode active material is a phosphate-based electro-active material of formula Li(Fe x Mni- x )PO4 wherein 0 ⁇ x ⁇ 1 , wherein x is preferably 1 (that is to say, lithium iron phosphate of formula LiFePC ).
• the electrode active material may preferably comprise one or more carbon-based materials and/or one or more silicon-based materials.
• the carbon-based materials may be selected from graphite, such as natural or artificial graphite, graphene, or carbon black.
• the carbon-based material is preferably graphite.
• the silicon-based compound may be one or more selected from the group consisting of chlorosilane, alkoxysilane, aminosilane, fluoroalkylsilane, silicon, silicon chloride, silicon carbide and silicon oxide.
• the silicon-based compound may be silicon oxide or silicon carbide.
• the silicon-based compounds are comprised in an amount ranging from 1 to 60 % by weight, preferably from 5 to 30 % by weight with respect to the total weight of the electro active compounds.
• One or more optional electroconductivity-imparting additives may be added in order to improve the conductivity of a resulting electrode made from the composition of the present invention.
• Conducting agents for batteries are known in the art.
• Examples thereof may include: carbonaceous materials, such as carbon black, graphite fine powder, carbon nanotubes, graphene, or fiber, or fine powder or fibers of metals such as nickel or aluminum.
• the optional conductive agent is preferably carbon black. Carbon black is available, for example, under the brand names, Super P® or Ketjenblack®.
• the conductive agent is different from the carbon-based material described above.
• the amount of optional conductive agent is preferably from 0 to 30 wt. % of the total solids in the electrode forming composition.
• the optional conductive agent is typically from 0 wt. % to 10 wt. %, more preferably from 0 wt. % to 5 wt. % of the total amount of the solids within the composition.
• the optional conductive agent is typically from 0 wt. % to 5 wt. %, more preferably from 0 wt. % to 2 wt.% of the total amount of the solids within the composition, while for anode forming compositions comprising silicon based electro active compounds it has been found to be beneficial to introduce a larger amount of optional conductive agent, typically from 0.5 to 30 wt. % of the total amount of the solids within the composition.
• step B) mixing electrode active material (AM), the polymer (A) as above defined, and optionally, at least one conductive agent is performed by dryblending these ingredients without the addition of any solvents, liquids, processing aids, or the like to the particle mixture. Dry-blending may be carried out, for example, in a mill, mixer or blender (such as a V-blender equipped with a high intensity mixing bar), until a uniform dry mixture is formed. The resulting material may be calendared many times to produce a conductive film of desired thickness and density. Those skilled in the art will identify, after perusal of this document, that blending time can vary based on batch size, materials, particle size, densities, as well as other properties, and yet remain within the scope hereof.
• step C) of the process of the invention the powdered dry mixture obtained in step B) is subjected to mechanical compaction step to provide a self-supporting dry film.
• the compacting of the dry mixture obtained in step B) can take place as a mechanical compaction, for example by means of a roller compactor or a tablet press, but it can also take place as rolling, build-up or by any other technique suitable for this purpose.
• the mechanical compaction step may be associated to a thermal consolidation step.
• the combination of an applied pressure and a heat treatment makes thermal consolidation possible at lower temperatures than if it were done alone.
• the mechanical compaction step is carried out by compression, suitably by compressing the dry mixture obtained in step B) between two metal foils.
• the compaction step can be carried out at a temperature lower than the highest melting temperature of the polymer (A).
• the compaction step is conveniently carried out at a temperature not exceeding 200 °C, preferably at a temperature lower than 180 °C.
• step D) the dry film obtained in step C) is applied onto an electrically conductive substrate to form the electrode.
• the sheet of substrate material may comprise a metal foil, an aluminum foil in particular.
• the dry film obtained in step C) can be applied onto the electrically conductive substrate without the need for any primer or adhesive layer.
• the electrode (E) of the invention is particularly suitable for use in electrochemical devices, in particular in secondary batteries.
• the present invention provides an electrochemical device being a secondary battery comprising:
• the positive electrode and the negative electrode is the electrode (E) according to the present invention.
• the electrochemical device is a secondary battery comprising:
• the positive electrode is the electrode (E) according to the present invention.
• the secondary battery of the invention is preferably an alkaline or an alkaline-earth secondary battery. [0073]
• the secondary battery of the invention is more preferably a lithium-ion secondary battery.
• An electrochemical device according to the present invention can be prepared by standard methods known to a person skilled in the art.
• PTFE PTFE homopolymer powder having specific gravity, measured according to ASTM D792, of 2160 and having rheometric pressure, measured according to ASTM D4895, of 9.50 MPa.;
• Lithium Iron Phosphate, LFP available as Life Power from Johnson Matthey;
• Carbon black available as SC65 available from Imerys S.A.; Galden HT80 available from Solvay Materials.
• the reactor was re-pressurized with a mixture of TFE 80% and VDF 20% by molar amount, the above mentioned mixture was then fed in 50 g amount.
• gaseous mixture of VDF/TFE with molar ratio of 75%/25% was added via a compressor, until reaching a pressure of 20 abs Bars.
• the polymers (A-1), (A-2), (A-3), (A-4), (C-1) and (C-2) in powder form were obtained from the corresponding latex by cryogenic coagulation or by electrolytic coagulation using:
• Films of comprising any of the polymers (A-1) to (A-4), (C-1) and (C-2) polymer were obtained by compressing the powder compositions between two aluminum foils. Lamination process occurred at a temperature lower than 180°C and at a pressure of 160 Bars. The material was kept in a heating for 6 minutes than was pressed at the operative pressure running 6 degassing steps (manually by releasing the pressure) for a total of 180 seconds. The samples were then cooled at room temperature by a cold press. The samples were kept in a cooling press at the same pressure as for the first step for a time period comprised between 4 to 6 minutes.
• the Applicant has surprisingly found that the polymer (A) can be suitably processed at a temperature well below its higher melting point, thus allowing to obtain extrudates of the binder by a convenient process.
• Example 1 electrode preparation with polymer (A-4)
• a dry mixture of 1.8 g of LFP and 0.1 g of SC65 was prepared by grinding for 2 minutes the two powders in a ceramic mortar with a pestle.
• the composite was then mixed for additional 5 minutes in a ceramic mortar with a pestle to fibrillate the polymer.
• the resulting positive electrode had the following composition: 90 wt.% of LFP, 5 wt.% of polymer (A-4) and 5 wt. % of carbon black. Electrode EC1 was thus obtained.
• a dry mixture of 1.8 g of LFP and 0.1 g of SC65 was prepared by grinding for 2 minutes the two powders in a ceramic mortar with a pestle.
• 0.1 g of PTFE was added to the homogeneous paste and the mixture mixed in a Vortex mixer at 16000 rpm for 0.5 minutes. A homogeneous composite was obtained.
• the composite was then mixed for additional 5 minutes in a ceramic mortar with a pestle to fibrillate the polymer.
• the resulting positive electrode had the following composition: 90 wt.% of LFP, 5 wt.% of PTFE and 5 wt. % of carbon black. Electrode CE1 was thus obtained.
• binders of the present invention have improved adhesion to current collectors, while at the same time they keep good electric properties, so that they can be suitably used as binders for electrodes.

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• 2022
  • 2022-11-25 KR KR1020247019775A patent/KR20240113505A/ko active Pending
  • 2022-11-25 US US18/714,504 patent/US20250023053A1/en active Pending
  • 2022-11-25 WO PCT/EP2022/083346 patent/WO2023094622A1/en not_active Ceased
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