EP4409652A1 - Revetement d'anode pour batterie li-ion tout solide - Google Patents

Revetement d'anode pour batterie li-ion tout solide

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Publication number
EP4409652A1
EP4409652A1 EP22792854.6A EP22792854A EP4409652A1 EP 4409652 A1 EP4409652 A1 EP 4409652A1 EP 22792854 A EP22792854 A EP 22792854A EP 4409652 A1 EP4409652 A1 EP 4409652A1
Authority
EP
European Patent Office
Prior art keywords
anode
coating
lithium
component
chosen
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
EP22792854.6A
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German (de)
English (en)
French (fr)
Inventor
Grégory Schmidt
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.)
Arkema France SA
Original Assignee
Arkema France SA
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Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4409652A1 publication Critical patent/EP4409652A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 generally relates to the field of the storage of electrical energy in rechargeable secondary batteries of the Li-ion type. More specifically, the invention relates to an anode coating for an all-solid Li-ion battery. The invention also relates to a process for preparing said coating. The invention also relates to an anode covered with this coating, to the method of manufacturing such an anode, as well as to Li-ion secondary batteries comprising such an anode.
  • a lithium secondary battery can be used as a power source for a variety of electronic devices ranging from cell phones, laptop computers and small household electronics to vehicles and high capacity energy storage devices and others, and the demand for secondary lithium batteries continues to grow.
  • An all-solid-state battery typically includes a positive electrode, a solid electrolyte, and a negative electrode.
  • the positive electrode includes a positive electrode active material and a solid electrolyte, and further includes an electronic conductive material and a binder.
  • the solid electrolyte comprises one or more elements from the following list: polymer, plasticizer, lithium salt, inorganic particle, ionic liquid.
  • the negative electrode includes a negative electrode active material and a solid electrolyte, and further includes a conductive material and a binder.
  • the object of the invention is therefore to provide a coating that can be applied directly to a negative electrode of a Li-ion battery, thus making it possible to have a physical separation between the solid electrolyte and the active material of the electrode.
  • the present invention provides a negative electrode comprising a first layer consisting of a usual negative electrode and a second layer consisting of an anode coating according to the present invention.
  • the invention also aims to provide a method of manufacturing said anode coating.
  • the invention finally relates to an anode having such a coating, and to the method of manufacturing such an anode.
  • the invention aims to provide rechargeable Li-ion secondary batteries comprising such an anode.
  • the technical solution proposed by the present invention is to provide an anode coating which makes it compatible with a solid electrolyte in an all-solid battery.
  • the invention relates firstly to an anode coating consisting of: a. one or more poly(vinylidene fluoride), b. a lithium salt, and c. a conductivity additive.
  • the invention also relates to a process for manufacturing an anode coating from an ink obtained by mixing all the constituents of the coating.
  • the invention also relates to an anode for a lithium-ion battery, said anode consisting of a layer of negative electrode active material covered with a coating layer according to the invention.
  • the invention also relates to a method for manufacturing a negative electrode of a Li-ion battery, said method comprising the following operations: providing an anode, depositing a coating layer on said anode.
  • Another object of the invention is a Li-ion secondary battery comprising a negative electrode, a positive electrode and an all-solid electrolyte, in which the anode is as described above.
  • the present invention makes it possible to overcome the drawbacks of the state of the art. It provides an ion-conductive coating having a homogeneous distribution of its dielectric constant while maintaining sufficient mechanical strength to prevent the formation of dendrites. This coating demonstrates good stability in reduction and good flexibility, thus making it possible to be able to withstand the variations in volume of the anode during the charging and discharging cycles.
  • the coating according to the invention makes it possible to stop the growth of dendrites which can cause short circuits, the good homogeneity of the dielectric constant makes it possible to avoid the formation of a zone highly concentrated in lithium ion .
  • This coating also makes it possible to form a stable and low-resistive solid-electrolyte interface (or SEI for “Solid Electrolyte Interface”) on the lithium metal, thus improving the performance and lifespan of all-solid-state batteries.
  • the invention relates to an anode coating consisting of: a. one or more poly(vinylidene fluoride) (component A), b. at least one lithium salt (component B), and c. at least one conductivity additive (component C).
  • said coating comprises the following characters, possibly combined. The contents indicated are expressed by weight, unless otherwise indicated.
  • the semi-crystalline fluorinated polymer used in the invention is a polymer based on vinylidene difluoride and is generically designated by the abbreviation PVDF.
  • the PVDF is a poly(vinylidene fluoride) homopolymer or a mixture of homopolymers of vinylidene fluoride.
  • the PVDF is a poly(vinylidene fluoride) homopolymer or a copolymer of vinylidene difluoride with at least one comonomer compatible with vinylidene difluoride.
  • the PVDF is semi-crystalline.
  • Comonomers compatible with vinylidene difluoride can be halogenated (fluorinated, chlorinated or brominated) or non-halogenated.
  • fluorinated comonomers examples include: vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2,3,3,3-tetrafluoropropene or 1 , 3,3,3- tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular 1,1,3,3,3-pentalluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkylvinylethers and in particular those of general formula Rf-O -CF-CF2, Rf being an alkyl group, preferably C1 to C4 (preferred examples being perfluoropropyl vinyl ether and perfluoromethyl vinyl ether).
  • the fluorinated comonomer can contain a chlorine or bromine atom. It can in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
  • Chlorofluoroethylene can denote either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene.
  • the 1-chloro-1-fluoroethylene isomer is preferred.
  • the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
  • the VDF copolymer can also comprise non-halogenated monomers such as ethylene, and/or acrylic or methacrylic comonomers.
  • the fluoropolymer preferably contains at least 50 mole percent vinylidene difluoride.
  • the PVDF is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP)) (P(VDF-HFP)), having a percentage by weight of hexafluoropropylene monomer units of 2 to 23%, preferably from 4 to 15% by weight relative to the weight of the copolymer.
  • the PVDF is a mixture of a poly(vinylidene fluoride) homopolymer and a VDF-HFP copolymer.
  • the PVDF is a copolymer of vinylidene fluoride and tetrafluoroethylene (TFE).
  • the PVDF is a copolymer of vinylidene fluoride and chlorotrifluoroethylene (CTFE).
  • the PVDF is a VDF-TFE-HFP terpolymer.
  • the PVDF is a VDF-TrFE-TFE terpolymer (TrFE being trifluoroethylene).
  • the mass content of VDF is at least 10%, the comonomers being present in variable proportions.
  • the PVDF is a mixture of two or more VDF-HFP copolymers.
  • the presence of HFP-type comonomer improves the chemical stability of the coating with respect to lithium metal.
  • the PVDF comprises monomer units bearing at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, or phosphonic.
  • the function is introduced by a chemical reaction which can be grafting, or a copolymerization of the fluorinated monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the fluorinated monomer, according to techniques well known to those skilled in the art.
  • the functional group carries a carboxylic acid function which is a group of (meth)acrylic acid type chosen from acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxyethylhexyl(meth)acrylate.
  • the units carrying the carboxylic acid function also comprise a heteroatom chosen from oxygen, sulphur, nitrogen and phosphorus.
  • the functionality is introduced via the transfer agent used during the synthesis process.
  • the transfer agent is a polymer with a molar mass less than or equal to 20,000 g/mol and carrying functional groups chosen from the groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, or phosphonic.
  • An example of such a transfer agent are acrylic acid oligomers.
  • the content of functional groups of the PVDF is at least 0.01% molar, preferably at least 0.1% molar, and at most 15% molar, preferably at most 10% molar.
  • the PVDF preferably has a high molecular weight.
  • high molecular weight as used herein, is meant a PVDF having a melt viscosity greater than 100 Pa.s, preferably greater than 500 Pa.s, more preferably greater than 1000 Pa.s, preferably greater than at 2000 Pa.s.
  • the viscosity is measured at 232° C., at a shear rate of 100 s 1 using a capillary rheometer or a parallel plate rheometer, according to standard ASTM D3825. Both methods give similar results.
  • PVDF homopolymers and the VDF copolymers used in the invention can be obtained by known polymerization methods such as emulsion polymerization.
  • they are prepared by an emulsion polymerization process in the absence of fluorinated surfactant.
  • Polymerization of PVDF results in a latex generally having a solids content of 10 to 60% by weight, preferably 10 to 50%, and having a weight average particle size of less than 1 micrometer, preferably less than 1000 nm , preferably less than 800 nm, and more preferably less than 600 nm.
  • the weight average size of the particles is generally at least 10 nm, preferably at least 50 nm, and advantageously the average size is in the range of 100 to 400 nm.
  • the polymer particles can form agglomerates, called secondary particles, the average size of which by weight is less than 5000 ⁇ m, preferably less than 1000 ⁇ m, advantageously between 1 and 80 micrometers, and of preferably from 2 to 50 micrometers. Agglomerates can break down into discrete particles during formulation and application to a substrate.
  • the PVDF homopolymer and the VDF copolymers are composed of bio-based VDF.
  • bio-based VDF means “derived from biomass”. This improves the ecological footprint of the membrane.
  • Bio-based VDF can be characterized by a renewable carbon content, i.e. carbon of natural origin and coming from a biomaterial or from biomass, of at least 1 atomic % as determined by the content of 14C according to standard NF EN 16640.
  • renewable carbon indicates that the carbon is of natural origin and comes from a biomaterial (or biomass), as indicated below.
  • the bio-carbon content of the VDF can be greater than 5%, preferably greater than 10%, preferably greater than 25%, preferably greater than or equal to 33%, preferably greater than 50% , preferably greater than or equal to 66%, preferably greater than 75%, preferably greater than 90%, preferably greater than 95%, preferably greater than 98%, preferably greater than 99%, advantageously equal to 100% .
  • the lithium salt are chosen from LiPFe (lithium hexafluorophosphate), LiFSI (bis(fluorosulfonyl)lithium imide), TFSI (bis(trifluoromethylsulfonyl)imide lithium, LiTDI (2-trifluoromethyl-4,5-lithium dicyano-imidazolate), LiPOFz, LiBttALL, I e Lil ⁇ BtC ALL, LiBF4, LiNOs, LiCICL and mixtures of two or more of cited salts.
  • LiPFe lithium hexafluorophosphate
  • LiFSI bis(fluorosulfonyl)lithium imide)
  • TFSI bis(trifluoromethylsulfonyl)imide lithium
  • LiTDI 2,-trifluoromethyl-4,5-lithium dicyano-imidazolate
  • LiPOFz LiBttALL, I e Lil ⁇ BtC ALL, LiBF4, LiNOs, LiCICL and mixtures of two
  • the conductivity additive can be an organic molecule or a mixture of organic molecules capable of swelling the fluoropolymer without dissolving it and having a dielectric constant greater than 1.
  • component C is chosen from linear ethers or cyclics, esters, lactones, nitriles, carbonates and ionic liquids.
  • ethers such as for example dimethoxyethane (DME), methyl ethers of oligoethylene glycols with 2 to 5 oxyethylene units, dioxolane, dioxane , dibutyl ether, tetrahydrofuran, and mixtures thereof.
  • DME dimethoxyethane
  • methyl ethers of oligoethylene glycols with 2 to 5 oxyethylene units dioxolane, dioxane , dibutyl ether, tetrahydrofuran, and mixtures thereof.
  • esters mention may be made of phosphoric acid esters or sulfite esters. Mention may be made, for example, of methyl formate, methyl acetate, methyl propionate, ethyl acetate, butyl acetate, gamma butyrolactone or mixtures thereof.
  • lactones mention may in particular be made of cyclohexanone.
  • nitriles mention may be made, for example, of acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2- methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, malononitrile, and mixtures thereof.
  • cyclic carbonates such as for example ethylene carbonate (EC) (CAS: 96-49-1), propylene carbonate (PC) (CAS: 108-32-7) , butylene carbonate (BC) (CAS: 4437-85-8), dimethyl carbonate (DMC) (CAS: 616-38-6), diethyl carbonate (DEC) (CAS: 105-58-8 ), methyl ethyl carbonate (EMC) (CAS: 623-53-0), diphenyl carbonate (CAS 102-09-0), methyl phenyl carbonate (CAS: 13509-27-8), diphenyl dipropyl carbonate (DPC) (CAS: 623-96-1), methyl propyl carbonate (MPC) (CAS: 1333-41-1), ethyl propyl carbonate (EPC), vinylene (VC) (CAS: 872-36-6), fluoroethylene carbonate (EEC) (CAS: 114435-02
  • EMIM:FSi PYR:FSI
  • EMIM:TFSI PYR:TFSI
  • EMIM:B0B PYR:BOB
  • EMIM:TDI PYR:TDI
  • EMIM :BF4 the PYR:BF4.
  • the mass composition of the anode coating according to the invention is:
  • Component A with a mass ratio between 20 and 80%
  • Component B with a mass ratio between 1 and 40%
  • Component C with a mass ratio between 2 and 50%, the sum of these ratios being 100%.
  • the invention also relates to a process for manufacturing the anode coating described above, using a solvent, from an ink obtained by mixing all the constituents of the coating in a solvent.
  • the inks used to make the coatings can be produced by any type of mixer known to those skilled in the art such as a planetary mixer, centrifugal mixer, orbital mixer, a stirrer shaft, an ultrathurax.
  • the different constituents of the ink are not added in a specific order.
  • the manufacture of the ink can be carried out at different temperatures ranging from room temperature to the boiling temperature of the solvent used to manufacture the ink.
  • the solvent used is preferably a polar solvent with a Hansen parameter greater than 2.
  • acetone acetyl triethyl citrate (ATEC), y-butyrolactone (GBL) , cyclohexanone (CHO), cyclopentanone (CPO), dibutyl phthalate (DBP), dibutyl sebacate (DBS), diethyl carbonate (DEC), diethyl phthalate (DEP), dihydrolevoglucosenone (Cyrene), dimethylacetamide ( DMAc), N,N-dimethylformamide (DMF), dimethyl sulf oxide (DMSO), 1,4-dioxane, 3-Heptanone, hexamethyl phosphoramide (HMPA), 3-hexanone, methyl ethyl ketone (MEK), N-methyl-2- pyrrolidinone (NMP), 3-octanone, 3-p
  • the porosity of the coated anode according to the invention is less than 10%, preferably less than 5%.
  • the porosity of the coated electrode is obtained according to the following calculation described in the publication of M.CAI, Nature Communications, 10, 2019, 4597: where VER represents the actual volume of the coated electrode and calculated by multiplying the area of the coated electrode with the thickness of the coated electrode. VdenseER represents the volume occupied by each of the constituents without any porosity and is calculated according to the following formula:
  • VdenseER is the sum of the volume occupied by each constituent of the coated electrode.
  • the thickness of this coating can range from 0.1 to 100 ⁇ m, preferentially from 0.1 to 50 ⁇ m and more preferentially from 0.1 to 35 ⁇ m.
  • the invention also relates to an anode for an all-solid lithium-ion battery, said anode comprising, preferably consisting of, an active material covered with a coating layer according to the invention.
  • said active material of the anode is deposited on a metallic support.
  • the active material at the negative electrode is chosen from graphite, lithium titanate of the LiffisOid type. titanium oxide TiCE, silicon or an alloy of lithium and silicon, a tin oxide, an intermetallic compound of lithium, lithium metal or mixtures thereof.
  • the active material is mixed with an electronically conductive material and a binder.
  • the electronic conductive material is chosen from carbon blacks, graphites, natural or synthetic, carbon fibers, carbon nanotubes, fibers and powders metals, and conductive metal oxides. Preferably, they are chosen from carbon blacks, graphites, natural or synthetic, carbon fibers and carbon nanotubes.
  • the binder used to manufacture the anode is a polymer chosen from polyolefins (for example: polyethylene or polypropylene), fluorinated polymers (PVDF) which may have acid functions, polyacrylic acids (PAA), polyacrylonitriles (PAN), cellulose-type polymers, polyphenylsulfone, polyethersulfone, a phenolic resin, a vinyl ester resin, an epoxy resin, PTFE or a liquid-crystal polymer.
  • PVDF fluorinated polymers
  • PAA polyacrylic acids
  • PAN polyacrylonitriles
  • cellulose-type polymers polyphenylsulfone, polyethersulfone, a phenolic resin, a vinyl ester resin, an epoxy resin, PTFE or a liquid-crystal polymer.
  • said anode comprises, preferably consists of, an active material covered with a coating layer according to the present invention comprising, preferably consisting of: a) at least one poly(vinylidene fluoride) (component A), b) at least one lithium salt (component B) and at least one conductivity additive (component C).
  • a coating layer comprising, preferably consisting of: a) at least one poly(vinylidene fluoride) (component A), b) at least one lithium salt (component B) and at least one conductivity additive (component C).
  • a porosity as defined in the present application.
  • the invention also relates to a method for manufacturing a negative electrode of a Li-ion battery, said method comprising the following operations: supplying an anode, depositing on said anode a coating layer according to the invention.
  • the present invention provides a negative electrode comprising, preferably consisting of, a metal support on which is deposited an active material covered with a coating layer according to the present invention comprising, preferably consisting of: a) at least one poly (vinylidene fluoride) (component A), b) at least one lithium salt (component B) and at least one conductivity additive (component C).
  • This coating can be produced by any deposition method known to those skilled in the art, such as solvent-based coating, soaking-withdrawal methods, centrifugal coating, spray coating or calendering. These deposition techniques can be carried out at different temperatures ranging from 5°C to 180°C.
  • the metal support of the anode is generally made of copper.
  • Metallic supports can be surface treated and have a conductive primer with a thickness of 5 ⁇ m or more.
  • the supports can also be wovens or nonwovens made of carbon fiber.
  • Another object of the invention is an all-solid Li-ion secondary battery comprising a negative electrode, a positive electrode and an all-solid electrolyte, in which the anode is as described above.
  • the cathode of said battery is also covered with a coating layer according to the invention.
  • VDF-HFP copolymer with a mass content of HFP of 23% are dissolved in 85.753 g of acetone using a planetary mixer at 2000 rpm for six times 1 min to obtain complete dissolution.
  • LiFSI LiFSI
  • tetraethylene glycol dimethyl ether Cas 143-24-8
  • a magnetic stirrer for 10 min at 21°C.
  • 8.826 g of a 15% PF solution in acetone are added.
  • LiFSI LiFSI
  • methoxypropionitrile Cas 110-67-8
  • a magnetic stirrer for 10 min at 21°C.
  • 7.972 g of a 15% FP solution in acetone are added.
  • LiFSI LiFSI
  • tetraethylene glycol dimethyl ether tetraethylene glycol dimethyl ether
  • a sheet of lithium metal with a thickness of 200 ⁇ m is coated with ink III using a coating blade.
  • the wet thickness deposited is 50 ⁇ m.
  • the thickness of the deposited film is measured at 38 ⁇ m.
  • the electrode is then calendered to obtain a 2 ⁇ m deposit on the lithium metal. Ionic conductivity is measured by impedance spectroscopy. The value obtained is 0.553 mS/cm.
  • a dendrite test was performed to compare the coating on the Li metal from Ink III against a standard liquid electrolyte.
  • Method the method consists in charging and discharging a symmetrical Li metal/Li metal battery, the potential of the battery is then measured. This potential is proportional to the surface of the electrodes so the appearance of dendrites results in an increase in potential.
  • Cathode Lithium metal coated or not
  • the battery is charged using a positive current of 0.25 mA to an energy density of 0.25 mAh.
  • the battery is then discharged using a negative current of 0.25 mA to an energy density of 0.25 mAh.
  • a porous PE separator is soaked in an electrolyte solution containing IM LiFSI in EC/EMC 3/7 by volume.
  • Table 1 shows the time required for a doubling of the initial battery potential.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
EP22792854.6A 2021-09-27 2022-09-23 Revetement d'anode pour batterie li-ion tout solide Pending EP4409652A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2110145A FR3127634A1 (fr) 2021-09-27 2021-09-27 Revetement d’anode pour batterie li-ion tout solide
PCT/FR2022/051795 WO2023047065A1 (fr) 2021-09-27 2022-09-23 Revetement d'anode pour batterie li-ion tout solide

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EP (1) EP4409652A1 (https=)
JP (1) JP2024534623A (https=)
KR (1) KR20240067957A (https=)
CN (1) CN118020162A (https=)
FR (1) FR3127634A1 (https=)
TW (1) TWI840969B (https=)
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CN121008653A (zh) 2024-05-24 2025-11-25 Lg电子株式会社 旋钮组件及包括该旋钮组件的烹饪设备
FR3163208A1 (fr) * 2024-06-07 2025-12-12 Arkema France Composition de revêtement pour anode
FR3163209A1 (fr) * 2024-06-07 2025-12-12 Arkema France Composition de revêtement pour anode
FR3163071A1 (fr) * 2024-06-07 2025-12-12 Arkema France Revetement d’anode pour batterie na-ion ou k-ion tout solide

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WO2016205653A1 (en) * 2015-06-19 2016-12-22 SolidEnergy Systems Multi-layer polymer coated li anode for high density li metal battery
SG11202000093PA (en) * 2016-10-11 2020-02-27 Grst Int Ltd Anode slurry for lithium ion battery
US10727531B2 (en) * 2018-06-21 2020-07-28 Global Graphene Group, Inc. Lithium metal secondary battery featuring an anode-protecting layer
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FR3127634A1 (fr) 2023-03-31
KR20240067957A (ko) 2024-05-17
CN118020162A (zh) 2024-05-10
US20240387886A1 (en) 2024-11-21
TW202324814A (zh) 2023-06-16
JP2024534623A (ja) 2024-09-20
TWI840969B (zh) 2024-05-01

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