WO2024083606A1 - Copolymères de fluorure de vinylidène pour électrodes de batterie au lithium - Google Patents

Copolymères de fluorure de vinylidène pour électrodes de batterie au lithium Download PDF

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WO2024083606A1
WO2024083606A1 PCT/EP2023/078181 EP2023078181W WO2024083606A1 WO 2024083606 A1 WO2024083606 A1 WO 2024083606A1 EP 2023078181 W EP2023078181 W EP 2023078181W WO 2024083606 A1 WO2024083606 A1 WO 2024083606A1
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polymer
electrode
moles
monomer
vdf
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PCT/EP2023/078181
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English (en)
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Michele Fiore
Ségolène BRUSSEAU
Julio A. Abusleme
Andrea Vittorio ORIANI
Roberto BIANCARDI
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2024083606A1 publication Critical patent/WO2024083606A1/fr

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    • 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
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—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
    • C08F214/22—Vinylidene fluoride
    • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—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
    • H01M4/62—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2203—Oxides; Hydroxides of metals of lithium
    • 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 pertains to vinylidene fluoride copolymers comprising recurring units derived from hydrophilic monomers and to their use as binder for electrodes in Li-ion batteries.
  • Fluoropolymers are known in the art to be suitable as binders for the manufacture of electrodes for use in electrochemical devices such as secondary batteries.
  • WO 2008/129041 discloses linear semi-crystalline vinylidene fluoride (VDF) copolymers comprising from 0.05% to 10% by moles of recurring units derived from (meth)acrylic monomers and uses thereof as binder in electrodes for lithium-ion batteries.
  • VDF linear semi-crystalline vinylidene fluoride
  • This invention provides a solution to this problem by combining easiness in the electrode fabrication process by dealing with electrode-forming formulation having low viscosity at low shear rates, with the provision of electrodes having a very high adhesion towards the current collector.
  • VDF vinylidene fluoride
  • Ri, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R is a C2-C10 hydrocarbon moiety comprising at least one carboxyl group and comprising no aliphatic hydroxyl group, wherein monomer (CA) in said polymer (F) is of at most 5.0 % by moles, with respect to the total moles of recurring units of polymer (F); and wherein of at least 50% of monomer (CA) is randomly distributed into said polymer (F) and, where the polymer (F) is characterized by containing end groups of formula (I): -(Ra)x-O-CO-O-CH 2 -CH 3 (I) wherein R a is a Ci -C5 linear or branched hydrocarbon group and x is an integer selected from 1 and zero, and the end-groups of formula (I) are present in an amount of at least 20% with respect to the total amount of end groups of polymer (F).
  • a second object of the present invention pertains to an electrode-forming composition (C) comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; and c) at least one solvent (S).
  • AM electrode active material
  • B binder
  • S solvent
  • the present invention pertains to the use of the electrode-forming composition (C) in a process for the manufacture of an electrode [electrode (E)], said process comprising:
  • step (III) applying the composition (C) provided in step (II) onto the at least one surface of the metal substrate provided in step (I), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface;
  • step (V) submitting the dried assembly obtained in step (IV) to a compression step to obtain the electrode (E) of the invention.
  • the present invention pertains to the electrode (E) obtainable by the process of the invention.
  • the present invention pertains to an electrochemical device comprising at least one electrode (E) of the present invention.
  • recurring unit derived from vinylidene fluoride also generally indicated as vinylidene difluoride 1 ,1 -difluoroethylene, VDF
  • VDF vinylidene difluoride 1 ,1 -difluoroethylene
  • the carboxyl group-containing vinyl monomers (CA) are compounds of formula (la): wherein
  • Ri, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R’H is a hydrogen or a C1-C15 hydrocarbon moiety comprising at least one carboxyl group and comprising no aliphatic hydroxyl group,.
  • R’H may further contain in the chain one or more oxygen atoms, carbonyl groups or ester groups.
  • aliphatic hydroxyl group it is intended to mean a hydroxyl group directly bonded to an aliphatic carbon.
  • Non-limitative examples of monomers (CA) of formula (I) include, notably:
  • the at least one monomer (CA) is acrylic acid (AA).
  • polymer (F) is prepared by a polymerization reaction that comprises continuously feeding monomer (CA) during VDF polymerization, a random distribution of monomer (CA) in the polymer chains is present, with sequences VDF-(CA)-VDF being obtained.
  • polymer (F) More preferably, in polymer (F) at least 70% of monomer (CA) is randomly distributed into said polymer (F).
  • randomly distributed monomer (CA) is intended to denote the presence of sequences VDF-(CA)-VDF, and the amount of randomly distributed monomer (CA) is determined as the percent ratio between the average number of said VDF-(CA)-VDF sequences and the total average number of (CA) monomer recurring units.
  • the average number of (CA) sequences equals the average total number of (CA) recurring units, so the fraction of randomly distributed units (CA) is 100%: this value corresponds to a perfectly random distribution of (CA) recurring units.
  • the analytical determination of the total amount of randomly distributed monomer (CA) may be carried out by measuring the sequences VDF-(CA)-VDF by 19 F-NMR and the total amount of monomer in the polymer by one or more of these techniques, 19 F-NMR , 1 H-NMR, titration of carboxyl groups, FT-IR or others.
  • Polymer (F) comprises preferably at least 0.01 %, more preferably at least 0.02 % moles of recurring units derived from said monomer (CA). [0028] Polymer (F) comprises preferably at most 5.0 %, more preferably at most 3.0 % moles, even more preferably at most 2.0 % moles, still more preferably at most 1.5% by moles of recurring units derived from monomer (CA) with respect to the total moles of recurring units of polymer (F).
  • the polymer (F) can be an elastomer or a semi-crystalline polymer, preferably being a semi-crystalline polymer.
  • the term “semi-crystalline” means a fluoropolymer that has, besides the glass transition temperature Tg, at least one crystalline melting point on DSC analysis.
  • a semi-crystalline fluoropolymer is hereby intended to denote a fluoropolymer having a heat of fusion of from 10 to 90 J/g, preferably of from 30 to 80 J/g, more preferably of from 35 to 75 J/g, as measured according to ASTM D3418-08.
  • the term "elastomer” is intended to designate a true elastomer or a polymer resin serving as a base constituent for obtaining a true elastomer.
  • True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10 % of their initial length in the same time.
  • the intrinsic viscosity of polymer (F), measured in dimethylformamide (DMF) at 25 °C, is between 0.05 l/g and 1.0 l/g, more preferably between 0.10 l/g and 0.70 l/g, even more preferably between 0.20 l/g and 0.50 l/g
  • the polymer (F) of the present invention usually has a melting temperature (T m ) comprised in the range from 120 to 200°C.
  • the polymer (F) of the present invention possesses a quasi-linear structure, with a very low amount of branching, which results in the insoluble fraction due to long branched chains being substantially negligible.
  • the polymer (F) of the present invention has preferably a low fraction of insoluble components in standard polar aprotic solvents for VDF polymers, such as NMP. More preferably, solutions of polymer (F) in said standard polar aprotic solvents remain homogeneous and stable for several weeks, with substantially no insoluble residue. [0038] Thanks to the low amount of insoluble components, the GPC and NMR analyses of polymer (F) are not affected, and there are no problems of reliability and reproducibility.
  • the melting temperature may be determined from a DSC curve obtained by differential scanning calorimetry (hereinafter, also referred to as DSC).
  • DSC differential scanning calorimetry
  • Tm melting temperature
  • the polymer (F) may further comprise recurring units derived from one or more fluorinated comonomers (CF) different from VDF.
  • fluorinated comonomer CF
  • fluorinated comonomer CF
  • Non-limitative examples of suitable fluorinated comonomers include, notably, the followings:
  • C2-C8 fluoro- and/or perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), pentafluoropropylene and hexafluoroisobutylene;
  • chloro- and/or bromo- and/or iodo-C2-Ce fluoroolefins such as chlorotrifluoroethylene (CTFE);
  • perfluoro(alkyl)vinyl ethers such as perfluoro(methyl)vinyl ether (PMVE), perfluoro(ethyl) vinyl ether (PEVE) and perfluoro(propyl)vinyl ether (PPVE);
  • polymer (F) is semi-crystalline and comprises from 0.1 to 10.0% by moles, preferably from 0.3 to 5.0% by moles, more preferably from 0.5 to 3.0% by moles of recurring units derived from said fluorinated comonomer (CF) with respect to the total moles of recurring units of polymer (F).
  • the polymer (F) more preferably consists of:
  • VDF vinylidene fluoride
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is zero.
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is 1 , and R a is a C2-C3 linear or branched alkyl radical.
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is zero and containing end groups of formula (I) wherein x is 1 , and R a is a C2-C3 linear or branched alkyl radical.
  • Polymer (F) may be obtained by a process that comprises:
  • VDF vinylidene fluoride
  • CA monomer
  • CF optionally comonomer
  • Suitable radical initiator systems include radical initiators such as di(ethyl) peroxydicarbonate and hydro-ethyl peroxydicarbonate.
  • the amount of radical initiator required for a polymerization is related to its activity and the temperature used for the polymerization.
  • the total amount of radical initiator used is generally between 100 to 30000 ppm by weight on the total monomers weight used.
  • the radical initiator may be added in pure form, in solution, in suspension, or in emulsion, depending upon the initiator chosen.
  • the radical initiator systems may include a chain transfer agent (CT A).
  • CT A chain transfer agent
  • Suitable CTA for the polymerization process for preparing the polymer (F) according to the present invention are those known in the art and are typically selected from the group consisting of short hydrocarbon chains like ethane and propane, esters such as ethyl acetate or diethyl maleate, diethylcarbonate. When an organic peroxide is used as the initiator, it could act also as effective CTA during the course of free radical polymerization.
  • the CTA may be added all at once at the beginning of the reaction, or it may be added in portions, or continuously throughout the course of the reaction. The amount of CTA and its mode of addition depend on the desired properties of polymer (F) to be obtained.
  • Preferred CTA for use in the process of the present invention is diethylcarbonate.
  • pressure is maintained above critical pressure of vinylidene fluoride.
  • the pressure is maintained at a value of more than 50 bars, preferably of more than 75 bars, even more preferably of more than 100 bars.
  • Monomer (CA) is suitably added to the reaction vessel as an aqueous solution.
  • continuous feeding or “continuously feeding” means that slow, small, incremental additions the aqueous solution of monomer (CA) take place during the polymerization.
  • the aqueous solution of monomer (CA) continuously fed during polymerization amounts for at least 50 % wt of the total amount of monomer (CA) supplied during the reaction (i.e. initial charge plus continuous feed). Preferably at least 60 % wt, more preferably at least 70 % wt, most preferably at least 80 % wt of the total amount of monomer (CA) is continuously fed during polymerization. An incremental addition of VDF monomer can be effected during polymerization.
  • the process of the invention is carried out at a temperature superior to the critical temperature of the VDF monomer, i.e. of at least 31°C.
  • the polymer (F) is typically provided in form of powder according to the process described above.
  • Polymer (F) in the form of powder may be optionally further extruded to provide polymer (F) in the form of pellets.
  • the polymer (F) as above detailed may be used as binder for electrodes in Li-ion batteries.
  • a second object of the present invention pertains to an electrode-forming composition (C) comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; and c) at least one solvent (S).
  • the term “electro-active material (AM)” 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 device.
  • the compound (AM) is preferably able to incorporate or insert and release lithium ions.
  • the nature of the compound (AM) in composition (C) depends on whether said composition is used in the manufacture of a positive electrode [electrode (Ep)] or a negative electrode [electrode (En)].
  • the compound (AM) may comprise a composite metal chalcogenide of formula LiMQ 2 , wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V or a metal such as Al and a mixture of thereof 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 or a metal such as Al and a mixture of thereof 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 or a metal such as Al and a mixture of thereof 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 or a metal such as Al and a mixture of thereof and Q is a chalcogen such as O or S.
  • M is the same as defined above.
  • the compound (AM) may comprise a lithiated or partially lithiated transition metal oxyanion-based electro-active material of formula MiM 2 (JC>4)fEi.f, wherein Mi is lithium, which may be partially substituted by another alkali metal representing less than 20% of the Mi metals, M 2 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 M 2 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 MiM 2 (JC>4)fEi.f electro-active material as defined above is preferably phosphate-based and may have an ordered or modified olivine structure.
  • the compound (AM) in the case of forming a positive electrode (Ep) has formula Li 3-x M’yM” 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. Still more preferably, the compound (AM) is a phosphate-based electro-active material of formula Li(Fe x Mni.
  • LFP active materials suitable for use in the electrodes of the present invention may have nanometric particle size, which means that the size is less than 1 micrometer, or micrometric particle size, which means particles means with size between 1 micrometer and 1 millimeter.
  • the compound (AM) may preferably comprise a carbon-based material and/or a silicon-based material.
  • the carbon-based material may be, for example, 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. More particularly, the silicon-based compound may be silicon oxide or silicon carbide.
  • the at least one silicon-based compound is comprised in the compound (AM) in an amount ranging from 1 to 30 % by weight, preferably from 5 to 20 % by weight with respect to the total weight of the compound (AM).
  • the solvent (S) may preferably be an organic polar one, examples of which may include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate, and trimethyl phosphate. These solvents may be used singly or in mixture of two or more species.
  • An optional conductive agent may be added in order to improve the conductivity of a resulting electrode (AM).
  • 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 electro-forming composition (C) of the invention may further optionally include at least one conductive agent.
  • the conductive agent is different from the carbon-based material described above.
  • an electrode-forming composition (C) for use in the preparation of a positive electrode (Ep) comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; c) at least one solvent (S); and d) at least one conductive agent, preferably selected from carbon black or graphite fine powder carbon nanotubes.
  • the polymer (F) of the present invention possesses a quasi-linear structure, and very low amount of insoluble fraction when dissolved in standard polar aprotic solvents such as NMP.
  • polymer (F) provides solutions in organic solvents, which are not detrimentally affected by the presence of insoluble residues, which are generally referred as “gels”, and are hence more adapted for use in formulating electrodes-forming compositions.
  • the present invention pertains to the use of the electrode-forming composition (C) for the manufacture of an electrode (E), said process comprising:
  • step (III) applying the composition (C) provided in step (II) onto the at least one surface of the metal substrate provided in step (I), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface;
  • step (V) submitting the dried assembly obtained in step (III) to a compression step to obtain the electrode (E) of the invention.
  • the present invention pertains to the electrode (E) obtainable by the process of the invention.
  • the Applicant has surprisingly found that the electrode (E) of the present invention shows outstanding adhesion of the binder to current collector.
  • the electrode (E) of the invention is thus particularly suitable for use in electrochemical devices, in particular in secondary batteries.
  • secondary battery is intended to denote a rechargeable battery.
  • the secondary battery of the invention is preferably an alkaline or an alkaline-earth metal secondary battery.
  • the secondary battery of the invention is more preferably a Lithium-ion secondary battery.
  • the present invention pertains to an electrochemical device comprising at least one electrode (E) of the present invention.
  • the electrochemical device according to the present invention being preferably a secondary battery, comprises a positive electrode and a negative electrode, wherein at least one of the positive electrode and the negative electrode is the electrode (E) of the present invention.
  • an electrochemical device is a secondary battery comprising a positive electrode and a negative electrode, wherein the negative electrode is the electrode (E) according to the present invention.
  • An electrochemical device according to the present invention can be prepared by standard methods known to a person skilled in the art.
  • Intrinsic viscosity (q) [dl/g] was measured using the following equation on the basis of dropping time, at 25°C, of a solution obtained by dissolving the polymer (F) in N,N-dimethylformamide at a concentration of about 0.2 g/dl using a Ubbelhode viscosimeter: where c is polymer concentration [g/dl], r
  • the amount of polar end groups of the polymers (F) arising from the ethyl chloroformate initiator precursor used in the polymerization process was determined by 1 H-NMR, measuring the intensity of the H atoms of the CH 2 group (in bold in following formula) with respect to the total intensity of CH 2 moieties of the polymer (F) backbone VDF monomer units: CH3-CH2-OCOO-CH2-CF2-
  • - IEG is the intensity, normalized to one hydrogen, of the integral of the end-group [EG]
  • IVDF is the intensity, normalized to one hydrogen, of the integrals of normal and reverse VDF recurring units.
  • the pressure was kept constantly equal to 120 bars during the whole polymerization run by feeding an aqueous solution of 4.15 g of AA per liter of solution. A total of 666 g of the solution was charged to the reactor. After 269 minutes the polymerization was stopped by degassing the suspension until reaching atmospheric pressure.
  • the obtained polymer was then collected by filtration and suspended against clean water in a stirred tank. After the washing treatment, the polymer was dried in an oven at 65°C overnight. 837 g of dry powder were collected.
  • a polymer comprising VDF-AA (0.2% by moles), having an intrinsic viscosity of 0.299 l/g in DMF at 25°C and a T 2 f of 170.3°C was obtained.
  • the polymer contained 2.0/10000 VDF units of end-group CH3CH2-OCOO-: 1.3 /10000 VDF units derived from the ethyl chloroformate initiator precursor and 0.7/10000 VDF units derived from diethylcarbonate.
  • the amount of end groups CH3CH2-OCOO- is 32.3% with respect to the overall amount of end groups of polymer (F)
  • the pressure was kept constantly equal to 120 bars during the whole polymerization run by feeding an aqueous solution of 18.27 g of AA per liter of solution. A total of 659 g of the solution was charged to the reactor. After 624 minutes the polymerization was stopped by degassing the suspension until reaching atmospheric pressure.
  • the polymer contained 2.5 /10000 VDF units of the end-group CH 3 CH 2 -OCOO- derived from the ethyl chloroformate initiator precursor.
  • the amount of end groups CH3CH 2 -OCOO- is 26.9% with respect to the overall amount of end groups of polymer (F).
  • Example 3 comparative Preparation of Polymer A
  • the pressure was kept constantly equal to 120 bars during the whole polymerization run by feeding an aqueous solution of 3.33 g of AA per liter of solution. A total of 830 g of the solution was charged to the reactor. After 354 minutes the polymerization was stopped by degassing the suspension until reaching atmospheric pressure. [00138] The polymer was then collected by filtration and suspended against clean water in a stirred tank. After the washing treatment, the polymer was dried in an oven at 65°C overnight. 987 g of dry powder were collected.
  • the polymer contained 1.1 /10000 VDF units of the end-group from TAPPI addition, the presence of 3.2/10000 VDF units of -CF2H and 2.1 /10000 VDF units of -CF2CH3 end-groups.
  • the polymer contained 1.1/10000 VDF units of end-group CH3CH2-OCOO- derived from diethylcarbonate.
  • the polymer B has been synthesized according to the teaching of WO 2008/129041 (SOLVAY SPECIALTY POLYMERS ITALY S.P.A.).
  • the characteristics of the polymer are the following:
  • Composition VDF-AA (0.9% by moles), polymer having an intrinsic viscosity of 0.274 l/g in DMF at 25°C and a T 2 f of 162.6°C.
  • End groups 2.3/10000 VDF units of the end-group from TAPPI addition, 6.8 /10000 VDF units of -CF2H and 3.1/10000 VDF units of -CF2CH3 end-groups.
  • Positive electrodes having final composition of 96.5% by weight of NMC 622 (Umicore, d50 11.6 pm), 1.5% by weight of anyone of polymer (F-1), (F-2), A and B, 2% by weight of conductive additive were prepared as follows.
  • a first dispersion was prepared by pre-mixing for 10 minutes in a centrifugal mixer 34.7 g of a 6% by weight solution of the polymer in NMP, 133.8 g of NMC622, 2.8 g of SC-65 and 8.8 g of NMP.
  • the final slurry was obtained by further stirring with high speed disk impeller at 1900 rpm for 70 minutes.
  • Positive electrodes were obtained by casting the obtained compositions on 15 pm thick Aluminium foil with doctor blade and drying the coated layers in a vacuum oven at temperature of 90°C for about 50 minutes. The thickness of the dried coating layers was about 110 pm.
  • Example 5 Adhesion and slurry viscosity
  • the polymers of examples 1 to 3 were used as binders and the electrode compositions have been produced according to the procedure shown above.
  • the slurry viscosity of the compositions as above defined was measured with an AntonPaar Rheolab QC using a Concentric cylinder setup (Measuring Cup: C- CC27/QC-LTD Bob: CC27/P6) with peltier temperature control at 25°C. Steady state viscosities were measured from shear rate of 0.1 to 200 1/s.
  • Adhesion Peeling Force between Aluminium foil and Electrode was measured as follows:

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Abstract

La présente invention concerne des copolymères de fluorure de vinylidène comprenant des unités récurrentes dérivées de monomères hydrophiles qui comprennent un groupe carboxyle, les polymères ayant des groupes terminaux de carbonate d'éthyle, et leur utilisation en tant que liants pour des électrodes dans des batteries Li-ion.
PCT/EP2023/078181 2022-10-18 2023-10-11 Copolymères de fluorure de vinylidène pour électrodes de batterie au lithium WO2024083606A1 (fr)

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EP22202256.8 2022-10-18

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060044522A (ko) * 2004-03-23 2006-05-16 가부시끼가이샤 구레하 비수계 전기화학소자 전극 형성용 바인더, 전극 합제, 전극구조체 및 전기 화학 소자
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
WO2018114753A1 (fr) * 2016-12-22 2018-06-28 Solvay Specialty Polymers Italy S.P.A. Polymère de fluorure de vinylidène
WO2022258551A1 (fr) * 2021-06-10 2022-12-15 Solvay Specialty Polymers Italy S.P.A. Liants à haute performance pour électrodes de batterie au lithium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060044522A (ko) * 2004-03-23 2006-05-16 가부시끼가이샤 구레하 비수계 전기화학소자 전극 형성용 바인더, 전극 합제, 전극구조체 및 전기 화학 소자
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
WO2018114753A1 (fr) * 2016-12-22 2018-06-28 Solvay Specialty Polymers Italy S.P.A. Polymère de fluorure de vinylidène
WO2022258551A1 (fr) * 2021-06-10 2022-12-15 Solvay Specialty Polymers Italy S.P.A. Liants à haute performance pour électrodes de batterie au lithium

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