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WO2025003026A1 - Polymères de (méth)acrylate en tant qu'additifs dans des électrodes de batterie - Google Patents

Polymères de (méth)acrylate en tant qu'additifs dans des électrodes de batterie Download PDF

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Publication number
WO2025003026A1
WO2025003026A1 PCT/EP2024/067585 EP2024067585W WO2025003026A1 WO 2025003026 A1 WO2025003026 A1 WO 2025003026A1 EP 2024067585 W EP2024067585 W EP 2024067585W WO 2025003026 A1 WO2025003026 A1 WO 2025003026A1
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Prior art keywords
polymer
acid ester
meth
monomer
composition
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Inventor
Maurizio Biso
Francesco LIBERALE
Pierre-Emmanuel Dufils
David James Wilson
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Solvay Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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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
    • 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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—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
    • H01M4/139—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 pertains to a binder for a secondary battery positive electrode, to a method of preparation of said electrode and to its use in a secondary battery.
  • the invention also relates to the secondary batteries manufactured by incorporating said electrode.
  • Electrochemical devices such as secondary batteries typically comprise a positive electrode, a negative electrode and an electrolyte.
  • the electrodes for secondary batteries are usually produced by mixing a binder with a powdery electrode active material.
  • PVDF polyvinylidene fluoride
  • Electrodes flexibility is indeed of primary importance for battery makers because it allows to increase electrode density and/or loading without cracking during the standard cell production process i.e. avoiding fracture of electrode (of either the coating or the collector) during winding or during lamination after winding. Moreover, flexible electrodes allow to reach higher electrode density in the standard pressing conditions or same density with milder pressing conditions. [0008] When electrodes cannot stand bending, there is the risk of mechanical failure, cracking of the electrodes, eventual materials detachment from current collector and/or battery failure during cycling.
  • EP 2953193 discloses that flexibility performances of Nickel-rich cathodes using PVDF homopolymer binders are improved when a nitrile group- containing acrylic polymer is added.
  • JP2005-123047 discloses a sheet-like positive electrode binder based on polyvinylidene fluoride containing acrylonitrile-butadiene rubber, which provides improved flexibility to a lithium nickel oxide cathode.
  • Modified polar PVDF polymers such as those comprising recurring units derived from hydrophilic (meth)acrylic monomers (e.g. acrylic acid), are well known in the art. Such copolymers have been developed aiming at adding to the mechanical properties and chemical inertness of PVDF suitable adhesion towards metals, e.g. aluminium or copper.
  • modified polar PVDF polymers when used in the preparation of a slurry for forming positive electrodes with certain active materials, an important drawback is that the slurry often undergoes to a rapid viscosity increase, leading to the formation of a gel, thus preventing their use as binder for cathodes.
  • composition (C) for use in the preparation of electrodes for electrochemical devices, said composition (C) comprising: a) at least one positive electrode active material (AM); b) one binder (B), wherein binder (B) comprises: bi) at least one vinylidene fluoride (VDF) copolymer [polymer (F)] that comprises:
  • R2 and R3 are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
  • - Rx is a C1-C20 hydrocarbon moiety comprising at least one functional group selected from a hydroxyl, a carboxyl, an epoxide, an ester, a phosphate and an ether group, in an amount of from 0.05 to 10 % by moles of with respect to the total moles of recurring units of polymer (F); b2) at least one polymer [polymer (A)] derived from the polymerization of at least one monomer (I) and of at least one monomer (II), the said monomers corresponding to the following:
  • R means hydrogen or an alkyl group with 1 to 3 carbon atoms
  • R 1 and R 2 are independently selected from the group consisting of H and optionally substituted alkyl group with 1 to 5 carbon atoms
  • Rh means a linear or branched alkyl residue with 1 to 30 carbon atoms, preferably with 1 to 15 carbons, more preferably with 1 to 5 carbons, optionally substituted by one or more nitrogen atom or by one or more hydroxyl, thiol or amino functional group;
  • - monomer (II) nitrile group-containing monomer; wherein the content of monomer (II) in the polymer (A) is lower than
  • the present invention pertains to the use of the electrode-forming composition (C) of the invention in a process for the manufacture of a positive electrode for electrochemical devices [electrode (E)], said process comprising:
  • composition (C) onto the at least one surface of the metal substrate, thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface;
  • the present invention pertains to the positive electrode (E) obtainable by the process of the invention.
  • the present invention pertains to an electrochemical device comprising a positive electrode (E) of the present invention.
  • parentheses “(%)” before and after symbols or numbers identifying formulae or parts of formulae has the mere purpose of better distinguishing that symbol or number with respect to the rest of the text; thus, said parentheses could also be omitted.
  • (meth)acrylic or “(meth)acrylate” are intended to cover both the acrylic/acrylate and methacrylic/methacrylate forms of the indicated material, e.g., a (meth)acrylate monomer.
  • the electrode active material (AM) of the positive electrode is preferably a compound capable of intercalating lithium ions or sodium ions.
  • the conventional active materials (AM) at the positive electrode of sodium- ion batteries are generally selected from Na-based layered transition-metal oxides, Prussian blue analogs and polyanion-type materials.
  • the active materials are Na-based layered transitionmetal oxides classified as O3-, P2-, and P3-types depending on the stacking sequence of oxygen layers.
  • P2-type structures generally respond to the general formula NaxMC wherein M stands for a transition metal ion such as Co, Mn and x is 2/3.
  • the active materials are Prussian blue analogs (PBA) of general formula AxP[R(CN)6]i-yn y .mH2O with A and alkali metal ion, P a N-coordinated transition metal ion, R a C-coordinated transition metal ion, ⁇ a [R(CN)e] vacancy, with 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 1 such as Nao.8i Fe[Fe(CN)6]o.79no.2i , NaFe2(CN)e, Na1 63Fei.89(CN)6, Nai.72MnFe(CN)e, Nai.76Nio.i2Mno.88[Fe(CN)6]o.98, Na2NixCoi-xFe(CN)e with 0 ⁇ x ⁇ 1 e.g. Na2CoFe(CN)e.
  • PBA Prussian blue analogs
  • phosphates NaMPCk such as NaFePCk, NaojFePCk or NaMnPCk; natrium (sodium) superionic conductor of NASICON-type structures of general formula NaxM2(XO 4 )3 (where 1 ⁇ x ⁇ 4 and
  • M V, Fe, Ni, Mn, Ti, Cr, Zr...;
  • X P, S, Si, Se, Mo ... ) - with single transition metal type such as Na3V2(PO 4 )3 (NVP), Na3Cr2(PO 4 )3, Na3Fe2(PO 4 )3; - with binary transition metal type such as Na2VTi(PO 4 )3, Na3FeV(PO 4 )3, Na 4 MnV(PO 4 ) 3 , Na 3 MnZr(PO 4 ) 3 , Na 3 MnTi(PO 4 ) 3 , Na 4 Fe 3 (PO 4 )2(P2O7) (NFPP); pyrophosphates Na2FeP2O7, Na2MnP2O7, Na2CoP2O7, Na 4 - xFe2+x/2(P2O7)2 with 2/3 ⁇ x ⁇ 7/8 e.g.
  • Na3(VOPO 4 )2F or Na3V2(PO 4 )2F3 NVPF
  • the active materials are fluorophosphates preferably selected from the list consisting of NaVPCMF, Na2CoPO4F, Na2FePO4F, Na2MnPO4F, Na3(VOi-xPO4)2Fi+2x (with 0 ⁇ x ⁇ 1 ) e.g. Na 3 (VOPO 4 )2F or Na 3 V2(PO 4 )2F3 (NVPF).
  • the conventional active materials (AM) at the positive electrode of lithium- ion batteries may comprise a composite metal chalcogenide of formula UMQ2, 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 0 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 0 or S.
  • Preferred examples thereof may include LiCoC , LiNiC>2, LiNixCoi-xO2 (0 ⁇ x ⁇ 1 ) and spinel- structured LiMn2O 4 .
  • the at least one positive electrode active material (AM) is selected from lithium-containing complex metal oxides of general formula (II)
  • LiNixM 1 y M 2 zQ 2 (II) wherein M 1 and M 2 are the same or different from each other and are transition metals selected from Co, Fe, Mn, Cr and V, 0.5 ⁇ x ⁇ 1 , wherein y+z 1 -x, and
  • 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, JO 4 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 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 (AM) is a phosphate-based electro-active material of formula LixAyDzPO 4 , wherein A is selected from the group consisting of Mn, Fe, Co, Ni and Cu; D is selected from the group consisting of Mg, Ca, Sr, Ba; x, y and z are numbers that satisfy the following relationships: 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1.5, 0 z ⁇ 1.5.
  • the A component is preferably Fe, Mn, and Ni, and particularly preferably Fe.
  • the D component is preferably Mg or Ca.
  • Examples of the compound having an olivine structure include lithium iron phosphate (LFP), lithium iron manganese phosphate (LMFP) and lithium manganese phosphate.
  • the positive electrode active material it is possible to use a material whose surface is partially or wholly covered with carbon in order to supplement the conductivity.
  • the amount of carbon coated is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, based on 100 parts by weight of the positive electrode active material.
  • Composition (C) of the invention further comprises a binder (B) that comprises: bi) at least one vinylidene fluoride (VDF) copolymer [polymer (F)], as above defined, and b2) at least one polymer [polymer (A)] as above defined.
  • the polymer (F) comprises recurring units derived from vinylidene fluoride (VDF) and recurring units derived from at least one hydrophilic vinyl monomer (MA) of formula (I): wherein:
  • R1 , R2 and R3, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
  • Rx is a C1-C20 hydrocarbon moiety comprising at least one functional group selected from a hydroxyl, a carboxyl, an epoxide, an ester, a phosphate and an ether group, in an amount of from 0.05 to 10 % by moles of with respect to the total moles of recurring units of polymer (F).
  • hydrophilic vinyl monomer as employed herein may comprise recurring units derived from one or more than one hydrophilic vinyl monomer (MA) as above described.
  • hydrophilic vinyl monomer (MA) is to be intended, both in the plural and the singular, that is to say that they denote both one or more than one hydrophilic vinyl monomer (MA).
  • the hydrophilic vinyl monomer (MA) preferably complies with formula (III): wherein each of Ri and R2 have the meanings as above defined, R3 is hydrogen, and ROH is a hydrogen or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group and/or at least a carboxylic group; more preferably, each of R1 , R2, R3 are hydrogen, while ROH has the same meaning as above detailed.
  • Non limitative examples of hydrophilic vinyl monomers (MA) are notably acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate; hydroxyethylhexyl(meth)acrylates.
  • the monomer (MA) is more preferably selected among:
  • HPA 2-hydroxypropyl acrylate
  • the monomer (MA) is AA and/or HEA.
  • Polymer (F) may still comprise other moieties such as defects, end-groups and the like, which do not affect nor impair its physico-chemical properties.
  • Polymer (F) is semi-crystalline.
  • the term semi-crystalline is intended to denote a polymer (F) which possesses a detectable melting point. It is generally understood that a semi-crystalline polymer (F) possesses a heat of fusion determined according to ASTM D 3418 of advantageously at least 0.4 J/g, preferably of at least 0.5 J/g, more preferably of at least 1 J/g.
  • Polymer (F) is preferably a linear copolymer, that is to say, it is composed of macromolecules made of substantially linear sequences of recurring units from VDF monomer and (MA) monomer; polymer (F) is thus distinguishable from grafted and/or comb-like polymers.
  • Polymer (F) comprises at least 0.05 % by moles, more preferably at least 0.1 % by moles, even more preferably at least 0.2 % by moles of recurring units derived from said hydrophilic vinyl monomer (MA).
  • Polymer (F) comprises preferably at most 2 % by moles, more preferably at most 1.8 % by moles, even more preferably at most 1.5% by moles of recurring units derived from said hydrophilic vinyl monomer (MA).
  • polymer (F) in polymer (F) the recurring units derived from hydrophilic vinyl monomer (MA) of formula (I) are comprised in an amount of from 0.2 to 1 % by moles with respect to the total moles of recurring units of polymer (F).
  • the polymer (F) has advantageously an intrinsic viscosity, measured in dimethylformamide at 25 °C, of above 0.15 l/g and at most 0.60 l/g, preferably in the range of 0.20 - 0.50 l/g, more preferably comprised in the range of 0.25 - 0.40 l/g.
  • 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).
  • polymer (F) 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).
  • the polymer (F) more preferably comprises recurring units derived from:
  • VDF vinylidene fluoride
  • CF fluorinated comonomer
  • the polymer (F) may be obtained by polymerization of a VDF monomer, at least one monomer (MA) and optionally at least one comonomer (CF), either in suspension in organic medium, according to the procedures described, for example, in WO 2008/129041 , or in aqueous emulsion, typically carried out as described in the art (see e.g. US 4,016,345, US 4,725,644 and US 6,479,591).
  • the procedure for preparing the polymer (F) in suspension comprises polymerizing in an aqueous medium in the presence of a radical initiator the vinylidene fluoride (VDF) monomer, monomer (MA) and optionally comonomer (CF), in a reaction vessel, said process comprising
  • 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.
  • continuous feeding means that slow, small, incremental additions the aqueous solution of hydrophilic vinyl monomer (MA) take place until polymerization has concluded.
  • the polymer (F) thus obtained has a high uniformity of monomer (MA) distribution in the polymer backbone, which advantageously maximizes the effects of the modifying monomer (MA) on both adhesiveness and/or hydrophilic behaviour of the resulting copolymer.
  • the Applicant has surprisingly found that the presence of the monomer (MA) uniformly distributed in the polymer (F) has the effect of improving the thermal stability of VDF copolymers, which otherwise is unsatisfactorily low, in particular lower than that of VDF homopolymers.
  • the amount of polymer (F) in composition (C) is suitably in the range of from 0.5 to 5 % by weight.
  • Polymer (A) is a copolymer derived from the polymerization of at least one monomer (I) and of at least one monomer (II), wherein
  • copolymer as used herein it is intended to denote a polymer having two or more different monomer units.
  • the copolymer could be a terpolymer with three or more different monomer units, or have four or more different monomer units.
  • the copolymer may be a random copolymer, a gradient copolymer, or a block copolymer formed by a controlled polymerization process.
  • the copolymer is formed by a free radical polymerization process or an anionic polymerization process, and the process can be any polymerization method known in the art, including but not limited to solution, suspension polymerization, and can be done in bulk, and semi-bulk.
  • the monomer (I) is selected from the group consisting of: acrylic acid ester or anhydride, methacrylic acid ester or anhydride, citraconic acid ester or anhydride, maleic acid ester or anhydride, fumaric acid ester or anhydride, itaconic acid ester or anhydride, crotonic acid ester or anhydride, ethacrylic acid ester or anhydride, methyl (meth)acrylic acid ester or anhydride, ethyl (meth)acrylic acid ester or anhydride, propyl (meth)acrylic acid ester or anhydride, isopropyl (meth)acrylic acid ester or anhydride, n-butyl (meth)acrylic acid ester or anhydride, 2-ethylhexyl (meth)acrylic acid ester or anhydride, n- hexyl (meth)acrylic acid ester or anhydride,
  • monomer (I) is selected from methyl methacrylic acid ester (MMA) and n-butyl (meth)acrylic acid ester.
  • the nitrile group-containing monomer (II) is preferably selected from acrylonitrile and methacrylonitrile.
  • the content of nitrile group-containing monomer (II) units in polymer (A) is lower than 20 % by moles, preferably lower than 15 % by moles.
  • polymer (A) is a copolymer derived from the polymerization of methyl methacrylic acid ester (MMA), n-butyl acrylic acid ester (BA) and acrylonitrile (AN).
  • MMA methyl methacrylic acid ester
  • BA n-butyl acrylic acid ester
  • AN acrylonitrile
  • polymer (A) comprises recurring units derived from methyl methacrylic acid ester (MMA) in an amount of from 10 to 45 % by moles, n-butyl acrylic acid ester (BA) in an amount of from 45 to 80 % by moles and acrylonitrile (AN) in an amount of from 5 to less than 20 % by moles.
  • MMA methyl methacrylic acid ester
  • BA n-butyl acrylic acid ester
  • AN acrylonitrile
  • the weight average molecular weight Mw of the polymer (A) is generally between 15 000 and 500 000, preferably between 20 000 and 75 000.
  • the polymer (A) is prepared by polymerizing a mixture of at least one monomer (I) and at least one monomer (II) according to any known method in the art.
  • the amount of polymer (A) in composition (C) is suitably in the range of from 0.1 to 0.5 % by weight.
  • the choice of the solvent (S) is not particularly limited, provided that it is suitable for solubilising polymer (F) and dispersing/dissolving polymer (A).
  • Solvent (S) is typically selected from the group consisting of:
  • alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol
  • ketones such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone,
  • - linear or cyclic amides such as N,N-diethylacetamide, N,N- dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
  • the electrode forming compositions of the present invention may further include one or more optional electroconductivity-imparting additives in order to improve the conductivity of an electrode made from the composition of the present invention.
  • Electroconductivity-imparting additives 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 agents are preferably carbon black or carbon nanotubes.
  • the amount of optional conductive agent is preferably from 0 to 30 % by weight with respect to the total solids in the electrode forming composition.
  • the optional conductive agent is typically from 0 % by weight to 10 % by weight, more preferably from 0 % by weight to 5 % by weight of the total amount of the solids within the composition (C).
  • Composition (C) may further comprise at least one wetting agent and/or at least one surfactant and one or more than one additional additives.
  • Composition (C) may further comprise at least one non-electroactive inorganic filler material.
  • non-electroactive inorganic filler material it is hereby intended to denote an electrically non-conducting inorganic filler material, which is suitable for the manufacture of an electrically insulating separator for electrochemical cells.
  • the non-electroactive inorganic filler material in the separator according to the invention typically has an electrical resistivity (p) of at least 0.1 x 1010 ohm cm, preferably of at least 0.1 x 1012 ohm cm, as measured at 20°C according to ASTM D 257.
  • Non-limitative examples of suitable non-electroactive inorganic filler materials include, notably, natural and synthetic silicas, zeolites, aluminas, titanias, metal carbonates, zirconias, silicon phosphates and silicates and the like.
  • Binder (B) for use in the composition (C) according to the present invention can be prepared by any known method in the art.
  • a suitable method comprises:
  • the weight ratio of polymer (F) to polymer (A) in binder (B) is conveniently in the range of from 95:5 to 70:30. In a preferred embodiment of the invention, the weight ratio of polymer (F) to polymer (A) in binder (B) is 90:10.
  • the electrode-forming composition (C) may be obtained by adding and dispersing a powdery electrode material, and optional additives, such as an electroconductivity-imparting additive and/or a viscosity modifying agent, into the thus-obtained binder mixture (B), to obtain a homogeneous slurry.
  • optional additives such as an electroconductivity-imparting additive and/or a viscosity modifying agent
  • the solution of polymer (F) in solvent (S) is notably comprising the polymer (F) in an amount of from 5 to 20 % by weight, preferably about 7 to 10 % by weight.
  • the solution of polymer (A) in solvent (S) is notably comprising the polymer (A) in an amount of from 0.1 to 15% by weight in 100 parts by weight of such a solvent.
  • the total solid content (TSC) of the composition (C) of the present invention is typically comprised between 50 and 85 % by weight, preferably from 60 and 80 % by weight, over the total weight of the composition (C).
  • the total solid content of the composition (C) is understood to be cumulative of all non-volatile ingredients thereof, notably including polymer (F), polymer (A), the electrode active material and any solid, non-volatile additional additive.
  • an amount of solvent sufficient to create a stable solution of polymer (F) is employed.
  • the amount of solvent used may range from the minimum amount needed to create a stable solution of polymer (F) to an amount needed to achieve a desired total solid content in an electrode mixture after the polymer (A), the active electrode material, the optional conductive material, and the other solid additives have been added.
  • composition (C) makes it possible to obtain high quality homogenous slurry compositions with neither gelation evidence nor inhomogeneity in all the preparation steps.
  • Said composition is suitable for use in the preparation of electrodes.
  • polymer (A) is a copolymer derived from the polymerization of methyl methacrylic acid ester (MMA), n-butyl acrylic acid ester (BA) and acrylonitrile (AN), with an AN content lower than 20 wt% in polymer (A).
  • MMA methyl methacrylic acid ester
  • BA n-butyl acrylic acid ester
  • AN acrylonitrile
  • composition (C) of the present invention is that it is possible to provide an electrode which comprises a relatively low content by weight of binder and to make it possible to increase the content of active material in the positive electrode, in order to maximise the capacity of the battery.
  • the electrode-forming composition (C) of the invention can be used in a process for the manufacture of a positive electrode [electrode (E)], said process comprising:
  • composition (C) As above defined;
  • composition (C) onto the at least one surface of the metal substrate, thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface;
  • the metal substrate is generally a foil, mesh or net made from a metal, such as from aluminium, nickel, titanium, and alloys thereof.
  • step (iii) of the process of the invention the electrode forming composition (C) is applied onto at least one surface of the metal substrate typically by any suitable procedures such as casting, printing and roll coating.
  • step (iii) may be repeated, typically one or more times, by applying the electrode forming composition (C) provided in step (ii) onto the assembly provided in step (iv).
  • drying may be performed either under atmospheric pressure or under vacuum.
  • drying may be performed under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001 % v/v).
  • the drying temperature will be selected so as to effect removal by evaporation of the aqueous medium from the electrode (E) of the invention.
  • the dried assembly obtained in step (iv) may further be submitted to a compression step such as a calendaring process, to achieve the target porosity and density of the electrode (E) of the invention.
  • the dried assembly obtained at step (iv) is hot pressed, the temperature during the compression step being comprised from 25°C and 130°C, preferably being of about 60°C.
  • Preferred target density for electrode (E) is comprised between 2 and 3 g/cc, preferably at least 2.1 g/cc.
  • the density of electrode (E) is calculated as the sum of the product of the densities of the components of the electrode multiplied by their mass ratio in the electrode formulation.
  • the present invention pertains to the positive electrode [electrode (E)] obtainable by the process of the invention. [00111 ] Therefore the present invention relates to a positive electrode (E) comprising:
  • composition (C’) comprising: a) at least one positive electrode active material (AM); b) a binder composition [binder (B’)] comprising: b’) at least one polymer (F) as above defined, b”) at least one polymer (A) as above defined; c) optionally, at least one electroconductivity-imparting additive.
  • composition (C’) directly adhered onto at least one surface of said metal substrate corresponds to the electrode forming composition (C) of the invention wherein the solvent has been at least partially removed during the manufacturing process of the electrode, for example in step (iv) (drying) and/or in the further compression step.
  • compositions (C) of the invention are also applicable to the composition (C’) directly adhered onto at least one surface of said metal substrate, in electrodes of the invention, except for the aqueous medium removed during the manufacturing process.
  • the preferred positive electrode (E) comprises:
  • the positive electrode (E) comprises of at least 95% by weight of active material (AM) and an electrode loading comprised between 8 and 20 mg/cm 2 , preferably of about 15 mg/cm 2 .
  • the positive electrode (E) of the invention is particularly suitable for use in electrochemical devices.
  • Non-limitative examples of suitable electrochemical devices include, notably, secondary batteries, especially, alkaline or an alkaline- earth secondary batteries such as lithium ion batteries, solid state batteries, lithium-metal batteries, lead-acid batteries, and capacitors, especially lithium ion-based capacitors and electric double layer capacitors (supercapacitors).
  • secondary batteries especially, alkaline or an alkaline- earth secondary batteries
  • lithium ion batteries solid state batteries
  • lithium-metal batteries lithium-metal batteries
  • lead-acid batteries and capacitors
  • capacitors especially lithium ion-based capacitors and electric double layer capacitors (supercapacitors).
  • 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.
  • Polymer (F-1 ) VDF-AA (1.0% by moles) polymer having an intrinsic viscosity of 0.30 l/g in DMF at 25°C.
  • Polymer 1 Acrylonitrile/butadiene rubber commercialized as BM-720H by ZEON Corporation.
  • NMC622 Cellcore®NMC KHX12: cathode electroactive material.
  • a solution of MMA (35.09 g), BA (155.68 g), and AN (9.22 g) was prepared separately. After purging with nitrogen, 15 wt% of the solution was introduced in the reactor.
  • a solution of MMA (37.54 g), BA (142.73 g), and AN (19.73 g) was prepared separately. After purging with nitrogen, 15 wt% of the solution was introduced in the reactor.
  • Polymer (A-1 ) was dissolved in NMP to obtain a 8% by weight solution.
  • NMC622 and Carbon black “SC65” were added simultaneously to the NMP solution of polymer (A-1 ) and polymer (F-1 ) with planetary mixing followed by dispersion phase to provide Composition 1 , a cathode slurry having a Total Solid Content (TSC) of 74% (96.3% NMC622, 2% carbon black, 1 .5% polymer (F-1 ) and 0.2% polymer (A-1 )).
  • TSC Total Solid Content
  • Polymer (A-2) was dissolved in NMP to obtain a 8% by weight solution.
  • NMC622 and carbon black were added simultaneously to the NMP solution of polymer (A-2) and polymer (F-1 ) with planetary mixing followed by dispersion phase to provide Composition 2, a cathode slurry having a Total Solid Content (TSC) of 74% (96.3% NMC622, 2% carbon black, 1.5% polymer (F-1 ) and 0.2% polymer (A-2)).
  • TSC Total Solid Content
  • NMC622 and carbon black were added to the NMP solution of polymer (F- 1 ) with planetary mixing followed by dispersion phase to provide Composition 3, a cathode slurry having a Total Solid Content (TSC) of 74% (96.5% NMC622, 2% carbon black, 1.5% polymer (F-1 )).
  • TSC Total Solid Content
  • Polymer 1 (BM-720H) was dissolved in NMP to obtain a 8% by weight solution.
  • NMC622 and carbon black were added simultaneously to the NMP solution of Polymer 1 and polymer (F-1 ) with planetary mixing followed by dispersion phase to provide Composition 4, a cathode slurry having a Total Solid Content (TSC) of 74% (96.3% NMC622, 2% carbon black, 1.5% polymer (F-1 ) and 0.2% Polymer 1 ).
  • TSC Total Solid Content
  • Composition 3 which comprises polymer (F-1 ) only.
  • Positive electrodes were obtained by applying the electrode-forming compositions 1 -4 as above described to both sides of a 15 pm thick aluminium foils so as to obtain a mass of dry positive electrode loading of 40 mg/cm 2 for each side.
  • the solvent was completely evaporated by drying in an oven at temperature of 90°C to fabricate a strip-shaped positive electrodes.
  • Flexibility was measured by a U-bending test, using the coating cracking diameter as parameter to assess and determine flexibility.
  • Double-sided electrodes are cut in stripes (2x10cm) and fixed at the two ends between two horizontal parallel plates of a dynamometer, placed at a distance of 20mm, having a bended shape. During the test, the plates are approached one to the other with the automated crossbeam movement with a speed of 10mm/min. The diameter of the bended electrode is progressively reduced, till a cracking in the electrode coating is observed.
  • Positive electrodes (E1 ), (EC-2), (EC-3) and (EC-4) were cut in stripes (10 cm long and 2.5 cm wide) and applied onto rigid aluminium foils having thickness of 2 mm, using a biadhesive tape of dimensions 2.5 x 8 cm, with the coated side of the electrode facing the aluminium plate. A portion of the electrode was kept from adhering to the tape, thus leaving one end of each stripe not in contact with the biadhesive tape, allowing for its pulling from the foil.
  • the electrodes of the invention have an improved adhesion to metal foil in comparison with standard electrodes of the prior art comprising polymer (F) only.
  • the electrodes of the invention show a huge improvement in the flexibility over electrodes prepared by using binders comprising polymer (F) only, but also over electrodes obtained by using binders comprising polymer (F) and an acrylate copolymer including less than 20% by moles of acrylonitrile.

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

Abstract

La présente invention concerne un liant pour une électrode positive de batterie secondaire, un procédé de préparation de ladite électrode et son utilisation dans une batterie secondaire. L'invention concerne également les batteries secondaires fabriquées par incorporation de ladite électrode.
PCT/EP2024/067585 2023-06-29 2024-06-24 Polymères de (méth)acrylate en tant qu'additifs dans des électrodes de batterie Pending WO2025003026A1 (fr)

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EP23182277.6 2023-06-29
EP23182277 2023-06-29

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016345A (en) 1972-12-22 1977-04-05 E. I. Du Pont De Nemours And Company Process for polymerizing tetrafluoroethylene in aqueous dispersion
US4725644A (en) 1986-05-06 1988-02-16 E. I. Du Pont De Nemours And Company Tetrafluoroethylene fine powder and preparation thereof
JP3085532B2 (ja) * 1998-09-10 2000-09-11 韓国科学技術研究院 均質状の固体ポリマーアロイ電解質及びその製造方法、それを利用した複合電極、並びにリチウム高分子電池及びリチウムイオン高分子電池並びにそれらの製造方法
US6479591B2 (en) 2000-07-20 2002-11-12 Ausimont S.P.A. Fine powders of polytetrafluoroethylene
JP2005123047A (ja) 2003-10-17 2005-05-12 Hitachi Maxell Ltd リチウム二次電池およびその製造方法
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
EP2953193A1 (fr) 2013-02-04 2015-12-09 Zeon Corporation Suspension destinée à des électrodes positives de batterie secondaire au lithium-ion
WO2017142328A1 (fr) * 2016-02-19 2017-08-24 삼성에스디아이 주식회사 Électrode positive pour batterie secondaire au lithium, élément d'enroulement pour batterie secondaire au lithium, et batterie secondaire au lithium
JP2017147206A (ja) * 2016-02-19 2017-08-24 三星エスディアイ株式会社Samsung SDI Co., Ltd. 非水電解質二次電池用正極、非水電解質二次電池用巻回素子、及び非水電解質二次電池
WO2022031131A1 (fr) * 2020-08-07 2022-02-10 주식회사 엘지에너지솔루션 Séparateur pour batterie secondaire et batterie secondaire le comprenant

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016345A (en) 1972-12-22 1977-04-05 E. I. Du Pont De Nemours And Company Process for polymerizing tetrafluoroethylene in aqueous dispersion
US4725644A (en) 1986-05-06 1988-02-16 E. I. Du Pont De Nemours And Company Tetrafluoroethylene fine powder and preparation thereof
JP3085532B2 (ja) * 1998-09-10 2000-09-11 韓国科学技術研究院 均質状の固体ポリマーアロイ電解質及びその製造方法、それを利用した複合電極、並びにリチウム高分子電池及びリチウムイオン高分子電池並びにそれらの製造方法
US6479591B2 (en) 2000-07-20 2002-11-12 Ausimont S.P.A. Fine powders of polytetrafluoroethylene
JP2005123047A (ja) 2003-10-17 2005-05-12 Hitachi Maxell Ltd リチウム二次電池およびその製造方法
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
EP2953193A1 (fr) 2013-02-04 2015-12-09 Zeon Corporation Suspension destinée à des électrodes positives de batterie secondaire au lithium-ion
WO2017142328A1 (fr) * 2016-02-19 2017-08-24 삼성에스디아이 주식회사 Électrode positive pour batterie secondaire au lithium, élément d'enroulement pour batterie secondaire au lithium, et batterie secondaire au lithium
JP2017147206A (ja) * 2016-02-19 2017-08-24 三星エスディアイ株式会社Samsung SDI Co., Ltd. 非水電解質二次電池用正極、非水電解質二次電池用巻回素子、及び非水電解質二次電池
WO2022031131A1 (fr) * 2020-08-07 2022-02-10 주식회사 엘지에너지솔루션 Séparateur pour batterie secondaire et batterie secondaire le comprenant

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