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WO2024231297A1 - Liant d'électrode positive pour batteries au lithium-ion - Google Patents

Liant d'électrode positive pour batteries au lithium-ion Download PDF

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Publication number
WO2024231297A1
WO2024231297A1 PCT/EP2024/062313 EP2024062313W WO2024231297A1 WO 2024231297 A1 WO2024231297 A1 WO 2024231297A1 EP 2024062313 W EP2024062313 W EP 2024062313W WO 2024231297 A1 WO2024231297 A1 WO 2024231297A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
polymer
monomer
composition
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.)
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PCT/EP2024/062313
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English (en)
Inventor
Francesco LIBERALE
Maurizio Biso
Riccardo Rino PIERI
Dominique Teychenne
Guillaume GODY
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Solvay Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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Publication of WO2024231297A1 publication Critical patent/WO2024231297A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • 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 Li-ion battery positive electrode, to a method of preparation of said electrode and to its use in a Li-ion battery.
  • the invention also relates to the Li-ion 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 lithium batteries are usually produced by mixing a binder with a powdery electrode active material.
  • PVDF polyvinylidene fluoride
  • US 2018/0355206 discloses the use of a copolymer of methyl methacrylate and methacrylic acid in admixture with PVDF for the preparation of LiNMC electrode slurries having good adhesion to the current collector; said mixture has a viscosity that makes it possible to easily spread the active substance over the metal current collector, thus facilitating the manufacture of an electrode for a lithium ion battery.
  • US 2015/0280238 discloses a stable electrode binder dispersion for use in the preparation of LFP cathodes for lithium ion battery, said dispersion comprising a PVDF dispersed in an organic diluent and a (meth)acrylic polymer dispersant.
  • Modified 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.
  • hydrophilic (meth)acrylic monomers e.g. acrylic acid
  • modified PVDF polymers when used in the preparation of a slurry for forming positive electrodes with certain active materials.
  • LiFePCM (LFP) active material when LiFePCM (LFP) active material is used, 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 LPF cathodes.
  • the present invention provides a positive electrode-forming composition capable of preventing gelation while, at the same time, enabling the manufacturing of electrodes having enhanced adhesion, reduced polymer swelling in contact with the electrolyte, lower resistivity, electrochemical stability and longer battery life.
  • binder (B) comprises: a) at least one vinylidene fluoride (VDF) polymer [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); b) at least one branched (meth)acrylic polymer [polymer (A)] derived from the polymerization of at least one (meth)acryloyl monomer [monomer (MAM)] with at least one molecule comprising at least two vinyl groups [monomer (BM)], wherein monomer (BM) is selected from the group consisting of divinyl aryl monomers such as divinyl benzene; (meth)acrylate diesters such as alkylene di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1 ,4-but
  • polymer (A) contains less than 1 % by moles of monomer (BM);
  • 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.
  • the terms “acrylic” and “acrylate” are used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids and derivatives thereof.
  • the terms “(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)e]i-y mbhO, with A being and alkali metal ion, P being a N-coordinated transition metal ion, R being a C-coordinated transition metal ion, y being a [R(CN)e] vacancy, with 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 1 , such as Nao.8i Fe[Fe(CN)6]o.79, NaFe2(CN)e, Nai.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
  • 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 LiMn2O4.
  • the electrode active material may comprise a lithiated or partially lithiated transition metal oxyanion-based electro-active material of formula MiM2(JO4)fEi-f, wherein Mi is lithium, which may be partially substituted by another alkali metal representing less than 20% of the Mi metals, M2 is a transition metal at the oxidation level of +2 selected from Fe, Mn, Ni or mixtures thereof, which may be partially substituted by one or more additional metals at oxidation levels between +1 and +5 and representing less than 35% of the M2 metals, including 0, JO4 is any oxyanion wherein J is either P, S, V, Si, Nb, Mo or a combination thereof, E is a fluoride, hydroxide or chloride anion, f is the molar fraction of the JO4 oxyanion, generally comprised between 0.75 and 1.
  • the MiM2(JO4)fEi-f electro-active material as defined above is preferably phosphate-based and may have an ordered or modified olivine structure.
  • the electrode active material has formula Li3-xM’ y M”2- y(JO4)3 wherein 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M’ and M” are the same or different metals, at least one of which being a transition metal, JO4 is preferably PO4 which may be partially substituted with another oxyanion, wherein J is either S, V, Si, Nb, Mo or a combination thereof.
  • the electrode active material is a phosphate-based electro-active material of formula LixAyDzPCM, 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) in an amount of 70% by mass or more, with respect to 100% by mass of the entire positive electrode active material (AM).
  • the positive electrode active material is composed only of a compound having an olivine structure.
  • the positive electrode active material consists only of lithium iron phosphate (LFP).
  • the active material (AM) has an average particle size of 3 pm or less.
  • the average particle size (D50) of the compound having an olivine structure is more preferably in the range of from 0.01 to 1.8 pm.
  • the average particle size of the positive electrode active material can be measured by a particle size distribution meter for dynamic light scattering. [0043] As the average particle size becomes smaller, the surface area becomes larger and the binder must be bound with a small amount of the binder, so that the flexibility of the binder is required.
  • the electrical characteristics such as the output characteristics when the positive electrode composition for a secondary battery is used as the positive electrode of the battery are excellent.
  • Composition (C) of the invention further comprises binder (B) comprising: a) at least one vinylidene fluoride (VDF) copolymer [polymer (F)] b) at least one branched (meth)acrylic polymer [polymer (A)]; c) at least one solvent (S); and d) optionally at least one electroconductivity-imparting additive.
  • binder (B) comprising: a) at least one vinylidene fluoride (VDF) copolymer [polymer (F)] b) at least one branched (meth)acrylic polymer [polymer (A)]; c) at least one solvent (S); and d) optionally at least one electroconductivity-imparting additive.
  • the polymer (F) comprises recurring units derived from vinylidene fluoride (VDF) and optionally recurring units derived from at least one monomer (MA) of formula (I) wherein:
  • 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).
  • the monomer (MA) preferably complies with formula (II): wherein each of R1 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 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 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 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 monomer (MA).
  • polymer (F) in polymer (F) the recurring units derived from 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: (a) C2-C8 fluoro- and/or perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), pentafluoropropylene and hexafluoroisobutylene;
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • pentafluoropropylene and hexafluoroisobutylene
  • CF fluorinated comonomers
  • 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
  • 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 at least one branched (meth)acrylic polymer (A), different from polymer (F), is a polymer comprising recurring units derived from at least one (meth)acryloyl monomer [monomer (MAM)] with at least one branching monomer, which is a molecule comprising at least two vinyl groups [monomer (BM)].
  • Polymer (A) is a copolymer.
  • 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 emulsion, solution, suspension polymerization, and can be done in bulk, and semi-bulk.
  • (meth)acryloyl monomer refers to the monomer having a (meth)acryloyl group in the molecule.
  • Non-limited examples of such monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, methoxy ethyl (meth)acrylate, 2-ethoxy ethyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate), isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate,
  • Polymer (A) may also include recurring units derived from other alpha, beta-ethylenically unsaturated monomers bearing functionalities such as carboxyl groups or substituted alkyl esters.
  • Suitable alpha, beta-ethylenically unsaturated monomers bearing functionalities can be selected from hydrophilic (meth)acryloyl monomer, such as monoethylenically unsaturated monocarboxylic acid and derivatives.
  • hydrophilic (meth)acryloyl monomer such as monoethylenically unsaturated monocarboxylic acid and derivatives.
  • This include, among others, acrylic acid, methacrylic acid (MAA), hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, crotonic acid, 2-carboxyethyl acrylate oligomers such as Sipomer®B-CEA.
  • methylmethacrylate polymer is used within the frame of the present invention for designating a polymer made of recurring units, wherein more than 50 % by moles of said recurring units being derived from methylmethacrylate (MMA).
  • Preferred (meth)acrylic polymers (A) for use in composition (C) of the present invention are methylmethacrylate polymers.
  • polymer (A) is a methylmethacrylate polymer that contains at least 50% by moles of methylmethacrylate monomer units, preferably at least 70% by moles of methylmethacrylate monomer units.
  • polymer (A) may contain from 1 to 45, preferably 3 to 30, and more preferably 5 to 20 % by moles of at least one co-monomer copolymerizable with methylmethacrylate, including but not limited to monomers (MAM) as above defined, or other alpha, beta- ethylenically unsaturated monomers bearing functionalities such as carboxyl groups or substituted alkyl esters.
  • MAM monomers
  • Polymer (A) contains at least one branching monomer (BM).
  • a branching monomer is a monomer that during the polymerization can react at least in two different positions, resulting in branched chain growth.
  • the (meth)acryloyl monomer (MAM) may grow in the polymerization reaction in two directions, reacting with another (meth)acryloyl monomer or with the branching monomer.
  • the branching monomer (BM) is a molecule comprising at least two vinyl groups.
  • the branching monomer (BM) may also comprise more than two vinyl groups. These vinyl groups are suitable for polymerization in an addition polymerization reaction. Many of such molecules are readily available, or may be prepared by reacting any di- or multifunctional molecule with a suitably reactive vinylic reactant. Examples include di- or multivinyl esters, di- or multivinyl amides, di- or multivinyl aryl compounds (including those with heterocyclic aryl groups), and di- or multivinyl alkyl/aryl ethers.
  • Branching monomers (BM) are selected from the group consisting of divinyl aryl monomers, such as divinyl benzene; (meth)acrylate diesters such as alkylene di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1 ,4-butylene glycol di(meth)acrylate; oligo alkylene glycol di(meth)acrylates such as e.g.
  • tetraethyleneglycol di(meth)acrylate poly(ethyleneglycol) di(meth)acrylate, poly (propyleneglycol) di(meth)acrylate; divinyl (meth)acrylamides such as methylene bisacrylamide; divinyl ethers such as poly(ethyleneglycol)divinyl ether; and tetra- or tri-(meth)acrylate esters such as pentaerythritol tetra (meth) acrylate, trimethylolpropane tri(meth)acrylate or glucose di- to penta (meth)acrylate.
  • divinyl (meth)acrylamides such as methylene bisacrylamide
  • divinyl ethers such as poly(ethyleneglycol)divinyl ether
  • tetra- or tri-(meth)acrylate esters such as pentaerythritol tetra (meth) acrylate, trimethylolpropane tri(meth)acryl
  • Preferred branching monomers are divinyl benzene, a,co-alkylene di(meth)acrylates or divinyl (meth)acrylamides, most preferred may be a,co-alkylene di(meth)acrylates such as ethylene glycol di(meth)acrylate and 1 ,4-butylene glycol di(meth)acrylate or divinyl (meth)acrylamides, such as methylene bisacrylamide.
  • the branching monomer (BM) is divinyl benzene (DVB).
  • Polymer (A) contains less than 1 % by moles of the at least one branching monomer (BM), preferably from 0.2 to less than 1 % by moles of the at least one branching monomer (BM).
  • the Applicant has surprisingly found that the presence in polymer (A) of the at least one branching monomer (BM) in an amount lower than 1 % by moles allows to obtain a solution of polymer (A) in solvent (S). With higher amounts of monomer (BM) in polymer (A), solubility of said polymer (A) in solvent (S) could be an issue.
  • the branched (meth)acrylic polymer (A) is prepared by polymerizing a mixture of at least one hydrophilic (meth)acryloyl monomer (MAM) with at least one monomer (BM), optionally in the presence of other alpha, beta- ethylenically unsaturated monomers bearing functionalities such as carboxyl groups or substituted alkyl esters.
  • MAM hydrophilic (meth)acryloyl monomer
  • BM monomer bearing functionalities such as carboxyl groups or substituted alkyl esters.
  • the branched (meth)acrylic polymer (A) includes hydrophilic (meth)acryloyl monomer such as monoethylenically unsaturated monocarboxylic acid
  • said polymer (A) may further be at least partially salified to obtain at least a fraction of the acidic moieties in the form of a salt.
  • branched (meth)acrylic polymer (A) that is at least partially salified.
  • the preparation of branched (meth)acrylic polymer (A) may thus further include a step of neutralization of at least a fraction of acid groups with a salt [salt (SA)] including a monovalent cation in a suitable solvent.
  • SA salt
  • the salt (SA) can be any salt capable of neutralizing the acid groups, and it is preferably selected from a salt capable of providing an alkali metal cation, a tertiary or quaternary ammonium cation, more preferably Na + , K + , Li + and or quaternary ammonium cation.
  • the polymer (A) for use in the composition (C) of the present invention preferably has a number average molecular weight (Mn) of at least 1 kDa, for example between 1 and 150 kDa. More preferably, the polymer (A) has a number average molecular weight (Mn) between 15 and 100 kDa.
  • the polymer (A) for use in the composition (C) of the present invention preferably has a weight average molecular weight (Mw) of about 1 kDa to 150 kDa, preferably from 5 kDa to 100 kDa.
  • Mw weight average molecular weight
  • polymer (A) is a methylmethacrylate polymer comprising 100% by moles of methylmethacrylate monomer units (methylmethacrylate homopolymer).
  • polymer (A) is a methylmethacrylate copolymer comprising at least 70% by moles of methylmethacrylate monomer units, up to 20% by moles of methacrylic acid monomer units and less than 1 % by moles of branching monomer (BM).
  • the choice of the solvent (S) is not particularly limited, provided that it is suitable for solubilising polymer (F) and 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 solution (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 5 to 10 % by weight in 100 parts by weight of such a solvent.
  • binder solution (B) comprising polymer (F) and polymer (A) as above detailed, it is preferred to dissolve separately the polymer (F) is solvent (S) and from 5 to 10 % by weight of the polymer (A) in 100 parts by weight of such a solvent.
  • binder solution (B) In order to prepare the binder solution (B), it is preferred to dissolve the polymer (F) and polymer (A) in a solvent (S) at a temperature of 20 - 50°C.
  • the binder solution (B) can be prepared by first dissolving polymer (F) in solvent (S), followed by addition of solid polymer (A) to the mixture prepared thereof.
  • the total solid content (TSC) of the composition (C) of the present invention is typically comprised between 15 and 70 % by weight, preferably from 40 to 60 % 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.
  • composition (C) When the solutions of polymer (F) and of polymer (A) are prepared separately and subsequently combined with an electrode active material and optional conductive material and other additives to prepare composition (C), an amount of solvent sufficient to create a stable solution is employed.
  • the amount of solvent used may range from the minimum amount needed to create a stable solution to an amount needed to achieve a desired total solid content in an electrode mixture after the active electrode material, optional conductive material, and other solid additives have been added.
  • Mixing of the two solutions is carried out by any known method in the art, such as by planetary mixing followed by dispersion phase.
  • composition (C) makes it possible to obtain homogeneous slurry compositions with no gelation evidence in all the preparation steps.
  • polymers (F) bearing polar groups in electrode-forming composition comprising the olivine type active material electrodes, and exploiting the properties of such polymers in electrodes, such as the greater adhesion to current collector, the improved flexibility and the good mechanical performances.
  • polymer (A) acts as a dispersant in binder compositions, and reduces the slurry viscosity versus compositions having the same TSC but comprising a polymer (F), an active material and an electroconductivityimparting additive only.
  • 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:
  • step (iii) applying the 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; (iv) drying the assembly provided in step (iii).
  • 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 electrode [electrode (E)] obtainable by the process of the invention.
  • an 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. Therefore all the preferred embodiments described in relation to the electrode forming 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:
  • a positive electrode active material AM having an olivine structure in an amount from 90 to 98 % by weight
  • jj the binder (B’) in an amount from 0.5 to 10 % by weight, preferably from 1 to 5 % by weight
  • jjj an electroconductivity-imparting additive in an amount from 0.5 to 5 % by weight, wherein the above mentioned % by weight are in respect to the total weight of j)+jj)+jjj).
  • 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/cm2, preferably of about 15 mg/cm2.
  • the electrode (E) according to the present invention is excellent in electrolyte swelling resistance.
  • the electrode (E) of the invention is particularly suitable for use in electrochemical devices, in particular in secondary batteries, showing reduced polymer swelling when in contact with electrolyte, lower resistivity and longer battery life.
  • the secondary battery of the invention is preferably an alkaline or an alkaline-earth secondary battery.
  • 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.
  • MMA methylmethacrylate, commercially available from Sigma-Aldrich [00145]
  • MAA methacrylic acid, commercially available from Sigma-Aldrich [00146]
  • DVB divinyl benzene, commercially available from Sigma-Aldrich [00147]
  • AMBN 2,2'-azobis(2-methylbutyronitrile), commercially available from
  • Nano-LFP LFP DY-3, density: 3.53 g/cm 3 , practical specific capacity: 153 mAh/g, commercially available from Shenzhen Dynanonic Co., Ltd.
  • Carbon nanotubes Orgacyl NMP0402. 4% thin multiwall carbon nanotube (MWCNT) in N-Methyl-2-pyrrolidone (NMP) solvent.
  • MWCNT thin multiwall carbon nanotube
  • NMP N-Methyl-2-pyrrolidone
  • Preparation 1 Polymer (A-1): Poly(MMA-MAA-DVB) 79.8/20/0.2 mol% in NMP
  • the mixture was purged with nitrogen for 20 minutes at room temperature and under stirring, after the nitrogen flow was left in the sky, the temperature of the cryotherm ostatic bath was programmed at 75°C over a temperature ramp of 1 hour.
  • a solution of monomers MMA 140.89 g, 1.393 mol
  • MAA 30.36 g, 0.349 mol
  • DVB 0.568 g, 3.492 mmol, 80% purity
  • Preparation 2 Polymer (A-2): Poly(MMA-MAA-DVB) 79.5/20/0.5 mol% in NMP
  • Preparation 3 Polymer (A-3): Poly(MMA-MAA-DVB) 79.65/20/0.35 mol% in NMP
  • A320 stirring blade, counter-blades, a condenser connected to a minichiller and a cryotherm ostatic bath were introduced, at room temperature, MMA (14.734 g, 0.147 mol), MAA (3.181 g, 0.037 mol), DVB (0.105 g, 0.647 mmol, 80% purity), AMBN (1.658 g, 8.623 mmol) and 658.175 g of NMP.
  • Preparation 4 Polymer (A-4): Poly(MMA-MAA-DVB) 79.5/20/0.5 mol% in NMP
  • Preparation 5 Polymer (A-5): Poly(MMA-MAA-DVB) 79.25/20/0.75 mol% in NMP
  • a 8% by weight solution of polymer (A-1) in NMP was prepared starting from the solution of polymer (A-1 ) in NMP obtained in Preparation 1 above [00161 ]
  • the solution of polymer (F-1 ) in NMP and the solution of polymer (A-1 ) in NMP were mixed in a 9:1 ratio (30.87 g of solution of polymer (F-1) and 3.43 g of solution of polymer (A-1 )).
  • Nano-LFP 75.07 g
  • carbon nanotubes (14.7 g of solution at 4% wt in NMP)
  • additional 15.94 g of NMP were added to the solution comprising polymer (F-1) and polymer (A-1 ) with planetary mixing followed by dispersion phase to provide COMPOSITION 1 , a cathode slurry having a Total Solid Content (TSC) of 56% (95.75% LFP, 0.75% carbon nanotubes and 3.5% binder).
  • TSC Total Solid Content
  • Nano-LFP 75.07 g
  • carbon nanotubes (14.7 g of solution at 4% wt in NMP)
  • additional 15.94 g of NMP were added to 34.3 g of the solution comprising HSV900 with planetary mixing followed by dispersion phase to provide COMPOSITION (C-1 ), a cathode slurry having a Total Solid Content (TSC) of 56% and an amount of binder of 3.5%.
  • C-1 COMPOSITION
  • TSC Total Solid Content
  • a 8% by weight solution of PMMA polymer in NMP was prepared starting from the solution of PMMA polymer in NMP obtained in Preparation 6 above: [00170] The solution of polymer (F-1 ) in NMP and the solution of PMMA polymer in NMP were mixed in a 9:1 ratio (30.87 g of solution of polymer (F-1) and 3.43 g of solution of PMMA polymer.
  • Nano-LFP 75.07 g
  • carbon nanotubes (14.7 g of solution at 4% wt in NMP)
  • additional 15.94 g of NMP were added to the solution comprising polymer (F-1) and PMMA polymer with planetary mixing followed by dispersion phase to provide COMPOSITION (C-2), a cathode slurry having a Total Solid Content (TSC) of 56% (95.75% LFP, 0.75% carbon nanotubes and 3.5% binder).
  • TSC Total Solid Content
  • *A good: visual homogeneous aspect at rest and under manual stirring. No evidence of agglomerates, nor phase separation, nor deposits on the container’s walls.
  • B medium: the slurry seems homogenous.
  • EXAMPLE 4 electrode-forming compositions gelation evaluation [00174] Viscosity of the compositions 1 , C-1 and C-2 immediately after their preparation (to viscosity) was measured, detecting -50% viscosity for the composition obtained in Example 1 vs those from Comparative Examples 1 and Comparative Example 2 (this last 2 compositions show comparable values).
  • Positive electrodes were obtained by applying the electrode-forming compositions as above described to 15 pm thick aluminium foils so as to obtain a mass of dry positive electrode loading of 15 mg/cm 2
  • the solvent was completely evaporated by drying in an oven at temperature of 90°C to fabricate a strip-shaped positive electrodes.
  • **A good: smooth aspect, no evidence of agglomerates on the dried electrode, nor inhomogeneity due to bubbles formation and evaporation. Manual handling was easy, electrodes have good flexibility when slightly bended and folded, with no evidence of active material cracking or detachment.
  • B medium: electrodes have an average homogeneous aspect. With accurate visual observation or with optical microscope, small agglomerates are detected. No material detachment nor cracking with gentle bending
  • the electrodes of the invention have an improved adhesion to metal foil in comparison with standard electrodes of the prior art comprising PVDF.

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Abstract

La présente invention concerne un liant pour électrode positive de batterie Li-ion, un procédé de préparation de ladite électrode et son utilisation dans une batterie Li-ion. L'invention concerne également les batteries Li-ion fabriquées par incorporation de ladite électrode.
PCT/EP2024/062313 2023-05-05 2024-05-03 Liant d'électrode positive pour batteries au lithium-ion Pending WO2024231297A1 (fr)

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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
US6479591B2 (en) 2000-07-20 2002-11-12 Ausimont S.P.A. Fine powders of polytetrafluoroethylene
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
US20150280238A1 (en) 2014-04-01 2015-10-01 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
US20160079007A1 (en) * 2013-03-27 2016-03-17 Jsr Corporation Binder composition for power storage devices
US20180355206A1 (en) 2015-11-24 2018-12-13 Arkema France Binder containing polyvinylidene fluoride capable of fixing to a metal and associated lithium-ion battery electrode
US10559828B2 (en) * 2013-02-04 2020-02-11 Zeon Corporation Slurry for lithium ion secondary battery positive electrodes
US20200235398A1 (en) * 2017-08-29 2020-07-23 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
US20230006210A1 (en) * 2019-12-27 2023-01-05 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery

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
US6479591B2 (en) 2000-07-20 2002-11-12 Ausimont S.P.A. Fine powders of polytetrafluoroethylene
WO2008129041A1 (fr) 2007-04-24 2008-10-30 Solvay Solexis S.P.A. Copolymères de fluorure de vinylidène
US10559828B2 (en) * 2013-02-04 2020-02-11 Zeon Corporation Slurry for lithium ion secondary battery positive electrodes
US20160079007A1 (en) * 2013-03-27 2016-03-17 Jsr Corporation Binder composition for power storage devices
US20150280238A1 (en) 2014-04-01 2015-10-01 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
US20180355206A1 (en) 2015-11-24 2018-12-13 Arkema France Binder containing polyvinylidene fluoride capable of fixing to a metal and associated lithium-ion battery electrode
US20200235398A1 (en) * 2017-08-29 2020-07-23 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
US20230006210A1 (en) * 2019-12-27 2023-01-05 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery

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