WO2024083593A1 - Liants d'électrode de batterie secondaire - Google Patents

Liants d'électrode de batterie secondaire Download PDF

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WO2024083593A1
WO2024083593A1 PCT/EP2023/078154 EP2023078154W WO2024083593A1 WO 2024083593 A1 WO2024083593 A1 WO 2024083593A1 EP 2023078154 W EP2023078154 W EP 2023078154W WO 2024083593 A1 WO2024083593 A1 WO 2024083593A1
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polymer
vdf
electrode
formula
perfluoro
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PCT/EP2023/078154
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English (en)
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Ségolène BRUSSEAU
Julio A. Abusleme
Rosita Lissette PENA CABRERA
Michele Fiore
Andrea Vittorio ORIANI
Roberto BIANCARDI
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2024083593A1 publication Critical patent/WO2024083593A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • 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

  • CN110183562 discloses the preparation of a high molecular weight PVDF by using di-isopropyl peroxydicarbonate as initiator.
  • the resulting PVDF is characterized by a high crystallinity, which makes the electrode slurry compositions comprising the same useless for preparing electrodes.
  • the high crystallinity PVDF is thus blended with VDF-based copolymers to obtain a polymer mixture suitable for use as electrode binder.
  • VDF-based polymer consisting of recurring units derived from VDF and, optionally, recurring units derived from at least one fluorinated comonomer (CF), different from VDF, said polymer (F) having 2 SSPI 2022/024 intrinsic viscosity, measured in dimethylformamide at 25 °C, in the range of from 0.25 l/g to 0.60 l/g, more preferably from 0.30 l/g to 0.50 l/g
  • the polymer (F) is characterized by containing end groups of formula (I): –(R a ) x -O-CO-O-CH 2 -CH 3 (I) wherein R a is a C 1 -C 5 linear or branched hydrocarbon group and x is an integer selected from 1 and zero and the end-groups of formula (I) are present in an amount of at least 0.2/10000 VDF units, preferably at least 1.0/10
  • a second object of the present invention pertains to an electrode-forming composition (C) comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; and c) at least one solvent (S).
  • AM electrode active material
  • B binder
  • S solvent
  • the present invention pertains to the use of the electrode-forming composition (C) in a process for the manufacture of an electrode [electrode (E)], said process comprising: (I) providing a metal substrate having at least one surface; (II) providing an electrode-forming composition (C) as above defined; (III) applying the composition (C) provided in step (II) onto the at least one surface of the metal substrate provided in step (I), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface; (IV) drying the assembly provided in step (III); (V) submitting the dried assembly obtained in step (IV) to a compression step to obtain the electrode (E) of the invention.
  • the present invention pertains to the electrode (E) obtainable by the process of the invention. [0013] In still a further object, the present invention pertains to an electrochemical device comprising at least one electrode (E) of the present invention.
  • VDF-based polymer it is intended to denote a VDF homopolymer (PVDF) and VDF-based copolymers including recurring units derived from VDF and recurring units derived from at least one fluorinated comonomer (CF), different from VDF.
  • the VDF-based polymer (F) of the present invention does not include any hydrogenated monomer bearing polar groups.
  • CTFE chlorotrifluoroethylene
  • polymer (F) is semi-crystalline and comprises from 0.1 to 20.0% by moles, preferably from 0.3 to 10.0% by moles, more preferably from 0.5 to 5.0% by moles of recurring units derived from said fluorinated comonomer (CF).
  • the polymer (F) can be an elastomer or a semi-crystalline polymer, preferably being a semi-crystalline polymer.
  • semi-crystalline means a fluoropolymer that has, besides the glass transition temperature Tg, at least one crystalline melting point on DSC analysis.
  • a semi-crystalline fluoropolymer is hereby intended to denote a fluoropolymer having a heat of fusion of from 10 to 90 J/g, preferably of from 30 to 80 J/g, more preferably of from 35 to 75 J/g, as measured according to ASTM D3418-08.
  • the term "elastomer” is intended to designate a true elastomer or a polymer resin serving as a base constituent for obtaining a true elastomer.
  • True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10 % of their initial length in the same time.
  • the polymer (F) of the present invention usually has a melting temperature (Tm) comprised in the range from 100 to 200°C.
  • the polymer (F) of the present invention possesses a quasi-linear structure, with a very low amount of branching, which results in the insoluble fraction due to long branched chains being substantially negligible.
  • the polymer (F) of the present invention has in fact preferably a low fraction of insoluble components in standard polar aprotic solvents for VDF polymers, such as NMP. More preferably, solutions of polymer (F) in said standard polar aprotic solvents remain homogeneous and stable for several weeks, with substantially no insoluble residue.
  • the melting temperature may be determined from a DSC curve obtained by differential scanning calorimetry (hereinafter, also referred to as DSC). In the case where the DSC curve shows a plurality of melting peaks (endothermic peaks), the melting temperature (Tm) is determined on the basis of the peak having the largest peak area.
  • DSC differential scanning calorimetry
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is zero.
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is 1, and R a is a C 2 -C 3 linear or branched alkyl radical, preferably C 3 linear or branched alkyl radicals.
  • the polymer (F) is characterized by containing end groups of formula (I) as above defined, wherein x is zero and containing end groups of formula (I) wherein x is 1, and R a is a C 2 -C 3 linear or branched alkyl radical, preferably C 3 linear or branched alkyl radicals.
  • Polymer (F) is characterized by having a particle size distribution with a D50 value lower than 240 microns, measured using laser diffraction according to the ISO 13320. [0033] D50 designates the particle diameter where half the population lies below this value and half lies above.
  • Polymer (F) may be obtained by a process that comprises: - polymerizing the vinylidene fluoride (VDF) and optionally comonomer (CF), in an aqueous medium in the presence of a radical initiator system that introduces in the polymer chain end groups of formula (I). - maintaining the pressure in said reactor vessel exceeding the critical pressure of the vinylidene fluoride.
  • Suitable radical initiator systems include radical initiators such as di(ethyl) peroxydicarbonate and hydro-ethyl peroxydicarbonate.
  • the amount of radical initiator required for a polymerization is related to its activity and the temperature used for the polymerization.
  • the total amount of radical initiator used is generally between 100 to 30000 ppm by weight on the total monomers weight used.
  • the radical initiator may be added in pure form, in solution, in suspension, or in emulsion, depending upon the initiator chosen.
  • the radical initiator systems may include a chain transfer agent (CTA).
  • CTA chain transfer agent
  • Suitable CTA for the polymerization process for preparing the polymer (F) according to the present invention are those known in the art and are typically selected from the group consisting of short hydrocarbon chains like ethane and propane, esters such as ethyl acetate or diethyl maleate, diethylcarbonate.
  • the CTA may be added all at once at the beginning of the reaction, or it may be added in portions, or continuously throughout the course of the reaction. The amount of CTA and its mode of addition depend on the desired properties of polymer (F) to be obtained.
  • Preferred CTA for use in the process of the present invention is diethylcarbonate.
  • pressure is maintained above critical pressure of vinylidene fluoride. Generally, 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.
  • the process of the invention is carried out at a temperature superior to the critical temperature of the VDF monomer, i.e. of at least 31°C. 6 SSPI 2022/024
  • the polymer (F) is typically provided in form of powder according to the process described above.
  • Polymer (F) in the form of powder may be optionally further extruded to provide polymer (F) in the form of pellets.
  • the polymer (F) as above detailed may be used as binder for electrodes in secondary batteries.
  • a second object of the present invention pertains to an electrode-forming composition (C) comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; and c) at least one solvent (S).
  • electrode-forming composition comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; and c) at least one solvent (S).
  • the term “electro-active material (AM)” is intended to denote a compound that is able to incorporate or insert into its structure and substantially release therefrom alkaline or alkaline-earth metal ions during the charging phase and the discharging phase of an electrochemical device.
  • the compound (AM) is preferably able to incorporate or insert and release lithium ions or sodium ions.
  • the nature of the compound (AM) in composition (C) depends on whether said composition is used in the manufacture of a positive electrode [electrode (Ep)] or a negative electrode [electrode (En)].
  • the electrode active material (AM) of positive electrodes 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 transition-metal 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 NaxMO 2 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 A x P[R(CN) 6 ] 1-y ⁇ y .mH 2 O with A and alkali metal ion, P a N- coordinated transition metal ion, R a C-coordinated transition metal ion, ⁇ a [R(CN) 6 ] vacancy, with 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 1 such as Na 0.81 Fe[Fe(CN) 6 ] 0.79 ⁇ 0.21 , NaFe 2 (CN) 6 , Na1 .63 Fe 1.89 (CN) 6 , Na 1.72 MnFe(CN) 6 , Na 1.76 Ni 0.12 Mn 0.88 [Fe(CN) 6 ] 0.98 , Na 2 Ni x Co 1-x Fe(CN)
  • Na 3 (VOPO 4 ) 2 F or Na 3 V 2 (PO 4 ) 2 F 3 (NVPF); fluoro sulfates such as NaMSO 4 F (with M Fe, Co, Ni); mixed phosphates/pyrophosphates of general formula Na 4 M 3 (PO 4 ) 2 (P 2 O 7 ) (with M representing transition metals) such as Na 4 Mn 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Co 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) (NFPP), Na 7 V 4 (P 2 O 7 ) 4 (PO 4 ); sulfates such as Na 2 Fe 2 (SO 4 ) 3 , Na 2+2x Fe 2-x (SO 4 ) 3 , Na 2+2x Co 2-x (SO 4 ) 3 , Na 2+2x Mn 2-x (SO 4 ) 3 (where 0 ⁇
  • the active materials are fluorophosphates preferably selected from the list consisting of NaVPO 4 F, Na 2 CoPO 4 F, Na 2 FePO 4 F, Na 2 MnPO 4 F, Na 3 (VO 1-x PO 4 ) 2 F 1+2x (with 0 ⁇ x ⁇ 1) e.g. Na 3 (VOPO 4 ) 2 F or Na 3 V 2 (PO 4 ) 2 F 3 (NVPF).
  • the conventional active materials (AM) at the positive electrode of lithium-ion batteries may comprise a composite metal chalcogenide of formula LiMQ2, wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V and Q is a chalcogen such as O or S.
  • M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V
  • Q is a chalcogen such as O or S.
  • it is preferred to use a lithium-based composite metal oxide of formula LiMO 2 wherein M is the same as defined above.
  • Preferred examples thereof may include LiCoO 2 , LiNiO 2 , LiNi x Co 1- x O 2 (0 ⁇ x ⁇ 1) and spinel-structured LiMn 2 O 4 .
  • the electrode active material may comprise a lithiated or partially lithiated transition metal oxyanion-based electro-active material of formula M 1 M 2 (JO 4 ) f E 1-f , wherein M 1 is lithium, which may be partially substituted by another 8 SSPI 2022/024 alkali metal representing less than 20% of the M 1 metals, M 2 is a transition metal at the oxidation level of +2 selected from Fe, Mn, Ni or mixtures thereof, which may be partially substituted by one or more additional metals at oxidation levels between +1 and +5 and representing less than 35% of the M 2 metals, including 0, 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 JO 4 oxyanion, generally comprised between 0.75 and 1.
  • the M 1 M 2 (JO 4 ) f E 1-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 Li 3-x M’ y M’’ 2-y (JO 4 ) 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, JO 4 is preferably PO 4 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 [0061] Li x A y D z PO 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. [0062] The A component is preferably Fe, Mn, and Ni, and particularly preferably Fe. [0063] 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.
  • LFP lithium iron phosphate
  • LMFP lithium iron manganese phosphate
  • AM lithium manganese phosphate
  • 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.
  • the compound having an olivine structure is present in 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 (AM) is composed only of a compound having an olivine structure. 9 SSPI 2022/024 [0069] Most preferably, the positive electrode active material (AM) consists only of lithium iron phosphate (LFP). [0070] In the positive electrode composition of the present invention, the active material (AM) has an average particle size of 3 ⁇ m or less. [0071] 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 ⁇ m. [0072] The average particle size of the positive electrode active material can be measured by a particle size distribution meter for dynamic light scattering.
  • the compound (AM) may preferably comprise a carbon-based material and/or a silicon-based material.
  • the carbon-based material may be, for example, graphite, such as natural or artificial graphite, graphene, or carbon black. [0077] These materials may be used alone or as a mixture of two or more thereof. [0078] The carbon-based material is preferably graphite. [0079]
  • the silicon-based compound may be one or more selected from the group consisting of chlorosilane, alkoxysilane, aminosilane, fluoroalkylsilane, silicon, silicon chloride, silicon carbide and silicon oxide. More particularly, the silicon-based compound may be silicon oxide or silicon carbide.
  • the at least one silicon-based compound is comprised in the compound (AM) in an amount ranging from 1 to 30 % by weight, preferably from 5 to 20 % by weight with respect to the total weight of the compound (AM).
  • the solvent (S) may preferably be an organic polar one, examples of which may include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate, and trimethyl phosphate.
  • An optional conductive agent may be added in order to improve the conductivity of a resulting electrode (AM).
  • AM a resulting electrode
  • Examples thereof may include: carbonaceous materials, such as carbon black, graphite fine powder carbon nanotubes, graphene, or fiber, or fine powder or fibers of metals such as nickel or aluminum.
  • the optional conductive agent is preferably carbon black. Carbon black is available, for example, under the brand names, Super P ® or Ketjenblack ® .
  • the electro-forming composition (C) of the invention may further optionally include at least one conductive agent. [0085] When present, the conductive agent is different from the carbon-based material described above.
  • an electrode-forming composition (C) for use in the preparation of a positive electrode (Ep) comprising: a) at least one positive electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) as above defined; c) at least one solvent (S); and d) at least one conductive agent, preferably selected from carbon black or graphite fine powder carbon nanotubes.
  • the polymer (F) of the present invention possesses a quasi-linear structure, and very low amount of insoluble fraction when dissolved in standard polar aprotic solvents such as NMP.
  • polymer (F) provides solutions in organic solvents, which are not detrimentally affected by the presence of insoluble residues, which are generally referred as “gels”, and are hence more adapted for use in formulating electrodes-forming compositions.
  • the present invention pertains to the use of the electrode-forming composition (C) for the manufacture of an electrode (E), said process comprising: (I) providing a metal substrate having at least one surface; (II) providing an electrode-forming composition (C) as above defined; (III) applying the composition (C) provided in step (II) onto the at least one surface of the metal substrate provided in step (I), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface; (IV) drying the assembly provided in step (III); 11 SSPI 2022/024 (V) submitting the dried assembly obtained in step (IV) to a compression step to obtain the electrode (E) of the invention.
  • the present invention pertains to the electrode (E) obtainable by the process of the invention.
  • the Applicant has surprisingly found that the electrode (E) of the present invention shows outstanding adhesion of the binder to current collector.
  • the electrode (E) of the invention is thus particularly suitable for use in electrochemical devices, in particular in secondary batteries.
  • the term “secondary battery” is intended to denote a rechargeable battery.
  • the secondary battery of the invention is preferably an alkaline or an alkaline-earth metal secondary battery.
  • the secondary battery of the invention is more preferably a sodium-ion or a lithium- ion secondary battery.
  • the present invention pertains to an electrochemical device comprising at least one electrode (E) of the present invention.
  • the electrochemical device according to the present invention being preferably a secondary battery, comprises: - a positive electrode and a negative electrode, wherein at least one of the positive electrode and the negative electrode is the electrode (E) of the present invention.
  • an electrochemical device is a secondary battery comprising: - a positive electrode and a negative electrode, wherein the negative electrode is the electrode (E) according to the present invention.
  • An electrochemical device according to the present invention can be prepared by standard methods known to a person skilled in the art.
  • EXPERIMENTAL PART Determination of intrinsic viscosity of polymer (F) 12 SSPI 2022/024
  • Intrinsic viscosity ( ⁇ ) [dl/g] was measured using the following equation on the basis of dropping time, at 25°C, of a solution obtained by dissolving the polymer (F) in N,N-dimethylformamide at a concentration of about 0.2 g/dl using a Ubbelhode viscosimeter: where c is polymer concentration [g/dl], ⁇ r is the relative viscosity, i.e.
  • ⁇ sp is the specific viscosity, i.e. ⁇ r -1
  • ⁇ is an experimental factor, which for polymer (F) corresponds to 3.
  • DSC analysis [00106] DSC analyses were carried out according to ASTM D 3418 standard; the melting point (T f2 ) was determined at a heating rate of 10°C/min.
  • Example 1 Preparation of Polymer F-1 [00113] In a 4L reactor equipped with an impeller running at a speed of 650 rpm were introduced in sequence: 2376 g of demineralized water and 0.4 g of PEO (Alkox® -E45 from Alroko) per kg of total monomers and 0.5 g of hydroxypropyl methylcellulose (Methocel®-K100 from Dow) per kg of total monomers and 12.4 g of trisodium phosphate. The oxygen present in the reactor was removed with a sequence of vacuum and purge of nitrogen at a fixed temperature of 14°C. This sequence was repeated 3 times.
  • PEO Alkox® -E45 from Alroko
  • the polymer was then collected by filtration and suspended against clean water in a stirred tank. After the washing treatment, the polymer was dried in an oven at 65°C overnight.882 g of dry powder were collected. [00118] A polymer having an intrinsic viscosity of 0.316 l/g in DMF at 25°C and a T 2 f of 172.1°C was obtained. [00119] The polymer contained 1.7/10000 VDF units of end-group CH 3 CH 2 -OCOO-: 0.7 /10000 VDF units derived from the ethyl chloroformate initiator precursor and 1.0/10000 VDF units derived from diethylcarbonate.
  • Example 2 Preparation of Polymer F-2 [00122] In a 80 l reactor equipped with an impeller running at a speed of 250 rpm were introduced in sequence: 52.4 Kg of demineralized water and 0.4 g of hydroxypropyl methylcellulose (Methocel®-K100 from Dow) per kg of VDF. The oxygen present in the reactor was removed with a sequence of vacuum and purge of nitrogen at a fixed temperature of 20°C. This sequence was repeated 3 times.
  • the polymer contained 2.2/10000 VDF units of end-group CH 3 CH 2 -OCOO derived from diethylcarbonate, 0.6/10000 VDF units of -C(CH 3 ) 3 from the initiator, 4.5 /10000 VDF units of -CF2H and 2.4/10000 VDF units of -CF2CH3 end-groups [00127]
  • the slurry components were added to the mixing cup in the following order: 33.6 g of a multi-walled carbon nanotubes dispersion at solid content of 4.1% by weight, 21.1 g of 8% by weight solution of a polymer in NMP, 150 g of NMC, 7.9 g of NMP. [00130] The mixture was then mixed using a high speed disk impeller at 500 rpm for 5 minutes, followed by 75 minutes at 1900 rpm. [00131] Positive electrodes were obtained by casting the as obtained dispersion on 15 ⁇ m thick Aluminum foil with doctor blade and drying the as coated layers in a vacuum oven at temperature of 90°C for about 50 minutes. The thickness of the dried coating layers was about 150 ⁇ m.
  • Example 3 Adhesion and slurry viscosity
  • the polymers of examples 1 and 2 have been used as binders and the electrode compositions have been produced according to the procedure shown above.
  • the slurry viscosity of the compositions as above defined was measured with an AntonPaar Rheolab QC using a Concentric cylinder setup (Measuring Cup: C- CC27/QC-LTD Bob: CC27/P6) with peltier temperature control at 25°C. Steady state viscosities were measured from shear rate of 0.1 to 10001/s.
  • a first dispersion was prepared by pre-mixing for 10 minutes in a centrifugal mixer 34.3 g of an 8% by weight solution of a polymer in NMP, 75.07 g of LFP, 14.7 g of graphite fine powder carbon nanotubes pre-dispersed in NMP at 4% by weight and 15.93 g of NMP. [00140] The mixture was then mixed using a high speed butterfly type impeller at 1500 rpm for 50 minutes. Additional 5.2 g of NMP were subsequently added to the dispersion, which was further mixed centrifugal mixer for 5 min.
  • Example 4 Adhesion and slurry viscosity
  • the polymers of examples 1 and 2 have been used as binders and the electrode compositions have been produced according to the procedure shown above. The values of slurry viscosity and adhesion, measured as above defined, are shown in Table 2.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne des polymères de fluorure de vinylidène contenant des groupes terminaux de carbonate d'éthyle et leur utilisation en tant que liants pour des électrodes dans des batteries secondaires.
PCT/EP2023/078154 2022-10-18 2023-10-11 Liants d'électrode de batterie secondaire WO2024083593A1 (fr)

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EP22202255.0 2022-10-18
EP22202255 2022-10-18
EP23157209.0 2023-02-17
EP23157209 2023-02-17

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WO2024083593A1 true WO2024083593A1 (fr) 2024-04-25

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060044522A (ko) * 2004-03-23 2006-05-16 가부시끼가이샤 구레하 비수계 전기화학소자 전극 형성용 바인더, 전극 합제, 전극구조체 및 전기 화학 소자
CN110183562A (zh) 2019-05-30 2019-08-30 浙江孚诺林化工新材料有限公司 一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途
WO2022063630A1 (fr) * 2020-09-23 2022-03-31 Solvay Specialty Polymers Italy S.P.A. Polymérisation de fluorure de vinylidène dans de l'eau à l'aide d'agents de suspension macromoléculaires
CN115043963A (zh) * 2022-06-28 2022-09-13 万华化学(四川)电池材料科技有限公司 一种高固体含量的聚偏氟乙烯分散液及其制备方法与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060044522A (ko) * 2004-03-23 2006-05-16 가부시끼가이샤 구레하 비수계 전기화학소자 전극 형성용 바인더, 전극 합제, 전극구조체 및 전기 화학 소자
CN110183562A (zh) 2019-05-30 2019-08-30 浙江孚诺林化工新材料有限公司 一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途
WO2022063630A1 (fr) * 2020-09-23 2022-03-31 Solvay Specialty Polymers Italy S.P.A. Polymérisation de fluorure de vinylidène dans de l'eau à l'aide d'agents de suspension macromoléculaires
CN115043963A (zh) * 2022-06-28 2022-09-13 万华化学(四川)电池材料科技有限公司 一种高固体含量的聚偏氟乙烯分散液及其制备方法与应用

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