[go: up one dir, main page]

WO2016181993A1 - Copolymère, liant pour électrode de pile secondaire, composition pour électrode de pile secondaire, et électrode pour pile secondaire - Google Patents

Copolymère, liant pour électrode de pile secondaire, composition pour électrode de pile secondaire, et électrode pour pile secondaire Download PDF

Info

Publication number
WO2016181993A1
WO2016181993A1 PCT/JP2016/064004 JP2016064004W WO2016181993A1 WO 2016181993 A1 WO2016181993 A1 WO 2016181993A1 JP 2016064004 W JP2016064004 W JP 2016064004W WO 2016181993 A1 WO2016181993 A1 WO 2016181993A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
vinylacetamide
binder
electrode
monomers
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.)
Ceased
Application number
PCT/JP2016/064004
Other languages
English (en)
Japanese (ja)
Inventor
菅原　篤
小西　淳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2017517964A priority Critical patent/JP6878273B2/ja
Publication of WO2016181993A1 publication Critical patent/WO2016181993A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • 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 relates to a copolymer, a binder for an electrode of a secondary battery, an electrode composition for a secondary battery, and an electrode for a secondary battery.
  • Secondary batteries are used as batteries for consumer devices such as mobile phones, and as batteries for vehicles such as hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles.
  • lithium ion batteries are widely used because they have excellent energy density and charge / discharge cycle life.
  • the positive electrode of the lithium ion battery has a current collector formed of aluminum foil or the like and an active material layer formed on the current collector.
  • the active material layer includes an active material containing a lithium transition metal oxide such as lithium cobalt oxide, a conductive aid such as carbon black, and a binder.
  • the binder contained in the active material layer plays a role as a binder for fixing the active material layer on the current collector.
  • the active material layer is generally formed by a method in which an active material layer material such as an active material is dispersed in a solvent in which a binder is dissolved to form an active material solution, which is applied onto a current collector.
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • Patent Document 1 discloses fluororubber mainly composed of a copolymer of hexafluoropropylene and vinylidene fluoride, and trifluorochloroethylene and fluoride. It has been proposed to use a fluororubber whose main component is a copolymer with vinylidene.
  • Patent Document 2 a fluorine-based polymer copolymer mainly composed of —CH 2 —CF 2 —, —CF (CF 3 ) —CF 2 —, and —CF 2 —CF 2 — is used as a binder. It has been proposed to use.
  • Patent Document 3 proposes the use of a polymer having an N-vinylformamide unit as a binder.
  • the binder for electrodes of the conventional secondary battery has insufficient binding force with the current collector. For this reason, in the electrode of the conventional secondary battery, the active material layer may peel from the current collector. In the secondary battery electrode, the separation of the active material layer greatly affects the performance life and safety of the secondary battery.
  • the electrode binder contained in the active material layer swells when immersed in the electrolytic solution.
  • the binder for an electrode contained in the active material layer swells, peeling of the active material layer from the current collector is promoted, or the internal resistance of the active material layer increases and the performance of the secondary battery may deteriorate. is there.
  • the conventional secondary battery electrode binder has insufficient ability to disperse a conductive additive such as carbon black. For this reason, when forming an active material layer, it was necessary to contain a dispersing agent in addition to a binder in the active material solution. The dispersant may be a factor that increases the internal resistance in the secondary battery. For this reason, it is desirable not to contain.
  • the present invention has been made in view of the above circumstances, and is soluble in water, soluble in NMP, which is usually used when forming an electrode of a secondary battery, binding with a current collector, electrical conductivity.
  • An object of the present invention is to provide a copolymer excellent in dispersibility of an auxiliary agent and suppressed in swelling when immersed in an electrolyte solution, and suitable as a material for a binder for an electrode of a secondary battery. .
  • this invention makes it a subject to provide the binder for electrodes of a secondary battery containing the said copolymer, the composition for electrodes of a secondary battery, and the electrode for secondary batteries.
  • N-vinylacetamide which is a water-soluble monomer
  • N-vinylacetamide is a water-soluble monomer
  • the present invention relates to the following matters.
  • a composition for an electrode of a secondary battery comprising the copolymer according to any one of (1) to (6), a solvent, an active material, and a conductive additive.
  • the electrode for secondary batteries containing the copolymer of description comprising the copolymer according to any one of (1) to (6), a solvent, an active material, and a conductive additive.
  • the copolymer of the present invention is excellent in solubility in water, solubility in NMP usually used when forming an electrode of a secondary battery, binding property with a current collector, and dispersibility of a conductive auxiliary agent. Swelling when immersed in an electrolytic solution is suppressed. Therefore, the copolymer of the present invention is suitable as a binder for electrodes of secondary batteries.
  • the composition for electrodes of the secondary battery of the present invention includes the copolymer of the present invention having excellent solubility in water and NMP and excellent dispersibility of the conductive assistant. For this reason, the composition for an electrode of the secondary battery of the present invention can be easily manufactured without using a dispersant by dissolving the copolymer in a solvent and dispersing the active material and the conductive additive therein. it can.
  • the composition for an electrode of the secondary battery of the present invention is excellent in binding property with the current collector by applying the composition on a current collector and drying, and swelling when immersed in an electrolytic solution. A suppressed active material layer can be formed.
  • the active material layer includes the copolymer of the present invention. For this reason, it has the active material layer which was excellent in the binding force of an active material layer and an electrical power collector, and the swelling at the time of being immersed in electrolyte solution was suppressed. Therefore, the secondary battery electrode of the present invention can suppress deterioration of the secondary battery.
  • the copolymer of this embodiment comprises an unsaturated carboxylic acid monomer, a salt of an unsaturated carboxylic acid monomer, an unsaturated carboxylic acid ester monomer, a vinyl ester monomer, and an unsaturated nitrile monomer.
  • a copolymer of at least one monomer selected from the group and N-vinylacetamide hereinafter sometimes referred to as “N-vinylacetamide copolymer”.
  • N-vinylacetamide used for the polymerization of N-vinylacetamide copolymer
  • other monomers are unsaturated carboxylic acid monomers, unsaturated carboxylic acids. It is at least one monomer selected from the group consisting of a salt of an acid monomer, an unsaturated carboxylic acid ester monomer, a vinyl ester monomer, and an unsaturated nitrile monomer.
  • the SP value ⁇ is non-polar compared with N-vinylacetamide (SP value ⁇ (fedors estimation method) 13 (cal / cm 3 ) 1/2 ) ( It is preferable to use one having a small SP value.
  • the N-vinylacetamide copolymer sufficiently contains a structural unit derived from N-vinylacetamide. Therefore, when another monomer having an SP value ⁇ of N-vinylacetamide or less (13 (cal / cm 3 ) 1/2 or less) is used, the SP value ⁇ of the N-vinylacetamide copolymer is It is close to NMP (SP value ⁇ (fedors estimation method) 11.3 (cal / cm 3 ) 1/2 ). An N-vinylacetamide copolymer having an SP value ⁇ close to NMP is preferable because of its excellent solubility in NMP.
  • Examples of the monomer having an SP value ⁇ that is non-polar compared to N-vinylacetamide and suitable as another monomer for polymerization of the N-vinylacetamide copolymer include those shown in Table 1.
  • Compounds. Table 1 shows SP values ⁇ calculated using the fedors estimation method for monomers that can be used as other monomers, N-vinylacetamide, and NMP.
  • the unsaturated carboxylic acid monomer used for the polymerization of the N-vinylacetamide copolymer has a structure containing a polymerizable unsaturated group and a carboxyl group.
  • the salt of the unsaturated carboxylic acid monomer used for the polymerization of the N-vinylacetamide copolymer is obtained by replacing the hydrogen atom of the carboxyl group contained in the unsaturated carboxylic acid monomer with a metal or the like.
  • the polymerizable unsaturated group of the monomer can be copolymerized with N-vinylacetamide.
  • the N-vinylacetamide copolymer obtained after polymerization has a structure containing a carboxyl group that is a polar group. For this reason, high hydrogen bond strength with the metal surface is obtained. Therefore, when an active material layer is provided on a current collector made of metal using an electrode binder containing this copolymer, an active material layer having excellent binding properties with the current collector can be obtained.
  • unsaturated carboxylic acid monomers and / or salts thereof used for other monomers include acrylic acid, methacrylic acid, crotonic acid, and ammonium salts, organic amine salts, and monovalent metal salts thereof. Divalent metal salts are preferred. Among these, it is preferable to use (meth) acrylic acid and / or a salt thereof as the unsaturated carboxylic acid monomer and / or a salt thereof. Acrylic acid or a salt thereof is preferable as the unsaturated carboxylic acid monomer and / or a salt thereof from the viewpoint of enhancing the binding property with the current collector and suppressing the swelling when immersed in the electrolytic solution.
  • the salt is preferably a sodium salt or an ammonium salt from the viewpoint of stability.
  • (meth) acrylic acid means acrylic acid or methacrylic acid.
  • the unsaturated carboxylic acid ester monomer used for the polymerization of the N-vinylacetamide copolymer is preferably one having an SP value ⁇ of 13 (cal / cm 3 ) 1/2 or less.
  • unsaturated carboxylic acid ester monomers include (meth) acrylic acid esters.
  • an N-vinylacetamide copolymer when an unsaturated carboxylic acid ester monomer is included as another monomer, the N-vinylacetamide copolymer obtained after the polymerization has an affinity for NMP rather than an amide group. Highly ester site is included. Therefore, an N-vinylacetamide copolymer having excellent solubility in NMP is obtained. Further, when an unsaturated carboxylic acid ester monomer is included as another monomer, the N amount obtained after polymerization can be adjusted by adjusting the ratio of the amount of N-vinylacetamide and the unsaturated carboxylic acid ester monomer. -The affinity of the vinyl acetamide copolymer to the electrolyte can be adjusted.
  • vinyl ester monomer used for the polymerization of the N-vinylacetamide copolymer those having an SP value ⁇ of 13 (cal / cm 3 ) 1/2 or less are preferable.
  • vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, vinyl decanoate, vinyl stearate, vinyl hexanoate, vinyl octoate, and vinyl palmitate. Etc.
  • vinyl ester monomers it is preferable to use vinyl acetate because the reaction rate and molecular size are similar to those of N-vinylacetamide.
  • the vinyl ester monomer is included as another monomer, it is preferable because of high copolymerizability with N-vinylacetamide. This is because the vinyl ester monomer is a non-conjugated monomer having a Q value (conjugation effect) of 0.2 or less, like N-vinylacetamide.
  • the unsaturated nitrile monomer used for the polymerization of the N-vinylacetamide copolymer is preferably one having an SP value ⁇ of 13 (cal / cm 3 ) 1/2 or less.
  • unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, ⁇ -alkylacrylonitrile and the like.
  • acrylonitrile is preferably used from the viewpoints of copolymerizability with N-vinylacetamide and electrochemical stability.
  • the N-vinylacetamide copolymer is a ratio of the number of moles of structural units derived from N-vinylacetamide to the number of moles of other structural units derived from N-vinylacetamide (structural units derived from N-vinylacetamide: other The structural unit is 1.00: 0.010 to 1.00: 0.250.
  • the N-vinylacetamide copolymer has a molar ratio of other structural units derived from N-vinylacetamide exceeding 0.250 when the structural unit derived from N-vinylacetamide is 1.00. And solubility in water is insufficient.
  • the N-vinylacetamide copolymer having a molar ratio of the above structural units exceeding 0.250 is a secondary battery electrode in which an active material layer containing this copolymer is provided on a current collector. When formed, the active material layer is greatly swollen by the electrolytic solution. For this reason, an active material layer peels from a collector, or the internal resistance of an active material layer increases, and the performance of a secondary battery deteriorates.
  • the N-vinylacetamide copolymer preferably has a molar ratio of the above structural units of 0.150 or less, more preferably 0.100 or less.
  • an N-vinylacetamide copolymer having a molar ratio of the above structural units of less than 0.010 is insufficient in solubility in NMP which is usually used when forming an electrode of a secondary battery. Further, the N-vinylacetamide copolymer having a molar ratio of the above structural units of less than 0.010 has insufficient compatibility with the fluorine-containing resin. For these reasons, the N-vinylacetamide copolymer has a molar ratio of the above structural units of 0.010 or more, preferably 0.050 or more.
  • the weight average molecular weight of the N-vinylacetamide copolymer is such that it is easy to adjust the viscosity when producing an electrode composition containing the N-vinylacetamide copolymer, the dispersibility of the conductive auxiliary agent, and the active material layer containing the same. From the standpoint of binding property to the current collector, it is preferably 0.1 to 3 million, more preferably 100,000 to 1.5 million.
  • the weight average molecular weight of the N-vinylacetamide copolymer is 10,000 or more, a secondary battery electrode binder in which swelling when immersed in an electrolytic solution is suppressed can be easily obtained.
  • the weight average molecular weight of the N-vinylacetamide copolymer is 3 million or less, when an electrode composition containing this copolymer is produced, an electrode composition having a viscosity that is easy to apply is easily obtained.
  • the weight average molecular weight of the N-vinylacetamide copolymer is a value calculated by the following method.
  • GPC gel permeation chromatography
  • GPC-MALS multi-angle light scattering detector
  • the N-vinylacetamide copolymer of this embodiment can be used alone as a binder for an electrode of a secondary battery.
  • the electrode binder may contain one or more fluorine-containing resins in addition to the N-vinylacetamide copolymer.
  • fluorine-containing resin include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), and polyvinyl fluoride (PVF).
  • the N-vinylacetamide copolymer is excellent in compatibility with the fluorine-containing resin. Therefore, the N-vinylacetamide copolymer and the fluorine-containing resin can be mixed and used at an arbitrary ratio.
  • the electrode binder containing a fluorine-containing resin is superior in the dispersibility of the conductive auxiliary agent compared to the case where the fluorine-containing resin is used alone, and when the electrode is immersed in an electrolytic solution.
  • the binder with the current collector is excellent.
  • the content of the fluorine-containing resin relative to the total amount of the N-vinylacetamide copolymer and the fluorine-containing resin is 90% by mass or less. More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less, and 1 mass% or more is preferable.
  • the smaller the content of the fluorine-containing resin in the electrode binder the more remarkable the effect due to the fact that the N-vinylacetamide copolymer is contained in the electrode binder.
  • the content of the fluorine-containing resin with respect to the total amount is 50% by mass or less, the peel strength described later is sufficiently obtained and the dispersibility of the conductive additive is excellent.
  • the electrode binder of the secondary battery of this embodiment preferably has a peel strength of 0.015 N / m or more measured by a method described later.
  • the peel strength is 0.015 N / m or more
  • a secondary battery electrode having an active material layer containing the electrode binder is formed, sufficient binding force between the active material layer and the current collector is obtained. It is done.
  • the electrode binder of the secondary battery of the present embodiment preferably has an electrolytic solution immersion swelling ratio measured by a method described later of 10% or less.
  • the electrolytic solution immersion swelling rate is 10% or less
  • the active material and the conductive material in the active material layer are electrically conductive.
  • the distance from the auxiliary agent can be kept appropriate.
  • it can prevent that a binder melt
  • the electrode binder for the secondary battery of the present embodiment may be used for the positive electrode of the secondary battery or for the negative electrode.
  • the N-vinylacetamide copolymer is used in the reaction apparatus for unsaturated carboxylic acid monomer, unsaturated carboxylic acid monomer salt, unsaturated carboxylic acid ester monomer, vinyl ester monomer, unsaturated It can be produced by polymerizing at least one monomer (other monomer) selected from the group consisting of nitrile monomers and N-vinylacetamide in the presence of a polymerization initiator.
  • the ratio of N-vinylacetamide in the total amount of monomers (total amount of N-vinylacetamide and other monomers) used for polymerization of the N-vinylacetamide copolymer is 85.0 to 99.99. It is preferably 9% by mass.
  • the proportion of N-vinylacetamide used for the polymerization of the N-vinylacetamide copolymer is 85.0 to 99.9% by mass
  • the number of moles of the structural unit derived from N-vinylacetamide and the above-mentioned N-vinylacetamide origin N-vinylacetamide copolymer having a ratio of other structural units to the number of moles (structural units derived from N-vinylacetamide: other structural units) of 1.00: 0.010 to 1.00: 0.250 A polymer is easily obtained.
  • the polymerization method for producing the N-vinylacetamide copolymer is not particularly limited.
  • polymerization methods such as solution polymerization, dropping polymerization, reverse phase suspension polymerization, emulsion polymerization, and precipitation polymerization can be used.
  • precipitation polymerization is particularly suitable as a method for polymerizing the N-vinylacetamide copolymer.
  • all of the monomers used for the polymerization may be supplied to the reaction vessel before the start of the polymerization, or a part of the monomers used for the polymerization may be You may supply to a reaction container.
  • all of the solvent used for the polymerization may be supplied to the reaction vessel before the start of polymerization, or a part of the solvent used for the polymerization is supplied to the reaction vessel during the polymerization. May be.
  • the solvent used for the polymerization reaction of the N-vinylacetamide copolymer it is preferable to use a solvent in which the monomer used for the polymerization of the N-vinylacetamide copolymer is dissolved and the resulting copolymer is precipitated. .
  • a solvent in which the above monomer is easily dissolved is used. After synthesizing the copolymer, the copolymer is precipitated using another solvent in which the copolymer is easily precipitated. May be.
  • a solvent that can be generally used in the polymerization reaction of a vinyl compound can be used.
  • Specific examples include water, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, methanol, ethanol, isopropanol, and the like.
  • an N-vinylacetamide copolymer having a weight average molecular weight of 0.1 to 1,500,000 can be easily obtained by producing by a polymerization method using an organic solvent as a solvent.
  • an N-vinylacetamide copolymer having a weight average molecular weight of about 5 to 3 million can be easily obtained by a polymerization method using water as a solvent.
  • polymerization initiator used for polymerization of the N-vinylacetamide copolymer those generally used for radical polymerization of vinyl compounds can be used without limitation.
  • persulfates such as sodium, potassium and ammonium, benzoyl peroxide, hydrogen peroxide, caproyl peroxide, peroxygen compounds such as sodium peracetello, sodium percarbonate, azobisisobutyronitrile, 2 , 2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [N- (carboxyethyl) -2-methylpropionamide], 2,2′-azobis ⁇ 2- [N- (2 Azo compounds such as -carboxylethyl) amidino] propane ⁇ , dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylpropionic acid), and the like.
  • azobisisobutyronitrile or dimethyl-2,2′-azobis (2-methylpropionate) that is soluble in an organic solvent is preferably used. Furthermore, it is most preferable to use dimethyl-2,2′-azobis (2-methylpropionate) containing no nitrile group and halogen as the polymerization initiator.
  • the amount of the polymerization initiator used is not limited as long as the polymerization reaction can be started and advanced. For example, the amount used is in the range of 0.005 to 5.0 parts by mass with respect to 100 parts by mass of the total monomers used for polymerization. And is not particularly specified.
  • the reaction temperature for producing the N-vinylacetamide copolymer is preferably 30 to 120 ° C. By setting the reaction temperature within the above range, polymerization can be performed at a reaction rate suitable for polymerization of the N-vinylacetamide copolymer.
  • the reaction temperature may be constant from the start to the end of the polymerization, or may be changed during the polymerization reaction.
  • the polymerization of the N-vinylacetamide copolymer is radical polymerization and is preferably carried out in a nitrogen gas atmosphere because of the large influence of oxygen.
  • the reaction product may be washed with a solvent as necessary.
  • the N-vinylacetamide copolymer thus obtained can be used alone as a binder for an electrode of a secondary battery. Further, when the binder for the electrode of the secondary battery of the present embodiment contains an N-vinylacetamide copolymer and one or more fluorine-containing resins, the N obtained by the above production method is used. A mixture of vinylacetamide copolymer and one or more fluorine-containing resins in the above-mentioned proportion can be used as a binder for an electrode of a secondary battery.
  • the composition for an electrode of the secondary battery of the present embodiment includes the N-vinylacetamide copolymer of the present embodiment, a solvent, an active material, and a conductive additive.
  • a solvent for example, a solvent in which an N-vinylacetamide copolymer such as NMP, water, methanol, butanol, propylene glycol monomethyl ether, dimethyl sulfoxide, and ethylene glycol is dissolved can be used.
  • the active material for example, a conventionally known material used as an active material such as a lithium transition metal oxide such as lithium cobaltate can be used depending on the use of the secondary battery.
  • a conductive support agent conventionally well-known things used as a conductive support agent can be used according to the use etc. of a secondary battery, such as carbon black, acetylene black, and graphite, for example.
  • the electrode composition of the secondary battery according to the present embodiment includes one or more fluorine-containing resins in addition to the N-vinylacetamide copolymer, the solvent, the active material, and the conductive auxiliary as necessary. It may be a thing and a conventionally well-known additive may be included.
  • the composition for electrodes of the secondary battery of the present embodiment can be produced, for example, by the method shown below. First, the N-vinylacetamide copolymer of this embodiment and one or more fluorine-containing resins contained as necessary are dissolved in a solvent. Next, an active material, a conductive additive, and an additive contained as necessary are dispersed in a solvent in which the N-vinylacetamide copolymer (or N-vinylacetamide copolymer and fluorine-containing resin) is dissolved. It is obtained by the method.
  • the electrode for secondary batteries of this embodiment has a current collector and an active material layer formed on the current collector.
  • a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil can be used.
  • the current collector it is particularly preferable to use an aluminum foil that has good binding properties with the binder for electrodes of the secondary battery of the present embodiment.
  • the active material layer includes an active material, a conductive additive, and the N-vinylacetamide copolymer of the present embodiment. The active material layer is manufactured by applying the electrode composition of the secondary battery of the present embodiment on a current collector and drying it.
  • the ratio of the number of moles of structural units derived from N-vinylacetamide to the number of moles of other structural units derived from N-vinylacetamide is 1.00: 0. .010 to 1.00: 0.250.
  • the N-vinylacetamide copolymer of this embodiment is excellent in solubility in water and NMP, binding property with the current collector, and dispersibility of the conductive auxiliary agent, and swelling when immersed in the electrolytic solution. It has been suppressed.
  • the N-vinylacetamide copolymer of this embodiment is easy to apply because it has a thickening property against NMP and water, and is suitable as a binder for electrodes of secondary batteries.
  • a solution in which the N-vinylacetamide copolymer of the present embodiment is dissolved in NMP or water can easily increase the viscosity and obtain a high binding force.
  • a kneading step for improving the viscosity and the binding force may not be performed, or the kneading step is performed. Even if it is a case, it can simplify compared with the case where PVDF is used, for example.
  • the electrode binder of the secondary battery of this embodiment does not contain a fluorine-containing resin, no corrosive acid component is generated even if the secondary battery produced using the binder becomes high temperature due to thermal runaway or the like. Therefore, it is preferable.
  • the electrode composition of the present embodiment includes the N-vinylacetamide copolymer of the present embodiment, which is excellent in solubility in NMP and water and excellent in dispersibility of the conductive assistant. For this reason, the electrode composition of the present embodiment can be easily dissolved without using a dispersant by dissolving the N-vinylacetamide copolymer in a solvent and dispersing the active material and the conductive additive therein. Can be manufactured.
  • the electrode composition of the present embodiment was coated on a current collector and dried, thereby being excellent in binding property with the current collector and suppressing swelling when immersed in an electrolytic solution. An active material layer can be formed.
  • the active material layer includes the N-vinylacetamide copolymer of the present embodiment. For this reason, it has the active material layer which was excellent in the binding force of an active material layer and an electrical power collector, and the swelling at the time of being immersed in electrolyte solution was suppressed. Therefore, according to the secondary battery electrode of the present embodiment, the deterioration of the secondary battery can be prevented.
  • Examples 1 to 8, Comparative Example 2 N-vinylacetamide and other monomers shown in Table 2 were used at a mass ratio shown in Table 2 (N-vinylacetamide / other monomers), and dimethyl-2,2′- was used as a polymerization initiator.
  • Azobis (2-methylpropionate) (trade name: V-601 (oil-soluble azo polymerization initiator), manufactured by Wako Pure Chemical Industries, Ltd.), the content (mass) shown in Table 3 with respect to 100 parts by mass of the total amount of monomers.
  • the copolymer (binder) of Examples 1 to 8 and Comparative Example 2 was obtained by polymerization according to the method shown below. Table 2 shows polymer forms of the binders of Examples 1 to 8 and Comparative Example 2.
  • Method for producing copolymers (binders) of Examples 1, 2, 4 to 6, 8 A three-neck separable flask was prepared as a reaction vessel, and a nitrogen gas insertion tube, a stirrer, a solvent dropping device, and a thermometer were attached. Next, initially charged ethyl acetate and 20% by mass of N-vinylacetamide in a mass ratio with respect to ethyl acetate are placed in the reaction vessel, and the reaction vessel is heated to the polymerization start temperature shown in Table 3 under nitrogen flow with stirring. The inside was heated up. Table 3 shows the volume ratio of the initially charged ethyl acetate to the reaction vessel.
  • Method for producing binder of Comparative Example 1 Polymerization was carried out in the same manner as in Examples 1, 2, 4 to 6 and 8, except that no other monomer was charged into the reaction vessel.
  • Table 3 shows the polymerization reaction conditions of Examples 1 to 8 and Comparative Examples 1 and 2.
  • binders of Examples 1 to 8 and Comparative Examples 1 and 2 were confirmed by NMR (nuclear magnetic resonance) measurement. Specifically, in 1 H-NMR examples 1 to 8 and comparative examples 1 and 2, binders (copolymers) of N-vinylacetamide and other monomers derived from methylene / methine / methyl The content was determined from the ratio of proton accumulation and the ratio of C ⁇ O accumulation derived from each monomer by 13 C-NMR. Using this, the proportion (molar ratio) of N-vinylacetamide-derived and other structural units was determined.
  • Example 8 For Example 8 containing two types of monomers as other monomers, the ratio (molar ratio) was calculated for each of the other two types of structural units derived from N-vinylacetamide, and the total was calculated. The value was the ratio (molar ratio) of other structural units derived from N-vinylacetamide. The results are shown in Table 4.
  • NMP N-methyl-2-pyrrolidone
  • pure water NMP was placed in a glass bottle with a tight stopper, and the binder was added and sealed so that the binder concentration was 5% by mass. And the glass bottle with a sealing stopper was shaken up and down manually 20 times, and NMP and the binder were mixed. Thereafter, the glass bottle with a tight stopper was left in a thermostat at 20 ° C., and the time required for complete dissolution was measured by visually confirming the dissolution state of the binder.
  • Viscometer DVE (Brookfield) viscometer Spindle: No. 4 spindle Rotation speed: 50 rpm Temperature: 20 ° C Measurement time: The viscometer spindle was placed in the binder solution, and the value 30 minutes after the spindle started rotating was taken as the measured value.
  • the binder was dissolved in NMP so as to have a concentration of 5% by mass, placed in a petri dish, and dried in vacuum at 150 ° C. for 4 hours to form a 1 mm thick film.
  • the obtained film was cut into a 1 cm horizontal square with a length of 1 cm, and the mass was precisely weighed.
  • the test tube containing the film and the electrolyte was placed in a warm bath adjusted to 95 to 98 ° C., and after 30 minutes, it was removed from the warm bath. Thereafter, the film was taken out from the electrolytic solution.
  • the electrolyte solution adhered to the film was wiped off, and the mass of the film was precisely weighed.
  • Electrolytic solution immersion swelling ratio (%) (film mass after immersion ⁇ film mass before immersion) / film mass before immersion) ⁇ 100
  • the peel strength of the specimen was measured at a speed of 500 mm / min using a tensile tester (ORIENTEC PTM-100).
  • the bonding area in the test body subjected to the tensile test is 21 cm 2 (3 cm ⁇ 7 cm), and the distance between chucks is 5 cm.
  • FIG. 1 shows the shape of the specimen subjected to the tensile test and the state of the tensile test. Three test specimens were prepared for each binder. The maximum value of the tensile test in the three specimens was averaged to obtain the peel strength of each binder.
  • Weight average molecular weight The binder was dissolved in distilled water at a concentration of 1% by mass and measured by the GPC (gel permeation chromatography) method under the following conditions. The weight average molecular weight (Mw) was calculated using the result. For the calculation of the weight average molecular weight, a calibration curve prepared from the measurement result of the absolute molecular weight (GPC-MALS) of N-vinylacetamide in each molecular weight band was used.
  • GPC-MALS absolute molecular weight
  • RI-201H (manufactured by SHODEX) Pump: LC-20AD (manufactured by Shimadzu Corporation) Column oven: AO-30C (manufactured by SHODEX) Analysis device: SIC4802 Data Station (manufactured by Shimadzu Corporation) Column: SB806 ⁇ 2 (manufactured by SHODEX) Eluent: DW (distilled water) Flow rate: 0.7ml / min
  • the binder was dissolved in NMP to a concentration of 5% by mass (Solution 1).
  • Polyvinylidene fluoride (PVDF) was dissolved in NMP so as to have a concentration of 5% by mass (solution 2).
  • Dissolving solution 1 and dissolving solution 2 were mixed at a ratio (mass ratio) of 1: 1 to form a mixed solution, and allowed to stand at room temperature for 24 hours. Then, about the mixed liquid, the presence or absence of turbidity and the presence or absence of separation of the dissolving liquid 1 and the dissolving liquid 2 were visually evaluated according to the following criteria.
  • the binders (copolymers) of Examples 1 to 8 were completely dissolved in NMP as compared with the binder of Comparative Example 1 using only N-vinylacetamide as a monomer. The time required for this is short and the solubility in NMP is excellent. In addition, the binders of Examples 1 to 8 have a shorter time required to completely dissolve in water than the binder (copolymer) of Comparative Example 2 having a small number of structural units derived from N-vinylacetamide. Excellent solubility in In addition, as shown in Table 5, the binders of Examples 1 to 8 have a sufficiently high solution viscosity, and a solution dissolved in NMP or water has a sufficient thickening property, which is preferable for coating. there were.
  • the binders of Examples 1 to 8 had an electrolytic solution immersion swelling ratio of 10% or less, and the swelling when immersed in the electrolytic solution was suppressed.
  • the binders of Examples 1 to 8 have a peel strength of 0.015 N / m or more, and are excellent in binding property to the current collector.
  • the binders of Examples 1 to 8 have an evaluation of ⁇ ⁇ ⁇ or ⁇ of the dispersibility of the conductive assistant, and are excellent in the dispersibility of the conductive assistant.
  • the binders of Examples 1 to 8 had a turbidity evaluation of ⁇ , no separation, and good compatibility with the fluorine-containing resin. Further, the binders of Examples 1 to 8 also had appropriate weight average molecular weights.
  • Comparative Example 1 using only N-vinylacetamide as a monomer has insufficient solubility in NMP. Moreover, the binder of the comparative example 1 was inferior in compatibility with fluorine-containing resin.
  • the binder of Comparative Example 2 having a small number of structural units derived from N-vinylacetamide has lower solubility in water than the binders of Examples 1 to 8. Furthermore, the binder of Comparative Example 2 has an electrolyte solution immersion swelling ratio exceeding 10%, and the swelling suppression effect when immersed in the electrolyte solution is lower than that of the binders of Examples 1 to 8.
  • Comparative Example 3 which is a fluorine-containing resin is insoluble in water. Further, the binder of Comparative Example 3 has a very large electrolytic solution immersion swelling rate. Further, the binder of Comparative Example 3 was evaluated as x for the dispersibility of the conductive additive. Further, the binder of Comparative Example 3 had a peel strength of less than 0.015 N / m, and the peel strength was insufficient.
  • Example 9 to 13 The binder (copolymer) of Example 1 or Example 2 and the binder of Comparative Example 3 which is a fluorine-containing resin were mixed. Ratio of binder of Example 1 or Example 2 to total mass of binder of Example 1 or Example 2 and fluorine-containing resin ⁇ [(Example 1 or Example 2) / (Example 1 or Example 2+ Comparative Example 3) ⁇ 100 (mass%)] was mixed so that the ratio shown in Table 5 was obtained. The mixed binder was dissolved in NMP so as to have a concentration of 5% by mass to obtain a solution, which was allowed to stand at 20 ° C. for 12 hours.
  • Comparative Example 4 The binder of Comparative Example 3 which is a fluorine-containing resin was dissolved in NMP so as to have a concentration of 5% by mass to obtain a solution, which was allowed to stand at 20 ° C. for 12 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un copolymère comprenant du N-vinylacétamide et au moins un monomère choisi dans le groupe constitué de monomères carboxyliques insaturés, de sels monomères carboxyliques insaturés, de monomères d'ester carboxylique insaturé, de monomères d'ester de vinyle et de monomères nitriles insaturés, ledit copolymère présentant un rapport de modes d'unités constitutives dérivées de N-vinylacétamide à moles d'unités constitutives non dérivées de N-vinylacétamide compris entre 1,00 à 0,010 et 1,00 à 0,250.
PCT/JP2016/064004 2015-05-11 2016-05-11 Copolymère, liant pour électrode de pile secondaire, composition pour électrode de pile secondaire, et électrode pour pile secondaire Ceased WO2016181993A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017517964A JP6878273B2 (ja) 2015-05-11 2016-05-11 共重合体、二次電池の電極用バインダー、二次電池の電極用組成物、二次電池用電極

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015096330 2015-05-11
JP2015-096330 2015-05-11

Publications (1)

Publication Number Publication Date
WO2016181993A1 true WO2016181993A1 (fr) 2016-11-17

Family

ID=57248191

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/064004 Ceased WO2016181993A1 (fr) 2015-05-11 2016-05-11 Copolymère, liant pour électrode de pile secondaire, composition pour électrode de pile secondaire, et électrode pour pile secondaire

Country Status (3)

Country Link
JP (1) JP6878273B2 (fr)
TW (1) TWI675046B (fr)
WO (1) WO2016181993A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019181871A1 (fr) * 2018-03-23 2019-09-26 日本ゼオン株式会社 Composition de liant de batterie secondaire, pâte conductrice d'électrode de batterie secondaire, composition de bouillie d'électrode de batterie secondaire, procédé de production de composition de bouillie d'électrode de batterie secondaire, électrode de batterie secondaire et batterie secondaire
WO2020196234A1 (fr) 2019-03-22 2020-10-01 昭和電工株式会社 Procédé de production d'une solution aqueuse d'un copolymère d'amide d'acide n-vinylcarboxylique
JP2020181655A (ja) * 2019-04-24 2020-11-05 松本油脂製薬株式会社 二次電池正極スラリー用分散剤組成物及びその用途
WO2020235515A1 (fr) 2019-05-20 2020-11-26 昭和電工株式会社 Composition pour fluide de revêtement à base d'eau
WO2021253675A1 (fr) * 2020-06-17 2021-12-23 Guangdong Haozhi Technology Co. Limited Composition de liant pour batterie secondaire
WO2024031518A1 (fr) * 2022-08-11 2024-02-15 宁德时代新能源科技股份有限公司 Suspension d'électrode, feuille d'électrode, batterie secondaire et dispositif électrique
US12160002B2 (en) 2020-06-17 2024-12-03 Grst International Limited Binder composition for secondary battery
US12486423B2 (en) 2019-05-20 2025-12-02 Resonac Corporation Composition for aqueous coating liquid

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05271517A (ja) * 1992-03-27 1993-10-19 Hisamitsu Pharmaceut Co Inc 高分子ゲル組成物
JPH08311290A (ja) * 1995-05-23 1996-11-26 Showa Denko Kk 吸液材料用組成物、吸液材料成形体およびその製造方法
JPH09143061A (ja) * 1995-11-20 1997-06-03 Showa Denko Kk 鎮痛剤用経皮吸収製剤
JPH1146576A (ja) * 1997-08-05 1999-02-23 Showa Denko Kk 育苗用培土固化方法
JPH11323332A (ja) * 1998-05-12 1999-11-26 Nippon Shokubai Co Ltd 含水土壌の改良剤および改良方法
JPH11323334A (ja) * 1998-05-14 1999-11-26 Nippon Shokubai Co Ltd 含水土壌の改良剤および改良方法
JP2002279980A (ja) * 2001-01-10 2002-09-27 Hitachi Maxell Ltd 電極およびそれを用いた電池
JP2003017045A (ja) * 2001-06-28 2003-01-17 Hitachi Maxell Ltd ペースト式水素吸蔵合金電極及びそれを用いたニッケル水素蓄電池
JP2003045420A (ja) * 2001-07-30 2003-02-14 Hitachi Maxell Ltd 非焼結式正極、その製造方法および前記正極を用いたアルカリ蓄電池
JP2008115170A (ja) * 2006-10-13 2008-05-22 Showa Denko Kk ユビキノン誘導体またはその塩を含む皮膚外用剤および化粧料ならびにこれらの使用方法
JP2013211345A (ja) * 2012-03-30 2013-10-10 Nihon Gore Kk 電気二重層キャパシタ用の分極性電極

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140110893A (ko) * 2011-12-02 2014-09-17 미쯔비시 레이온 가부시끼가이샤 비수 이차 전지 전극용 바인더 수지, 비수 이차 전지 전극용 바인더 수지 조성물, 비수 이차 전지 전극용 슬러리 조성물, 비수 이차 전지용 전극, 및 비수 이차 전지

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05271517A (ja) * 1992-03-27 1993-10-19 Hisamitsu Pharmaceut Co Inc 高分子ゲル組成物
JPH08311290A (ja) * 1995-05-23 1996-11-26 Showa Denko Kk 吸液材料用組成物、吸液材料成形体およびその製造方法
JPH09143061A (ja) * 1995-11-20 1997-06-03 Showa Denko Kk 鎮痛剤用経皮吸収製剤
JPH1146576A (ja) * 1997-08-05 1999-02-23 Showa Denko Kk 育苗用培土固化方法
JPH11323332A (ja) * 1998-05-12 1999-11-26 Nippon Shokubai Co Ltd 含水土壌の改良剤および改良方法
JPH11323334A (ja) * 1998-05-14 1999-11-26 Nippon Shokubai Co Ltd 含水土壌の改良剤および改良方法
JP2002279980A (ja) * 2001-01-10 2002-09-27 Hitachi Maxell Ltd 電極およびそれを用いた電池
JP2003017045A (ja) * 2001-06-28 2003-01-17 Hitachi Maxell Ltd ペースト式水素吸蔵合金電極及びそれを用いたニッケル水素蓄電池
JP2003045420A (ja) * 2001-07-30 2003-02-14 Hitachi Maxell Ltd 非焼結式正極、その製造方法および前記正極を用いたアルカリ蓄電池
JP2008115170A (ja) * 2006-10-13 2008-05-22 Showa Denko Kk ユビキノン誘導体またはその塩を含む皮膚外用剤および化粧料ならびにこれらの使用方法
JP2013211345A (ja) * 2012-03-30 2013-10-10 Nihon Gore Kk 電気二重層キャパシタ用の分極性電極

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019181871A1 (fr) * 2018-03-23 2019-09-26 日本ゼオン株式会社 Composition de liant de batterie secondaire, pâte conductrice d'électrode de batterie secondaire, composition de bouillie d'électrode de batterie secondaire, procédé de production de composition de bouillie d'électrode de batterie secondaire, électrode de batterie secondaire et batterie secondaire
KR20210125535A (ko) 2019-03-22 2021-10-18 쇼와 덴코 가부시키가이샤 N-비닐카르복실산아미드 공중합체 수용액의 제조 방법
WO2020196234A1 (fr) 2019-03-22 2020-10-01 昭和電工株式会社 Procédé de production d'une solution aqueuse d'un copolymère d'amide d'acide n-vinylcarboxylique
JP2020181655A (ja) * 2019-04-24 2020-11-05 松本油脂製薬株式会社 二次電池正極スラリー用分散剤組成物及びその用途
CN113874408A (zh) * 2019-05-20 2021-12-31 昭和电工株式会社 水性涂覆液用组合物
WO2020235515A1 (fr) 2019-05-20 2020-11-26 昭和電工株式会社 Composition pour fluide de revêtement à base d'eau
KR20220003597A (ko) 2019-05-20 2022-01-10 쇼와 덴코 가부시키가이샤 수성 도공액용 조성물
EP3974457A4 (fr) * 2019-05-20 2023-06-07 Resonac Corporation Composition pour fluide de revêtement à base d'eau
CN113874408B (zh) * 2019-05-20 2023-09-15 株式会社力森诺科 水性涂覆液用组合物
JP7517333B2 (ja) 2019-05-20 2024-07-17 株式会社レゾナック 水性塗工液用組成物
KR102750227B1 (ko) * 2019-05-20 2025-01-07 가부시끼가이샤 레조낙 수성 도공액용 조성물
US12486423B2 (en) 2019-05-20 2025-12-02 Resonac Corporation Composition for aqueous coating liquid
WO2021253675A1 (fr) * 2020-06-17 2021-12-23 Guangdong Haozhi Technology Co. Limited Composition de liant pour batterie secondaire
US12160002B2 (en) 2020-06-17 2024-12-03 Grst International Limited Binder composition for secondary battery
WO2024031518A1 (fr) * 2022-08-11 2024-02-15 宁德时代新能源科技股份有限公司 Suspension d'électrode, feuille d'électrode, batterie secondaire et dispositif électrique

Also Published As

Publication number Publication date
TWI675046B (zh) 2019-10-21
JP6878273B2 (ja) 2021-05-26
JPWO2016181993A1 (ja) 2018-03-01
TW201710308A (zh) 2017-03-16

Similar Documents

Publication Publication Date Title
JP6878273B2 (ja) 共重合体、二次電池の電極用バインダー、二次電池の電極用組成物、二次電池用電極
TWI746131B (zh) 電池用黏合劑、鋰離子電池負極片以及鋰離子電池
EP3502151B1 (fr) Adhésif copolymère d'acrylonitrile et son utilisation dans une batterie au lithium-ion
JP5912814B2 (ja) 二次電池用水系電極バインダー
JP6015649B2 (ja) 二次電池電極用バインダ樹脂組成物、二次電池電極用スラリー、二次電池用電極、リチウムイオン二次電池
CN106663811B (zh) 正极及其制造方法
CN109075343B (zh) 粘合剂组合物、电极合剂、电极、以及非水电解质二次电池
CN103155247B (zh) 非水电解质二次电池用负极混合剂、非水电解质二次电池用负极和非水电解质二次电池
CN114560973B (zh) 一种锂离子电池正极水性粘结剂及其制备方法
JP2015018776A (ja) 電池用水系電極組成物用バインダー
CN106433530A (zh) 一种硫正极用水基电极粘结剂及制备方法
JPWO2018008262A1 (ja) バインダー組成物、電極合剤、電極、非水電解質二次電池、およびバインダー組成物の製造方法
CN116445109A (zh) 一种正极粘结剂及应用其的锂离子电池正极、锂离子电池
CN100539254C (zh) 用于电池用隔离物的担载反应性聚合物的多孔质薄膜和其利用
JP2022061830A (ja) バインダー組成物、電極合剤、電極、および非水電解質二次電池
JP2015195114A (ja) 電極組成物用水系バインダ
JP6450453B2 (ja) リチウムイオン二次電池の電極用バインダー
JP6061563B2 (ja) 二次電池用水系電極バインダー
CN105957993A (zh) 一种锂电池用可热交联聚合物电解质膜的制备方法
JP6145638B2 (ja) 二次電池用水溶性結着性組成物、二次電池電極用合剤、二次電池用電極、リチウムイオン二次電池
JP2012059648A (ja) 二次電池電極のバインダー用樹脂、およびこれを用いてなるバインダー液、二次電池電極、二次電池
WO2025086916A1 (fr) Liant et procédé de préparation s'y rapportant, batterie et dispositif électrique
CN116836324A (zh) 一种pvdf共聚物及其制备方法和在锂离子电池中应用
CN118765291A (zh) 含氟聚合物、底涂浆料、二次电池、及用电装置
JP2016072147A (ja) 電池用電極スラリー用組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16792718

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017517964

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16792718

Country of ref document: EP

Kind code of ref document: A1