WO2020012942A1 - Composition pour dispositifs de stockage d'électricité, suspension pour électrodes de dispositif de stockage d'électricité, électrode de dispositif de stockage d'électricité, et dispositif de stockage d'électricité - Google Patents

Composition pour dispositifs de stockage d'électricité, suspension pour électrodes de dispositif de stockage d'électricité, électrode de dispositif de stockage d'électricité, et dispositif de stockage d'électricité Download PDF

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WO2020012942A1
WO2020012942A1 PCT/JP2019/025000 JP2019025000W WO2020012942A1 WO 2020012942 A1 WO2020012942 A1 WO 2020012942A1 JP 2019025000 W JP2019025000 W JP 2019025000W WO 2020012942 A1 WO2020012942 A1 WO 2020012942A1
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Prior art keywords
storage device
polymer
electricity storage
mass
composition
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PCT/JP2019/025000
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English (en)
Japanese (ja)
Inventor
泰良 大橋
圭吾 麻生
大介 助口
悠太 浅井
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Jsr株式会社
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Priority claimed from JP2018130444A external-priority patent/JP7086760B2/ja
Priority claimed from JP2018130445A external-priority patent/JP7043998B2/ja
Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to KR1020217000412A priority Critical patent/KR20210028644A/ko
Priority to CN201980045795.9A priority patent/CN112385063B/zh
Publication of WO2020012942A1 publication Critical patent/WO2020012942A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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 includes a composition for a power storage device, a slurry for a power storage device electrode containing the composition and an active material, a power storage device electrode formed by applying and drying the slurry on a current collector, and the electrode. Storage device.
  • An electrode used in such an electricity storage device is manufactured by applying a composition (slurry for an electrode) containing an active material and a polymer that functions as a binder to the surface of a current collector and drying the composition.
  • the properties required for the polymer used as the binder include the capacity maintenance when charging and discharging are repeated (hereinafter, also referred to as “charge and discharge durability characteristics"), the binding capacity between active materials, and the current collection with active materials.
  • Fine powder of the active material, etc. from the applied and dried composition coating film hereinafter also referred to as "active material layer", depending on the ability to adhere to the body, the abrasion resistance in the step of winding the electrode, and subsequent cutting. But not falling off.
  • an active material using such a material having a large lithium storage capacity involves a large volume change due to insertion and extraction of lithium. For this reason, when a conventionally used electrode binder is applied to such a material having a large lithium storage capacity, it cannot withstand the volume change due to charge and discharge, and the structure of the active material layer is destroyed. The properties deteriorate significantly.
  • Patent Literatures 2 and 3 As a technique for synthesizing an electrode binder exhibiting good charge / discharge durability characteristics, a technique for controlling the surface acid amount of particulate binder particles (see Patent Literatures 2 and 3), or a technique having an epoxy group or a hydroxy group. Techniques for improving the above characteristics using a binder (see Patent Documents 4 and 5) have been proposed. In addition, a technique of restraining the active material with a rigid molecular structure of polyimide to suppress the volume change of the active material (see Patent Document 6) and a technique of using a water-soluble polymer such as polyacrylic acid (Patent Document 7) has also been proposed.
  • JP-A-2004-185810 International Publication No. 2011/096463 International Publication No. 2013/191080 JP 2010-205722 A JP 2010-3703 A JP 2011-204592 A WO 2015/099800
  • some embodiments according to the present invention provide a composition for a power storage device capable of producing a power storage device electrode having excellent flexibility, abrasion resistance, and powder falling resistance, and exhibiting good charge / discharge durability characteristics. Some embodiments according to the present invention also provide a slurry for an electrode of a power storage device containing the composition. Further, some aspects according to the present invention provide an electricity storage device electrode that is excellent in flexibility, abrasion resistance, and powder falling resistance, and that exhibits good charge / discharge durability characteristics. Further, some embodiments according to the present invention provide an electricity storage device having excellent charge / discharge durability characteristics.
  • the present invention has been made to solve at least a part of the problems described above, and can be realized as any of the following embodiments.
  • the composition for an electricity storage device A polymer (A) and a liquid medium (B),
  • the polymer (A) is: 20 to 70 parts by mass of a repeating unit (a1) derived from a conjugated diene compound, 10 to 50 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid, Containing
  • SEC size exclusion chromatography
  • the pH can be between 7 and 11.
  • the value of the ratio (V9 / V4) of the viscosity (V9 [mPa ⁇ s]) at pH 9 and the viscosity (V4 [mPa ⁇ s]) at pH 4 of the water (20% solid content concentration) of the polymer (A) is It can be 10 or more.
  • the viscosity of the polymer (A) at a pH of 9 with water having a solid content of 20% may be 200 to 100,000 mPa ⁇ s.
  • the polymer (A) comprises a repeating unit (a3) derived from an unsaturated carboxylic acid ester having a hydroxyl group or an ether group, a repeating unit (a4) derived from (meth) acrylamide, and an ⁇ , ⁇ -unsaturated nitrile compound And 10 to 70 parts by mass of at least one type of repeating unit selected from the group consisting of (a5).
  • composition for an electricity storage device When the polymer (A) is subjected to differential scanning calorimetry (DSC) in accordance with JIS K7121, an endothermic peak can be observed at 70 ° C. or lower.
  • DSC differential scanning calorimetry
  • the liquid medium (B) can be water.
  • composition for an electricity storage device electrode according to the present invention The composition for a power storage device according to any one of the above-described embodiments and an active material are included.
  • the slurry for the electricity storage device electrode can further contain at least one polymer selected from the group consisting of styrene-butadiene copolymer, acrylic polymer, and fluoropolymer.
  • Thickeners may be further included.
  • One embodiment of the electricity storage device electrode according to the present invention A current collector; and an active material layer formed by applying and drying the slurry for the power storage device electrode according to any one of the above aspects on the surface of the current collector.
  • One embodiment of the power storage device according to the present invention includes: The power storage device electrode of the above aspect is provided.
  • composition for an electric storage device it is possible to produce an electric storage device electrode which can improve flexibility, abrasion resistance and powder falling resistance, and exhibit good charge / discharge durability characteristics.
  • the composition for a power storage device according to the present invention exerts the above effects particularly when the power storage device electrode contains a material having a large lithium storage capacity as an active material, for example, a carbon material such as graphite or a silicon material. That is, since a material having a large lithium storage capacity can be used as an active material, battery performance is also improved.
  • (meth) acrylic acid ⁇ is a concept that includes both “acrylic acid ⁇ ” and “methacrylic acid ⁇ ”.
  • ⁇ (meth) acrylate is a concept that includes both “ ⁇ acrylate” and “ ⁇ methacrylate”.
  • (meth) acrylamide” is a concept that includes both “acrylamide” and “methacrylamide”.
  • a numerical range described using “to” means that the numerical values described before and after “to” are included as the lower limit and the upper limit.
  • composition for electricity storage device contains a polymer (A) and a liquid medium (B).
  • the composition for an electricity storage device according to the present embodiment is used as a material for producing an electricity storage device electrode (active material layer) having improved flexibility, abrasion resistance, and powder fall resistance, and also having excellent charge / discharge durability characteristics. It can also be used as a material for forming a protective film for suppressing a short circuit caused by dendrite generated during charge and discharge.
  • the composition for an electric storage device contains a polymer (A).
  • the polymer (A) is a repeating unit (a1) derived from a conjugated diene compound (hereinafter simply referred to as a “repeat unit (a1 ) ”) And 20 to 70 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid (hereinafter, also simply referred to as“ repeating unit (a2) ”).
  • the copolymer contains a copolymer fraction having a molecular weight of 1,000,000 or less in an amount of 30% by mass or more based on the whole copolymer.
  • the polymer (A) may contain a repeating unit derived from another monomer copolymerizable therewith, in addition to the repeating unit.
  • Examples of the other monomer include an unsaturated carboxylic acid ester having a hydroxyl group or an ether group, (meth) acrylamide, an ⁇ , ⁇ -unsaturated nitrile compound, and an unsaturated carboxylic acid ester (provided that the hydroxyl group or the ether group is Unsaturated carboxylic acid ester), a cationic monomer, an aromatic vinyl compound, a compound having a sulfonic acid group, and the like.
  • the polymer (A) contained in the composition for an electricity storage device may be in the form of a latex dispersed in a liquid medium (B) or may be in a state of being dissolved in the liquid medium (B). But may be in a state of being dissolved in the liquid medium (B) or in a state in which a part of the hydrophobic portion of the polymer (A) is associated and partially dissolved in the liquid medium (B). Is preferred.
  • the slurry for an electricity storage device electrode produced by mixing with the active material hereinafter, also simply referred to as “slurry”. Is preferred because the stability of the slurry becomes good and the applicability of the slurry to the current collector becomes good.
  • the content ratio of the repeating unit (a1) derived from the conjugated diene compound is 20 to 70 parts by mass when the total of the repeating units contained in the polymer (A) is 100 parts by mass.
  • the lower limit of the content of the repeating unit (a1) is preferably 25 parts by mass, and more preferably 30 parts by mass.
  • the upper limit for the content of the repeating unit (a1) is preferably 65 parts by mass, and more preferably 55 parts by mass.
  • the polymer (A) having high hydrophobicity is present in a state of being dissolved or partially dissolved in the liquid medium (B).
  • the adsorptivity to substances and fillers is improved, and a slurry having good dispersibility can be produced.
  • an electrode plate having excellent abrasion resistance and powder falling off property without exhibiting hard brittleness of the active material layer can be obtained.
  • An electricity storage device having durability characteristics can be obtained.
  • the conjugated diene compound is not particularly limited, but includes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, isoprene And the like, and one or more selected from these. Among these, 1,3-butadiene and isoprene are particularly preferred.
  • the content ratio of the repeating unit (a2) derived from the unsaturated carboxylic acid is from 10 to 50 parts by mass when the total of the repeating units contained in the polymer (A) is 100 parts by mass.
  • the lower limit of the content of the repeating unit (a2) is preferably 11 parts by mass, more preferably 13 parts by mass, and particularly preferably 15 parts by mass.
  • the upper limit of the content of the repeating unit (a2) is preferably 48 parts by mass, and more preferably 45 parts by mass.
  • a polymer (A) having a suitable glass transition temperature (Tg) is obtained, and the dispersibility of the active material and the filler is improved. Furthermore, the polymer exhibits good charge / discharge durability by improving affinity with a silicon material as an active material and resistance of the polymer (A) to an electrolytic solution and suppressing swelling of the silicon material.
  • unsaturated carboxylic acid examples include, but are not particularly limited to, mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and 2- (meth) acryloyloxyethyl succinic acid. And at least one selected from these.
  • mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and 2- (meth) acryloyloxyethyl succinic acid. And at least one selected from these.
  • the polymer (A) may contain a repeating unit (a3) derived from an unsaturated carboxylic acid ester having a hydroxyl group or an ether group.
  • a repeating unit (a3) derived from an unsaturated carboxylic acid ester having a hydroxyl group or an ether group.
  • the content ratio of the repeating unit (a3) when the total of the repeating units contained in the polymer (A) is 100 parts by mass, the lower limit is preferably 5 parts by mass, and more preferably 7 parts by mass. And more preferably 10 parts by mass.
  • the upper limit is preferably 60 parts by mass, more preferably 50 parts by mass, and particularly preferably 45 parts by mass.
  • the glass transition temperature (Tg) of the polymer (A) is suitable, and a flexible electrode plate can be manufactured.
  • the charge and discharge durability characteristics of the power storage device are improved. Further, the affinity between the polymer (A) and the active material or the filler becomes good, and a slurry having a good dispersibility of the active material or the filler can be obtained.
  • Examples of the unsaturated carboxylic acid ester having a hydroxyl group include, but are not particularly limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Examples include acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, glycerin mono (meth) acrylate, and glycerin di (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate and glycerin monomethacrylate are preferred. These monomers can be used alone or in combination of two or more.
  • Examples of the unsaturated carboxylic acid ester having an ether group include, but are not particularly limited to, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and glycidyl (meth) acrylate. , Tetrahydrofurfuryl (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. No.
  • 2-ethoxyethyl (meth) acrylate polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate are preferred. These monomers can be used alone or in combination of two or more.
  • the polymer (A) may contain a repeating unit (a4) derived from (meth) acrylamide.
  • the lower limit of the content of the repeating unit (a4) is preferably 5 parts by mass, and more preferably 7 parts by mass, when the total of the repeating units contained in the polymer (A) is 100 parts by mass. And more preferably 10 parts by mass.
  • the upper limit is preferably 40 parts by mass, more preferably 30 parts by mass, and particularly preferably 20 parts by mass.
  • the (meth) acrylamide is not particularly limited, but is acrylamide, methacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacryl Amide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, N-methylol methacrylamide, N-methylol acrylamide, diacetone acrylamide, maleic amide, acrylamide tert-butyl sulfonic acid and the like. .
  • These (meth) acrylamides may be used alone or in combination of two or more.
  • the polymer (A) may contain a repeating unit (a5) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
  • the lower limit is preferably 5 parts by mass, and more preferably 7 parts by mass. And more preferably 10 parts by mass.
  • the upper limit is preferably 60 parts by mass, more preferably 50 parts by mass, and particularly preferably 40 parts by mass.
  • Tg glass transition temperature
  • the ⁇ , ⁇ -unsaturated nitrile compound is not particularly limited, but includes acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, etc., and at least one selected from these. Can be. Among these, one or more selected from acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable.
  • the polymer (A) may contain 10 to 70 parts by mass of at least one kind of repeating unit selected from the group consisting of the repeating unit (a3), the repeating unit (a4), and the repeating unit (a5). preferable.
  • the lower limit is preferably 15 parts by mass, and more preferably 20 parts by mass.
  • the upper limit is preferably 69 parts by mass, more preferably 60 parts by mass, even more preferably 50 parts by mass, and particularly preferably 45 parts by mass.
  • the polymer (A) may contain a repeating unit derived from another monomer copolymerizable therewith, in addition to the repeating units (a1) to (a5).
  • a repeating unit (a6) derived from an unsaturated carboxylic acid ester (however, excluding the unsaturated carboxylic acid ester having a hydroxyl group or an ether group) (hereinafter, simply referred to as a “repeating unit (a6) ),
  • a8 sulfonic acid group
  • the unsaturated carboxylic acid ester is not particularly limited, but (meth) acrylic acid ester is preferable.
  • Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, and n- (meth) acrylate.
  • methyl (meth) acrylate ethyl (meth) acrylate, butyl (meth) acrylate and cyclohexyl (meth) acrylate, and methyl (meth) acrylate Is particularly preferred.
  • aromatic vinyl compound examples include, but are not particularly limited to, styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like. It can be more than a species. Of these, styrene is particularly preferred.
  • the compound having a sulfonic acid group include, but are not particularly limited to, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfobutyl (meth) acrylate, Compounds having a sulfonic acid group such as acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamidopropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and alkali salts thereof may be used. .
  • the cationic monomer is not particularly limited, but is at least one monomer selected from the group consisting of a secondary amine (salt), a tertiary amine (salt), and a quaternary ammonium salt. Is preferred. Specific examples of these cationic monomers include, but are not particularly limited to, 2- (dimethylamino) ethyl (meth) acrylate, quaternary salt of dimethylaminoethyl (meth) acrylate methyl chloride, 2- (meth) acrylate (Diethylamino) ethyl, 3- (dimethylamino) propyl (meth) acrylate, 3- (diethylamino) propyl (meth) acrylate, 4- (dimethylamino) phenyl (meth) acrylate, 2- (meth) acrylate [(3,5-dimethylpyrazolyl) carbonylamino] ethyl, 2- (0- [1'-methyl
  • the polymer (A) preferably has only one endothermic peak in a temperature range of 70 ° C. or lower when measured by differential scanning calorimetry (DSC) in accordance with JIS K7121.
  • the temperature of the endothermic peak (that is, the glass transition temperature (Tg)) is more preferably in the range of 60 ° C. or lower, and particularly preferably in the range of 50 ° C. or lower.
  • the polymer (A) has better flexibility and adhesion to the active material layer. It is preferable because it can impart properties.
  • the polymer (A) was calculated from an integrated molecular weight distribution curve obtained by plotting the cumulative weight fraction against the molecular weight, as measured by size exclusion chromatography (SEC) according to JIS K7252.
  • the copolymer fraction having a molecular weight of 10,000 or less is contained in the copolymer in an amount of 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more.
  • the conjugated diene component having high hydrophobicity can be present in the form of an aqueous solution when the pH is adjusted to 7 to 11, and the adsorption to the active material or the filler can be achieved.
  • the dispersibility is improved, a slurry having good dispersibility can be produced.
  • the conjugated diene component having flexibility can cover the active material, an electrode plate having excellent abrasion resistance and powder falling resistance can be provided without the active material layer showing hard brittleness.
  • the method for producing the polymer (A) is not particularly limited, but includes a known emulsifier (surfactant), a polymerization initiator, a molecular weight modifier in a solvent containing water as a main component, An emulsion polymerization method performed in the presence of a chain transfer agent or the like can be used.
  • the emulsion polymerization method for synthesizing the polymer (A) may be performed in a single-stage polymerization, a two-stage polymerization, or a multi-stage polymerization.
  • these known emulsifiers (surfactants), polymerization initiators, molecular weight regulators, chain transfer agents, and the like, and synthesis methods compounds described in Japanese Patent No. 5477610 can be used.
  • the polymerization temperature during the synthesis of the polymer (A) is not particularly limited, but it is preferable to synthesize the polymer (A) in the range of 30 to 95 ° C. in consideration of the production time and the conversion (reaction rate) of the monomer to the copolymer. , 40 to 85 ° C. is more preferable.
  • a pH adjuster or EDTA as a metal ion sealing agent or a salt thereof may be used for the purpose of improving production stability.
  • the pH Before or after the polymerization, the pH may be adjusted with a general neutralizing agent such as ammonia, an organic amine, potassium hydroxide, sodium hydroxide, and lithium hydroxide. In this case, the pH is adjusted to 6 or less. It is preferable to adjust within the range. It is also possible to use EDTA or a salt thereof as a metal ion sealing agent.
  • a general neutralizing agent such as ammonia, an organic amine, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
  • the pH is adjusted to 6 or less. It is preferable to adjust within the range. It is also possible to use EDTA or a salt thereof as a metal ion sealing agent.
  • the pH to 7 to 11 After the completion of the above polymerization, it is preferable to adjust the pH to 7 to 11 by adding a neutralizing agent to the obtained polymerization mixture.
  • the neutralizing agent used here is not particularly limited, and examples thereof include metal hydroxides such as sodium hydroxide and potassium hydroxide; and ammonia.
  • the polymer (A) By setting the pH in the above range, the polymer (A) can be dissolved or partially dissolved in the liquid medium (B). By concentrating the polymerization mixture after the neutralization treatment, it is possible to increase the solid content while maintaining good stability of the polymer (A).
  • the composition for an electric storage device according to the present embodiment contains a liquid medium (B).
  • the liquid medium (B) is preferably an aqueous medium containing water, and more preferably water.
  • the aqueous medium may contain a non-aqueous medium other than water. Examples of the non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, and sulfone compounds. One or more selected from these are used. Can be.
  • the use of the aqueous medium as the liquid medium (B) in the composition for an electricity storage device according to the present embodiment reduces the degree of adverse effects on the environment and increases the safety for operators.
  • the content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably not substantially contained, in 100 parts by mass of the aqueous medium. preferable.
  • substantially not contained means that a non-aqueous medium is not intentionally added as a liquid medium, and a non-aqueous medium which is inevitably mixed when preparing a composition for an electricity storage device. May be included.
  • composition for an electricity storage device according to the present embodiment can contain additives other than the above-described components as necessary.
  • additives include polymers other than the polymer (A), preservatives, thickeners, and the like.
  • the composition for an electricity storage device may contain a polymer other than the polymer (A).
  • a polymer other than the polymer (A) examples include, but are not particularly limited to, SBR (styrene butadiene rubber) polymer, acrylic polymer containing unsaturated carboxylic acid ester or a derivative thereof as a constituent unit, PVDF (polyvinylidene fluoride), and the like. Fluorinated polymers and the like can be mentioned. These polymers may be used alone or in combination of two or more. By containing a polymer other than the polymer (A), flexibility and adhesion may be further improved.
  • the content ratio of the polymer (A) in the composition for an electricity storage device according to the present embodiment is determined based on a total of 100 parts by mass of the polymer (A), the polymer other than the polymer (A), and the thickener.
  • the amount is preferably from 10 to 80 parts by mass, more preferably from 15 to 65 parts by mass, and particularly preferably from 20 to 50 parts by mass.
  • the composition for an electricity storage device according to the present embodiment may contain a preservative.
  • a preservative When the composition for an electricity storage device is stored by containing a preservative, it may be possible to suppress the growth of bacteria and fungi and the generation of foreign substances when the composition for an electricity storage device is stored.
  • preservatives include compounds described in Japanese Patent No. 5477610.
  • the composition for an electricity storage device according to the present embodiment may contain a thickener.
  • a thickener By containing a thickener, the applicability and the charge / discharge characteristics of the obtained electricity storage device may be further improved in some cases.
  • the thickener include cellulose compounds such as carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose; poly (meth) acrylic acid; an ammonium salt or an alkali metal salt of the cellulose compound or the poly (meth) acrylic acid; Polyvinyl alcohol-based (co) polymers such as alcohols, modified polyvinyl alcohols and ethylene-vinyl alcohol copolymers; copolymers of vinyl esters with unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid Water-soluble polymers such as saponified products can be mentioned. Among these, alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid and the like are preferable.
  • Examples of commercial products of these thickeners include alkali metal salts of carboxymethyl cellulose such as CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (all manufactured by Daicel Corporation).
  • the content ratio of the thickener is 5 parts by mass or less based on 100 parts by mass of the total solid content of the composition for an electricity storage device. And more preferably 0.1 to 3 parts by mass.
  • composition for power storage device 1.4.1. pH
  • the pH of the composition for an electricity storage device according to the present embodiment is preferably from 7 to 11, more preferably from 8 to 10, and particularly preferably from 8.5 to 9.5.
  • the viscosity of the composition for an electric storage device can be increased by dissolving or partially dissolving the polymer (A) in the liquid medium (B).
  • problems such as insufficient leveling property and liquid dripping can be suppressed, and it becomes easy to manufacture an electrode plate having both good electrical characteristics and good adhesion.
  • ⁇ " PH in this specification refers to physical properties measured as follows. This is a value measured at 25 ° C. using a pH meter using a glass electrode calibrated with a neutral phosphate standard solution and a borate standard solution as the pH standard solution in accordance with JIS Z8802: 2011. Examples of such a pH meter include “HM-7J” manufactured by Toa DK Corporation and “D-51” manufactured by Horiba, Ltd.
  • the pH of the composition for an electric storage device is not affected by the monomer composition of the polymer (A), but is not determined only by the monomer composition. That is, it is generally known that the pH of the composition for an electric storage device changes depending on polymerization conditions and the like even with the same monomer composition, and the examples in the specification of the present application show only one example. Absent.
  • the viscosity of the polymer (A) at a pH of 9 with 20% solid content water is preferably 200 to 100,000 mPa ⁇ s, more preferably 220 to 95,000 mPa ⁇ s, and 250 to 90,000 mPa ⁇ s. 000 mPa ⁇ s is particularly preferable. It is preferable that the viscosity at pH 9 is equal to or higher than the lower limit, because the dispersibility of the active material and the filler becomes good and a uniform slurry can be prepared. It is preferable that the viscosity at pH 9 is equal to or less than the upper limit value, because the coating property of the slurry becomes good.
  • the viscosity of water having a solid content of 20% of the polymer (A) is a value measured at a temperature of 25.0 ° C. using a B-type viscometer in accordance with JIS Z 8803.
  • a B-type viscometer for example, "RB-80L” or “TVB-10” manufactured by Toki Sangyo Co., Ltd. can be used.
  • the value of the ratio (V9 / V4) of the viscosity (V9 [mPa ⁇ s]) at pH 9 and the viscosity (V4 [mPa ⁇ s]) at pH4 of water having a solid content concentration of 20% of the polymer (A) is: It is preferably 10 or more, more preferably 20 or more, and particularly preferably 50 or more.
  • the viscosity ratio (V9 / V4) is equal to or more than the above value, the dispersibility of the active material and the filler becomes good, and it is easy to form a uniform active material layer and a protective film.
  • the slurry for an electricity storage device according to the present embodiment contains the composition for an electricity storage device described above.
  • the composition for an electricity storage device according to the present embodiment can also be used as a material for forming a protective film for suppressing a short circuit caused by dendrite generated due to charge and discharge, It can also be used as a material for producing an electricity storage device electrode (active material layer) with improved flexibility, abrasion resistance and powder falling resistance.
  • a slurry for an electricity storage device for forming a protective film (hereinafter, also referred to as a “slurry for forming a protection film”) and a slurry for an electricity storage device for forming an active material layer of an electrode for an electricity storage device (hereinafter, referred to as “storing electricity”) Also referred to as “device electrode slurry”).
  • slurry for forming a protective film refers to coating the slurry on the surface of the electrode or the separator or both and then drying it to form a protective film on the surface of the electrode or the separator or both. Refers to a dispersion used for forming.
  • the slurry for forming a protective film according to the present embodiment may be composed only of the above-described composition for a power storage device, or may further contain an inorganic filler.
  • each component contained in the protective film forming slurry according to the present embodiment will be described in detail. Note that the composition for a power storage device is as described above, and a description thereof will be omitted.
  • the protective film forming slurry according to the present embodiment can improve the toughness of the formed protective film by containing the inorganic filler.
  • the inorganic filler it is preferable to use at least one kind of particles selected from the group consisting of silica, titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), and magnesium oxide (magnesia).
  • titanium oxide and aluminum oxide are preferable from the viewpoint of further improving the toughness of the protective film.
  • rutile-type titanium oxide is more preferable.
  • the average particle size of the inorganic filler is preferably 1 ⁇ m or less, more preferably in the range of 0.1 to 0.8 ⁇ m.
  • the average particle size of the inorganic filler is preferably larger than the average pore size of the separator that is a porous membrane. Thereby, damage to the separator can be reduced, and it is possible to prevent the inorganic filler from clogging the micropores of the separator.
  • the slurry for forming a protective film according to the present embodiment preferably contains 0.1 to 20 parts by mass of the above-mentioned composition for an electric storage device in terms of solid content based on 100 parts by mass of the inorganic filler. More preferably, it is contained in an amount of up to 10 parts by mass.
  • the content ratio of the composition for a power storage device is in the above range, the balance between the toughness of the formed protective film and the permeability of lithium ions is improved, and as a result, the resistance increase rate of the obtained power storage device is lower. can do.
  • the material described in “1.2. Liquid Medium (B)” of the above-described composition for an electric storage device can be used as needed in the slurry for forming a protective film according to the present embodiment.
  • the amount of the liquid medium to be added can be adjusted as necessary so as to obtain the optimum viscosity of the slurry according to the coating method or the like.
  • the “slurry for power storage device electrode” in this specification is used to form an active material layer on the surface of the current collector by applying it to the surface of the current collector and then drying it. Refers to the resulting dispersion.
  • the slurry for an electricity storage device electrode according to the present embodiment contains the above-described composition for an electricity storage device and an active material.
  • the components contained in the slurry for an electric storage device electrode according to the present embodiment will be described. Note that the composition for a power storage device is as described above, and a description thereof will be omitted.
  • active material used in the slurry for an electricity storage device electrode according to the present embodiment include a carbon material, a silicon material, an oxide containing a lithium atom, a lead compound, a tin compound, an arsenic compound, an antimony compound, and an aluminum compound. Is mentioned. Specific examples of these include compounds described in Japanese Patent No. 5999399.
  • the active material layer may contain an active material exemplified below.
  • a conductive polymer such as polyacene; A X B Y O Z (where A is an alkali metal or a transition metal, B is at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese; Represents an oxygen atom, and X, Y and Z are numbers in the range of 1.10>X> 0.05, 4.00>Y> 0.85, 5.00>Z> 1.5.) And other metal oxides and the like.
  • the slurry for an electricity storage device electrode according to the present embodiment can be used when producing any of the electricity storage device electrodes of the positive electrode and the negative electrode.
  • Lithium iron phosphate has a fine primary particle size, and is known to be a secondary aggregate thereof. When charge and discharge are repeated, aggregation collapses in the active material layer and dissociation between the active materials occurs. This is considered to be one of the factors that peel off from the current collector and that the conductive network inside the active material layer is easily broken.
  • the power storage device electrode manufactured using the slurry for a power storage device electrode according to the present embodiment does not have the above-described problem even when lithium iron phosphate is used, and exhibits good electrical characteristics. be able to.
  • the reason is that the polymer (A) can firmly bind lithium iron phosphate, and at the same time, can maintain the state in which lithium iron phosphate is firmly bound during charge and discharge. It is thought to be from.
  • the active material when producing a negative electrode, it is preferable that the active material contains a silicon material among the active materials exemplified above. Since the silicon material has a large lithium storage capacity per unit weight as compared with other active materials, by containing the silicon material as the negative electrode active material, the storage capacity of the obtained power storage device can be increased, As a result, the output and energy density of the power storage device can be increased.
  • the negative electrode active material is a mixture of a silicon material and a carbon material. Since the change in volume of a carbon material due to charge and discharge is small, by using a mixture of a silicon material and a carbon material as a negative electrode active material, the effect of the volume change of the silicon material can be reduced, and the active material layer and the active material layer can be collected. The ability to adhere to the electric body can be further improved.
  • silicon (Si) When silicon (Si) is used as an active material, while silicon has a high capacity, a large volume change occurs when occluding lithium. For this reason, the silicon material has the property that it is pulverized, peeled from the current collector, or separated from the active materials due to repeated expansion and contraction, and the conductive network inside the active material layer is easily broken. As a result, the cycle characteristics are extremely deteriorated in a short time.
  • the electricity storage device electrode manufactured using the electricity storage device electrode slurry according to the present embodiment even when a silicon material is used, the above-described problem does not occur, and good electrical characteristics can be exhibited. it can.
  • the reason for this is that the polymer (A) can firmly bind the silicon material, and at the same time, the polymer (A) expands and contracts even if the silicon material expands in volume due to occlusion of lithium. This is considered to be because the state in which the material was firmly bound can be maintained.
  • the content ratio of the silicon material in 100% by mass of the active material is preferably 1% by mass or more, more preferably 1 to 50% by mass, still more preferably 5 to 45% by mass. It is particularly preferred that the content be set to 4040% by mass.
  • the content ratio of the silicon material in 100% by mass of the active material is within the above range, a power storage device having an excellent balance between improvement in output and energy density of the power storage device and charge / discharge durability characteristics can be obtained.
  • the active material preferably has a granular shape.
  • the average particle size of the active material is preferably from 0.1 to 100 ⁇ m, more preferably from 1 to 20 ⁇ m.
  • the average particle size of the active material is a volume average particle size calculated from the particle size distribution measured by a particle size distribution measuring device using a laser diffraction method as a measurement principle. Examples of such a laser diffraction type particle size distribution measuring apparatus include HORIBA @ LA-300 series and HORIBA @ LA-920 series (all manufactured by Horiba, Ltd.).
  • the liquid medium that can be additionally added to the slurry for an electricity storage device electrode according to the present embodiment may be the same as or different from the liquid medium (B) contained in the composition for an electricity storage device, It is preferable to use by selecting from the liquid media exemplified in “1.2. Liquid Medium (B)” above.
  • the usage ratio of the liquid medium (including the amount brought in from the power storage device composition) in the slurry for the power storage device electrode according to the present embodiment is determined by the solid content concentration in the slurry (total mass of components other than the liquid medium in the slurry). Is the ratio to the total mass of the slurry. The same applies hereinafter.) Is preferably 30 to 70% by mass, more preferably 40 to 60% by mass.
  • the slurry for a power storage device electrode according to the present embodiment can contain a pH adjuster or a corrosion inhibitor for the purpose of suppressing corrosion of the current collector according to the type of the active material.
  • pH adjusting agent examples include, for example, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium formate, ammonium chloride, sodium hydroxide, potassium hydroxide and the like. Sulfuric acid, ammonium sulfate, sodium hydroxide and potassium hydroxide are preferred. Further, it can be used by selecting from the compounds described in the method for producing the polymer (A).
  • ammonium metavanadate, sodium metavanadate, potassium metavanadate, ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium paratungstate, sodium paratungstate, potassium paratungstate, molybdate examples thereof include ammonium, sodium molybdate, and potassium molybdate. Among these, ammonium paratungstate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, and ammonium molybdate are preferable.
  • the slurry for power storage device electrode according to the present embodiment is manufactured by any method as long as it contains the above-described composition for power storage device and an active material. Alternatively, it can be manufactured by a method described in, for example, Japanese Patent No. 5999399.
  • the power storage device electrode according to the present embodiment includes a current collector, and an active material layer formed by applying and drying the above-described slurry for a power storage device electrode on the surface of the current collector. It is.
  • Such a power storage device electrode is formed by applying the above-mentioned slurry for a power storage device electrode to a surface of a current collector such as a metal foil to form a coating film, and then drying the coating film to form an active material layer.
  • the electricity storage device electrode manufactured as described above is obtained by binding the above-mentioned polymer (A), the active material, and an active material layer containing an optional component added as necessary to a current collector. As a result, it has excellent flexibility, abrasion resistance and powder falling resistance, and exhibits good charge / discharge durability.
  • the current collector is not particularly limited as long as it is made of a conductive material, and examples thereof include a current collector described in Japanese Patent No. 5999399.
  • the electricity storage device electrode manufactured in this manner is excellent in flexibility, abrasion resistance, and powder falling resistance, and exhibits good charge / discharge durability characteristics.
  • the content ratio of the silicon element in 100 parts by mass of the active material layer is preferably 2 to 30 parts by mass, and preferably 2 to 20 parts by mass. More preferably, it is particularly preferably 3 to 10 parts by mass.
  • the content of the silicon element in the active material layer is within the above range, the power storage capacity of a power storage device manufactured using the same is improved, and an active material layer with a uniform distribution of the silicon element is obtained. .
  • the content of the silicon element in the active material layer can be measured, for example, by a method described in Japanese Patent No. 5999399.
  • the power storage device includes the above-described power storage device electrode, further contains an electrolytic solution, and can be manufactured using a component such as a separator according to a conventional method.
  • a component such as a separator according to a conventional method.
  • a specific manufacturing method for example, a negative electrode and a positive electrode are overlapped with a separator interposed therebetween, and this is wound in accordance with the shape of the battery, folded, stored in a battery container, and an electrolytic solution is injected into the battery container. And sealing.
  • the shape of the battery can be an appropriate shape such as a coin type, a cylindrical type, a square type, a laminate type, and the like.
  • the electrolyte may be liquid or gel, and may be selected from known electrolytes used for power storage devices that effectively exhibit the function as a battery, depending on the type of active material.
  • the electrolytic solution can be a solution in which the electrolyte is dissolved in a suitable solvent.
  • these electrolytes and solvents for example, compounds described in Japanese Patent No. 5999399 are exemplified.
  • composition for power storage device (1) Preparation of composition for power storage device In a temperature-controllable autoclave equipped with a stirrer, 300 parts by mass of water, 0.5 part by mass of sodium dodecylbenzenesulfonate, potassium persulfate 0.5 parts by mass, 0.3 parts by mass of ⁇ -methylstyrene dimer, 1.8 parts by mass of dodecyl mercaptan, and 70 parts by mass of 1,3-butadiene, which is a polymerizable monomer component shown in Table 1, and methacrylic acid 30 parts by mass of an acid were sequentially charged, and a polymerization reaction was carried out at 50 ° C.
  • reaction mixture containing a latex polymer (A1).
  • reaction mixture was cooled and divided into two, and one was adjusted to pH 4.0 and the other was adjusted to pH 9.0 using a 2% by mass aqueous sodium hydroxide solution.
  • the residual monomer was removed by steam distillation, and concentrated under reduced pressure, whereby the composition for an electricity storage device containing 20% by mass of the polymer (A1) and having a pH of 4.0 and the polymer (A1) were 20% by mass. % Of the composition for an electricity storage device having a pH of 9.0.
  • the pH was adjusted by dropping a 2% by mass aqueous solution of sodium hydroxide while measuring the pH at 25 ° C. using a pH meter (manufactured by Horiba, Ltd.).
  • This graphite-coated silicon oxide is a conductive powder (active material) in which the surface of the silicon oxide is coated with graphite, the average particle diameter is 10.5 ⁇ m, and the obtained graphite-coated silicon oxide is 100% in total.
  • the ratio of the graphite coating in the case of mass% was 2 mass%.
  • the negative electrode active material was used for an electricity storage device electrode containing no Si.
  • a slurry (C) was prepared.
  • PVDF Polymer # 1120
  • conductive aid trade name "DENKA BLACK 50% pressed product” manufactured by Denka Corporation
  • 100 parts by mass of LiCoO 2 manufactured by Hayashi Kasei Co., Ltd.
  • NMP N-methylpyrrolidone
  • the slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 5 minutes and further under reduced pressure (about 2.5 ⁇ 10 4 Pa) at 1,800 rpm for 1.5 minutes.
  • This positive electrode slurry was uniformly applied to the surface of the current collector made of aluminum foil by a doctor blade method so that the film thickness after solvent removal was 80 ⁇ m, and heated at 120 ° C. for 20 minutes to remove the solvent. .
  • a counter electrode positive electrode was obtained by pressing with a roll press machine so that the density of the active material layer was 3.0 g / cm 3 .
  • a lithium ion battery cell (power storage device) was assembled by mounting a positive electrode manufactured by punching out to a diameter of 16.16 mm, and closing the external body of the two-pole type coin cell with screws and sealing.
  • “1C” indicates a current value at which a cell having a certain electric capacity is discharged at a constant current and discharge is completed in one hour.
  • “0.1 C” refers to a current value at which discharge is completed in 10 hours
  • “10 C” refers to a current value at which discharge is completed in 0.1 hours.
  • composition for power storage device (1) Preparation of composition for power storage device”, the type and amount of each monomer are described in Tables 1 to 3 below, respectively. A composition for an electricity storage device containing 20% by mass of a polymer component was obtained in the same manner as in Example 1 except that the conditions were as described above.
  • the amount of the thickener and the amount of SBR were respectively as described in Tables 1 to 3 below, and the same as in Example 1 described above. Electrode slurries were prepared, and an electricity storage device electrode and an electricity storage device were prepared, respectively, and evaluated in the same manner as in Example 1 above.
  • composition for power storage device (1) Preparation of composition for power storage device”, except that the type and amount of each monomer were as described in Table 1 below. Similarly, a composition for an electricity storage device containing 20% by mass of the polymer (A4) was obtained. Then, 0.5 parts by mass of the polymer (A4) was added to a biaxial planetary mixer (trade name “TK Hibismix 2P-03”, manufactured by Primix Co., Ltd.) (solid content, pH 9 obtained above).
  • TK Hibismix 2P-03 manufactured by Primix Co., Ltd.
  • Parts (in terms of solid content), 10 parts by mass (in terms of solid content) of the above-obtained graphite-coated silicon oxide powder, and 103 parts by mass of water were added, and the mixture was stirred at 60 rpm for 1 hour. Then, using a stirring deaerator (manufactured by Shinky Co., Ltd., trade name "Awatori Neritarou”), the mixture was stirred and mixed at 200 rpm for 2 minutes and at 1800 rpm for 1.5 minutes, thereby converting Si into the negative electrode active material.
  • a slurry for an electric storage device electrode (C / Si (10%)) containing 10% by mass was prepared.
  • the negative electrode active material was used for an electricity storage device electrode containing no Si.
  • a slurry (C) was prepared.
  • An electricity storage device electrode and an electricity storage device were prepared in the same manner as in Example 1 except that the slurry for an electricity storage device electrode prepared above was used, and evaluated in the same manner as in Example 1.
  • composition for power storage device (1) Preparation of composition for power storage device”, the type and amount of each monomer are described in Tables 1 to 3 below, respectively. A composition for an electricity storage device containing 20% by mass of a polymer component was obtained in the same manner as in Example 1 except that the conditions were as described above.
  • the amounts of the thickener and the aqueous binder were as shown in Tables 1 to 3 below, respectively, in the same manner as in Example 4 above. Electrode slurries were prepared, and an electricity storage device electrode and an electricity storage device were prepared, respectively, and evaluated in the same manner as in Example 1 above.
  • the slurry for an electrode of an electricity storage device prepared using the composition for an electricity storage device according to the present invention shown in Examples 1 to 20 is the same as that of Comparative Examples 1 to 8. It was found that the flexibility of the electrode plate was superior to that of Comparative Example. The flexibility of the electrode plate tends to depend on the flexibility of the polymer as the binder component and the state of covering of the active material with the polymer.
  • the composition for an electric storage device shown in Examples 1 to 20 contains the polymer (A) of the alkali thickening type, and the polymer (A) is dissolved or partially dissolved in the liquid medium (B) in the alkali region. Dissolve. Thereby, it is considered that the flexible polymer (A) containing the diene component can cover the active material in a mesh-like manner, thereby exhibiting high flexibility of the electrode plate.
  • compositions for power storage devices of Comparative Examples 1 and 3 to 6 have high flexibility of the polymer, but can only bond the active materials to each other because of the particle shape, which is inferior to the flexibility of the electrode plate. Will have a limited contribution.
  • the composition for an electricity storage device of Comparative Example 2 is very excellent in that the binder is water-soluble and covers the active material in a mesh-like manner, but the binder is too hard and the flexibility of the electrode plate is low. It is thought that it has been.
  • the compositions for electricity storage devices of Comparative Examples 7 and 8 each contained an alkali-thickening polymer containing no diene component, and n-butyl acrylate was added as a highly flexible component instead of the diene component. However, the effect as in the example was not exhibited. Although the detailed principle is unknown, it is assumed that the diene component plays a very important role.
  • the composition for an electricity storage device of Examples 1 to 20 can provide an electrode plate having better charge / discharge durability characteristics as compared with the compositions of the electricity storage device of Comparative Examples 1 to 8. .
  • charge / discharge durability characteristics adhesion between active materials and adhesion between an active material layer and a current collector are important.
  • the alkali-thickening type binders shown in Examples 1 to 20 have adhesiveness due to the volume change of the active material due to charge / discharge due to the network-like coverage of the active material with the polymer (A) and the rubber elasticity of the diene component. Is not impaired, it is considered that good charge / discharge durability was exhibited.
  • compositions for electricity storage devices of Comparative Examples 1 and 3 to 6 contain a diene component as a binder, but can only bond the active materials to each other because of the particle shape. It is considered that the film was peeled off and the capacity could not be maintained.
  • the composition for an electricity storage device of Comparative Example 2 contains a binder that does not exhibit rubber elasticity, but exhibits a high elastic modulus without breaking in a minute deformation region such as expansion and contraction of an active material, and thus has a relatively good capacity. It is considered that the maintenance rate was shown.
  • composition for an electricity storage device of Comparative Examples 7 and 8 contains a binder that swells very easily in the electrolytic solution, it hardly contributes to the maintenance of the structure of the active material layer, and easily peels off from the active material and the electrode. Therefore, it is considered that the adhesion could not be maintained. Further, it is considered that the capacity retention rate was significantly deteriorated because the components eluted in the electrolytic solution caused an increase in resistance and promoted the deterioration of the active material.
  • the electrode has good flexibility, but has poor charge / discharge durability (particularly remarkable when an Si-based active material is used).
  • binders that can achieve both characteristics at a high level, and there is no binder that can be manufactured at low cost industrially.
  • the alkali-thickened butadiene copolymer described in Examples of the present application can achieve both electrode flexibility and charge / discharge durability characteristics, and uses the same SBR production equipment as the process until alkali thickening. Therefore, it can be manufactured relatively inexpensively.
  • the present invention is not limited to the above embodiment, and various modifications are possible.
  • the present invention includes a configuration substantially the same as the configuration described in the embodiment (for example, a configuration having the same function, method, and result, or a configuration having the same object and effect).
  • the invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
  • the invention also includes a configuration having the same function and effect as the configuration described in the above embodiment, or a configuration capable of achieving the same object.
  • the invention also includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

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Abstract

La présente invention concerne une composition pour dispositifs de stockage d'électricité, qui est excellente en termes de flexibilité, de résistance au frottement et de chute de particules, et qui permet de produire une électrode de dispositif de stockage d'électricité qui présente de bonnes caractéristiques de durabilité de charge et de décharge. Une composition pour dispositifs de stockage d'électricité selon la présente invention contient un polymère (A) et un milieu liquide (B) ; et le polymère (A) contient de 20 à 70 parties en masse d'une unité de répétition (a1) qui est dérivée d'un composé diène conjugué et de 10 à 50 parties en masse d'une unité de répétition (a2) qui est dérivée d'un acide carboxylique insaturé si le total des unités de répétition contenues dans le polymère (A) est pris comme 100 parties en masse. Par rapport à la courbe de distribution de poids moléculaire intégrale du polymère (A) telle qu'elle est déterminée par chromatographie d'exclusion stérique (SEC) conformément à la norme JIS K7252, une fraction de copolymère ayant un poids moléculaire inférieur ou égal à 1 000 000 est contenue dans une quantité supérieure ou égale à 30 % en masse par rapport à tous les copolymères.
PCT/JP2019/025000 2018-07-10 2019-06-24 Composition pour dispositifs de stockage d'électricité, suspension pour électrodes de dispositif de stockage d'électricité, électrode de dispositif de stockage d'électricité, et dispositif de stockage d'électricité WO2020012942A1 (fr)

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KR1020217000412A KR20210028644A (ko) 2018-07-10 2019-06-24 축전 디바이스용 조성물, 축전 디바이스 전극용 슬러리, 축전 디바이스 전극 및 축전 디바이스
CN201980045795.9A CN112385063B (zh) 2018-07-10 2019-06-24 蓄电设备用组合物、蓄电设备电极用浆料、蓄电设备电极和蓄电设备

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JP2018130444A JP7086760B2 (ja) 2018-07-10 2018-07-10 蓄電デバイス用組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極及び蓄電デバイス
JP2018-130445 2018-07-10
JP2018130445A JP7043998B2 (ja) 2018-07-10 2018-07-10 蓄電デバイス用組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極及び蓄電デバイス
JP2018-130444 2018-07-10

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CN116200150B (zh) * 2023-03-09 2024-05-14 深圳好电科技有限公司 一种锂离子电池正极粘结剂及其制备方法和应用

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