WO2022039002A1 - 蓄電デバイス用バインダー組成物、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 - Google Patents

蓄電デバイス用バインダー組成物、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 Download PDF

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WO2022039002A1
WO2022039002A1 PCT/JP2021/028324 JP2021028324W WO2022039002A1 WO 2022039002 A1 WO2022039002 A1 WO 2022039002A1 JP 2021028324 W JP2021028324 W JP 2021028324W WO 2022039002 A1 WO2022039002 A1 WO 2022039002A1
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Prior art keywords
storage device
power storage
polymer
mass
repeating unit
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PCT/JP2021/028324
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English (en)
French (fr)
Japanese (ja)
Inventor
卓哉 中山
香奈 増田
定叡 平口
穎成 林
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JSR Corp
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JSR Corp
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Priority to JP2022543347A priority Critical patent/JP7682900B2/ja
Priority to KR1020237008970A priority patent/KR20230054404A/ko
Priority to CN202180050876.5A priority patent/CN116075952A/zh
Priority to EP21858150.2A priority patent/EP4203108A4/en
Priority to US18/042,119 priority patent/US12612515B2/en
Publication of WO2022039002A1 publication Critical patent/WO2022039002A1/ja
Anticipated expiration legal-status Critical
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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 comprises a binder composition for a power storage device, a slurry for a power storage device electrode containing the binder composition and an active material, a power storage device electrode formed by applying and drying the slurry on a current collector, and the present invention.
  • the present invention relates to a power storage device provided with a power storage device electrode.
  • Lithium-ion batteries, lithium-ion capacitors, and the like are expected as such storage devices.
  • the electrodes used in such a power storage device are manufactured by applying and drying a composition (slurry for a power storage device electrode) containing an active material and a polymer functioning as a binder on the surface of a current collector.
  • a composition slurry for a power storage device electrode
  • the properties required for a polymer used as a binder include the ability to bond active substances to each other, the ability to adhere the active material to the current collector, the abrasion resistance in the process of winding the electrodes, and the subsequent cutting. Examples thereof include powder drop resistance in which fine powder of the active material does not fall off from the coated / dried composition coating film (hereinafter, also referred to as “active material layer”).
  • Patent Documents 1 and 2 do not have sufficient repetitive charge / discharge characteristics and durability at high temperatures, and are further suitable for application to a power storage device as a drive power source for an electric vehicle. There was a need for improvement.
  • a power storage device electrode having excellent repetitive charge / discharge characteristics by reducing internal resistance and excellent charge / discharge durability characteristics at high temperatures by improving adhesion is manufactured.
  • a binder composition for a possible power storage device is provided.
  • some aspects of the present invention provide a slurry for a power storage device electrode containing the binder composition.
  • some aspects of the present invention provide a power storage device electrode having excellent repetitive charge / discharge characteristics by reducing internal resistance and excellent charge / discharge durability characteristics at high temperatures by improving adhesion. do.
  • some aspects of the present invention provide a power storage device having excellent repetitive charge / discharge characteristics and excellent charge / discharge durability characteristics at high temperatures.
  • the present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.
  • One aspect of the binder composition for a power storage device is Contains the polymer (A) and the liquid medium (B),
  • the polymer (A) is: Repeating unit (a1) derived from conjugated diene compound (a1) 15-60% by mass, Repeating unit (a2) derived from unsaturated carboxylic acid (a2) 1 to 10% by mass, Contains, There is one peak top of tan ⁇ (loss elastic modulus / storage elastic modulus) of the dynamic viscoelasticity of the polymer (A) in the range of ⁇ 40 ° C. or higher and lower than 50 ° C., and 50 ° C. or higher and 150 ° C. or lower.
  • the polymer (A) may further contain 35 to 75% by mass of the repeating unit (a3) derived from the aromatic vinyl compound.
  • the total amount of the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3) can be 80% by mass or more.
  • the polymer (A) may contain at least one of a repeating unit (a4) derived from an unsaturated carboxylic acid ester and a repeating unit (a5) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
  • a repeating unit (a4) derived from an unsaturated carboxylic acid ester
  • a repeating unit (a5) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
  • the total amount of the repeating unit (a1), the repeating unit (a2), the repeating unit (a4), and the repeating unit (a5) can be 65% by mass or more.
  • the Martens hardness calculated by using the pico-denter of the polymer (A) may be 15 MPa or more.
  • the polymer (A) is a polymer particle, and the polymer (A) is a polymer particle.
  • the number average particle diameter of the polymer particles may be 50 nm or more and 500 nm or less.
  • the liquid medium (B) may be water.
  • One aspect of the slurry for power storage device electrodes according to the present invention is It contains a binder composition for a power storage device according to any one of the above embodiments, and an active material.
  • a silicon material may be contained as the active material.
  • One aspect of the power storage device electrode according to the present invention is A current collector and an active material layer formed by applying and drying a slurry for a power storage device electrode according to any one of the above on the surface of the current collector are provided.
  • One aspect of the power storage device according to the present invention is The storage device electrode of the above-described embodiment is provided.
  • the internal resistance can be reduced, so that the charge / discharge characteristics are excellent, and the adhesion can be improved, so that the charge / discharge durability characteristics at high temperature can be obtained.
  • An excellent power storage device electrode can be manufactured.
  • the binder composition for a power storage device according to the present invention exerts the above-mentioned effect particularly when the power storage device electrode contains a material having a large occlusion of lithium as an active material, for example, a carbon material such as graphite or a silicon material. As described above, since a material having a large lithium occlusion can be used as the active material of the power storage device electrode, the battery performance is also improved.
  • FIG. 1 is a diagram showing the relationship between the measured temperature and tan ⁇ in the dynamic viscoelasticity measurement of the film produced in Example 3.
  • (meth) acrylic acid- in the present specification 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”.
  • under high temperature means an environment in a temperature range of approximately 40 ° C to 80 ° C.
  • the binder composition for power storage device contains a polymer (A) and a liquid medium (B).
  • the polymer (A) contains 15 to 60% by mass of the repeating unit (a1) derived from the conjugated diene compound, and is not, when the total of the repeating units contained in the polymer (A) is 100% by mass. It contains 1 to 10% by mass of a repeating unit (a2) derived from a saturated carboxylic acid. Further, there is one peak top of tan ⁇ (loss elastic modulus / storage elastic modulus) of the dynamic viscoelasticity of the polymer (A) in the range of ⁇ 40 ° C. or higher and lower than 50 ° C., and 50 ° C.
  • the binder composition for a power storage device is for producing a power storage device electrode (active material layer) having improved binding ability between active materials, adhesion ability between the active material and a current collector, and powder drop resistance. It can also be used as a material for forming a protective film for suppressing a short circuit caused by dendrites generated during charging and discharging.
  • a power storage device electrode active material layer
  • a protective film for suppressing a short circuit caused by dendrites generated during charging and discharging.
  • the binder composition for a power storage device contains the polymer (A).
  • the polymer (A) is a repeating unit (a1) derived from a conjugated diene compound when the total of the repeating units contained in the polymer (A) is 100% by mass (hereinafter, simply “repeating unit (a1)”. ) ”) Is contained in an amount of 15 to 60% by mass, and a repeating unit (a2) derived from an unsaturated carboxylic acid (hereinafter, also simply referred to as a“ repeating unit (a2) ”) is contained in an amount of 1 to 10% by mass.
  • the polymer (A) may contain a repeating unit derived from another monomer copolymerizable with the repeating unit in addition to the repeating unit.
  • the polymer (A) contained in the binder composition for a power storage device may be in the form of latex dispersed in the liquid medium (B), or may be dissolved in the liquid medium (B). Although it may be in a state, it is preferably in the form of latex dispersed in the liquid medium (B).
  • the stability of the slurry for power storage device electrodes hereinafter, also simply referred to as “slurry” produced by mixing with the active material becomes stable. This is preferable because 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 15 to 60% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a1) is preferably 17% by mass, more preferably 20% by mass.
  • the upper limit of the content ratio of the repeating unit (a1) is preferably 57% by mass, more preferably 55% by mass.
  • the polymer (A) contains the repeating unit (a1) in the above range, the dispersibility of the active material and the filler becomes good, and a uniform active material layer and a protective film can be produced. Structural defects are eliminated, and good repetitive charge / discharge characteristics are exhibited. Further, the polymer (A) coated on the surface of the active material can be imparted with elasticity, and the polymer (A) can be expanded and contracted to improve the adhesion, so that the polymer (A) exhibits good charge / discharge durability characteristics. become.
  • the conjugated diene compound is not particularly limited, but 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chlor-1,3-butadiene and the like can be used. One or more selected from these can be used. Of these, 1,3-butadiene is particularly preferable.
  • the content ratio of the repeating unit (a2) derived from the unsaturated carboxylic acid is 1 to 10% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a2) is preferably 1.2% by mass, more preferably 1.5% by mass.
  • the upper limit of the content ratio of the repeating unit (a3) is preferably 9% by mass, more preferably 8% by mass.
  • the unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids and dicarboxylic acids (including anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. One or more selected from these can be used.
  • the unsaturated carboxylic acid it is preferable to use one or more selected from acrylic acid, methacrylic acid, and itaconic acid.
  • the polymer (A) may contain repeating units derived from other monomers copolymerizable with the repeating units (a1) and (a2).
  • Examples of such a repeating unit include a repeating unit (a3) derived from an aromatic vinyl compound (hereinafter, also simply referred to as “repeating unit (a3)”) and a repeating unit (a4) derived from an unsaturated carboxylic acid ester. (Hereinafter, also simply referred to as “repeating unit (a4)”), repeating unit (a5) derived from ⁇ , ⁇ -unsaturated nitrile compound (hereinafter, also simply referred to as “repeating unit (a5)”), (meth) acrylamide.
  • Repeat unit (a6) derived from hereinafter, also simply referred to as “repeating unit (a6)”
  • repeating unit (a7) derived from a compound having a sulfonic acid group (hereinafter, also simply referred to as “repeating unit (a7)”).
  • repeating units derived from cationic monomers and the like are repeated.
  • the content ratio of the repeating unit (a3) derived from the aromatic vinyl compound is preferably 35 to 75% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a3) is preferably 38% by mass, more preferably 40% by mass.
  • the upper limit of the content ratio of the repeating unit (a3) is preferably 72% by mass, more preferably 70% by mass.
  • the aromatic vinyl compound is not particularly limited, and examples thereof include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorstyrene, and divinylbenzene, and one or more selected from these can be mentioned. Can be used.
  • the repeating unit (a1) is based on the total of the repeating units contained in the polymer (A) being 100% by mass.
  • the total amount of the repeating unit (a2) and the repeating unit (a3) is preferably 80% by mass or more, and more preferably 85% by mass or more.
  • the dispersibility of the active material and the filler is good, and the polymer (A) dispersed in the electrode is good.
  • the polymer (A) may contain a repeating unit (a4) derived from an unsaturated carboxylic acid ester.
  • the content ratio of the repeating unit (a4) is preferably 0 to 60% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a4) is preferably 1% by mass, more preferably 2% by mass.
  • the upper limit of the content ratio of the repeating unit (a4) is preferably 55% by mass, more preferably 50% by mass.
  • the affinity between the polymer (A) and the electrolytic solution becomes good, and the binder becomes an electric resistance component in the power storage device.
  • (meth) acrylic acid ester can be preferably used.
  • Specific examples of the (meth) acrylic acid ester include, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid.
  • the polymer (A) may contain a repeating unit (a5) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
  • the content ratio of the repeating unit (a5) is preferably 0 to 60% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a5) is preferably 0.5% by mass, more preferably 1% by mass.
  • the upper limit of the content ratio of the repeating unit (a5) is preferably 55% by mass, more preferably 50% by mass.
  • the polymer (A) contains the repeating unit (a5) in the above range, it is possible to reduce the dissolution of the polymer (A) in the electrolytic solution, and it is possible to suppress the deterioration of the adhesion due to the electrolytic solution. In some cases. In addition, it may be possible to suppress an increase in internal resistance due to the polymer component dissolved in the power storage device becoming an electrical resistance component.
  • the ⁇ , ⁇ -unsaturated nitrile compound is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, and the like, and one selected from these. More than seeds can be used. Among these, one or more selected from the group consisting of acrylonitrile and methacrylonitrile is preferable, and acrylonitrile is particularly preferable.
  • the polymer (A) contains at least one of a repeating unit (a4) derived from an unsaturated carboxylic acid ester and a repeating unit (a5) derived from an ⁇ , ⁇ -unsaturated nitrile compound, the polymer (A) contains.
  • the total of the repeating units contained in is 100% by mass
  • the total amount of the repeating unit (a1), the repeating unit (a2), the repeating unit (a4) and the repeating unit (a5) is 65% by mass or more. It is preferably 68% by mass or more, and more preferably 68% by mass or more.
  • the total amount of the repeating unit (a1), the repeating unit (a2), the repeating unit (a4) and the repeating unit (a5) is within the above range, the dispersibility of the active material and the filler is good and the dispersion is dispersed in the electrode. Fusing of the polymer (A) to each other can be suppressed, and the adhesion and the permeability of the electrolytic solution are improved, so that good repeat charge / discharge characteristics and good charge / discharge durability characteristics are exhibited.
  • the polymer (A) may contain a repeating unit (a6) derived from (meth) acrylamide.
  • the content ratio of the repeating unit (a6) is preferably 0 to 10% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a6) is preferably 1% by mass, more preferably 2% by mass.
  • the upper limit of the content ratio of the repeating unit (a6) is preferably 8% by mass, more preferably 5% by mass.
  • the flexibility of the obtained active material layer becomes appropriate, and the adhesion between the current collector and the active material layer may be improved. Further, since the bonding ability between active materials containing a carbon material such as graphite or a silicon material can be enhanced, an active material layer having better flexibility and adhesion to a current collector may be obtained.
  • the (meth) acrylamide is not particularly limited, but is limited to acrylamide, methacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diacetoneacrylamide, and N, N-diethylmethacrylate.
  • the polymer (A) may contain a repeating unit (a7) derived from a compound having a sulfonic acid group.
  • the content ratio of the repeating unit (a7) is preferably 0 to 10% by mass when the total of the repeating units contained in the polymer (A) is 100% by mass.
  • the lower limit of the content ratio of the repeating unit (a7) is preferably 0.5% by mass, more preferably 1% by mass.
  • the upper limit of the content ratio of the repeating unit (a7) is preferably 8% by mass, more preferably 5% by mass.
  • the compound having a sulfonic acid group is not particularly limited, but is limited to vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfobutyl (meth) acrylate, 2-acrylamide-2.
  • -Compounds such as methylpropanesulfonic acid, 2-hydroxy-3-acrylamidepropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and alkali salts thereof are mentioned, and one selected from these. The above can be used.
  • the polymer (A) may contain a repeating unit derived from a cationic monomer.
  • 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 preferable.
  • Specific examples of these cationic monomers are not particularly limited, but are 2- (dimethylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt, and 2- (meth) acrylate.
  • the measurement sample in this dynamic viscoelasticity measurement is a film of the polymer (A).
  • the polymer (A) was dried at 40 ° C. for 24 hours to prepare a uniform film having a thickness of 1.0 ⁇ 0.3 mm, and this film was dried at 160 ° C. in a vacuum dryer. After drying for 30 minutes, it was cut into strips of 10 mm ⁇ 10 mm.
  • the measurement sample is fixed on a parallel plate (product name "PP-12") using the following dynamic viscoelasticity measuring device, and the measurement is performed in the temperature range of ⁇ 70 ° C. to 180 ° C. under the following measurement conditions.
  • -Measurement conditions shear mode, measurement frequency 0.01 to 1 Hz, temperature rise speed 0.1 ° C / min -Dynamic viscoelasticity measuring device: Model "MCR 301" manufactured by Antonio Par.
  • the value of "tan ⁇ (Tp2) / tan ⁇ (Tp1)" of the polymer (A) used in the present embodiment is 0.5 or more, preferably 0.75 or more, and more preferably 1 or more. be.
  • the value of "tan ⁇ (Tp2) / tan ⁇ (Tp1)" of the polymer (A) is within the above range, it indicates that the viscosity is high at a temperature near the peak top temperature of tan ⁇ (Tp1), and this viscosity is high. It is considered that the adhesion can be guaranteed by the height of the.
  • the polymer (A) is hard at a temperature near the peak top temperature of tan ⁇ (Tp2), and that the polymer (A) is hard, so that it is crushed like other binders at the time of electrode production. Since the particle shape can be maintained without the need for it, it is considered that the permeability of the electrolytic solution to the active material can be enhanced. As described above, the polymer (A) used in the present embodiment can reduce the internal resistance by increasing the permeability of the electrolytic solution into the active material, so that an electrode exhibiting good repetitive charge / discharge characteristics is produced. be able to. Further, since the polymer (A) used in the present embodiment can improve the adhesion, it is possible to produce an electrode showing good charge / discharge durability characteristics at high temperature.
  • the temperature Tp1 (° C.) of the peak top of tan ⁇ in the dynamic viscoelasticity measurement of the polymer (A) is preferably in the temperature range of ⁇ 35 ° C. or higher and 45 ° C. or lower, more preferably ⁇ 30 ° C. or higher and 40 ° C. or lower. It is preferable to do so. Further, it is preferable that one peak top is present in the above temperature range. The presence of one Tp in the above temperature range indicates that the viscosity is high in the same temperature range. It is considered that due to this high viscosity, the high binding force of the polymer (A) can be maintained in the same temperature range, and good adhesion can be exhibited.
  • the temperature Tp2 (° C.) of the peak top of tan ⁇ in the dynamic viscoelasticity measurement of the polymer (A) is preferably in the temperature range of 60 ° C. or higher and 145 ° C. or lower, more preferably 70 ° C. or higher and 140 ° C. or lower. Is preferable. Further, it is preferable that one peak top is present in the above temperature range. The presence of one Tp in the above temperature range indicates that a polymer having a uniform crosslinked composition is formed in the same temperature range. It is considered that the hardness of the polymer (A) can be exhibited and the internal resistance can be reduced by increasing the amount of the uniform cross-linking composition of the polymer (A) in the same temperature range.
  • Examples of the method for adjusting the temperature Tp at the peak top of tan ⁇ include a method for adjusting the monomer composition at the time of polymerization (A) polymerization.
  • the tan ⁇ (Tp1) of the polymer (A) is preferably 0.01 to 0.5, more preferably 0.01 to 0.45, and particularly preferably 0.01 to 0.4.
  • the fact that the tan ⁇ (Tp1) of the polymer (A) is in the above range indicates that the polymer (A) is viscous but not too hard and has sufficient binding force for retaining the electrode structure.
  • the tan ⁇ (Tp2) of the polymer (A) is preferably 0.1 to 3, more preferably 0.2 to 2.5, and particularly preferably 0.3 to 2.
  • the fact that the tan ⁇ (Tp2) of the polymer (A) is in the above range indicates that the polymer (A) is not too soft and has sufficient hardness to suppress the fusion of the particles. ..
  • Examples of the method for adjusting tan ⁇ (Tp) include changing the glass transition temperature and gel content of the polymer (A), and changing the method of adding the monomer during the polymerization of the polymer (A).
  • the Martens hardness calculated by using the pico-denter of the polymer (A) used in the present embodiment is preferably 15 MPa or more, more preferably 20 MPa or more, and particularly preferably 25 MPa or more. be.
  • the fact that the Martens hardness of the polymer (A) is within the above range indicates that the polymer (A) is hard, and that the polymer (A) is hard, so that it is crushed like other binders when the electrode is prepared. Since the particle shape can be maintained without the need for it, it is considered that the permeability of the electrolytic solution to the active material can be enhanced. Since such a polymer (A) can reduce the internal resistance by increasing the permeability of the electrolytic solution into the active material, it is possible to produce an electrode exhibiting good repetitive charge / discharge characteristics.
  • the Martens hardness of the polymer (A) can be measured using a pico denter.
  • the measurement sample in this pico-denter is a thin film of the polymer (A).
  • about 1 g of the polymer (A) is added onto a 1 cm ⁇ 1 cm Si wafer to form a coating film using a spin coat under the following equipment and conditions, and the coating film is hot. It was dried on a plate at 150 ° C. for 30 minutes.
  • the Martens hardness is calculated under the following test conditions using the following pico-denter.
  • -Spin coating rotation conditions Application was performed according to 150 rpm ⁇ 5 seconds, 250 rpm ⁇ 5 seconds, 1000 rpm ⁇ 30 seconds.
  • -Spin coating device Mikasa Co., Ltd., model "MS-A-150"
  • -Pico indenter test conditions Pushed in at a pressure of 0.1 mN for 5 seconds, kept for 1 second, and then released over 5 seconds.
  • -Pico indenter device Helmut Fischer, model "HM500"
  • the number average particle size of the particles is preferably 50 nm or more and 500 nm or less, more preferably 60 nm or more and 450 nm or less, and particularly preferably 70 nm or more and 400 nm or less. Is.
  • the number average particle diameter of the particles of the polymer (A) is within the above range, the particles of the polymer (A) are likely to be adsorbed on the surface of the active material, so that the polymer (A) moves with the movement of the active material. Particles can also follow and move. As a result, migration can be suppressed, and deterioration of electrical characteristics may be reduced.
  • the number average particle size of the particles of the polymer (A) can be calculated from the average value of the particle size obtained from the images of 50 particles observed by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Examples of the transmission electron microscope include "H-7650” manufactured by Hitachi High-Technologies Corporation.
  • the electrolytic solution swelling degree of the polymer (A) is preferably 100 to 500% by mass, more preferably 120 to 450% by mass, and particularly preferably 140 to 400% by mass.
  • the degree of swelling of the electrolytic solution is within the above range, the polymer (A) can be appropriately swelled with respect to the electrolytic solution.
  • the solvated lithium ion can easily reach the active material, the internal resistance of the electrode can be reduced, and better repetitive charge / discharge characteristics can be realized.
  • the degree of swelling of the electrolytic solution is within the above range, a large volume change does not occur, so that the adhesion is excellent.
  • the degree of swelling of the electrolytic solution of the polymer (A) can be measured by the method described in Examples described later.
  • the method for producing the polymer (A) is not particularly limited, but is, for example, an emulsification polymerization method carried out in the presence of a known emulsifier (surfactant), chain transfer agent, polymerization initiator and the like. Can be by.
  • a known emulsifier surfactant
  • chain transfer agent chain transfer agent
  • polymerization initiator the compounds described in Japanese Patent No. 5999399 can be used.
  • the emulsification polymerization method for synthesizing the polymer (A) may be carried out by one-step polymerization or by multi-step polymerization of two-step polymerization or more.
  • the mixture of the above monomers is preferably prepared at 40 to 80 ° C. in the presence of an appropriate emulsifier, chain transfer agent, polymerization initiator and the like. It can be carried out by emulsion polymerization for 4 to 36 hours.
  • the polymer (A) is synthesized by two-stage polymerization
  • the ratio of the monomer used for the first-stage polymerization is the total mass of the monomer (total of the mass of the monomer used for the first-stage polymerization and the mass of the monomer used for the second-stage polymerization). On the other hand, it is preferably in the range of 20 to 100% by mass, and more preferably in the range of 25 to 100% by mass.
  • the type of the monomer used for the second-stage polymerization and its usage ratio may be the same as or different from the type of the monomer used for the first-stage polymerization and its usage ratio.
  • the polymerization conditions at each stage are preferably as follows from the viewpoint of the dispersibility of the particles of the obtained polymer (A).
  • First-stage polymerization preferably a temperature of 40 to 80 ° C.: preferably a polymerization time of 2 to 36 hours: preferably a polymerization conversion rate of 50% by mass or more, more preferably 60% by mass or more.
  • Second-stage polymerization preferably a temperature of 40-80 ° C; preferably a polymerization time of 2-18 hours.
  • the polymerization reaction can proceed in a state where the dispersion stability of the particles of the obtained polymer (A) is good.
  • the total solid content concentration is preferably 48% by mass or less, more preferably 45% by mass or less.
  • the pH is adjusted by adding a neutralizing agent to the polymerization mixture after the completion of the emulsion polymerization. It is preferable to adjust the pH to about 5 to 10.5, preferably 5 to 10, and more preferably 5.5 to 9.5.
  • the neutralizing agent used here is not particularly limited, and examples thereof include metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia and the like.
  • the content ratio of the polymer (A) in the binder composition for a power storage device according to the present embodiment is preferably 10 to 100% by mass, more preferably 10 to 100% by mass, based on 100% by mass of the polymer component. It is preferably 20 to 95% by mass, and particularly preferably 25 to 90% by mass.
  • the polymer component includes a polymer (A), a polymer other than the polymer (A) described later, a thickener and the like.
  • the binder composition for a power storage device 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, sulfone compounds and the like, and one or more selected from these may be used. Can be done.
  • the content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably not substantially contained in 100% by mass of the aqueous medium.
  • substantially free means that a non-aqueous medium is not intentionally added as a liquid medium, and the non-aqueous medium is inevitably mixed when preparing a binder composition for a power storage device. It may include a medium.
  • the binder composition for a power storage device according to the present embodiment may contain additives other than the above-mentioned components, if necessary.
  • additives include polymers other than the polymer (A), preservatives, thickeners and the like.
  • the binder composition for a power storage device may contain a polymer other than the polymer (A).
  • a polymer other than the polymer (A) include, but are not limited to, an acrylic polymer containing an unsaturated carboxylic acid ester or a derivative thereof as a constituent unit, a fluoropolymer such as PVDF (polyvinylidene fluoride), and the like. These polymers may be used alone or in combination of two or more. By containing these polymers, flexibility and adhesion may be further improved.
  • the binder composition for a power storage device may contain a preservative.
  • a preservative By containing a preservative, it may be possible to suppress the growth of bacteria, mold and the like to generate foreign substances when the binder composition for a power storage device is stored.
  • Specific examples of the preservative include compounds described in Japanese Patent No. 5477610.
  • the binder composition for a power storage device according to the present embodiment may contain a thickener. By containing the thickener, the coatability of the slurry and the charge / discharge characteristics of the obtained power storage device may be further improved.
  • the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; poly (meth) acrylic acid; the cellulose compound or the ammonium salt or alkali metal salt of the poly (meth) acrylic acid; polyvinyl.
  • Polyvinyl alcohol-based (co) polymers such as alcohols, modified polyvinyl alcohols, and ethylene-vinyl alcohol copolymers; Examples thereof include water-soluble polymers such as saponified products.
  • alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid and the like are preferable.
  • Examples of commercially available 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% by mass or less with respect to 100% by mass of the total solid content of the binder composition for a power storage device. It is preferably present, and more preferably 0.1 to 3% by mass.
  • the pH of the binder composition for a power storage device according to the present embodiment is preferably 5 to 10, more preferably 6 to 9.5, and particularly preferably 6.5 to 9.
  • the pH is within the above range, problems such as insufficient leveling property and liquid dripping can be suppressed, and it becomes easy to manufacture a power storage device electrode having both good electrical characteristics and adhesion. ..
  • PH in the present specification means physical properties measured as follows. It is a value measured according to JIS Z8802: 2011 with a pH meter using a glass electrode calibrated with a neutral phosphate standard solution and a borate standard solution as a pH standard solution at 25 ° C. Examples of such a pH meter include “HM-7J” manufactured by DKK-TOA CORPORATION and "D-51” manufactured by HORIBA, Ltd.
  • the pH of the binder composition for a power storage device is affected by the monomer composition constituting the polymer (A), but it is not determined only by the monomer composition. .. That is, it is generally known that the pH of the binder composition for a power storage device changes depending on the polymerization conditions and the like even if the monomer composition is the same, and the examples of the present specification show an example thereof. Not too much.
  • the polymer composition is the same, all unsaturated carboxylic acids are charged into the polymerization reaction solution from the beginning, and then other monomers are sequentially added and added, and monomers other than unsaturated carboxylic acids are added.
  • the amount of carboxy group derived from the unsaturated carboxylic acid exposed on the surface of the obtained polymer is different from the case where the unsaturated carboxylic acid is added to the polymerization reaction solution at the end. It is considered that the pH of the binder composition for a power storage device is significantly different even if the order in which the monomers are added is changed by the polymerization method.
  • the slurry for power storage device according to the embodiment of the present invention contains the above-mentioned binder composition for power storage device.
  • the above-mentioned binder composition for a power storage device can also be used as a material for producing a protective film for suppressing a short circuit caused by dendrites generated during charging and discharging, and can also be used as a material for binding active materials to each other. It can also be used as a material for producing a power storage device electrode (active material layer) having improved adhesion ability between the active material and the current collector and powder drop resistance.
  • a slurry for a power storage device for producing a protective film (hereinafter, also referred to as “slurry for a protective film”) and a slurry for a power storage device for producing an active material layer of a power storage device electrode (hereinafter, “storage device electrode”). It is also referred to as “slurry for use”).
  • Protective film slurry "Protective film slurry” is used to apply this to the surface of an electrode or separator or both, and then dry it to form a protective film on the surface of the electrode or separator or both.
  • the slurry for a protective film according to the present embodiment may be composed only of the binder composition for a power storage device described above, or may further contain an inorganic filler.
  • each component contained in the protective film slurry according to the present embodiment will be described in detail. Since the binder composition for a power storage device is as described above, the description thereof will be omitted.
  • the slurry for a protective film according to the present embodiment can improve the toughness of the protective film by containing the inorganic filler.
  • the inorganic filler at least one inorganic oxide particle selected from the group consisting of silica, titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), and magnesium oxide (magnesia) can be used. preferable.
  • titanium oxide particles or aluminum oxide particles 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 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 which is a porous film. This can reduce damage to the separator and prevent the inorganic filler from clogging the microporous separator.
  • the protective film slurry according to the present embodiment preferably contains 0.1 to 20 parts by mass of the above-mentioned binder composition for a power storage device in terms of solid content with respect to 100 parts by mass of the inorganic filler. It is more preferable that the content is up to 10 parts by mass.
  • the content ratio of the binder composition for a power storage device is within the above range, the balance between the toughness of the protective film and the permeability of lithium ions is good, and as a result, the resistance increase rate of the obtained power storage device is further reduced. Can be done.
  • a liquid medium may be further added to the slurry for a protective film according to the present embodiment.
  • the amount of the liquid medium added can be adjusted as necessary so that the optimum slurry viscosity can be obtained according to the coating method and the like. Examples of such a liquid medium include the materials described in "1.2. Liquid medium (B)" above.
  • Slurry for power storage device electrodes is a dispersion used to form an active material layer on the surface of a current collector by applying it to the surface of the current collector and then drying it. Say that.
  • the slurry for a power storage device electrode according to the present embodiment contains the above-mentioned binder composition for a power storage device and an active material.
  • a slurry for a power storage device electrode often contains a binder component such as an SBR-based copolymer and a thickener such as carboxymethyl cellulose in order to improve adhesion.
  • the slurry for a power storage device electrode according to the present embodiment can improve the adhesion even when it contains only the above-mentioned polymer (A) as a polymer component.
  • the slurry for the power storage device electrode according to the present embodiment may contain a polymer other than the polymer (A) or a thickener in order to further improve the adhesion.
  • the components contained in the slurry for the power storage device electrode according to the present embodiment will be described.
  • Polymer (A) The composition, physical properties, production method, etc. of the polymer (A) are as described above, and thus description thereof will be omitted.
  • the content ratio of the polymer component in the slurry for the power storage device electrode according to the present embodiment is preferably 1 to 8 parts by mass, more preferably 1 to 7 parts by mass, and particularly, with respect to 100 parts by mass of the active material. It is preferably 1.5 to 6 parts by mass.
  • the polymer component includes a polymer (A), a polymer other than the polymer (A) added as needed, a thickener and the like.
  • Active material examples include carbon materials, silicon materials, oxides containing lithium atoms, lead compounds, tin compounds, arsenic compounds, antimony compounds, and aluminum compounds.
  • Conductive polymer such as polyacene, A X BYO Z (However, 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, and O is Represents an oxygen atom, where X, Y and Z are numbers in the range 1.10>X> 0.05, 4.00>Y> 0.85 and 5.00>Z> 1.5, respectively.) Examples thereof include the represented composite metal oxide and other metal oxides. Specific examples of these include the compounds described in Japanese Patent No. 5999399.
  • the slurry for a power storage device electrode according to the present embodiment can be used when producing any power storage device electrode of a positive electrode or a negative electrode, and is preferably used for both 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 charging and discharging are repeated, the aggregation collapses in the active material layer and the active materials dissociate from each other. It is considered that one of the factors is that it is easily separated from the current collector and the conductive network inside the active material layer is easily broken.
  • the electricity storage device electrode produced by using the energy storage device electrode slurry according to the present embodiment has good electrical characteristics without causing the above-mentioned problems even when lithium iron phosphate is used as the positive electrode active material. Can be shown. It is considered that the reason for this is that the polymer (A) can firmly bind lithium iron phosphate and at the same time maintain a state in which lithium iron phosphate is firmly bound even during charging and discharging. ..
  • the active material exemplified above contains a silicon material. Since the silicon material has a large occlusion amount of lithium per unit weight as compared with other active materials, the storage capacity of the obtained power storage device can be increased by containing the silicon material as the negative electrode active material. As a result, the output and energy density of the power storage device can be increased.
  • the negative electrode active material is more preferably a mixture of a silicon material and a carbon material. Since the volume change of carbon material due to charge and discharge is smaller than that of silicon material, the influence of volume change of silicon material can be mitigated by using a mixture of silicon material and carbon material as the negative electrode active material. The adhesion ability between the layer and the current collector can be further improved.
  • silicon When silicon (Si) is used as an active material, silicon has a high capacity, but causes a large volume change when occluding lithium. For this reason, the silicon material has the property that it is atomized by repeated expansion and contraction, causing peeling from the current collector and separation between the active materials, and the conductive network inside the active material layer is easily broken. Due to this property, the charge / discharge durability characteristics of the power storage device are extremely deteriorated in a short time.
  • the power storage device electrode produced by using the slurry for the power storage device electrode according to the present embodiment can exhibit good electrical characteristics without causing the above-mentioned problems even when a silicon material is used.
  • the reason for this is that the polymer (A) can firmly bind the silicon material, and at the same time, even if the silicon material expands in volume due to occlusion of lithium, the polymer (A) expands and contracts to form silicon. It is considered that this is because the material can be maintained in a tightly bound state.
  • the content ratio of the silicon material in 100% by mass of the active material is preferably 1% by mass or more, more preferably 2 to 50% by mass, still more preferably 3 to 45% by mass, and 10%. It is particularly preferable to use ⁇ 40% by mass.
  • a power storage device having an excellent balance between the improvement of the output and energy density of the power storage device and the charge / discharge durability characteristics can be obtained.
  • the shape of the active material is preferably particulate.
  • the average particle size of the active material is preferably 0.1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m.
  • the average particle size of the active material means a volume average particle size calculated from the particle size distribution measured by using a particle size distribution measuring device based on a laser diffraction method. Examples of such a laser diffraction type particle size distribution measuring device include the HORIBA LA-300 series and the HORIBA LA-920 series (all manufactured by HORIBA, Ltd.).
  • a liquid medium may be further added to the slurry for the storage device electrode according to the present embodiment in addition to the amount brought in from the binder composition for the power storage device.
  • the liquid medium to be added may be the same as or different from the liquid medium (B) contained in the binder composition for a power storage device, but may be different from the above “1.2. Liquid medium (B)”. It is preferable to select and use from the liquid media exemplified in 1.
  • the content ratio of the liquid medium (including the amount brought in from the binder composition for the power storage device) in the slurry for the power storage device electrode according to the present embodiment is the solid content concentration in the slurry (total of the components other than the liquid medium in the slurry).
  • the ratio of the mass to the total mass of the slurry; the same shall apply hereinafter) is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
  • a conductivity-imparting agent may be further added to the slurry for a power storage device electrode according to the present embodiment for the purpose of imparting conductivity and buffering the volume change of the active material due to the inflow and outflow of lithium ions.
  • the conductivity-imparting agent examples include activated carbon, acetylene black, ketjen black, furnace black, graphite, carbon fiber, and carbon such as fullerene.
  • acetylene black or ketjen black can be preferably used.
  • the content ratio of the conductivity-imparting agent is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the active material.
  • a pH adjuster and / or a corrosion inhibitor may be further added to the slurry for the power storage device electrode according to the present embodiment for the purpose of suppressing corrosion of the current collector according to the type of the active material.
  • Examples of the pH adjuster include 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 preferable. Further, it can also be selected and used from the neutralizing agents described in the method for producing the polymer (A).
  • Corrosion inhibitors include ammonium metavanadate, sodium metavanadate, potassium metavanadate, ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium paratungstate, sodium paratungstate, potassium paratungstate, molybdate.
  • Ammonium, sodium molybdate, potassium molybdate and the like can be mentioned, and among these, ammonium paratungstate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, ammonium molybdenate and the like are preferable.
  • Cellulose fibers may be further added to the slurry for electricity storage device electrodes according to this embodiment.
  • By adding cellulose fiber it may be possible to improve the adhesion of the active material to the current collector. It is considered that the fibrous cellulose fibers can prevent the active substances from falling off and improve the adhesion to the current collector by fibrously binding the adjacent active substances to each other by line adhesion or line contact.
  • the average fiber length of the cellulose fibers can be selected from a wide range of 0.1 to 1000 ⁇ m, for example, preferably 1 to 750 ⁇ m, more preferably 1.3 to 500 ⁇ m, still more preferably 1.4 to 250 ⁇ m, and particularly preferably 1. It is 0.8 to 25 ⁇ m.
  • the average fiber length is within the above range, the surface smoothness (coating film uniformity) is good, and the adhesion of the active material to the current collector may be improved.
  • the fiber length of the cellulose fiber may be uniform, and the coefficient of variation of the fiber length ([standard deviation of fiber length / average fiber length] ⁇ 100) is, for example, preferably 0.1 to 100, more preferably 0. It is 5 to 50, particularly preferably 1 to 30.
  • the maximum fiber length of the cellulose fiber is, for example, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the average fiber length of the cellulose fiber is preferably 0.01 to 5 times, more preferably 0.02 to 3 times, and particularly preferably 0.03 to 2 times, the average thickness of the active material layer.
  • the average fiber diameter of the cellulose fiber is preferably 1 nm to 10 ⁇ m, more preferably 5 nm to 2.5 ⁇ m, still more preferably 20 nm to 700 nm, and particularly preferably 30 nm to 200 nm.
  • the cellulose fiber is preferably a cellulose nanofiber having an average fiber diameter of nanometer size (for example, a cellulose nanofiber having an average fiber diameter of about 10 nm to 500 nm, preferably about 25 nm to 250 nm).
  • the fiber diameter of the cellulose fiber is also uniform, and the coefficient of variation of the fiber diameter ([standard deviation of fiber diameter / average fiber diameter] ⁇ 100) is preferably 1 to 80, more preferably 5 to 60, and particularly preferably 10 to. It is 50.
  • the maximum fiber diameter of the cellulose fiber is preferably 30 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the ratio (aspect ratio) of the average fiber length to the average fiber diameter of the cellulose fiber is, for example, preferably 10 to 5000, more preferably 20 to 3000, and particularly preferably 50 to 2000.
  • the aspect ratio is within the above range, the adhesion of the active material to the current collector becomes good, and the surface smoothness (coating film uniformity) of the electrode may be good without weakening the breaking strength of the fiber. be.
  • the material of the cellulose fiber may be formed of a polysaccharide having a ⁇ -1,4-glucan structure.
  • the cellulose fiber include cellulose fiber derived from higher plants (for example, wood fiber (for example, wood pulp such as coniferous tree and broadleaf tree), bamboo fiber, sugar cane fiber, seed hair fiber (for example, cotton linter, bombax cotton, capoc, etc.), etc.
  • Natural cellulose fibers such as gin skin fibers (eg, hemp, kozo, honey mata, etc.), leaf fibers (eg, Manila hemp, New Zealand hemp, etc.), animal-derived cellulose fibers (eg, squirrel cellulose, etc.) ), Cellulose fibers derived from bacteria (for example, cellulose contained in Natadecoco), chemically synthesized cellulose fibers (for example, rayon, cellulose ester (for example, cellulose acetate), cellulose ether (for example, hydroxyethyl cellulose (HEC)), Hydroxyalkyl cellulose such as hydroxypropyl cellulose, cellulose derivatives such as methyl cellulose and alkyl cellulose such as ethyl cellulose)) and the like can be mentioned. These cellulose fibers may be used alone or in combination of two or more.
  • gin skin fibers eg, hemp, kozo, honey mata, etc.
  • leaf fibers eg, Manila hemp, New Zealand hemp, etc.
  • cellulose fibers derived from higher plants such as wood fibers (wood pulp such as coniferous trees and broadleaf trees) and seed hair fibers (cotton linters), are easy to prepare nanofibers having an appropriate aspect ratio.
  • wood fibers wood pulp such as coniferous trees and broadleaf trees
  • seed hair fibers cotton linters
  • Cellulose fibers derived from pulp such as pulp are preferable.
  • the method for producing the cellulose fiber is not particularly limited, and is a conventional method, for example, JP-A-60-129921, JP-A-2011-26760, JP-A-2012-25833, depending on the target fiber length and fiber diameter.
  • the methods described in Japanese Patent Application Laid-Open No. 2012-36517, Japanese Patent Application Laid-Open No. 2012-36518, Japanese Patent Application Laid-Open No. 2014-181421, and the like may be used.
  • the slurry for power storage device electrode according to this embodiment is manufactured by any method as long as it contains the above-mentioned binder composition for power storage device and active material. You may. From the viewpoint of more efficiently and inexpensively producing a slurry having better dispersibility and stability, an active material and optional additive components used as necessary are added to the binder composition for a power storage device, and these are mixed. It is preferable to manufacture by doing so. As a specific manufacturing method, for example, the method described in Japanese Patent No. 5999399 can be mentioned.
  • the power storage device electrode according to an embodiment of the present invention comprises a current collector and an active material layer formed by applying and drying the above-mentioned storage device electrode slurry on the surface of the current collector. To prepare. Such a power storage device electrode is formed by applying the above-mentioned slurry for a power storage device electrode to the 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. Can be manufactured. In the power storage device electrode manufactured in this manner, an active material layer containing the above-mentioned polymer (A), an active material, and an optional component added as needed is bonded to the surface of the current collector. Therefore, it has excellent repetitive charge / discharge characteristics and excellent charge / discharge durability characteristics at high temperatures.
  • the current collector is not particularly limited as long as it is made of a conductive material, and examples thereof include the current collector described in Japanese Patent No. 5999399.
  • the content ratio of the silicon element in 100% by mass of the active material layer is preferably 2 to 30% by mass, preferably 2 to 20% by mass. Is more preferable, and 3 to 10% by mass is particularly preferable.
  • the content of the silicon element in the active material layer is within the above range, the storage capacity of the power storage device produced by using the content is improved, and an active material layer having a uniform distribution of silicon elements can be obtained.
  • the content of the silicon element in the active material layer can be measured by, for example, the method described in Japanese Patent No. 5999399.
  • the power storage device can be manufactured according to a conventional method by providing the above-mentioned power storage device electrode, further containing an electrolytic solution, and using parts such as a separator.
  • a specific manufacturing method for example, a negative electrode and a positive electrode are overlapped with each other via a separator, which is wound or folded according to the shape of the battery to be stored in a battery container, and an electrolytic solution is injected into the battery container.
  • the method of sealing the battery can be mentioned.
  • the shape of the battery can be an appropriate shape such as a coin type, a cylindrical type, a square shape, or a laminated type.
  • the electrolytic solution may be in the form of a liquid or a gel, and depending on the type of the active material, a known electrolytic solution used for a power storage device that effectively exhibits the function as a battery may be selected.
  • the electrolytic solution can be a solution in which the electrolyte is dissolved in a suitable solvent. Examples of such an electrolyte and a solvent include compounds described in Japanese Patent No. 5999399.
  • the above-mentioned power storage device can be applied to lithium ion secondary batteries, electric double layer capacitors, lithium ion capacitors, etc. that require discharge at a large current density.
  • a lithium ion secondary battery is particularly preferable.
  • known members for a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor can be used as members other than the binder composition for the power storage device. Is.
  • Binder Composition for Power Storage Device A binder composition for power storage device containing the polymer (A) was obtained by two-stage polymerization as shown below. In the reactor, a monomer mixture consisting of 200 parts by mass of water, 15 parts by mass of 1,3-butadiene, 15 parts by mass of styrene and 2 parts by mass of acrylic acid, and 0.1 part by mass of tert-dodecylmercaptan as a chain transfer agent.
  • the unreacted monomer is removed from the particle dispersion of the polymer (A) thus obtained and concentrated, a 2.5% aqueous sodium hydroxide solution is added, and then water is removed using an evaporator.
  • a binder composition for a power storage device containing particles of the polymer (A) having a solid content concentration of 40% by mass and a pH of 8.0 was obtained.
  • the weight (Y (g)) of the residue obtained by evaporating and removing the dissolved EC / DEC / EMC was measured. Further, after the EC / DEC / EMC adhering to the surface of the insoluble matter (film) separated by the above filtration was absorbed by paper and removed, the weight (Z (g)) of the insoluble matter (film) was measured. ..
  • the electrolytic solution swelling degree was measured by the following formula (2)
  • This graphite-coated silicon oxide is a conductive powder (active material) whose surface is coated with graphite, and its average particle size is 10.5 ⁇ m, and the entire obtained graphite-coated silicon oxide is 100.
  • the ratio of the graphite coating when it was set to mass% was 2% by mass.
  • Artificial graphite (manufactured by Showa Denko Materials Co., Ltd., trade name "MAG") 90.25 parts by mass (solid content conversion value), which is highly crystalline graphite as a negative electrode active material, oxidation of the graphite coating film obtained above. 4.75 parts by mass (solid content conversion value) of silicon powder and 1 part by mass of carbon (acetylene black manufactured by Denka Co., Ltd.) as a conductivity-imparting agent were added, and the mixture was stirred at 60 rpm for 1 hour to obtain a paste. ..
  • a slurry for device electrodes (C / Si 100/0) was prepared.
  • a two-pole coin cell (a two-pole coin cell) is a glove box in which the dew point is Ar-substituted so that the dew point is -80 ° C or lower, and the negative electrode manufactured above is punched to a diameter of 15.95 mm. It was placed on the product name "HS Flat Cell” manufactured by Hosen Co., Ltd.).
  • a separator made of a polypropylene porous film punched to a diameter of 24 mm (manufactured by Cellguard Co., Ltd., trade name "Cellguard # 2400") was placed, and further, 500 ⁇ L of an electrolytic solution was injected so as not to allow air to enter, and then the above A lithium ion battery cell (storage device) was assembled by placing a positive electrode produced in 1 above on which it was punched to a diameter of 16.16 mm and sealing the outer body of the bipolar coin cell by closing it with a screw.
  • Capacity retention rate (%) (Discharge capacity in the 100th cycle) / (Discharge capacity in the 1st cycle) (3) (Evaluation criteria)
  • ⁇ 5 points Capacity retention rate is 95% or more.
  • ⁇ 1 point Capacity retention rate is 75% or more and less than 80%.
  • the discharge was started at a constant current (1.0 C), and the time when the voltage reached 3.0 V was regarded as the discharge completion (cutoff), and the discharge capacity in the first cycle was calculated. In this way, charging and discharging were repeated 100 times. After repeating charging and discharging 100 times, charging and discharging were performed in the same manner as in the 0th cycle, the discharge capacity at the 101st time was evaluated, the resistance increase rate was calculated by the following formula (4), and the evaluation was performed according to the following criteria.
  • Resistance increase rate (%) (Discharge capacity at 101st cycle-100 discharge capacity at 100th cycle) / (Discharge capacity at 0th cycle-1 Discharge capacity at 1st cycle) x 100 (4) (Evaluation criteria) ⁇ 5 points: The resistance increase rate is 100% or more and less than 150%. ⁇ 4 points: The resistance increase rate is 150% or more and less than 200%. ⁇ 3 points: The resistance increase rate is 200% or more and less than 250%. -2 points: The resistance increase rate is 250% or more and less than 300%. ⁇ 1 point: The resistance increase rate is 300% or more and less than 350%. ⁇ 0 points: Resistance increase rate is 350% or more.
  • “1C” indicates a current value at which a cell having a certain electric capacity is discharged with a constant current and the discharge is completed in 1 hour.
  • “0.1C” means a current value at which the discharge ends over 10 hours
  • “10C” means a current value at which the discharge ends over 0.1 hours.
  • binder composition for power storage device (1) Preparation of binder composition for power storage device", the type and amount of each monomer and the amount of emulsifier are shown in the table below. Binder compositions for power storage devices containing polymer particles having a solid content concentration of 40% by mass were obtained in the same manner except as described in 1 to 3, and their physical characteristics were evaluated. Note that FIG. 1 shows a graph showing the relationship between the measured temperature and tan ⁇ in the dynamic viscoelasticity measurement of the film produced in Example 3.
  • a slurry for a power storage device electrode was prepared in the same manner as in Example 1 above except that the binder composition for a power storage device prepared above was used, and a power storage device electrode and a power storage device were produced, respectively, in the same manner as in the above Example 1. It was evaluated in the same manner as 1.
  • Example 13 In Example 4, the thickener was added to 0.9 parts by mass of CMC (trade name "CMC2200", manufactured by Daicel Co., Ltd.) and CNF (trade name "Cerish KY-100G", manufactured by Daicel Co., Ltd., fiber diameter 0. 07 ⁇ m)
  • CMC trade name "CMC2200", manufactured by Daicel Co., Ltd.
  • CNF trade name "Cerish KY-100G", manufactured by Daicel Co., Ltd., fiber diameter 0. 07 ⁇ m
  • a slurry for a power storage device electrode was prepared in the same manner as in Example 4 except that the amount was 0.1 part by mass, and a power storage device electrode and a power storage device were prepared, respectively, and evaluated in the same manner as in Example 1 above. The results are shown in Table 4 below.
  • Example 14 In Example 4, the thickener was added to 0.8 parts by mass of CMC (trade name "CMC2200", manufactured by Daicel Corporation) and CNF (trade name "Cerish KY-100G", manufactured by Daicel Corporation, fiber diameter 0. 07 ⁇ m) Except for 0.2 parts by mass, a slurry for a power storage device electrode was prepared in the same manner as in Example 4, and a power storage device electrode and a power storage device were prepared, respectively, and evaluated in the same manner as in Example 1 above. The results are shown in Table 4 below.
  • Tables 1 to 3 below show the polymer compositions used in Examples 1 to 12 and Comparative Examples 1 to 5, measurement results of each physical property, and evaluation results.
  • Table 4 below shows the composition of the polymer components used in Examples 13 and 14 and the evaluation results.
  • the slurry for the electricity storage device electrode prepared by using the binder composition for the electricity storage device according to the present invention shown in Examples 1 to 12 is the slurry for the energy storage device electrode of Comparative Examples 1 to 5.
  • the active materials can be bonded to each other more appropriately and the fusion of the particles in the electrode can be suppressed, so that the internal resistance can be reduced and the charge / discharge durability characteristics are good at high temperature.
  • a power storage device electrode having the above was obtained.
  • the reason for this is that the polymer (A) contained in the binder compositions of Examples 1 to 12 shown in Tables 1 to 2 above is compared with the case of Comparative Examples 1 to 5 shown in Table 3 above.
  • the temperature Tp (° C.) of the peak top of tan ⁇ -1 is present in the range of ⁇ 40 ° C. or higher and lower than 50 ° C., which suggests that the viscosity is high. It is presumed that this makes it possible to maintain a high binding force.
  • the temperature Tp (° C.) of the peak top of tan ⁇ -2 of the polymer (A) is present in the range of 50 ° C. or higher and 150 ° C. or lower, which increases the degree of cross-linking of the polymer on the high temperature side. It suggests that. As a result, it becomes possible to maintain the particle shape of the binder when the electrode is produced.
  • the slurry for the power storage device electrode prepared by using the binder composition for the power storage device according to the present invention shown in Examples 13 and 14 contains the CNF of the thickener. It was found that even when used in combination, the active materials can be suitably bonded to each other, and the adhesion between the active material layer and the current collector can be maintained well.
  • the present invention is not limited to the above embodiment, and various modifications are possible.
  • the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect).
  • the present 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 present invention also includes a configuration having the same action and effect as the configuration described in the above embodiment or a configuration capable of achieving the same object.
  • the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

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PCT/JP2021/028324 2020-08-20 2021-07-30 蓄電デバイス用バインダー組成物、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 Ceased WO2022039002A1 (ja)

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KR1020237008970A KR20230054404A (ko) 2020-08-20 2021-07-30 축전 디바이스용 결합제 조성물, 축전 디바이스 전극용 슬러리, 축전 디바이스 전극 및 축전 디바이스
CN202180050876.5A CN116075952A (zh) 2020-08-20 2021-07-30 蓄电装置用粘合剂组合物、蓄电装置电极用浆料、蓄电装置电极和蓄电装置
EP21858150.2A EP4203108A4 (en) 2020-08-20 2021-07-30 BINDING AGENT COMPOSITION FOR ENERGY STORAGE DEVICE, ELECTRODE SLUDGE FOR ENERGY STORAGE DEVICE, ELECTRODE FOR ENERGY STORAGE DEVICE AND ENERGY STORAGE DEVICE
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WO2025023017A1 (ja) * 2023-07-27 2025-01-30 株式会社Ｅｎｅｏｓマテリアル 蓄電デバイス用バインダー組成物、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
EP4325605A4 (en) * 2021-04-15 2025-07-09 Eneos Mat Corporation BINDER COMPOSITION FOR ENERGY STORAGE DEVICES, SUSPENSION FOR ELECTRODES OF ENERGY STORAGE DEVICE, ELECTRODE OF ENERGY STORAGE DEVICE, AND ENERGY STORAGE DEVICE
JP2025532568A (ja) * 2023-02-17 2025-10-01 香港時代新能源科技有限公司 ポリマー、極板及びそれに関連する電池セル、電池と電力消費装置
WO2026004464A1 (ja) * 2024-06-25 2026-01-02 日本特殊陶業株式会社 キャパシタ及びその製造方法
US12612515B2 (en) 2020-08-20 2026-04-28 Eneos Materials Corporation Power storage device binder composition, power storage device electrode slurry, power storage device electrode, and power storage device

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US12612515B2 (en) 2020-08-20 2026-04-28 Eneos Materials Corporation Power storage device binder composition, power storage device electrode slurry, power storage device electrode, and power storage device
EP4325605A4 (en) * 2021-04-15 2025-07-09 Eneos Mat Corporation BINDER COMPOSITION FOR ENERGY STORAGE DEVICES, SUSPENSION FOR ELECTRODES OF ENERGY STORAGE DEVICE, ELECTRODE OF ENERGY STORAGE DEVICE, AND ENERGY STORAGE DEVICE
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