WO2014051067A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2014051067A1
WO2014051067A1 PCT/JP2013/076296 JP2013076296W WO2014051067A1 WO 2014051067 A1 WO2014051067 A1 WO 2014051067A1 JP 2013076296 W JP2013076296 W JP 2013076296W WO 2014051067 A1 WO2014051067 A1 WO 2014051067A1
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Prior art keywords
positive electrode
active material
mass
polymer
negative electrode
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PCT/JP2013/076296
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English (en)
Japanese (ja)
Inventor
拓己 杉本
郁也 召田
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日本ゼオン株式会社
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Priority to CN201380027027.3A priority Critical patent/CN104396060B/zh
Priority to KR1020147030177A priority patent/KR102060429B1/ko
Priority to JP2014538635A priority patent/JP6168063B2/ja
Publication of WO2014051067A1 publication Critical patent/WO2014051067A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery, and more particularly to a lithium ion secondary battery capable of increasing the capacity.
  • portable terminals such as notebook personal computers, mobile phones, and PDAs (Personal Digital Assistants) have been widely used.
  • a secondary battery used for the power source of these portable terminals a nickel hydrogen secondary battery, a lithium ion secondary battery, and the like are frequently used.
  • Mobile terminals are required to have more comfortable portability, and are rapidly becoming smaller, thinner, lighter, and higher in performance. As a result, mobile terminals are used in various places.
  • batteries are required to be smaller, thinner, lighter, and higher performance, as with mobile terminals.
  • the binder for fixing the active material on the current collector and the conductive material for ensuring conductivity It is required to reduce materials such as.
  • Patent Document 1 For the purpose of increasing the capacity of lithium ion secondary batteries, a negative electrode for lithium ion secondary batteries using an alloy-based active material containing Si or the like has been developed (for example, Patent Document 1). Along with the increase in capacity, the voltage during charging and discharging is also increasing, and electrolytes composed of ethylene carbonate, propylene carbonate, etc. cannot withstand high voltages and may decompose, so combined with fluorine electrolyte additives It has also been done.
  • a fluorine-containing polymer such as polyvinylidene fluoride (PVdF) has been used as a binder for forming the electrode layer. Since the fluorine-containing polymer is not dissolved in the electrolytic solution, stable binding properties are expected, but fluorine-containing polymers such as PVdF are hard and difficult to bend. For this reason, depending on the shape and size of the battery, when only the fluorine-containing polymer is used when the electrode is wound and then crushed and formed into a predetermined shape, cracks may occur in the electrode layer.
  • PVdF polyvinylidene fluoride
  • Patent Document 2 a fluorine-containing polymer and nitrile rubber are used in combination as a binder for forming an electrode layer of a lithium ion secondary battery.
  • the active material density relatively decreases, so that a sufficient battery capacity may not be obtained.
  • the degree of swelling of the electrode layer with respect to the electrolytic solution also increases, and the peel strength particularly at the time of a high potential cycle is lowered, and the cycle characteristics may be deteriorated.
  • Patent Document 3 a fluorine-containing polymer and a crosslinked acrylate polymer are used in combination as a binder.
  • the cross-linked acrylate polymer since the cross-linked acrylate polymer is used, swelling of the electrode layer with respect to the electrolytic solution is suppressed.
  • the cross-linked acrylate polymer since the cross-linked acrylate polymer is present in the form of particles, the dispersibility becomes insufficient. Cycle characteristics may deteriorate.
  • an object of the present invention is to provide a high-capacity lithium ion secondary battery that is flexible, does not generate cracks in the electrode layer when bent, and has excellent high potential cycle characteristics.
  • the present inventors have used a nitrile group-containing acrylic polymer as a binder for the positive electrode, and the swelling degree of the nitrile group-containing acrylic polymer with respect to the nonaqueous electrolyte solution and By setting the THF-insoluble content in a specific range, the nitrile group-containing acrylic polymer dissolves in the dispersion medium of the positive electrode slurry composition but does not dissolve in the electrolyte solution having a similar solubility parameter (SP value). It was found that it can be swollen in an appropriate range.
  • SP value solubility parameter
  • the capacity can be increased, and as a binder for the positive electrode, the nitrile group-containing material can be used.
  • acrylic polymer and fluorine-containing polymer in combination, it is flexible, there is no generation of cracks in the electrode layer when bent, and an electrode with a high active material density can be obtained.
  • output characteristics and high potential cycle characteristics It was found that an excellent high-capacity lithium ion secondary battery can be obtained. The present invention has been completed based on these findings.
  • the gist of the present invention is as follows.
  • a lithium ion secondary battery comprising a negative electrode, a positive electrode and a non-aqueous electrolyte,
  • the negative electrode includes an alloy-based active material
  • the positive electrode includes a positive electrode active material, a positive electrode binder and a conductive material
  • the positive electrode binder includes a nitrile group-containing acrylic polymer and a fluorine-containing polymer,
  • the degree of swelling of the nitrile group-containing acrylic polymer with respect to the non-aqueous electrolyte is 3 times or less, and the THF-insoluble content is 30% by mass or less.
  • the conductive material has a particle size of 5 to 40 nm. Lithium ion secondary battery.
  • the content ratio of the nitrile group-containing acrylic polymer is 50 to 5% by mass and the content ratio of the fluorine-containing polymer is 50 to 95% by mass.
  • an alloy-based active material is used for the negative electrode in order to improve capacity
  • a conductive material powder finely divided is used for the positive electrode
  • a fluorine-containing polymer and a nitrile group-containing acrylic polymer are used as a binder.
  • the lithium ion secondary battery according to the present invention includes a negative electrode, a positive electrode, and a non-aqueous electrolyte.
  • the negative electrode includes an alloy-based active material
  • the positive electrode includes a positive electrode active material, a positive electrode binder, and a conductive material.
  • the positive electrode binder includes a nitrile group-containing acrylic polymer and a fluorine-containing polymer.
  • the swelling degree of the nitrile group-containing acrylic polymer with respect to the nonaqueous electrolytic solution is 3 times or less, and the THF insoluble content is 30% by mass or less.
  • the particle diameter of the positive electrode conductive material is 5 to 40 nm.
  • the negative electrode includes a current collector and a negative electrode active material layer laminated on the current collector.
  • the negative electrode active material layer contains, as the negative electrode active material (a), an alloy-based active material (a1) and, if necessary, other carbon-based active materials (a2).
  • the negative electrode active material is a substance that delivers electrons (lithium ions) in the negative electrode.
  • an alloy-based active material (a1) is used, and a carbon-based active material (a2) can be used as necessary.
  • the negative electrode active material preferably includes an alloy-based active material and a carbon-based active material.
  • An alloy-based active material includes an element into which lithium can be inserted, and has a theoretical electric capacity of 500 mAh / g or more when lithium is inserted (the upper limit of the theoretical electric capacity) Is not particularly limited, but can be, for example, 5000 mAh / g or less.), Specifically, a single metal forming a lithium alloy and an alloy thereof, and oxides and sulfides thereof Nitride, silicide, carbide, phosphide and the like are used.
  • Examples of simple metals and alloys that form lithium alloys include Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, and Zn.
  • the compound to contain is mentioned.
  • silicon (Si), tin (Sn) or lead (Pb) simple metals, alloys containing these atoms, or compounds of these metals are preferable.
  • a Si simple metal capable of inserting and extracting lithium at a low potential is more preferable.
  • the alloy-based active material may further contain one or more nonmetallic elements.
  • SiOC, SiO x , and SiC that can insert and desorb lithium at a low potential are preferable, and SiOC SiO x is more preferred.
  • SiOC can be obtained by firing a polymer material containing silicon.
  • the range of 0.8 ⁇ x ⁇ 3 and 2 ⁇ y ⁇ 4 is preferably used in view of the balance between capacity and cycle characteristics.
  • Lithium alloy-forming elemental metal and its oxides, sulfides, nitrides, silicides, carbides and phosphides include lithium-insertable element oxides, sulfides, nitrides, silicides and carbides And phosphides, and oxides are particularly preferable.
  • an oxide such as tin oxide, manganese oxide, titanium oxide, niobium oxide, vanadium oxide, or a lithium-containing metal composite oxide containing a metal element selected from the group consisting of Si, Sn, Pb, and Ti atoms is preferable.
  • a lithium titanium composite oxide represented by Li x Ti y M z O 4 (0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3, 0 ⁇ z ⁇ 1.6, M includes Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb), among which Li 4/3 Ti 5/3 O 4 , Li 1 Ti 2 O 4 and Li 4/5 Ti 11/5 O 4 are preferred.
  • active materials containing silicon are preferable. By using an active material containing silicon, the electric capacity of the secondary battery can be increased. Furthermore, among the active materials containing silicon, SiO x C y , SiO x , and SiC are more preferable. In an active material containing a combination of silicon and carbon, it is assumed that Si (silicon) is inserted at a high potential, and Li is inserted into and desorbed from C (carbon) at a low potential. Since the shrinkage is suppressed, the effect of the present invention is more easily obtained.
  • the alloy-based active material is preferably a particle-sized one.
  • the shape of the particles is spherical, a higher density electrode can be formed during electrode molding.
  • the volume average particle diameter is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 20 ⁇ m, and particularly preferably 1 to 10 ⁇ m.
  • the volume average particle diameter of the alloy-based active material is within this range, the slurry composition used for producing the negative electrode can be easily produced.
  • the volume average particle diameter in this invention can be calculated
  • the tap density of the alloy-based active material is not particularly limited, but is preferably 0.6 g / cm 3 or more.
  • the specific surface area of alloy-formable active material is preferably 3.0 ⁇ 20.0m 2 / g, more preferably 3.5 ⁇ 15.0m 2 / g, particularly preferably 4.0 ⁇ 10.0 m 2 / g.
  • the “BET specific surface area” means a BET specific surface area determined by a nitrogen adsorption method, and is a value measured according to ASTM D3037-81.
  • the carbon-based active material refers to an active material having carbon as a main skeleton into which lithium can be inserted, and specifically includes a carbonaceous material and a graphite material.
  • the carbonaceous material is generally a carbon material having a low graphitization degree (that is, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or less.
  • the minimum of the temperature of the said heat processing is not specifically limited, For example, it can be 500 degreeC or more.
  • the graphite material is a graphite material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher.
  • the upper limit of the said processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
  • Examples of the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
  • graphitizable carbon examples include carbon materials made from tar pitch obtained from petroleum or coal. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fibers, pyrolytic vapor grown carbon fibers, and the like.
  • MCMB is carbon fine particles obtained by separating and extracting mesophase spherules produced in the process of heating pitches at around 400 ° C.
  • the mesophase pitch-based carbon fiber is a carbon fiber using as a raw material mesophase pitch obtained by growing and coalescing the mesophase microspheres.
  • Pyrolytic vapor-grown carbon fibers are (1) a method for pyrolyzing acrylic polymer fibers, (2) a method for spinning by spinning a pitch, and (3) using nanoparticles such as iron as a catalyst. It is a carbon fiber obtained by a catalytic vapor deposition (catalytic CVD) method in which hydrocarbon is vapor-phase pyrolyzed.
  • catalytic CVD catalytic vapor deposition
  • non-graphitizable carbon examples include phenol resin fired bodies, polyacrylonitrile-based carbon fibers, pseudo-isotropic carbon, furfuryl alcohol resin fired bodies (PFA), and hard carbon.
  • Examples of the graphite material include natural graphite and artificial graphite.
  • Examples of artificial graphite include artificial graphite heat-treated at 2800 ° C or higher, graphitized MCMB heat-treated at 2000 ° C or higher, graphitized mesophase pitch carbon fiber heat-treated at 2000 ° C or higher. It is done.
  • a graphite material is preferable.
  • the density of the negative electrode active material layer is 1.6 g / cm 3 or more (the upper limit of the density is not particularly limited, but 2.2 g / cm 3) or less.) Can be easily produced. If the negative electrode has a negative electrode active material layer in which the density of the negative electrode active material layer is in the above range, the effect of the present invention is remarkably exhibited.
  • the carbon-based active material is preferably a particle-sized one.
  • the shape of the particles is spherical, a higher density electrode can be formed during electrode molding.
  • the carbon-based active material is a particle
  • the volume-average particle size of the carbon-based active material is preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
  • the volume average particle diameter of the carbon-based active material is within this range, it becomes easy to prepare a slurry composition used for manufacturing the negative electrode.
  • the tap density of the carbon-based active material is not particularly limited, but is preferably 0.6 g / cm 3 or more.
  • the specific surface area of the carbon-based active material preferably 3.0 ⁇ 20.0m 2 / g, more preferably 3.5 ⁇ 15.0m 2 / g, particularly preferably 4.0 ⁇ 10.0m 2 / g is there.
  • the specific surface area can be measured by, for example, the BET method.
  • the negative electrode active material one type of alloy-based active material may be used alone, or two or more types may be used in combination at any ratio. Moreover, the active material which combined the alloy type active material and the carbon type active material can be mentioned as a preferable aspect of a negative electrode active material.
  • the mixing method is not particularly limited, and conventionally known dry mixing and wet mixing may be mentioned. .
  • the alloy-based active material (a1) and the carbon-based active material (a2) are used in combination, the alloy-based active material (a1) with respect to 100 parts by mass of the carbon-based active material (a2). Is preferably contained in an amount of 1 to 50 parts by mass.
  • a battery having a larger capacity than the negative electrode obtained using only the conventional carbon-based active material can be obtained, and the adhesion strength of the negative electrode can be increased. It is possible to prevent deterioration and cycle characteristics. If it is a negative electrode which has a negative electrode active material layer which uses an alloy type active material (a1) and a carbon type active material (a2) together in the said range, the effect of this invention will show up notably.
  • the negative electrode binder is a component that binds the electrode active material to the surface of the current collector in the negative electrode, has excellent performance of holding the negative electrode active material, and adheres to the current collector. It is preferable to use one having a high value.
  • a polymer is used as the binder material.
  • a polymer, a homopolymer, or a copolymer may be used as a binder material.
  • the polymer for the binder for the negative electrode is not particularly limited, and examples thereof include polymer compounds such as fluoropolymers, diene polymers, acrylate polymers, polyimides, polyamides, polyurethanes, among others, fluoropolymers.
  • a diene polymer or an acrylate polymer is preferable, a withstand voltage can be increased, and an energy density of an electrochemical element can be increased, and a diene polymer or an acrylate polymer is more preferable, and the strength of the electrode is improved. Diene polymers are particularly preferred.
  • the diene polymer is a polymer including a structural unit formed by polymerizing a conjugated diene monomer (hereinafter sometimes referred to as “conjugated diene monomer unit”). Examples include diene homopolymers; copolymers of different types of conjugated dienes; copolymers obtained by polymerizing monomer mixtures containing conjugated dienes, or hydrogenated products thereof.
  • Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, and 2-chloro- Examples include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 2,4-hexadiene. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable.
  • a conjugated diene may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the conjugated diene monomer unit in the diene polymer is preferably 20% by mass to 60% by mass, and preferably 30% by mass to 55% by mass.
  • the diene polymer includes a structural unit formed by polymerizing a nitrile group-containing monomer (hereinafter sometimes referred to as “nitrile group-containing monomer unit”). Also good.
  • nitrile group-containing monomer include ⁇ , ⁇ -unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, and the like. Among them, acrylonitrile is preferable.
  • the proportion of the nitrile group-containing monomer unit in the diene polymer is preferably in the range of 5 to 40% by mass, more preferably 5 to 30% by mass.
  • a nitrile group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the diene polymer may contain a structural unit formed by polymerizing another monomer in addition to the monomer unit.
  • Other monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid; styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene.
  • Styrene monomers such as chloromethylstyrene, hydroxymethylstyrene, ⁇ -methylstyrene and divinylbenzene; olefins such as ethylene and propylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Amide monomers such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone Butyl vinyl ketone, hexyl vinyl ketone, such as isopropenyl vinyl ketone; N- vinylpyrrolidone, vinylpyridine, and a heterocyclic containing vinyl compounds such as vinyl imidazole.
  • the said other monomer may be used individually by 1 type, respectively, and may be used combining two or more types by arbitrary ratios.
  • the acrylate polymer is represented by the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group). It is a polymer containing a monomer unit formed by polymerizing a monomer derived from a compound (hereinafter sometimes referred to as “(meth) acrylate monomer unit”).
  • the monomer constituting the (meth) acrylate ester monomer unit include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, Acrylic acid esters such as n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n methacrylate Methacryl such as butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl me
  • acrylate esters are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
  • the ratio of the (meth) acrylic acid ester monomer unit in the acrylate polymer is usually 50% by mass or more, preferably 70% by mass or more.
  • the acrylate polymer preferably contains a nitrile group-containing monomer unit in addition to the (meth) acrylic acid ester monomer unit.
  • the nitrile group-containing monomer include acrylonitrile and methacrylonitrile. Among them, acrylonitrile is preferable in that the binding strength between the current collector and the electrode mixture layer is increased and the electrode strength can be improved.
  • the ratio of the nitrile group-containing monomer unit in the acrylate polymer is preferably in the range of 5 to 35% by mass, more preferably 10 to 30% by mass.
  • the acrylate polymer may be a monomer unit formed by polymerizing a copolymerizable carboxylic acid group-containing monomer (hereinafter referred to as “carboxylic acid group-containing monomer unit”). May be written.)).
  • carboxylic acid group-containing monomer include monobasic acid-containing monomers such as acrylic acid and methacrylic acid; dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid.
  • a dibasic acid-containing monomer is preferable, and itaconic acid is particularly preferable in terms of enhancing the binding property with the current collector and improving the electrode strength.
  • the proportion of the carboxylic acid group-containing monomer unit in the acrylate polymer is preferably in the range of 1 to 50% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.
  • the acrylate polymer may contain a structural unit obtained by polymerizing another copolymerizable monomer in addition to the above monomer.
  • the other monomers include carboxylic acid esters having two or more carbon-carbon double bonds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate; perfluorooctylethyl acrylate and perfluoro Unsaturated esters containing fluorine in the side chain such as octylethyl methacrylate; styrene, chlorostyrene, vinyltoluene, t-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, Styrene monomers such as ⁇ -methylstyrene and divinylbenzene; Amide monomers such as acrylamide, N-methylolacrylamide
  • Heterocycle-containing vinyl compounds such as allyl glycidyl ether; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate.
  • the content ratio of these copolymerizable other monomer units in the acrylate polymer may be appropriately adjusted depending on the purpose of use.
  • binders for negative electrodes include polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl isobutyl ether, poly Vinyl polymers such as acrylonitrile, polymethacrylonitrile, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyallyl acetate, and polystyrene; main chains such as polyoxymethylene, polyoxyethylene, polycyclic thioether, and polydimethylsiloxane An ether polymer containing a hetero atom in the polycondensate ester polymer such as polylactone, polycyclic anhydride, polyethylene terephthalate, polycarbonate; nylon 6, nylon 66, poly- - phenylene isophthalamide, poly -p- phenylene
  • the shape of the binder for the negative electrode is not particularly limited, but it has good adhesion to the current collector, and since it can suppress deterioration of the capacity of the created electrode and repeated charge / discharge, it is particulate. It is preferable that The particulate binder is not particularly limited as long as it retains and exists in the state of being dispersed in a dispersion medium. However, it is preferable that the particulate binder can be present in a state of retaining the particle shape even in the negative electrode active material layer. In the present invention, the “state in which the particle state is maintained” does not have to be a state in which the particle shape is completely maintained, and may be in a state in which the particle shape is maintained to some extent. Examples of the particulate binder include those in which the binder particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
  • the glass transition temperature (Tg) of the binder for negative electrode is preferably 50 ° C. or lower, more preferably ⁇ 40 to 0 ° C.
  • Tg glass transition temperature
  • the number average particle diameter is not particularly limited, but is usually 0.01 to 1 ⁇ m, preferably 0.03 to 0.8 ⁇ m, more preferably. 0.05 to 0.5 ⁇ m.
  • the number average particle diameter of the binder is within this range, excellent adhesion can be imparted to the negative electrode active material layer even with a small amount of use.
  • the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph. The shape of the particles can be either spherical or irregular. These binders can be used alone or in combination of two or more.
  • the amount of the binder for the negative electrode is usually in the range of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material. is there. When the amount of the binder is within this range, sufficient adhesion between the obtained negative electrode active material layer and the current collector can be secured, the capacity of the electrochemical device can be increased, and the internal resistance can be decreased.
  • the conductive material negative electrode active material layer may contain a conductive material.
  • the particle diameter of the conductive material contained in the negative electrode active material layer is a number average particle diameter of 5 to 40 nm, preferably 10 to 38 nm, more preferably 15 to 36 nm.
  • conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used.
  • the content of the conductive material is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the negative electrode active material.
  • the negative electrode active material layer may further contain, as an optional component, a reinforcing material, a leveling agent, an electrolytic solution additive having a function of inhibiting electrolytic decomposition, and the like.
  • a reinforcing material such as aluminum, copper, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • the reinforcing material various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used.
  • a reinforcing material By using a reinforcing material, a tough and flexible negative electrode can be obtained, and excellent long-term cycle characteristics can be exhibited.
  • the content of the reinforcing material is usually 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the negative electrode active material. By including the reinforcing material in the above range, high capacity and high load characteristics can be exhibited.
  • leveling agent examples include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.
  • surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.
  • the electrolytic solution additive vinylene carbonate used in the electrolytic solution can be used.
  • the content of the electrolytic solution additive is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the negative electrode active material.
  • the obtained secondary battery is excellent in cycle characteristics and high temperature characteristics.
  • Other additives include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the slurry composition adjusted when producing the negative electrode can be controlled, and the leveling property of the negative electrode active material layer obtained thereby can be improved.
  • the content of the nanoparticles is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the negative electrode active material.
  • thickener examples include cellulose compounds such as carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxyethylmethylcellulose (ammonium salts and alkali metal salts thereof). Salt), oxidized starch, phosphate starch, casein, various modified starches, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polysulfonic acid, polycarboxylic acid, acrylic acid or methacrylic acid copolymer (these Ammonium salts and alkali metal salts (including salts such as sodium salts and lithium salts) Rukoto can.
  • cellulose compounds such as carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxyethylmethylcellulose (
  • cellulose compounds including salts such as ammonium salts and alkali metal salts thereof
  • polysulfonic acid from the viewpoint of excellent stability of the slurry when producing the negative electrode and the suppression of swelling of the obtained negative electrode
  • acrylic acid or methacrylic acid copolymer including salts such as ammonium salts and alkali metal salts thereof
  • acrylic acid or methacrylic acid copolymers are copolymerizable components other than acrylic acid and methacrylic acid, such as methyl acrylate and methyl methacrylate.
  • the content of the thickener is preferably 0.05 to 10 parts by mass, more preferably 0.08 to 3 parts by mass with respect to 100 parts by mass of the negative electrode active material.
  • the slurry composition for a lithium ion secondary battery negative electrode includes the negative electrode active material (a), the binder for negative electrode (b), the conductive material (c), and the like. Are mixed in a dispersion medium.
  • a dispersion medium either water or an organic solvent can be used.
  • organic solvents examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexanone and ethylcyclohexanone.
  • Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone; Alkyl nitriles such as acetonitrile and propionitrile; Tetrahydrofuran and Ethylene Ethers such as glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; N- Amides such as methylpyrrolidone and N, N-dimethylformamide can be mentioned.
  • dispersion media may be used alone or in combination of two or more as a mixed solvent.
  • a dispersion medium having excellent dispersibility of each component and having a low boiling point and high volatility is preferable because it can be removed in a short time and at a low temperature.
  • acetone, toluene, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, water, N-methylpyrrolidone, or a mixed solvent thereof is preferable.
  • the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
  • a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
  • a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
  • Lithium ion secondary battery negative electrode A lithium ion secondary battery negative electrode is obtained by applying and drying the above-described slurry composition for a lithium ion secondary battery negative electrode on a current collector.
  • the method for producing a negative electrode for a lithium ion secondary battery includes a step of forming a negative electrode active material layer by applying and drying the slurry composition for a negative electrode on one or both sides of a current collector.
  • the method for applying the negative electrode slurry composition onto the current collector is not particularly limited.
  • Examples of the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
  • drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • the drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
  • the porosity of the negative electrode active material layer is increased by pressure treatment using a die press or a roll press. It is preferable to have a lowering step.
  • the porosity of the negative electrode active material layer is preferably 5 to 30%, more preferably 7 to 20%. If the porosity of the negative electrode active material layer is too high, charging efficiency and discharging efficiency may be deteriorated. If the porosity is too low, it is difficult to obtain a high volume capacity, and the negative electrode active material layer is likely to be peeled off from the current collector, which may cause defects. Further, when a curable polymer is used as the binder, it is preferably cured.
  • the thickness of the negative electrode active material layer in the negative electrode of the lithium ion secondary battery is usually 5 to 300 ⁇ m, preferably 30 to 250 ⁇ m. When the thickness of the negative electrode active material layer is in the above range, it is possible to obtain a secondary battery that exhibits high load characteristics and cycle characteristics.
  • the content ratio of the negative electrode active material in the negative electrode active material layer is preferably 85 to 99% by mass, more preferably 88 to 97% by mass.
  • the content ratio of the negative electrode active material in the negative electrode active material layer is in the above range, it is possible to obtain a secondary battery that exhibits flexibility and binding properties while exhibiting high capacity.
  • the density of the negative electrode active material layer is preferably 1.6 ⁇ 1.9g / cm 3, more preferably 1.65 ⁇ 1.85g / cm 3. When the density of the negative electrode active material layer is within the above range, a high-capacity secondary battery can be obtained.
  • the current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but is preferably a metal material because of its heat resistance, for example, iron, copper, aluminum, nickel, stainless steel. Examples include steel, titanium, tantalum, gold, and platinum. Among these, copper is particularly preferable as the current collector used for the negative electrode of the lithium ion secondary battery.
  • the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable.
  • the current collector may be used after roughening in advance in order to increase the adhesive strength with the negative electrode active material layer.
  • Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • a mechanical polishing method an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
  • a primer layer or the like may be formed on the current collector surface in order to increase the adhesive strength or conductivity of the negative electrode active material layer.
  • the positive electrode includes a current collector and a positive electrode active material layer laminated on the current collector.
  • the positive electrode active material layer includes a positive electrode active material (A), a positive electrode binder (B), and a conductive material (C), and includes other components as necessary.
  • Positive electrode active material As the positive electrode active material, an active material capable of inserting and removing lithium ions is used. Such a positive electrode active material is roughly classified into an inorganic compound and an organic compound.
  • Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
  • Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
  • Transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle characteristics and capacity.
  • lithium-containing composite metal oxide examples include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn lithium composite oxide (Li (Co Mn Ni) O 2 ), lithium-excess layered compound (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 ), Ni—Mn—Al lithium composite oxide, Ni—Co—Al lithium composite oxide, etc. It is done.
  • the lithium-containing composite metal oxide having a spinel structure examples include Li [Mn 3/2 M 1/2 ] O 4 in which lithium manganate (LiMn 2 O 4 ) or a part of Mn is substituted with another transition metal. (Where M is Cr, Fe, Co, Ni, Cu, etc.).
  • lithium-containing composite metal oxide having an olivine structure examples include Li X MPO 4 (wherein M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti).
  • the positive electrode active material made of an organic compound for example, a conductive polymer such as polyacetylene or poly-p-phenylene can be used. Further, an iron-based oxide having poor electrical conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. Further, those compounds obtained by partial element substitution of these compounds may be used.
  • the positive electrode active material for a lithium ion secondary battery may be a mixture of the above inorganic compound and organic compound.
  • the volume average particle diameter of the positive electrode active material is usually 1 to 50 ⁇ m, preferably 2 to 30 ⁇ m.
  • the average particle diameter of the positive electrode active material is in the above range, the amount of the positive electrode binder in the positive electrode active material layer can be reduced, and the decrease in the capacity of the battery can be suppressed.
  • a slurry containing a positive electrode active material and a positive electrode binder (hereinafter sometimes referred to as “positive electrode slurry composition”) is usually prepared.
  • This positive electrode slurry composition can be easily prepared to have a viscosity suitable for application, and a uniform positive electrode active material layer can be obtained.
  • the content ratio of the positive electrode active material in the positive electrode active material layer is preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass.
  • Binder for positive electrode contains a nitrile group-containing acrylic polymer (B1) and a fluorine-containing polymer (B2).
  • Nitrile group-containing acrylic polymer The nitrile group-containing acrylic polymer is a polymer containing a nitrile group-containing monomer unit and a (meth) acrylic acid ester monomer unit.
  • a nitrile group-containing monomer unit is a structural unit formed by polymerizing a nitrile group-containing monomer, and a (meth) acrylate monomer unit is a (meth) acrylate monomer Refers to a structural unit formed by polymerizing.
  • the nitrile group-containing acrylic polymer (B1) contains a nitrile group-containing monomer unit, preferably a (meth) acrylic acid ester monomer unit, and, if necessary, an ethylenically unsaturated acid monomer unit. And monomer units derived from other monomers such as crosslinkable monomers. These monomer units are structural units formed by polymerizing the monomers.
  • the content ratio of each monomer is usually the same as the content ratio of each monomer unit in the nitrile group-containing acrylic polymer.
  • nitrile group-containing monomer examples include acrylonitrile and methacrylonitrile.
  • acrylonitrile is preferable because it can improve the adhesion to the current collector and the electrode strength.
  • the content ratio of the nitrile group-containing monomer unit in the nitrile group-containing acrylic polymer (B1) is preferably in the range of 5 to 35% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass. is there.
  • the amount of the nitrile group-containing monomer unit is within this range, the adhesion to the current collector is excellent, and the strength of the obtained electrode is improved.
  • the (meth) acrylic acid ester monomer unit has the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group or a cycloalkyl group). It is a structural unit formed by polymerizing a monomer derived from the compound represented by
  • Specific examples of the compound represented by the general formula (1) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, Acrylates such as isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, meta Methacrylates such as isobutyl acrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl
  • (Meth) acrylic acid ester monomer may be used alone or in combination of two or more at any ratio. Therefore, the nitrile group-containing acrylic polymer (B1) may contain only one type of (meth) acrylic acid ester monomer, or may contain two or more types in combination at any ratio.
  • the content ratio of the (meth) acrylic acid ester monomer unit in the nitrile group-containing acrylic polymer (B1) is preferably 35 to 85% by mass, more preferably 45 to 75% by mass, and particularly preferably 50 to 70% by mass. %.
  • the electrode active material is highly flexible and the swellability is suppressed in the electrolytic solution. Moreover, heat resistance is high and the internal resistance of the obtained electrode for electrochemical devices can be reduced.
  • the nitrile group-containing acrylic polymer may contain an ethylenically unsaturated acid monomer unit in addition to the monomer unit having the nitrile group and the (meth) acrylic acid ester monomer unit.
  • the ethylenically unsaturated acid monomer unit is a structural unit formed by polymerizing an ethylenically unsaturated acid monomer.
  • the ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphinyl group, and is not limited to a specific monomer.
  • ethylenically unsaturated acid monomer examples include an ethylenically unsaturated carboxylic acid monomer, an ethylenically unsaturated sulfonic acid monomer, and an ethylenically unsaturated phosphoric acid monomer.
  • ethylenically unsaturated carboxylic acid monomer examples include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
  • ethylenically unsaturated monocarboxylic acids examples include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of derivatives of ethylenically unsaturated monocarboxylic acids include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, And ⁇ -diaminoacrylic acid.
  • ethylenically unsaturated dicarboxylic acids examples include maleic acid, fumaric acid, and itaconic acid.
  • acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • Examples of derivatives of ethylenically unsaturated dicarboxylic acids include methyl maleate such as methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid; and diphenyl maleate, nonyl maleate And maleate esters such as decyl maleate, dodecyl maleate, octadecyl maleate and fluoroalkyl maleate.
  • ethylenically unsaturated sulfonic acid monomer examples include vinyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, (meth) acryl sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide- 2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like.
  • ethylenically unsaturated phosphoric acid monomer examples include (meth) acrylic acid-3-chloro-2-propyl phosphate, (meth) acrylic acid-2-ethyl phosphate, 3-allyloxy-2-hydroxypropane Such as phosphoric acid.
  • alkali metal salts or ammonium salts of the above ethylenically unsaturated acid monomers can be used.
  • the above ethylenically unsaturated acid monomers may be used alone or in combination of two or more at any ratio. Therefore, the nitrile group-containing acrylic polymer (B1) may contain only one type of ethylenically unsaturated acid monomer, or may contain two or more types in combination at any ratio.
  • the ethylenically unsaturated acid monomer may be an ethylenically unsaturated carboxylic acid monomer or an ethylenically unsaturated sulfonic acid.
  • the monomer is used alone or in combination with an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated sulfonic acid monomer.
  • the ethylenically unsaturated carboxylic acid monomer and the ethylenically unsaturated sulfonic acid are preferred.
  • a combination with a monomer is more preferred.
  • ethylenically unsaturated carboxylic acid monomers from the viewpoint of expressing good dispersibility in the nitrile group-containing acrylic polymer (B1), ethylenically unsaturated monocarboxylic acid is preferable, and acrylic acid is more preferable.
  • methacrylic acid particularly preferably methacrylic acid.
  • 2-acrylamido-2-hydroxypropanesulfonic acid 2-acrylamido-2-hydroxypropanesulfonic acid
  • 2-nitrile group-containing acrylic polymer (B1) is preferably used from the viewpoint of exhibiting good dispersibility.
  • Acrylamide-2-methylpropanesulfonic acid more preferably 2-acrylamido-2-methylpropanesulfonic acid.
  • the content of the ethylenically unsaturated acid monomer unit in the nitrile group-containing acrylic polymer (B1) is preferably 10 to 30% by mass, more preferably 12 to 28% by mass, and particularly preferably 14 to 26% by mass. It is a range.
  • the ethylenically unsaturated carboxylic acid in the nitrile group-containing acrylic polymer (B1)
  • the content ratio of the acid monomer is preferably 10 to 30% by mass, more preferably 12 to 28% by mass, and the content ratio of the ethylenically unsaturated sulfonic acid monomer is preferably 0.1 to 10% by mass. %.
  • the nitrile group-containing acrylic polymer (B1) may contain a conjugated diene monomer unit in addition to the monomer unit having the nitrile group and the (meth) acrylate monomer unit.
  • the conjugated diene monomer unit is a structural unit formed by polymerizing a conjugated diene monomer and / or a structural unit formed by polymerizing a conjugated diene monomer and hydrogenating it.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene, and the like. 1,3-butadiene and isoprene Is preferred, and 1,3-butadiene is more preferred.
  • the said conjugated diene monomer may be used individually by 1 type, and may combine 2 or more types by arbitrary ratios. Therefore, the nitrile group-containing acrylic polymer (B1) may contain only one type of conjugated diene monomer unit, or may contain two or more types in combination at any ratio.
  • the content ratio of the conjugated diene monomer unit (content ratio including the hydrogenated monomer unit) in the nitrile group-containing acrylic polymer (B1) is preferably 20 to 98% by mass, more preferably 20 to 80% by mass. %, Particularly preferably in the range of 20 to 70% by mass.
  • the nitrile group-containing acrylic polymer (B1) further includes a crosslinkable monomer unit within a range that does not affect the THF-insoluble content of the nitrile group-containing acrylic polymer (B1). May be included.
  • the crosslinkable monomer unit is a structural unit capable of forming a crosslinked structure during or after polymerization by heating or energy irradiation of the crosslinkable monomer.
  • a monomer having thermal crosslinkability can be usually mentioned. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule. Ionic monomers.
  • thermally crosslinkable groups contained in the monofunctional monomer include epoxy groups, N-methylolamide groups, oxetanyl groups, oxazoline groups, and combinations thereof.
  • an epoxy group is more preferable in terms of easy adjustment of crosslinking and crosslinking density.
  • crosslinkable monomer having an epoxy group as a thermally crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl.
  • Unsaturated glycidyl ethers such as ether; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate Glycidyl crotonate Unsaturated carboxylic acids such as glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of
  • crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable group and having an olefinic double bond have a methylol group such as N-methylol (meth) acrylamide (meta ) Acrylamides.
  • crosslinkable monomer having an oxetanyl group as a thermally crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl) ) -4-Trifluoromethyloxetane.
  • crosslinkable monomer having an oxazoline group as a heat crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
  • multifunctional monomers having two or more olefinic double bonds include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl Ethers, allyl or vinyl ethers of polyfunctional alcohols other than those mentioned above, triallylamine, methylene bisacrylamide, and divinylbenzene.
  • crosslinkable monomer in particular, allyl (meth) acrylate, ethylene di (meth) acrylate, allyl glycidyl ether, and glycidyl methacrylate can be preferably used.
  • the above crosslinkable monomers may be used alone or in combination of two or more at any ratio. Therefore, the nitrile group-containing acrylic polymer (B1) may contain only one type of crosslinkable unsaturated acid monomer, or may contain two or more types in combination at any ratio.
  • the content ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.8%. It is 5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 2% by mass or less.
  • the dispersibility of a nitrile group containing acrylic polymer (B1) can be made favorable by making the ratio of a crosslinkable monomer unit below the upper limit of the said range. Therefore, by setting the content ratio of the crosslinkable monomer unit within the above range, both the degree of swelling and the dispersibility can be improved.
  • the nitrile group-containing acrylic polymer (B1) may contain an aromatic vinyl monomer unit, an ethylenically unsaturated carboxylic acid amide monomer unit, and the like.
  • aromatic vinyl monomers examples include styrene, ⁇ -methyl styrene, vinyl toluene, chlorostyrene, hydroxymethyl styrene and the like.
  • Examples of the ethylenically unsaturated carboxylic acid amide monomer include (meth) acrylamide, N-methoxymethyl (meth) acrylamide and the like.
  • the dispersibility of the nitrile group-containing acrylic polymer (B1) when slurried is high and a highly uniform active material layer can be formed, and the resistance of the positive electrode active material layer can be reduced. Can be reduced.
  • These monomer units may be contained in a proportion of 10% by mass or less.
  • the content ratio of each monomer is usually each monomer unit in the nitrile group-containing acrylic polymer (for example, (meth) acrylic acid ester monomer unit, ethylenically unsaturated acid monomer unit, The content ratio of the conjugated diene monomer unit and the crosslinkable monomer unit) is the same.
  • the degree of swelling of the nitrile group-containing acrylic polymer (B1) with respect to the non-aqueous electrolyte is 1.0 to 3 times, in order to avoid the volume of the polymer from changing significantly in the electrolyte, preferably It is 1.0 to 2.8 times, more preferably 1.0 to 2.6 times.
  • the nonaqueous electrolytic solution is an electrolytic solution constituting the lithium ion secondary battery of the present invention.
  • the degree of swelling with respect to the nonaqueous electrolytic solution can be controlled by, for example, the content ratio of each monomer unit described above. Specifically, it increases when the content ratio of the nitrile group-containing monomer unit is increased. Moreover, it decreases when the content of the ethylenically unsaturated monomer unit is increased.
  • the tetrahydrofuran (THF) insoluble amount of the nitrile group-containing acrylic polymer (B1) is 30% by mass or less, preferably 25% by mass or less, in order to appropriately dissolve the polymer in the slurry dispersion medium. More preferably, it is in the range of 20% by mass or less.
  • the THF-insoluble matter is an indicator of the amount of gel, and if the amount of THF-insoluble matter is large, it exists in the form of particles in a slurry using an organic solvent such as N-methylpyrrolidone (hereinafter sometimes referred to as NMP). The dispersibility in a slurry may be impaired.
  • the THF-insoluble content can be controlled by the polymerization reaction temperature, the monomer addition time, the polymerization initiator amount, and the like. Specifically, the amount of insoluble matter is reduced by increasing the polymerization reaction temperature, increasing the polymerization initiator, and the chain transfer agent.
  • the electrolyte solution and the organic solvent that is the slurry dispersion medium have close solubility parameters (SP values)
  • SP values solubility parameters
  • the swelling degree of the polymer used as the binder with respect to the electrolyte solution is within an appropriate range, the slurry dispersion medium In some organic solvents, such a polymer may not be dissolved (the amount of insoluble THF is excessive). On the contrary, if such a polymer is easily dissolved in an organic solvent, the degree of swelling of the polymer with respect to the electrolytic solution may be reduced. In some cases, the degree of swelling and the amount insoluble in THF are both within the appropriate range.
  • the production method of the nitrile group-containing acrylic polymer (B1) is not particularly limited, as described above, the monomer mixture containing the monomer constituting the nitrile group-containing acrylic polymer (B1) is emulsion-polymerized, If necessary, it can be obtained by hydrogenation.
  • the method for emulsion polymerization is not particularly limited, and a conventionally known emulsion polymerization method may be employed.
  • the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
  • a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
  • the method of hydrogenation is not specifically limited, A well-known method should just be employ
  • Examples of the polymerization initiator used for emulsion polymerization include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as oxide and t-butylperoxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc. Et That.
  • inorganic peroxides can be preferably used.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the peroxide initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
  • the amount of the polymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture used for the polymerization.
  • a chain transfer agent used during emulsion polymerization.
  • the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenols such as 2,6-di-t-butyl-4-methylphenol and st
  • alkyl mercaptans are preferable, and t-dodecyl mercaptan can be more preferably used.
  • chain transfer agents can be used alone or in combination of two or more.
  • the amount of the chain transfer agent used is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the monomer mixture.
  • a surfactant may be used during emulsion polymerization.
  • the surfactant may be any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • Specific examples of the anionic surfactant include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and the like.
  • alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium lauryl benzene sulfonate, sodium hexadecyl benzene sulfonate
  • fats such as sodium lauryl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate Group sulfonates; and the like.
  • the amount of the surfactant used is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture.
  • seed latex refers to a dispersion of fine particles that becomes the nucleus of the reaction during emulsion polymerization.
  • the fine particles often have a particle size of 100 nm or less.
  • the fine particles are not particularly limited, and general-purpose polymers such as diene polymers are used. According to the seed polymerization method, copolymer particles having a relatively uniform particle diameter can be obtained.
  • the polymerization temperature for carrying out the polymerization reaction is not particularly limited, but is usually 0 to 100 ° C., preferably 40 to 80 ° C. Emulsion polymerization is performed in such a temperature range, and the polymerization reaction is stopped at a predetermined polymerization conversion rate by adding a polymerization terminator or cooling the polymerization system.
  • the polymerization conversion rate for stopping the polymerization reaction is preferably 93% by mass or more, more preferably 95% by mass or more.
  • the amount of THF insolubles in the copolymer obtained can be appropriately adjusted by adjusting the polymerization temperature to the above range.
  • the dispersion medium (latex )
  • the dispersion medium may be replaced, or the dispersion medium may be evaporated to obtain a particulate copolymer in powder form.
  • nitrile group-containing acrylic polymer (B1) In the dispersion of the nitrile group-containing acrylic polymer (B1), known dispersants, thickeners, anti-aging agents, antifoaming agents, antiseptics, antibacterial agents, anti-blistering agents, pH adjusting agents, and the like are necessary. Can also be added.
  • a fluorine-containing polymer (B2) is used as the binder for the fluorine-containing polymer positive electrode.
  • the positive electrode binder contains a fluorine-containing polymer, the stability of the slurry is improved, and the swelling of the binder with respect to the electrolytic solution is suppressed, and the cycle characteristics are improved.
  • the positive electrode binder contains a nitrile group-containing acrylic polymer in addition to the fluorine-containing polymer, cycle characteristics at a high potential are further improved.
  • the fluorine-containing polymer (B2) is a polymer containing a fluorine-containing monomer unit.
  • the fluorine-containing monomer unit is a structural unit formed by polymerizing a fluorine-containing monomer.
  • the fluorine-containing polymer is a homopolymer of a fluorine-containing monomer, a copolymer of a fluorine-containing monomer and another fluorine-containing monomer copolymerizable therewith, a fluorine-containing monomer Copolymer of copolymer and monomer copolymerizable therewith, copolymerization of fluorine-containing monomer and other fluorine-containing monomer copolymerizable therewith and monomer copolymerizable therewith Coalescence is mentioned.
  • fluorine-containing monomer examples include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, vinyl fluoride, and perfluoroalkyl vinyl ether, and vinylidene fluoride is preferable.
  • the proportion of the fluorine-containing monomer unit in the fluorine-containing polymer is usually 70% by mass or more, preferably 80% by mass or more.
  • Monomers copolymerizable with fluorine-containing monomers include 1-olefins such as ethylene, propylene, 1-butene; styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene, etc.
  • Aromatic vinyl compounds such as (meth) acrylonitrile (abbreviations for acrylonitrile and methacrylonitrile; hereinafter the same); methyl (meth) acrylate, butyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid ester compounds such as ethylhexyl; (meth) acrylamide compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide; (meth) acrylic acid, itaconic acid, fumar Acid, crotonic acid, maleic acid, etc.
  • unsaturated nitrile compounds such as (meth) acrylonitrile (abbreviations for acrylonitrile and methacrylonitrile; hereinafter the same); methyl (meth) acrylate, butyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid ester compounds such as ethyl
  • Xyl group-containing vinyl compounds epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; amino group-containing unsaturated compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Sulphonic acid group-containing unsaturated compounds such as styrene sulfonic acid, vinyl sulfonic acid and (meth) allyl sulfonic acid; Sulfuric acid group-containing unsaturated compounds such as 3-allyloxy-2-hydroxypropanesulfuric acid; (meth) acrylic acid-3- And phosphate group-containing unsaturated compounds such as propyl-2-propyl phosphate and 3-allyloxy-2-hydroxypropane phosphate.
  • epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate
  • the ratio of the monomer unit copolymerizable with the fluorine-containing monomer in the fluorine-containing polymer (B2) is usually 30% by mass or less, preferably 20% by mass or less.
  • a polymer containing vinylidene fluoride as a fluorine-containing monomer specifically, a homopolymer of vinylidene fluoride, or other fluorine copolymerizable with vinylidene fluoride.
  • a copolymer with a monomer and a copolymer of vinylidene fluoride with another fluorine-containing monomer copolymerizable therewith and a monomer copolymerizable therewith.
  • a homopolymer of vinylidene fluoride (polyvinylidene fluoride), a vinylidene fluoride-hexafluoropropylene copolymer, and polyvinyl fluoride are preferable, and polyvinylidene fluoride is more preferable.
  • the fluorine-containing polymer (B2) may be one kind alone, or two or more kinds may be used in combination. It is particularly preferable to use a low molecular weight substance and a high molecular weight substance in combination. Specifically, a fluorine-containing polymer having a melt viscosity of less than 35 kpoise measured at ASTM D3835 / 232 ° C. 100 sec ⁇ 1 has a low molecular weight, and a polymer having a molecular weight of 35 kpoise or higher has a high molecular weight. preferable.
  • examples of the high molecular weight polyvinylidene fluoride include KYNAR HSV900 manufactured by Arkema, Solef 6020, Solef 6010, Solef 1015, Solef 5130, KF7208 manufactured by Kureha.
  • examples of the low molecular weight polyvinylidene fluoride include KYNAR710 720 740 760 760A manufactured by Arkema, Solef 6008 manufactured by Solvay, and KF1120 manufactured by Kureha.
  • the weight ratio of the low molecular weight body to the high molecular weight body of the fluorine-containing polymer is: Preferably, it is 30/70 to 70/30.
  • the weight-average molecular weight in terms of polystyrene by gel permeation chromatography of the fluorine-containing polymer (B2) is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000, particularly Preferably, it is 400,000 to 1,000,000.
  • the weight average molecular weight of the fluorine-containing polymer (B2) By setting the weight average molecular weight of the fluorine-containing polymer (B2) within the above range, detachment (powder off) of the positive electrode active material and conductive material in the positive electrode active material layer is suppressed, and viscosity adjustment of the positive electrode slurry is possible. It becomes easy.
  • the glass transition temperature (Tg) of the fluorine-containing polymer (B2) is preferably 0 ° C. or lower, more preferably ⁇ 20 ° C. or lower, particularly preferably ⁇ 30 ° C. or lower.
  • the lower limit of Tg of the fluorine-containing polymer (B2) is not particularly limited, but is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 40 ° C. or higher.
  • Tg of a fluorine-containing polymer (B2) exists in the said range, detachment
  • the Tg of the fluorine-containing polymer (B2) can be adjusted by combining various monomers. Tg can be measured based on JIS K 7121; 1987 using a differential scanning calorimeter.
  • the melting point (Tm) of the fluorine-containing polymer (B2) is preferably 190 ° C. or less, more preferably 150 to 180 ° C., and further preferably 160 to 170 ° C.
  • Tm of the fluorine-containing polymer (B2) can be adjusted by combining various monomers or controlling the polymerization temperature. Tm can be measured based on JIS K 7121; 1987 using a differential scanning calorimeter.
  • the production method of the fluorine-containing polymer (B2) is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. Among these, the suspension polymerization method and the emulsion polymerization method are preferable, and the emulsion polymerization method is more preferable.
  • productivity of the fluorine-containing polymer (B2) can be improved, and a fluorine-containing polymer (B2) having a desired average particle diameter can be obtained. it can.
  • any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
  • polymerization initiators used for polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
  • Organic peroxides, azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like.
  • the fluorine-containing polymer (B2) is used in the state of a dispersion liquid or a dissolved solution dispersed in a dispersion medium.
  • the dispersion medium is not particularly limited as long as it can uniformly disperse or dissolve the fluorine-containing polymer (B2), and water or an organic solvent can be used.
  • organic solvents examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexanone and ethylcyclohexanone.
  • Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone; Alkyl nitriles such as acetonitrile and propionitrile; Tetrahydrofuran and ethylene glycol Ethers such as diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; Amides such as tilpyrrolidone and N, N-dimethylformamide may be mentioned.
  • These dispersion media may be used alone or in combination of two or more as a mixed solvent.
  • a mixed solvent since it is industrially used at the time of electrode slurry preparation, it is difficult to volatilize in production, and as a result, volatilization of the electrode slurry can be suppressed, and the smoothness of the resulting positive electrode is improved.
  • N-methylpyrrolidone, cyclohexanone, toluene and the like are preferable.
  • the solid content concentration of the dispersion containing the fluorine-containing polymer is usually 1 to 25% by mass from the viewpoint of handleability. 3 to 20% by mass is preferable, and 5 to 15% by mass is more preferable.
  • the viscosity when the fluorine-containing polymer (B2) is dissolved in N-methylpyrrolidone (hereinafter sometimes referred to as “NMP”) so as to form an 8% solution is preferably 10 to 5000 mPa ⁇ s. More preferably, it is 100 to 2000 mPa ⁇ s.
  • NMP N-methylpyrrolidone
  • the 8% NMP solution viscosity of the fluorine-containing polymer (B2) is obtained by dissolving the fluorine-containing polymer (B2) in NMP so as to be an 8% solution. It can be measured based on JIS K 7117-1;
  • the binder for the positive electrode contains the nitrile group-containing acrylic polymer (B1) and the fluorine-containing polymer (B2) described above.
  • the positive electrode binder contains a nitrile group-containing acrylic polymer (B1) and a fluorine-containing polymer (B2), so that the positive electrode with excellent bending properties of the wound body, initial capacity, output characteristics, high potential cycle A lithium secondary ion battery having excellent characteristics can be obtained.
  • the proportion of the nitrile group-containing acrylic polymer (B1) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% with respect to 100% by mass of the total amount of the binder for the positive electrode. % By mass.
  • the proportion of the fluorine-containing polymer (B2) is 50 to 95% by mass, preferably 60 to 90% by mass, and more preferably 70 to 85% by mass with respect to 100% by mass of the total amount of the binder for positive electrode.
  • the binder for positive electrode may contain other polymers that can be used as a binder, if necessary, in addition to the above-mentioned nitrile group-containing acrylic polymer (B1) and fluorine-containing polymer (B2). .
  • other polymers that may be used in combination include resins such as polyacrylic acid derivatives and polyacrylonitrile derivatives, and soft heavy polymers such as acrylate soft polymers, diene soft polymers, olefin soft polymers, and vinyl soft polymers. Coalescence is mentioned. These may be used alone or in combination of two or more.
  • the other polymer is contained in an amount of 30% by mass or less, further 0.1 to 20% by mass, particularly 0.2 to 10% by mass with respect to 100% by mass of the total amount of the binder for the positive electrode. May be.
  • the amount of the binder for the positive electrode is preferably in the range of 0.5 to 2 parts by mass, more preferably 1 to 2 parts by mass, and particularly preferably 1.5 to 2 parts by mass with respect to 100 parts by mass of the positive electrode active material. It is. When the amount of the binder for the positive electrode is within such a range, sufficient adhesion between the obtained positive electrode active material layer and the current collector can be secured, the capacity of the lithium secondary battery can be increased, and the internal resistance can be decreased. it can.
  • the conductive material positive electrode contains a conductive material.
  • the particle diameter of the conductive material contained in the positive electrode is 5 to 40 nm, preferably 10 to 38 nm, more preferably 15 to 36 nm in terms of number average particle diameter. If the particle size of the conductive material in the positive electrode is too small, aggregation tends to occur and uniform dispersion becomes difficult. As a result, the internal resistance of the positive electrode active material layer increases and the capacity tends to be difficult to improve. However, by using the positive electrode binder described above, the atomized conductive material can be uniformly dispersed, and the capacity can be improved.
  • the number average particle size of the conductive material is obtained by ultrasonically dispersing the conductive material in water at 0.01% by mass, and then measuring a dynamic light scattering particle size / particle size distribution measuring device (for example, Nikkiso Co., Ltd., particle size distribution measurement). It can be determined by measuring using a device Nanotrac Wave-EX150).
  • the specific surface area (BET type) of the conductive material in the positive electrode is preferably 400 m 2 / g or less, more preferably 300 m 2 / g or less, and particularly preferably 200 m 2 / g or less. If the specific surface area of the conductive material is too large, aggregation tends to occur and uniform dispersion becomes difficult. As a result, the internal resistance of the positive electrode active material layer increases and it is difficult to improve the capacity.
  • a conductive material one type of conductive material having the above-described specific surface area may be used alone, or two or more types of conductive materials having different specific surface areas may be used together with the BET specific surface area of the conductive material after mixing. May be used in combination so as to have a size within the above-described range.
  • conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used as in the negative electrode.
  • the content of the conductive material is preferably 1 to 3 parts by mass, more preferably 1.2 to 2.8 parts by mass, and particularly preferably 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material. Part by mass.
  • the content of the conductive material is too small, the internal resistance of the positive electrode increases and it may be difficult to increase the capacity. Moreover, when there is too much content of an electrically conductive material, it will become difficult to make the electrode high-density, and initial capacity may fall.
  • positive electrode components or the positive electrode may further contain, as an optional component, a reinforcing material, a leveling agent, an electrolytic solution additive having a function of suppressing electrolytic decomposition, etc. Furthermore, the thickener etc. which are contained in the slurry prepared at the time of positive electrode manufacture may remain
  • the slurry composition for a lithium ion secondary battery positive electrode includes the positive electrode active material (A), the positive electrode binder (B), the conductive material (C), and the like. Obtained by mixing these additives in a dispersion medium.
  • a dispersion medium either water or an organic solvent can be used.
  • organic solvents examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexanone and ethylcyclohexanone.
  • Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone; Alkyl nitriles such as acetonitrile and propionitrile; Tetrahydrofuran and Ethylene Ethers such as glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; N- Amides such as methylpyrrolidone and N, N-dimethylformamide are exemplified.
  • These dispersion media may be used alone or in combination of two or more as a mixed solvent.
  • a dispersion medium having excellent dispersibility of non-conductive particles and having a low boiling point and high volatility is preferable because it can be removed at a low temperature in a short time.
  • acetone, toluene, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, water, N-methylpyrrolidone, or a mixed solvent thereof is preferable.
  • the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
  • a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
  • a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
  • Lithium ion secondary battery positive electrode A lithium ion secondary battery positive electrode is obtained by applying the slurry composition for a lithium ion secondary battery positive electrode described above to a current collector and drying it.
  • the method for producing a positive electrode for a lithium ion secondary battery includes a step of forming the positive electrode active material layer by applying and drying the slurry composition for positive electrode on one or both sides of the current collector.
  • the method for applying the positive electrode slurry composition onto the current collector is not particularly limited. Examples of the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
  • drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • the drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
  • the positive electrode slurry composition is applied onto a current collector, dried, and then subjected to pressure treatment using a die press or a roll press to increase the porosity of the positive electrode active material layer. It is preferable to have a lowering step.
  • the porosity of the positive electrode active material layer is preferably 5 to 30%, more preferably 7 to 20%. If the porosity of the positive electrode active material layer is too high, charging efficiency and discharging efficiency may be deteriorated.
  • the porosity of the positive electrode active material layer is too low, it is difficult to obtain a high volume capacity, and the positive electrode active material layer is likely to be peeled off from the current collector, and a defect may be easily generated. Further, when a curable polymer is used as the positive electrode binder, it is preferably cured.
  • the thickness of the positive electrode active material layer in the lithium ion secondary battery positive electrode is usually 5 to 300 ⁇ m, preferably 30 to 250 ⁇ m. When the thickness of the positive electrode active material layer is in the above range, a secondary battery having high load characteristics and cycle characteristics can be obtained.
  • the content ratio of the positive electrode active material in the positive electrode active material layer is preferably 85 to 99% by mass, more preferably 88 to 97% by mass.
  • the content ratio of the positive electrode active material in the positive electrode active material layer is within the above range, it is possible to obtain a secondary battery that exhibits flexibility and binding properties while exhibiting high capacity.
  • the density of the positive electrode active material layer is preferably 3.0 to 4.0 g / cm 3 , and more preferably 3.4 to 4.0 g / cm 3 . When the density of the positive electrode active material layer is in the above range, a high-capacity secondary battery can be obtained.
  • the current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but is preferably a metal material because of its heat resistance, for example, iron, copper, aluminum, nickel, stainless steel. Examples include steel, titanium, tantalum, gold, and platinum. Among these, aluminum is particularly preferable as the current collector used for the positive electrode of the lithium ion secondary battery.
  • the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable.
  • the current collector may be used after being roughened. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
  • a primer layer or the like may be formed on the current collector surface in order to increase the adhesive strength or conductivity of the positive electrode active material layer.
  • the lithium ion secondary battery according to the present invention includes the above-described negative electrode and positive electrode, has a non-aqueous electrolyte, and usually includes a separator.
  • Nonaqueous Electrolytic Solution is not particularly limited, and a nonaqueous electrolytic solution obtained by dissolving a lithium salt as a supporting electrolyte in a nonaqueous solvent can be used.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more.
  • the amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered, and the charging characteristics and discharging characteristics of the battery are degraded.
  • the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
  • Alkyl carbonates such as carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds are used.
  • dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These can be used alone or in admixture of two or more.
  • Examples of the electrolytic solution other than the above include a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide and polyacrylonitrile with an electrolytic solution, and an inorganic solid electrolyte such as lithium sulfide, LiI, and Li 3 N.
  • an additive containing an additive in the electrolytic solution in addition to carbonate compounds such as vinylene carbonate (VC), fluorine-containing carbonates such as fluoroethylene carbonate and ethyl methyl sulfone are preferable.
  • fluorine electrolyte additives such as fluorine-containing carbonate have a high withstand voltage. As the capacity increases, the voltage during charging and discharging is also increasing, and electrolytes made of ethylene carbonate, propylene carbonate, etc. cannot withstand high voltages and may decompose, so the above fluorine electrolyte additives Is preferably blended into the electrolyte.
  • the separator separator is a porous substrate having pores
  • usable separators include (a) a porous separator having pores, and (b) a porous material having a polymer coating layer formed on one or both sides.
  • the separator include (c) a porous separator on which a porous resin coat layer containing an inorganic ceramic powder is formed.
  • Non-limiting examples of these include solids such as polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers.
  • polymer films for polymer electrolytes or gel polymer electrolytes separators coated with a gelled polymer coating layer, or separators coated with a porous membrane layer made of a dispersant for inorganic fillers or inorganic fillers.
  • the manufacturing method of the lithium ion secondary battery of this invention is not specifically limited.
  • the above-described negative electrode and positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolyte is injected into the battery container and sealed.
  • an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
  • the shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square shape, a flat type, a wound type pouch cell, and the like.
  • the electrode layer is flexible and the electrode layer does not crack when bent, it can be preferably applied to the production of a wound pouch cell.
  • a film punched to 16 mm ⁇ was dipped in 20 g of a non-aqueous electrolyte and completely swollen at 60 ° C. for 72 hours. Thereafter, the swollen film was taken out, and the surface non-aqueous electrolyte was gently wiped, and the weight was measured (weight is assumed to be “B”).
  • the sheet-like positive electrode and the sheet-like negative electrode were wound using a core having a diameter of 20 mm with a separator interposed therebetween to obtain a wound body.
  • a separator a polypropylene microporous film having a thickness of 20 ⁇ m was used.
  • the wound body was compressed from one direction at a speed of 10 mm / second until a thickness of 4.5 mm was reached.
  • the wound body was disassembled after compression, the positive electrode was observed, and evaluation was performed according to the following evaluation criteria.
  • the obtained nonaqueous electrolyte battery was subjected to constant current charging at 140 mA until the battery voltage was 4.2 V in a 25 ° C. environment, and constant voltage charging was performed until the charging current was 14 mA at 4.2 V. Subsequently, constant current discharge was performed at 140 mA until the battery voltage reached 3 V, and the initial capacity was obtained.
  • the initial capacity at this time was evaluated according to the following evaluation criteria. A ... 700 mAh or more B ... 697 mAh or more but less than 700 mAh C ... 694 mAh or more but less than 697 mAh D ... 690 mAh or more but less than 694 mAh E ... less than 690 mAh
  • the negative electrode active material, the positive electrode active material used for the positive electrode, the positive electrode binder, and the conductive material are as follows.
  • the particle diameter of the active material described below means the volume average particle diameter
  • the particle diameter of the conductive material means the number average particle diameter.
  • Gr / SiOx Mixture of 90 parts of spherical artificial graphite (particle diameter: 12 ⁇ m) and 10 parts of alloy-based active material SiOx (particle diameter: 10 ⁇ m)
  • Gr / SiOC 90 parts of spherical artificial graphite (particle diameter: 12 ⁇ m) and alloy system Mixture with 10 parts of active material SiOC (volume average particle size: 10 ⁇ m)
  • Gr spherical artificial graphite (particle size: 12 ⁇ m)
  • LCO lithium cobalt oxide (LiCoO 2 ) (particle diameter: 12 ⁇ m)
  • LNM Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 (particle diameter: 15 ⁇ m)
  • Nitrile group-containing acrylic polymers (B1-1) to (B1-11) were prepared as follows.
  • the polymerization conversion rate determined from the solid content concentration was 96%. Further, 500 parts of N-methylpyrrolidone was added to 100 parts of this aqueous dispersion, and after evaporating all of water and residual monomers under reduced pressure, 81 parts of N-methylpyrrolidone was evaporated to obtain a polymer (B1-1). An 8% by mass NMP solution was obtained. The obtained polymer (B1-1) had a nonaqueous electrolyte swelling degree of 1.7 times and a THF-insoluble matter content of 10% or less.
  • a 400 milliliter (total solid content 48 grams) solution prepared by adjusting the total solid content of the polymer to 12% by mass with water was charged into a 1 liter autoclave equipped with a stirrer, and nitrogen gas was added for 10 minutes. After removing the dissolved oxygen in the polymer by flowing, 75 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 180 ml of water to which nitric acid of 4 times moles of Pd had been added and added. After the inside of the system was replaced twice with hydrogen gas, the autoclave contents were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “first-stage hydrogenation reaction”) for 6 hours. ) At this time, the iodine value of the polymer was 35 mg / 100 mg.
  • the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
  • the contents are returned to room temperature, the inside of the system is set to a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration becomes 40%, and an aqueous dispersion of the nitrile group-containing acrylic polymer (B1-12) Got.
  • 320 parts of N-methylpyrrolidone was added to 100 parts of this aqueous dispersion, water and residual monomers were all evaporated under reduced pressure, and N-methylpyrrolidone was added to obtain 8 parts by mass of the polymer (B1-12).
  • % NMP solution was obtained.
  • the obtained polymer (B1-12) had a nonaqueous electrolyte swelling degree of 2.9 times and a THF insoluble content of 10% or less.
  • the iodine value of the nitrile group-containing acrylic polymer (B1-12) was 10 mg / 100 mg.
  • Example 1 [Production of slurry composition for positive electrode and positive electrode] 100 parts of lithium cobaltate LCO (LiCoO 2 ) (particle diameter: 12 ⁇ m) as the positive electrode active material, and acetylene black (AB35, Denka Black powder manufactured by Denki Kagaku Kogyo Co., Ltd.) as the positive electrode conductive material: particle diameter 35 nm, specific surface area 68 m 2 / G) 2.0 parts, 1.6 parts of a mixed polyvinylidene fluoride (1: 1 mixture of KYNAR HSV900 and KYNAR720 made by Arkema) as a fluorine-containing polymer for the positive electrode binder, and a nitrile group-containing acrylic polymer As a solid composition, 0.4 part of solid B and an appropriate amount of NMP were stirred with a planetary mixer to prepare a positive electrode slurry composition.
  • LiCoO 2 lithium cobaltate LCO
  • AB35 Denka Black powder manufactured by Denki Kagaku Kogyo Co
  • An aluminum foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the positive electrode slurry composition was applied to both sides of an aluminum foil so that the coating amount after drying was 25 mg / cm 2 , dried at 60 ° C. for 20 minutes, 120 ° C. for 20 minutes, and then heated at 150 ° C. for 2 hours. Thus, a positive electrode raw material was obtained.
  • This positive electrode original fabric was rolled by a roll press to produce a sheet-like positive electrode comprising a positive electrode active material layer having a density of 3.9 g / cm 3 and an aluminum foil. This was cut into a width of 4.8 mm and a length of 50 cm, and an aluminum lead was connected.
  • slurry composition for negative electrode and negative electrode 90 parts of spherical artificial graphite (particle diameter: 12 ⁇ m) and 10 parts of SiOx (particle diameter: 10 ⁇ m) as the negative electrode active material, 1 part of styrene butadiene rubber (particle diameter: 180 nm, glass transition temperature: ⁇ 40 ° C.) as the binder, As a thickener, 1 part of carboxymethylcellulose and an appropriate amount of water were stirred with a planetary mixer to prepare a slurry composition for a negative electrode.
  • a copper foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the negative electrode slurry composition was applied to both sides of the copper foil so that the coating amount after drying was 10 mg / cm 2 , dried at 60 ° C. for 20 minutes, 120 ° C. for 20 minutes, and then heat-treated at 150 ° C. for 2 hours. Thus, a negative electrode raw material was obtained.
  • This negative electrode original fabric was rolled with a roll press to prepare a sheet-like negative electrode comprising a negative electrode active material layer having a density of 1.8 g / cm 3 and a copper foil. This was cut into a width of 5.0 mm and a length of 52 cm, and a nickel lead was connected.
  • the obtained sheet-like positive electrode and sheet-like negative electrode were wound using a core having a diameter of 20 mm with a separator interposed therebetween to obtain a wound body.
  • a separator a polypropylene microporous film having a thickness of 20 ⁇ m was used.
  • the wound body was compressed from one direction at a speed of 10 mm / second until a thickness of 4.5 mm was reached.
  • the ratio of the major axis to the minor axis of the substantially ellipse is 7.7.
  • the electrode plate group was housed together with 3.2 g of a non-aqueous electrolyte in a predetermined aluminum laminate case. And after connecting a negative electrode lead and a positive electrode lead to a predetermined location, the opening part of the case was sealed with heat, and the nonaqueous electrolyte battery was completed.
  • This battery is a pouch having a width of 35 mm, a height of 48 mm, and a thickness of 5 mm, and the nominal capacity of the battery is 700 mAh.
  • Table 2 shows the initial capacity, output characteristics, and high potential cycle characteristics of the obtained battery.
  • Example 2 Example 1 except that the negative electrode active material was changed to Gr / SiOC (a mixture of 90 parts of spherical artificial graphite (particle diameter: 12 ⁇ m) and 10 parts of alloy-based active material SiOC (volume average particle diameter: 10 ⁇ m)). Same as above. The results are shown in Table 2.
  • Example 3 Except that the positive electrode conductive material was changed to acetylene black (AB23, acetylene black (Denka Black powder product manufactured by Denki Kagaku Kogyo Co., Ltd .: particle diameter 23 nm, specific surface area 133 m 2 / g), the same as Example 1. Is shown in Table 2.
  • Example 4 The same procedure as in Example 1 was conducted except that the positive electrode active material was changed to LNM (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 (particle diameter: 15 ⁇ m)). The results are shown in Table 2.
  • Nitrile group-containing acrylic polymers (B1-2) to (B1-9) are used in place of the nitrile group-containing acrylic polymer (B1-1) in the positive electrode binder, and the blending amounts are as shown in Table 2.
  • the procedure was the same as Example 1 except that the change was made. The results are shown in Table 2.
  • Example 13 The same procedure as in Example 1 was conducted except that high molecular weight polyvinylidene fluoride was used instead of the mixed polyvinylidene fluoride in the positive electrode binder. The results are shown in Table 2.
  • Example 14 The same procedure as in Example 1 was conducted except that low molecular weight polyvinylidene fluoride was used instead of the mixed polyvinylidene fluoride in the positive electrode binder. The results are shown in Table 2.
  • Example 15 As the positive electrode conductive material, 1.8 parts of acetylene black (Denka black powdered product manufactured by Denki Kagaku Kogyo Co., Ltd .: particle diameter 23 nm, specific surface area 133 m 2 / g) and HiPCO (Unimid Corporation carbon nanotube: particle diameter 26 nm, specific surface area) 700 m 2 / g) Same as Example 1 except that the mixture was changed to 0.2 parts. The results are shown in Table 2.
  • acetylene black Denki Kagaku Kogyo Co., Ltd .: particle diameter 23 nm, specific surface area 133 m 2 / g
  • HiPCO Unimid Corporation carbon nanotube: particle diameter 26 nm, specific surface area
  • Example 16 Example 1 was repeated except that the nitrile group-containing acrylic polymer (B1-12) was used instead of the nitrile group-containing acrylic polymer (B1-1) of the positive electrode binder. The results are shown in Table 2.
  • Example 17 [Production of slurry composition for negative electrode] Disperse polyacrylic acid (manufactured by Aldrich, viscosity average molecular weight 1.25 million) and an appropriate amount of water so as to form a 10% aqueous solution, and then add lithium hydroxide to reach pH 7. An aqueous solution of lithium polyacrylate was prepared.
  • As a negative electrode active material 90 parts of spherical artificial graphite (particle diameter: 12 ⁇ m) and 10 parts of SiOx (particle diameter: 10 ⁇ m), an aqueous solution of the above polyacrylic acid lithium salt in an amount corresponding to 1 part in solid content, was stirred with a planetary mixer to prepare a slurry composition for a negative electrode.
  • the negative electrode slurry composition was the same as Example 1 except that the negative electrode slurry composition was changed to the above negative electrode slurry composition. The results are shown in Table 2.
  • Example 1 The negative electrode active material was the same as that of Example 1 except that only the spherical artificial graphite (particle diameter: 12 ⁇ m) was changed. The results are shown in Table 2.
  • Example 2 The same procedure as in Example 1 was conducted except that the positive electrode conductive material was changed to acetylene black (AB48, acetylene black (Denka Black powder product manufactured by Denki Kagaku Kogyo Co., Ltd .: particle diameter 48 nm, specific surface area 39 m 2 / g). Is shown in Table 2.
  • acetylene black AB48, acetylene black (Denka Black powder product manufactured by Denki Kagaku Kogyo Co., Ltd .: particle diameter 48 nm, specific surface area 39 m 2 / g).
  • Example 3 (Comparative Example 3) Example 1 was repeated except that 2 parts of the nitrile group-containing acrylic polymer (B1-1) was used without using the fluorine-containing polymer of the positive electrode binder. The results are shown in Table 2.
  • Example 4 The same procedure as in Example 1 was conducted except that 2 parts of mixed polyvinylidene fluoride was used without using the nitrile group-containing acrylic polymer of the positive electrode binder. The results are shown in Table 2.
  • Example 5 (Comparative Examples 5 and 6) The same as Example 1 except that the nitrile group-containing acrylic polymer (B1-10) or (B1-11) was used instead of the nitrile group-containing acrylic polymer (B1-1) in the positive electrode binder. did. The results are shown in Table 2.

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Abstract

L'invention vise à fournir une batterie secondaire au lithium-ion à capacité élevée qui est souple et qui possède d'excellentes caractéristiques de cycle à potentiel élevé, tout en évitant l'apparition de fissures dans une couche d'électrode lorsqu'elle est pliée. A cet effet, une batterie secondaire au lithium-ion selon la présente invention est caractérisée en ce qu'elle comprend une électrode négative, une électrode positive et une solution d'électrolyte non aqueux, et est également caractérisée en ce que : l'électrode négative contient un matériau actif à base d'alliage ; l'électrode positive contient un matériau actif d'électrode positive, un liant pour électrodes positives, et un matériau conducteur ; le liant pour électrodes positives contient un polymère acrylique contenant des groupements nitriles et un polymère contenant du fluor ; le polymère acrylique contenant des groupements nitriles possède un degré de gonflement de trois fois ou moins par rapport à la solution d'électrolyte non aqueux et une fraction insoluble de THF de 30 % en masse ou moins ; et le matériau conducteur possède des diamètres de particule de 5 à 40 nm.
PCT/JP2013/076296 2012-09-28 2013-09-27 Batterie secondaire au lithium-ion WO2014051067A1 (fr)

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