WO2014115802A1 - Méthode de production de liant pour électrodes de batterie rechargeable au lithium, et liant pour électrodes de batterie rechargeable au lithium - Google Patents

Méthode de production de liant pour électrodes de batterie rechargeable au lithium, et liant pour électrodes de batterie rechargeable au lithium Download PDF

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WO2014115802A1
WO2014115802A1 PCT/JP2014/051374 JP2014051374W WO2014115802A1 WO 2014115802 A1 WO2014115802 A1 WO 2014115802A1 JP 2014051374 W JP2014051374 W JP 2014051374W WO 2014115802 A1 WO2014115802 A1 WO 2014115802A1
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secondary battery
lithium secondary
electrode
binder
mass
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PCT/JP2014/051374
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English (en)
Japanese (ja)
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充 花崎
一成 深瀬
智規 倉田
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昭和電工株式会社
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Publication of WO2014115802A1 publication Critical patent/WO2014115802A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a binder for a lithium secondary battery electrode. Moreover, this invention relates to the lithium secondary battery which has a binder for lithium secondary battery electrodes obtained by this manufacturing method, and an electrode using the same.
  • This application claims priority based on Japanese Patent Application No. 2013-10330 filed in Japan on January 23, 2013, the contents of which are incorporated herein by reference.
  • PVDF polyvinylidene fluoride
  • NMP N-methylolpyrrolidone
  • SBR styrene-butadiene rubber
  • Patent Document 4 discloses a specific amount of styrene, an ethylenically unsaturated carboxylic acid ester, and an aqueous binder that has high resistance to swelling with respect to an electrolytic solution and is excellent in binding properties between active materials and between an active material and a current collector. It has been proposed to use a binder obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated carboxylic acid and an internal crosslinking agent as essential components in the presence of a surfactant. .
  • An object of this invention is to provide the binder for lithium secondary battery electrodes excellent in electrolyte solution resistance, and the binding property also including the case where it dries rapidly at high temperature.
  • the present invention relates to the following [1] to [13].
  • An aqueous medium containing at least an ethylenically unsaturated monomer containing styrene, an ethylenically unsaturated carboxylic acid ester, and an ethylenically unsaturated carboxylic acid as a polymerization initiator using an oxidizing agent and a reducing agent.
  • the manufacturing method of the binder for lithium secondary battery electrodes characterized by carrying out emulsion polymerization in inside.
  • Production method. [3] The method for producing a binder for a lithium secondary battery electrode according to [1] or [2], wherein the reducing agent is at least one selected from sodium hydroxymethanesulfinate, sodium ascorbate, and sodium hydrogensulfite.
  • aqueous emulsion for lithium secondary battery electrodes in which the binder for lithium secondary battery electrodes according to [6] is dispersed in an aqueous medium.
  • a slurry for a lithium secondary battery electrode comprising an electrode active material and the binder for a lithium secondary battery electrode according to [6].
  • a slurry for a lithium secondary battery electrode obtained by mixing an electrode active material and the aqueous emulsion for a lithium secondary battery electrode according to [7] or [8]. [11] The slurry for a lithium secondary battery electrode according to [9] or [10], wherein the electrode active material is a carbon material. [12] A current collector and an electrode active material layer laminated on the current collector, the electrode active material layer comprising an electrode active material and the lithium secondary battery electrode according to the above [6] And an electrode for a lithium secondary battery. [13] A lithium secondary battery having a positive electrode and a negative electrode, wherein at least one of the positive electrode and the negative electrode is the electrode according to [12].
  • the binder for lithium secondary battery electrodes which can obtain the binder for lithium secondary battery electrodes excellent in electrolysis solution resistance and the bindability also including the case where it dries rapidly at high temperature is obtained.
  • the manufacturing method of can be provided.
  • the binder for lithium secondary battery electrodes excellent in electrolyte solution resistance and the binding property also at the time of high temperature drying can be provided.
  • the lithium secondary battery electrode binder of the present embodiment (hereinafter, also simply referred to as “electrode binder”) is an ethylenically unsaturated material containing at least styrene, an ethylenically unsaturated carboxylic acid ester, and an ethylenically unsaturated carboxylic acid. It is obtained by polymerizing a saturated monomer.
  • the “ethylenically unsaturated monomer” is a generic term for the above three types of ethylenically unsaturated monomers and other ethylenically unsaturated monomers that may be added as necessary. Is. However, even when the surfactant described later has an ethylenically unsaturated group, these surfactants are not included in the ethylenically unsaturated monomer.
  • the binder for lithium secondary battery electrodes of the present invention contains styrene, the binding property between the active materials is good. In particular, when a carbon material is used as the active material, the effect can be further exhibited.
  • the amount of styrene used is preferably 15 to 70% by mass, more preferably 30 to 60% by mass, based on the total ethylenically unsaturated monomer. When the amount of styrene used is 15% by mass or more, the binding property between the active materials and the adhesion between the active material and the current collector tend to be excellent. On the other hand, when the amount of styrene used is 70% by mass or less, an electrode obtained by applying an electrode slurry containing an electrode binder and an active material is difficult to break.
  • the ethylenically unsaturated carboxylic acid ester preferably contains an ethylenically unsaturated carboxylic acid ester having a polar group and another ethylenically unsaturated carboxylic acid ester.
  • the polar group include a hydroxy group and a glycidyl group.
  • ethylenically unsaturated carboxylic acid ester having a polar group examples include hydroxyalkyl ester of (meth) acrylic acid and glycidyl (meth) acrylate.
  • examples of the hydroxyalkyl ester of (meth) acrylic acid include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate is preferred.
  • “(Meth) acryl” means methacryl or acryl.
  • the amount of the ethylenically unsaturated carboxylic acid ester having a polar group is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total ethylenically unsaturated monomer. %.
  • the amount of the ethylenically unsaturated carboxylic acid ester having a polar group is 0.1% by mass or more, the effect of adding the ethylenically unsaturated carboxylic acid ester having a polar group tends to appear.
  • the amount of the ethylenically unsaturated carboxylic acid ester having a polar group is 10% by mass or less, the binding properties between the active materials and between the active material and the current collector tend to be good.
  • ethylenically unsaturated carboxylic acid esters include, for example, (meth) acrylic acid esters and vinyl esters of saturated fatty acids.
  • (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Iso-butyl acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth ) Cyclohexyl acrylate, isononyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and
  • vinyl esters of saturated fatty acids include vinyl acetate and vinyl propionate.
  • (meth) acrylic acid ester from the viewpoint of ease of emulsion polymerization and durability, it is preferable to use (meth) acrylic acid ester, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid. It is particularly preferable to use lauryl or isobornyl (meth) acrylate.
  • the amount of other ethylenically unsaturated carboxylic acid ester to be used is preferably 25 to 85% by mass, more preferably 30 to 80% by mass, based on the total ethylenically unsaturated monomer.
  • the amount of other ethylenically unsaturated carboxylic acid ester used is 25% by mass or more, the effect of adding other ethylenically unsaturated carboxylic acid ester tends to appear.
  • the amount of other ethylenically unsaturated carboxylic acid ester used is 85% by mass or less, the binding properties between the active materials and between the active material and the current collector tend to be good.
  • Examples of the ethylenically unsaturated carboxylic acid include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or a half ester thereof.
  • Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and the like. Of these ethylenically unsaturated carboxylic acids, acrylic acid and itaconic acid are preferred.
  • An ethylenically unsaturated carboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the ethylenically unsaturated carboxylic acid to be used is preferably 1 to 10% by mass, more preferably 1 to 5% by mass with respect to the total ethylenically unsaturated monomers.
  • the amount of the ethylenically unsaturated carboxylic acid used is 1% by mass or more, emulsion polymerization stability and mechanical stability are improved, and the heat resistance of the obtained electrode tends to be improved.
  • the amount of the ethylenically unsaturated carboxylic acid used is 10% by mass or less, the binding properties between the active materials and between the active material and the current collector tend to be improved.
  • a compound having at least one polymerizable ethylenically unsaturated group and having a polar group such as an amide group or a nitrile group can be used.
  • the compound having a polymerizable ethylenically unsaturated group and having an amide group include (meth) acrylamide, N-methylol (meth) acrylamide and the like.
  • the compound having a polymerizable ethylenically unsaturated group and having a nitrile group include (meth) acrylonitrile.
  • an internal crosslinking agent may be used in order to further improve the swelling resistance of the obtained binder dry film for lithium secondary battery electrodes to the electrolyte solvent.
  • the internal cross-linking agent has at least one ethylenically unsaturated bond and has an ethylenically unsaturated monomer and a reactive group reactive with other functional groups, or Any material having two or more ethylenically unsaturated bonds may be used.
  • vinyltrimethoxysilane And silane coupling agents such as vinyltriethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, and ⁇ -methacryloyloxypropyltriethoxysilane.
  • the internal crosslinking agent having two or more ethylenically unsaturated bonds include divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, triallyl cyanurate and the like. These internal cross-linking agents may be used alone or in combination of two or more.
  • the amount used is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total ethylenically unsaturated monomer.
  • the amount of the internal crosslinking agent used is 0.1% by mass or more, the swelling resistance of the dry film against the electrolytic solution tends to be improved.
  • the amount of the internal cross-linking agent used is 5% by mass or less, the emulsion polymerization stability is good and the adhesion between the active material and the current collector tends to be improved. Even if an internal cross-linking agent is not used, it is not necessary to use an internal cross-linking agent when the obtained binder for an electrode has sufficient electrolytic solution resistance.
  • the binder for a lithium secondary battery electrode of the present embodiment is obtained by emulsion polymerization of the above ethylenically unsaturated monomer in an aqueous medium using an oxidizing agent and a reducing agent as polymerization initiators.
  • persulfate As the oxidizing agent, persulfate, organic peroxide and hydrogen peroxide can be used.
  • persulfates include potassium persulfate, ammonium persulfate, and sodium persulfate.
  • organic peroxide examples include t-butyl hydroperoxide, t-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and benzoyl peroxide.
  • oxidizing agents it is preferable to use one or more selected from the group consisting of potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, and t-butyl peroxybenzoate from the viewpoint of polymerization stability.
  • the amount of the oxidizing agent used is preferably 0.01% by mass or more based on the total ethylenically unsaturated monomer because the stability of the emulsion polymerization tends to be improved, and the amount of the oxidizing agent used is 1% by mass or less.
  • the reducing agent examples include sodium hydroxymethanesulfinate (Longalite), sodium ascorbate, sodium hydrogen sulfite, potassium sulfite, sodium sulfite, ammonium sulfite, tartaric acid or a salt thereof.
  • sodium hydroxymethanesulfinate, sodium ascorbate, and sodium bisulfite are preferable.
  • the amount of the reducing agent used is preferably 0.01% by mass or more with respect to the total ethylenically unsaturated monomer because the effect of adding the reducing agent is likely to appear. This is preferable because the elution resistance of the film is improved. More preferably, it is 0.02 mass% or more and 0.5 mass% or less.
  • the method for adding the polymerization initiator to the reaction mixture is not particularly limited, but is first selected from potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, and t-butyl peroxybenzoate as the oxidizing agent.
  • potassium persulfate ammonium persulfate
  • sodium persulfate sodium persulfate
  • t-butyl hydroperoxide t-butyl peroxybenzoate
  • t-butyl peroxybenzoate t-butyl peroxybenzoate
  • oxidizing agent one or more selected from t-butyl hydroperoxide, t-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, reducing agent
  • sodium hydroxymethanesulfinate Longalite
  • sodium ascorbate sodium hydrogen sulfite
  • potassium sulfite sodium sulfite
  • ammonium sulfite ammonium sulfite
  • aqueous medium examples include water and a mixed solvent of water and an organic solvent, preferably water.
  • organic solvent examples include alcohols such as methyl alcohol, ethanol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, and benzyl alcohol, and nitrogen-containing organic solvents such as N-methylpyrrolidone.
  • the ratio of water to the organic solvent is preferably 449: 1 to 4: 1.
  • surfactant As the surfactant used in the emulsion polymerization, usual anionic surfactants and nonionic surfactants are used.
  • anionic surfactant include alkyl benzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid salt and the like.
  • nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic finyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the surfactant is preferably reactive, and examples of such surfactant include those represented by the following formulas (1) to (4): (In the formula, R is an alkyl group, and l is an integer of 10 to 40) (In the formula, m is an integer of 10 to 40, and n is an integer of 10 to 12) (Wherein R is an alkyl group, M 1 is NH 4 or Na) (Wherein R is an alkyl group, and M 2 is Na)
  • the amount of the surfactant used is preferably 0.3 to 3 parts by mass based on 100 parts by mass of the total ethylenically unsaturated monomer.
  • the amount of the surfactant used is 0.3 parts by mass or more, the polymerization stability tends to be good, and the dispersed particle size of the resulting aqueous emulsion becomes small, so it is dispersed in the aqueous emulsion. Sedimentation of the electrode binder tends not to occur.
  • the usage-amount of surfactant is 3 mass parts or less, it exists in the tendency for the adhesive force of an active material and a collector to improve.
  • the surfactant is added to the above ethylenically unsaturated monomer. Is not included.
  • emulsion polymerization method a polymerization method charged in a lump, a polymerization method while continuously supplying each component, and the like can be used, and the emulsion polymerization is performed with stirring.
  • the polymerization is usually preferably carried out at a temperature of 30 to 90 ° C, more preferably 40 to 80 ° C.
  • Aqueous emulsion for lithium secondary battery electrode Since the above-mentioned binder for lithium secondary battery electrodes is emulsion-polymerized in an aqueous medium, it is obtained as an aqueous emulsion dispersed in an aqueous medium.
  • This aqueous emulsion can be used as it is for the production of a slurry for lithium secondary battery electrodes, which will be described later, as an aqueous emulsion for lithium secondary battery electrodes (hereinafter also simply referred to as “aqueous emulsion for electrodes”).
  • the aqueous emulsion for electrodes may be a reaction mixture itself after completion of polymerization, or a pH adjusted by adding a base thereto. Further, if necessary, an aqueous medium may be added to adjust the non-volatile content, or other additives may be added.
  • the aqueous emulsion for electrodes comprises a (meth) acrylic acid (co) polymer and one or more poly (meth) acrylic acid polymers selected from the group consisting of ammonium salts and alkali metal salts in an aqueous phase. It is preferable to further include.
  • an electrode active material is added to the aqueous emulsion for electrodes to prepare a slurry for lithium secondary battery electrodes. The material layer exhibits excellent adhesion to the current collector.
  • a film having a thickness of 0.5 mm made of an electrode binder is prepared. This film can be produced by pouring an aqueous emulsion on a flat plate, drying at 50 ° C. for 2.5 hours, and then drying under reduced pressure (gauge pressure: ⁇ 95 kPa) at 50 ° C. for 12 hours. Next, the produced film is cut into 25 mm ⁇ 25 mm.
  • the cut film is immersed in 5 g of warm water at 60 ° C., allowed to stand for 24 hours, and GC-MS measurement is performed on the extract into warm water, so that a poly (meth) acrylic acid polymer is present in the aqueous phase. I can confirm that.
  • the content of the poly (meth) acrylic acid polymer is preferably 0.1 to 2% by mass, more preferably 0.2 to 1% by mass in the aqueous phase.
  • the content of the poly (meth) acrylic acid polymer is 0.2% by mass or more, the effect of the poly (meth) acrylic acid polymer is easily obtained.
  • the content of the poly (meth) acrylic acid polymer is 1% by mass or less, it is preferable from the viewpoint of dispersibility of the active material.
  • the content of the poly (meth) acrylic acid polymer is determined by GC-MS measurement of the extract obtained by immersing the binder single-layer film obtained by drying the aqueous emulsion for electrodes of the aqueous emulsion for electrodes for 24 hours in warm water at 60 ° C. It can be almost quantified by measuring the non-volatile content.
  • the weight average molecular weight of the poly (meth) acrylic acid polymer is preferably 8000 to 100,000, and more preferably 10,000 to 80,000.
  • the molecular weight of the poly (meth) acrylic acid polymer can be determined as a pullulan-converted molecular weight using aqueous gel permeation chromatography.
  • the poly (meth) acrylic acid polymer is a poly (meth) acrylic acid copolymer or a salt thereof
  • the structure derived from (meth) acrylic acid or a salt thereof in the poly (meth) acrylic acid copolymer The unit preferably occupies 80 to 98% by mass.
  • the poly (meth) acrylic acid polymer is added to the mixture by adding a (meth) acrylic acid derivative such as (meth) acrylic acid or an ester thereof in the above emulsion polymerization process, and using an oxidizing agent and a reducing agent. Or by adding a poly (meth) acrylic acid polymer in the middle of the polymerization, it can be included in the reaction mixture in advance. In addition, the poly (meth) acrylic acid polymer can be separately added to the reaction mixture after the completion of the emulsion polymerization.
  • the pH of the aqueous emulsion for electrodes is preferably from 2 to 10, and more preferably from 5 to 9. When the pH is within this range, the polymerization stability during emulsion polymerization and the mechanical stability and chemical stability of the resulting electrode binder can be improved.
  • PH is measured using a pH meter at a liquid temperature of 25 ° C. with a glass electrode as a standard electrode.
  • the pH can be adjusted by adding a basic substance during or after the emulsion polymerization.
  • ammonia triethylamine, ethanolamine, caustic soda, etc.
  • these may be used individually by 1 type and may be used in combination of 2 or more type.
  • the non-volatile content concentration of the aqueous emulsion for electrodes is preferably 10 to 65% by mass, and more preferably 15 to 60% by mass. A nonvolatile content concentration of 15% by mass or more is preferable from the viewpoint of dispersibility of the active material.
  • the nonvolatile content concentration is 60% by mass or less, the nonvolatile content of the slurry can be increased, which is preferable in terms of the drying property of the slurry.
  • the nonvolatile content concentration is obtained by weighing about 1 g of the aqueous emulsion for electrodes on an aluminum dish having a diameter of 5 cm, drying at 105 ° C. for 1 hour, and weighing the residue.
  • the viscosity of the aqueous emulsion for electrodes at 23 ° C. is preferably 1 to 5000 mPa ⁇ s, more preferably 2 to 3000 mPa ⁇ s.
  • the viscosity is 1 mPa ⁇ s or more, it is preferable in terms of adjusting the viscosity in producing the slurry for electrodes.
  • a viscosity of 5000 mPa ⁇ s or less is preferable from the viewpoint of dispersibility of the active material.
  • Viscosity is measured using a B-type viscometer by selecting a rotor corresponding to the viscosity of the aqueous emulsion at a rotation speed of 60 rpm. For example, when measuring the viscosity of an aqueous emulsion of about several mPa ⁇ s to several hundred mPa ⁇ s, the rotor no. 1 is used.
  • the volume-based 50% median diameter of the aqueous emulsion for electrodes is preferably 0.05 to 0.4 ⁇ m, and more preferably 0.10 to 0.35 ⁇ m.
  • the dispersed particle diameter can be measured by, for example, a microtrack method.
  • the elution rate of the binder film for a lithium secondary battery electrode with respect to methyl ethyl carbonate is preferably 12% by mass or less, more preferably 8% by mass or less.
  • the elution rate is preferably as small as possible from the viewpoint of battery performance, but is usually 1% by mass or more from the viewpoint of ease of production of the electrode binder.
  • the dissolution rate is measured by the following procedure. First, a film having a thickness of 0.5 mm made of an electrode binder is prepared. This film can be produced by pouring an aqueous emulsion on a flat plate, drying at 50 ° C. for 2.5 hours, and then drying at 50 ° C. for 12 hours under reduced pressure (gauge pressure: ⁇ 95 kPaG). Next, the produced film is cut into 25 mm ⁇ 25 mm. After weighing out the cut film, it is immersed in methyl ethyl carbonate at 60 ° C. for 24 hours. The film after the immersion is taken out, dried and weighed again, and the value obtained by the following formula (5) is taken as the dissolution rate. (Change in film mass before and after immersion / Mass of film before immersion) ⁇ 100 (5)
  • the glass transition temperature (Tg) of the binder for lithium secondary battery electrodes is preferably 30 ° C. or lower. When Tg is 30 ° C. or lower, cracks tend not to occur in an electrode obtained by applying a slurry containing an active material and an electrode binder.
  • the lithium secondary battery electrode slurry of the present embodiment (hereinafter also simply referred to as electrode slurry) is obtained by dispersing or dissolving the above-mentioned lithium secondary battery electrode binder and electrode active material in an aqueous medium.
  • electrode slurry As an aqueous medium, what was mentioned as what can be used for the synthesis
  • the electrode slurry is usually prepared by mixing the above-described aqueous emulsion for lithium secondary battery electrodes, an electrode active material, and other additives as required.
  • the compounding amount of the aqueous emulsion for electrodes is usually 0.25 to 0.5 parts by mass, more preferably 0.5 to 1.0 parts by mass in 100 parts by mass of the slurry for electrodes.
  • the aqueous emulsion for electrodes is 0.25 part by mass or more, sufficient binding properties tend to be easily obtained between the electrode active materials or between the electrode active material and the current collector.
  • the aqueous emulsion for an electrode is 0.5 part by mass or less, a sufficient capacity of the electrode active material can be filled in the electrode active material layer, so that a battery with a large capacity tends to be obtained.
  • the electrode active material may be any material that can be doped / undoped with lithium, and known electrode active materials used for lithium secondary battery electrodes may be used alone or in appropriate combination.
  • examples of the electrode active material used for the negative electrode slurry include a conductive polymer, a carbon material, lithium titanate, and silicon.
  • the electrode active material when the electrode active material is a carbon material, the effect of improving the binding property is remarkable due to the binder obtained by the production method of the present invention.
  • examples of the carbon material include cokes, polymer charcoal, carbon black, carbon fiber, and graphite.
  • coke include coke, petroleum coke, pitch coke, and coal coke.
  • Examples of carbon black include acetylene black.
  • Examples of graphites include artificial graphite and natural graphite.
  • the electrode active material is not particularly limited as long as it is a positive electrode active material that can be used for a lithium secondary battery.
  • the lithium composite oxide include lithium cobalt oxide (LiCoO 2 ) and Ni—Co—Mn lithium composite oxide.
  • the chalcogen compound include TiS 2 and V 2 O 5 .
  • the compounding amount of the electrode active material is preferably 30 to 70% by mass in the slurry.
  • the blending amount is 30% by mass or more, an electrode active material layer sufficiently containing the electrode active material can be formed, and thus a large-capacity battery can be easily obtained.
  • the electrode active material is 70% by mass or less, other necessary components such as an electrode binder can be sufficiently added.
  • the slurry for a lithium secondary battery electrode may contain a known additive in addition to the electrode active material, the electrode binder, and the aqueous medium.
  • the additive include a thickener and a conductive aid.
  • thickener examples include cellulose and its derivatives, poly (meth) acrylic acid-based polymers, vinyl acetamide (NVA) (co) polymers, polyvinyl alcohol, and polyvinylpyrrolidone.
  • NVA vinyl acetamide
  • Examples of cellulose derivatives include carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
  • Carboxymethyl cellulose may be an ammonium salt or an alkali metal salt.
  • Examples of the poly (meth) acrylic acid polymer include (meth) acrylic acid (co) polymers, ammonium salts and alkali metal salts thereof.
  • Examples of the NVA copolymer include NVA-sodium acrylate copolymer.
  • carboxymethylcellulose poly (meth) acrylic acid polymer
  • NVA (co) polymer because a slurry in which an active material is dispersed can be easily prepared.
  • the thickener is a poly (meth) acrylic acid polymer
  • the poly (meth) acrylic acid polymer may be derived from the above-described aqueous emulsion for electrodes, and what is an aqueous emulsion for electrodes? It can also be added to the slurry separately.
  • the addition amount is preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the active material.
  • the coating properties of the electrode slurry become good, and the active materials in the active material layer formed by applying and drying the electrode slurry In addition, the binding property between the active material and the current collector is further improved.
  • conductive support agent As a conductive support agent, the well-known thing used for the electrode active material layer of a lithium secondary battery can be used. Specific examples include carbon black and vapor grown carbon fiber.
  • the electrode of the lithium secondary battery of the present embodiment has a current collector and an electrode active material layer laminated on the current collector, and the electrode active material layer includes the electrode active material and the electrode of the present invention. And a binder for a lithium secondary battery electrode obtained by the production method.
  • the current collector is not particularly limited as long as it is metallic such as iron, copper, aluminum, nickel, and stainless steel. Further, the shape of the current collector is not particularly limited, but it is usually preferable to use a sheet having a thickness of 0.001 to 0.5 mm.
  • Electrode active material layer An electrode active material layer is normally manufactured by apply
  • the slurry can be applied by a common method, for example, reverse roll method, direct roll method, doctor blade method, knife method, extrusion method, curtain method, gravure method, bar method, dip method and squeeze. I can raise the law.
  • the extrusion method is preferred.
  • the application of the slurry for the lithium secondary battery electrode to the current collector may be performed on one side or both sides of the current collector. You may apply
  • the coating thickness of the slurry is not particularly limited and can be determined appropriately according to the size of the battery, but is usually about 50 to 200 ⁇ m. Further, the length and width of the coating layer can be appropriately determined according to the size and shape of the battery.
  • a general method can be used as a method for drying the slurry.
  • the drying temperature is preferably in the range of 40 to 350 ° C., and more preferably 60 to 100 ° C. from the viewpoint of productivity.
  • the drying time can be appropriately determined according to the drying temperature.
  • pressing You may press the electrode after drying as needed.
  • a pressing method a general method can be used, but a mold pressing method and a calendar pressing method are particularly preferable.
  • the pressing pressure is not particularly limited, but is preferably 0.2 to 3 t / cm 2 .
  • the electrode may have a layer other than the current collector and the electrode active material layer as necessary.
  • the other layer include a conductive layer provided between the current collector and the electrode active material layer, and a protective layer provided on the side of the electrode active material layer opposite to the current collector.
  • the conductive layer is provided for the purpose of improving the adhesion between the current collector and the electrode active material layer or reducing the contact resistance between the current collector and the electrode active material layer, and the thickness is usually 1 to 10 ⁇ m.
  • the thickness is preferably 1 to 5 ⁇ m.
  • the protective layer is an insulating layer provided so that the positive electrode and the negative electrode do not contact or conduct even when the separator of the lithium secondary battery is melted at high temperature.
  • -Containing inorganic particles The formation method is not particularly limited.
  • the insulating inorganic particles and a resin such as poly (N-vinylpyrrolidone) are mixed and applied to the electrode active material layer.
  • the peel strength of the electrode active material layer with respect to the current collector is preferably 7 mN / mm or more, more preferably 8 mN / mm or more. If the binder has a good binding strength and exhibits a peel strength of 7 mN or more, when a lithium secondary battery is produced using the binder, the electrode active materials, and the electrode active material and the current collector are strong. Thus, a lithium secondary battery with low internal resistance and excellent durability can be obtained. From the viewpoint of the performance of the obtained lithium secondary battery, the larger the peel strength, the better, but it is usually 20 mN / mm or less.
  • the peel strength test is a value obtained by laminating the test piece coated surface and the SUS plate using a double-sided tape, and peeling 180 ° at a peel width of 25 mm and a peel speed of 100 mm / min.
  • the lithium secondary battery has a positive electrode, a negative electrode and an electrolyte, and a separator as necessary, and these are enclosed in an exterior body.
  • the lithium secondary battery may be a stacked type or a wound type.
  • At least one of the positive electrode and the negative electrode is an electrode of the above-described lithium secondary battery. It is preferable that at least the negative electrode is an electrode of the above-described lithium secondary battery.
  • the other electrode is not particularly limited, and is manufactured using a known material and manufacturing method used for the electrode of the lithium secondary battery. Can be appropriately selected and used.
  • the shape of the battery may be any shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape.
  • Electrodes As the electrolyte, a known one used for a lithium secondary battery can be used, and examples thereof include a nonaqueous electrolytic solution in which a lithium salt is dissolved in a nonaqueous solvent, a gel electrolyte, and a solid electrolyte.
  • the electrode binder obtained by the above-described manufacturing method has both excellent electrolyte resistance and binding properties. It is particularly preferred to use it.
  • the lithium salt used in the electrolyte for example, LiClO 4, LiBF 6, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5 ) 4 , CF 3 SO 3 Li, CH 3 SO 3 Li, LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, lower fatty acid lithium carboxylate and the like.
  • These lithium salts can be appropriately selected and used according to the type of active material.
  • Non-aqueous solvents used in the electrolyte include, for example, carbonates, lactones, ethers, sulfoxides, dioxolane and derivatives thereof, nitrogen-containing organic solvents, organic acid esters, sulfolane and derivatives thereof, phosphoric acid triesters, diglymes, and triglymes. Oxazolidinone and sultone.
  • Examples of the carbonate ester include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), and vinylene carbonate (VC). It is done.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • MEC methyl ethyl carbonate
  • VC vinylene carbonate
  • lactones include ⁇ -butyrolactone and ⁇ -valerolactone.
  • ether examples include trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane and tetrahydrofuran.
  • Examples of dioxolane and its derivatives include 1,3-dioxolane and 4-methyl-1,3-dioxolane.
  • Examples of the sulfoxide include dimethyl sulfoxide.
  • Examples of the sulfolane derivative include methyl sulfolane.
  • nitrogen-containing organic solvents include acetonitrile, nitromethane, and dimethylformamide.
  • organic acid ester examples include methyl formate, methyl acetate, ethyl acetate, butyl acetate, and methyl propionate.
  • Examples of oxazolidinone include 3-methyl-2-oxazolidinone.
  • Examples of sultone include 1,3-propane sultone, 1,4-butane sultone, and naphtha sultone.
  • the lithium secondary battery has a separator between the positive electrode and the negative electrode.
  • a separator There is no restriction
  • An example of the separator is a porous polyolefin film.
  • a heat-resistant protective layer may be provided on the surface of the separator in order to prevent the separator from being completely melted at a high temperature and short-circuiting the positive electrode and the negative electrode.
  • an insulating inorganic particle such as alumina and an insulating resin such as poly (N-vinylpyrrolidone) are mixed and applied to the surface of the separator substrate.
  • Example 1-1 Synthesis of aqueous emulsion for lithium secondary battery electrode
  • a separable flask having a condenser, a thermometer, a stirrer, and a dropping funnel 159.5 parts by mass of ion-exchanged water and a surfactant (trade name Eleminol JS-20 (40% product) manufactured by Sanyo Chemical Industries, Ltd.) 1 .5 mass parts was charged and the temperature was raised to 65 ° C.
  • a surfactant trade name Eleminol JS-20 (40% product) manufactured by Sanyo Chemical Industries, Ltd.
  • Example 1-2 An aqueous emulsion for electrode 2 was synthesized in the same manner as in Example 1 except that the polymerization temperature during synthesis of the aqueous emulsion for electrode was 80 ° C.
  • Example 1-3 After dropping the monomer emulsion, after aging for 1 hour, 0.5 parts by mass of t-butyl peroxybenzoate as an oxidizing agent and 0.5 parts by mass of sodium ascorbate as a reducing agent are each dissolved in 10 parts by mass of ion-exchanged water. Aqueous emulsion 3 for electrodes was synthesized in the same manner as in Example 1-1 except that the product was added and then aged for 1 hour.
  • Example 1-4 In Example 1-3, the oxidizing agent to be added was changed to 1.0 part by mass of t-butyl hydroperoxide dissolved in 10 parts by mass of ion-exchanged water, and the reducing agent to be added was sodium hydrogen sulfite 1.
  • Aqueous emulsion 4 for electrodes was synthesized in the same manner as in Example 1-3, except that 0 part by mass was dissolved in 10 parts by mass of ion-exchanged water.
  • Example 1-5 After completion of dropping of the monomer emulsion, 15 parts by mass of acrylic acid was added, and 0.5 parts by mass of t-butyl peroxybenzoate and 1.0 part by mass of t-butyl hydroperoxide were added as ionizing water. Other than using 10 parts by weight dissolved in 10 parts by weight, 0.5 parts by weight sodium ascorbate and 1.0 part by weight sodium bisulfite dissolved in 10 parts by weight of ion-exchanged water as the reducing agent to be added, In the same manner as in Example 1-3, an aqueous emulsion 5 for electrodes was synthesized.
  • Comparative Example 1 The polymerization temperature at the time of the synthesis of the aqueous emulsion for electrodes was 80 ° C., and the hydroxy initiator was not used as a polymerization initiator, but sodium hydroxymethanesulfinate, and the amount of potassium persulfate as an oxidizing agent was 2.0 parts by mass.
  • a comparative electrode aqueous emulsion 1 was synthesized in the same manner as in Example 1-1 except that it was used.
  • Table 1 shows the results of evaluating the following items regarding the binder for lithium ion secondary battery electrodes in the aqueous emulsion for electrodes obtained in Examples 1-1 to 1-5.
  • Table 2 shows the results of a similar evaluation of the binder for electrodes in the aqueous emulsion for comparative electrodes obtained in Comparative Examples.
  • Elution rate Measured by the method described above.
  • Tensile strength and elongation The aqueous emulsion for electrodes was dried at 23 ° C. and 50% RH for 7 days to produce a binder film for electrodes having a thickness of 0.3 ⁇ m.
  • the obtained film was cut into a width of 10 mm, and a tensile test was performed using a tensile tester at a distance between chucks of 10 mm and a tensile speed of 100 mm / min to measure tensile strength and elongation.
  • Example 2-1 (Preparation of slurry for lithium ion secondary battery electrode and preparation of electrode) (Examples 2-1 to 2-5 and Comparative Example 2-1) 95 parts by mass of an electrode active material (trade name SCMG (registered trademark) manufactured by Showa Denko KK), 2 parts by mass of acetylene black (trade name C65 manufactured by Timcal Co., Ltd.) as a conductive assistant, carboxymethylcellulose (manufactured by Nippon Paper Chemicals Co., Ltd.) 1 part by mass (trade name Metroze MAC200LC) and 2 parts by mass of each of the aqueous emulsions for electrodes shown in Table 1 and Table 2 were mixed to prepare slurry 1 to 5 for electrode and slurry 1 for reference electrode.
  • an electrode active material trade name SCMG (registered trademark) manufactured by Showa Denko KK
  • acetylene black trade name C65 manufactured by Timcal Co., Ltd.
  • carboxymethylcellulose manufactured by Nippon Paper Chemicals Co., Ltd.
  • Electrodes 1 to 5 and comparative electrode 1 were produced.
  • the drying conditions were two types: drying at 50 ° C. for 5 minutes on a hot plate, drying at 110 ° C. for 5 minutes, and drying in a hot air dryer at 70 ° C. and a wind speed of 1 m / second for 100 seconds.
  • Comparative Example 2-2 Comparative electrode slurry 2 in the same manner as in Comparative Example 2-1, except that 0.02 parts by mass of a sodium polyacrylate aqueous solution (weight average molecular weight 6.0 ⁇ 10 4 , pH 7.1) was added as a thickener. And a comparative electrode 2 were prepared.
  • a sodium polyacrylate aqueous solution weight average molecular weight 6.0 ⁇ 10 4 , pH 7.1
  • Comparative Example 2-3 Except that a commercially available styrene-butadiene latex (non-volatile content 40% by mass, viscosity 12 mPa ⁇ s, pH 7.7, particle size 0.14 ⁇ m) was used as the aqueous emulsion for the comparative electrode, the same as Example 2-1. Preparation of the comparative electrode slurry 3 and preparation of the comparative electrode 3 were performed.
  • the internal resistance value of the battery at ⁇ 20 ° C. was measured by the following procedure. First, in order to eliminate the remaining capacity of the battery, the battery was discharged at a constant current of 0.2 C until the lower limit voltage (2.75 V) was reached. Thereafter, the battery was charged at a constant current of 1 C until the upper limit voltage (4.2 V) was reached, and further charged at a constant voltage (4.2 V) until 1.5 hours had passed to obtain a full charge. Next, the battery was discharged at a constant current of 0.1 C, and the remaining capacity of the battery was adjusted to 80%.
  • Table 1 shows the measurement results for the electrodes of Examples, and Table 2 shows the results for the electrodes of Comparative Examples.
  • the peel strength of the electrode active material layer As shown in Table 1, when the binder for a lithium secondary battery electrode produced by the production method of the present invention is used, the peel strength of the electrode active material layer, particularly the peel strength and rapid electrolyte resistance when rapid drying is performed. An excellent electrode for a lithium secondary battery is obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un liant pour électrodes de batterie rechargeable au lithium, qui a une excellente résistance à la solution électrolyte et d'excellentes propriétés liantes même dans les cas où le liant est séché rapidement à haute température. Dans une méthode de production d'un liant pour électrodes de batterie rechargeable au lithium de la présente invention, des monomères éthyléniques non saturés, qui comprennent au moins le styrène, un ester d'acide carboxylique éthylénique non saturé et un acide carboxylique éthylénique non saturé sont polymérisés par émulsion dans une substance aqueuse en utilisant un oxydant et un agent réducteur comme initiateurs de polymérisation.
PCT/JP2014/051374 2013-01-23 2014-01-23 Méthode de production de liant pour électrodes de batterie rechargeable au lithium, et liant pour électrodes de batterie rechargeable au lithium WO2014115802A1 (fr)

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WO2017026345A1 (fr) * 2015-08-11 2017-02-16 昭和電工株式会社 Suspension épaisse destinée à une électrode positive d'une batterie secondaire au lithium-ion, électrode positive destinée à une batterie secondaire au lithium-ion obtenue à l'aide de la suspension épaisse destinée à une électrode positive d'une batterie secondaire au lithium-ion et procédé de production associé, et batterie secondaire au lithium-ion pourvue de l'électrode positive destinée à une batterie secondaire au lithium-ion et procédé de production associé
JP2017069108A (ja) * 2015-09-30 2017-04-06 日本ゼオン株式会社 リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
WO2017122540A1 (fr) * 2016-01-13 2017-07-20 昭和電工株式会社 Composition de liant hydraulique pour électrode de pile rechargeable, bouillie pour électrode de pile rechargeable, liant, électrode de pile rechargeable et pile rechargeable
JP2018106935A (ja) * 2016-12-27 2018-07-05 凸版印刷株式会社 非水電解質二次電池用負極剤、非水電解質二次電池用負極及び非水電解質二次電池
CN114478898A (zh) * 2022-02-17 2022-05-13 惠州市赛力达化工有限公司 一种锂电池负极代sbr用乳液聚合粘合剂及其制备方法

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JP2019053942A (ja) * 2017-09-19 2019-04-04 日本エイアンドエル株式会社 電気化学デバイス用電極の製造方法
EP3691005A4 (fr) * 2017-09-29 2021-08-04 Sumitomo Seika Chemicals Co., Ltd. Liant pour électrode de batterie secondaire à électrolyte non aqueux, mélange d'électrode pour batterie secondaire à électrolyte non aqueux, électrode pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et appareil électrique
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WO2017026345A1 (fr) * 2015-08-11 2017-02-16 昭和電工株式会社 Suspension épaisse destinée à une électrode positive d'une batterie secondaire au lithium-ion, électrode positive destinée à une batterie secondaire au lithium-ion obtenue à l'aide de la suspension épaisse destinée à une électrode positive d'une batterie secondaire au lithium-ion et procédé de production associé, et batterie secondaire au lithium-ion pourvue de l'électrode positive destinée à une batterie secondaire au lithium-ion et procédé de production associé
JPWO2017026345A1 (ja) * 2015-08-11 2018-05-31 昭和電工株式会社 リチウムイオン二次電池の正極用スラリー、リチウムイオン二次電池の正極用スラリーを用いて得られるリチウムイオン二次電池用正極およびその製造方法、並びに、リチウムイオン二次電池用正極を備えたリチウムイオン二次電池およびその製造方法
US10811686B2 (en) 2015-08-11 2020-10-20 Showa Denko K.K. Slurry for positive electrode of lithium-ion secondary battery, positive electrode for lithium-ion secondary battery obtained using slurry for positive electrode of lithium-ion secondary battery and production method therefor, and lithium-ion secondary battery provided with positive electrode for lithium-ion secondary battery and production method therefor
JP2017069108A (ja) * 2015-09-30 2017-04-06 日本ゼオン株式会社 リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
WO2017122540A1 (fr) * 2016-01-13 2017-07-20 昭和電工株式会社 Composition de liant hydraulique pour électrode de pile rechargeable, bouillie pour électrode de pile rechargeable, liant, électrode de pile rechargeable et pile rechargeable
JPWO2017122540A1 (ja) * 2016-01-13 2018-11-01 昭和電工株式会社 二次電池電極用水系バインダー組成物、二次電池電極用スラリー、バインダー、二次電池電極、および二次電池
US11063260B2 (en) 2016-01-13 2021-07-13 Showa Denko K.K. Aqueous binder composition for secondary battery electrode, slurry for secondary battery electrode, binder, secondary battery electrode, and secondary battery
JP2018106935A (ja) * 2016-12-27 2018-07-05 凸版印刷株式会社 非水電解質二次電池用負極剤、非水電解質二次電池用負極及び非水電解質二次電池
CN114478898A (zh) * 2022-02-17 2022-05-13 惠州市赛力达化工有限公司 一种锂电池负极代sbr用乳液聚合粘合剂及其制备方法

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