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WO2016208480A1 - Composition de suspension destinée à des électrodes négatives de batterie secondaire à électrolyte non aqueux et son utilisation - Google Patents

Composition de suspension destinée à des électrodes négatives de batterie secondaire à électrolyte non aqueux et son utilisation Download PDF

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Publication number
WO2016208480A1
WO2016208480A1 PCT/JP2016/067888 JP2016067888W WO2016208480A1 WO 2016208480 A1 WO2016208480 A1 WO 2016208480A1 JP 2016067888 W JP2016067888 W JP 2016067888W WO 2016208480 A1 WO2016208480 A1 WO 2016208480A1
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Prior art keywords
negative electrode
organic hollow
hollow particles
secondary battery
electrolyte secondary
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PCT/JP2016/067888
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English (en)
Japanese (ja)
Inventor
勝志 三木
良貢 佐々木
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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Priority to CN201680037357.4A priority Critical patent/CN107735891B/zh
Priority to KR1020177037681A priority patent/KR102707155B1/ko
Priority to JP2017525286A priority patent/JP6294570B2/ja
Publication of WO2016208480A1 publication Critical patent/WO2016208480A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 slurry composition for a non-aqueous electrolyte secondary battery negative electrode, a non-aqueous electrolyte secondary battery negative electrode obtained by applying the slurry composition for a negative electrode to a current collector, and a non-aqueous electrolyte secondary battery including the negative electrode And an organic hollow particle used in a slurry composition for a negative electrode of a nonaqueous electrolyte secondary battery.
  • Patent Document 1 proposes that the cycle characteristics are improved by having a negative electrode active material layer containing hollow or porous inorganic particles in a negative electrode in a nonaqueous electrolyte secondary battery.
  • Patent Document 2 proposes that in a secondary battery, cycle characteristics are improved by using a battery electrode containing an electrode active material and crosslinked polymer particles.
  • An object of the present invention is to provide a slurry composition used for a nonaqueous electrolyte secondary battery negative electrode having improved cycle characteristics, a nonaqueous electrolyte secondary battery negative electrode obtained by applying the slurry composition to a current collector, It is providing the organic hollow particle used for the slurry composition for nonaqueous electrolyte secondary batteries provided with a negative electrode, and a nonaqueous electrolyte secondary battery negative electrode.
  • the present inventor has made various studies, and as a result, used a negative electrode obtained by using a slurry composition for a negative electrode of a nonaqueous electrolyte secondary battery containing specific organic hollow particles for a nonaqueous electrolyte secondary battery. As a result, the inventors have found that the above-described problems can be solved, and have reached the present invention.
  • the slurry composition for a non-aqueous electrolyte secondary battery negative electrode of the present invention includes organic hollow particles whose outer shell is made of a thermoplastic resin, a negative electrode binder, and a negative electrode active material.
  • the ratio (d1 / d2) between (d1) and the outer diameter (d2) is more than 0.7 and not more than 0.999.
  • the slurry composition for a nonaqueous electrolyte secondary battery negative electrode of the present invention preferably satisfies at least one of the following structural requirements (1) to (5).
  • the thermoplastic resin is a polymer of a polymerizable component containing a nitrile monomer.
  • the organic hollow particle is an expanded body of thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent contained therein and vaporized by heating.
  • the true specific gravity of the organic hollow particles is 0.01 to 0.5.
  • the volume-based cumulative 50% particle diameter (D50) of the organic hollow particles is 0.1 to 50 ⁇ m.
  • the content of the organic hollow particles in the negative electrode slurry composition is 0.001 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.
  • the non-aqueous electrolyte secondary battery negative electrode of the present invention is obtained by applying the negative electrode slurry composition to a current collector.
  • the non-aqueous electrolyte secondary battery of the present invention includes the above-described negative electrode, positive electrode, non-aqueous electrolyte, and separator.
  • the organic hollow particles used in the slurry composition for a nonaqueous electrolyte secondary battery negative electrode of the present invention have an outer shell made of a thermoplastic resin, and the ratio of the inner pore diameter (d1) to the outer pore diameter (d2) of the organic hollow particles ( d1 / d2) is more than 0.7 and not more than 0.999.
  • the organic hollow particles of the present invention further satisfy at least one constituent requirement among the above (1) to (4).
  • a nonaqueous electrolyte secondary battery negative electrode and a nonaqueous electrolyte secondary battery having excellent cycle characteristics can be obtained.
  • the nonaqueous electrolyte secondary battery negative electrode and the nonaqueous electrolyte secondary battery of the present invention are excellent in cycle characteristics.
  • the organic hollow particles used in the slurry composition for a non-aqueous electrolyte secondary battery negative electrode of the present invention a non-aqueous electrolyte secondary battery negative electrode and a non-aqueous electrolyte secondary battery having excellent cycle characteristics can be obtained.
  • FIG. 1 is a schematic view showing an example of organic hollow particles A.
  • FIG. It is the schematic which shows an example of a nonaqueous electrolyte secondary battery.
  • the nonaqueous electrolyte secondary battery 1 of the present invention includes a battery container 6 as shown in FIG.
  • the battery container 6 has a cylindrical shape.
  • the shape of the battery container is not limited to a cylindrical shape.
  • the shape of the departure container may be, for example, a flat shape.
  • An electrode body 2 impregnated with a nonaqueous electrolyte is accommodated in the battery container 6.
  • the electrode body 2 is formed by winding a negative electrode 3, a positive electrode 4, and a separator 5 disposed between the negative electrode 3 and the positive electrode 4.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode active material layer of the present invention has voids introduced by organic hollow particles.
  • a production process including a step of applying a slurry composition for a negative electrode of a non-aqueous electrolyte secondary battery, which will be described in detail later (hereinafter sometimes referred to as “slurry composition for negative electrode”) on a negative electrode current collector, and drying. It can be manufactured by a method. Specifically, after preparing the negative electrode slurry composition, the negative electrode slurry composition is applied onto the negative electrode current collector.
  • the slurry composition for negative electrode may be applied only to one surface of the negative electrode current collector, or may be applied to both surfaces. Since the slurry composition for negative electrodes is excellent in dispersibility, uniform application
  • coating is easy. Moreover, a more uniform negative electrode active material layer can be produced by filtering the negative electrode slurry composition before coating.
  • the coating amount of the negative electrode slurry composition on the negative electrode current collector is preferably 10 to 20 mg / cm 2 .
  • the negative electrode current collector for example, a metal, carbon, a conductive polymer, or the like can be used, and a metal is preferably used.
  • a metal copper, aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance.
  • high-purity aluminum disclosed in JP 2001-176757 A can be suitably used.
  • the current collector is in the form of a film or a sheet, and the thickness thereof is appropriately selected depending on the purpose of use, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
  • the coating method there is no restriction
  • a film of the negative electrode slurry composition is formed on the surface of the current collector.
  • membrane of the slurry composition for negative electrodes can be suitably set according to the thickness of the target negative electrode active material layer.
  • a solvent such as water is removed from the negative electrode slurry composition film by drying.
  • a negative electrode active material layer including a negative electrode binder, a negative electrode active material, and organic hollow particles and including a water-soluble polymer and / or a conductive auxiliary agent used as necessary is formed on the surface of the current collector.
  • a water electrolyte secondary battery negative electrode is obtained.
  • the drying temperature and drying time are not particularly limited. For example, you may heat-process at 120 degreeC or more for 1 hour or more. Examples of the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • After forming the negative electrode active material layer on the surface of the current collector it is preferable to apply pressure treatment to the negative electrode active material layer using a die press or a roll press. By the pressure treatment, the porosity of the negative electrode can be lowered.
  • the negative electrode active material layer includes a curable polymer, the polymer may be cured after the formation of the negative electrode active material layer.
  • the negative electrode slurry composition of the present invention includes a negative electrode binder, a negative electrode active material, and organic hollow particles. If necessary, a water-soluble polymer or a conductive aid may be included.
  • the content of the organic hollow particles in the negative electrode slurry composition is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0.001 parts by weight with respect to 100 parts by weight of the negative electrode active material. 05 to 3.5 parts by weight. When there is too much content of the organic hollow particle in the slurry composition for negative electrodes, the output characteristic of the nonaqueous electrolyte secondary battery obtained may fall.
  • the slurry composition for negative electrodes of this invention may contain the hollow particle and porous particle which consist of inorganic materials.
  • the hollow particles and porous particles made of an inorganic material include inorganic hollow bodies such as silica and titania; inorganic porous particles such as porous alumina oxide and the like.
  • the method or order of dispersing or dissolving the negative electrode binder, the negative electrode active material, the organic hollow particles, and the water-soluble polymer and / or the conductive additive added as necessary in the solvent is not particularly limited.
  • the negative electrode binder is preferably an aqueous binder, and an SBR binder, a polyacrylate binder, or the like can be used.
  • the negative electrode active material a material that can normally occlude and release lithium can be used in the negative electrode of the nonaqueous electrolyte secondary battery.
  • the negative electrode active material include a carbon material, a material alloyed with lithium, and a metal oxide such as tin oxide.
  • the material to be alloyed with lithium include one or more metals selected from the group consisting of silicon, germanium, tin and aluminum, or one or more types selected from the group consisting of silicon, germanium, tin and aluminum. The thing which consists of an alloy containing a metal is mentioned.
  • the carbon material examples include natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbead (MCMB), coke, hard carbon, fullerene, and carbon nanotube.
  • MCF mesophase pitch-based carbon fiber
  • MCMB mesocarbon microbead
  • coke hard carbon
  • fullerene fullerene
  • carbon nanotube carbon nanotube
  • graphite such as artificial graphite and natural graphite is preferable.
  • the negative electrode active material preferably used for the nonaqueous electrolyte secondary battery is a negative electrode active material containing a metal.
  • a negative electrode active material containing at least one selected from the group consisting of tin, silicon, germanium and lead is preferable. The negative electrode active material containing these elements can reduce the irreversible capacity.
  • the water-soluble polymer is not particularly limited, but for example, cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose, and hydroxypropylcellulose, as well as ammonium salts or alkali metal salts thereof, alginates such as propylene glycol alginate, and alginic acid.
  • cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose, and hydroxypropylcellulose, as well as ammonium salts or alkali metal salts thereof, alginates such as propylene glycol alginate, and alginic acid.
  • Alginates such as sodium, polyacrylic acid, and polyacrylic acid (or methacrylic acid) salts such as sodium polyacrylic acid (or methacrylic acid), polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polycarboxylic acid, oxidation Starch, phosphate starch, casein, various modified starches, chitin, chitosan derivatives, xanthan gum, polycarboxylic acid Chloride, polyoxyalkylene-based surfactant and the like.
  • “(modified) poly” means “unmodified poly” or “modified poly”.
  • These water-soluble polymers can be used alone or in combination of two or more.
  • a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable.
  • the conductive auxiliary agent is not particularly limited as long as it is a conductive material, but a conductive particulate material is preferable.
  • conductive carbon black such as furnace black, acetylene black, and ketjen black
  • natural graphite And graphite such as artificial graphite
  • carbon fibers such as polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and vapor grown carbon fiber.
  • the average particle diameter when the conductive additive is a particulate material is not particularly limited, but is preferably smaller than the average particle diameter of the negative electrode active material, from the viewpoint of expressing sufficient conductivity with a smaller amount of use.
  • the thickness is preferably 0.001 to 10 ⁇ m, more preferably 0.01 to 5 ⁇ m, and still more preferably 0.03 to 1 ⁇ m.
  • the organic hollow particles used in the slurry composition for a nonaqueous electrolyte secondary battery negative electrode have an outer shell made of a thermoplastic resin.
  • the organic hollow particles are preferably composed of an outer shell and a hollow portion surrounded by the outer shell.
  • the organic hollow particles are (almost) spherical and have a hollow portion corresponding to a large cavity inside. If the shape of the organic hollow particles is exemplified by familiar articles, a soft tennis ball can be mentioned.
  • the hollow part is (substantially) spherical and is in contact with the inner surface of the outer shell.
  • the hollow portion is basically filled with gas and may be in a liquefied state. In general, the hollow portion is preferably one large hollow portion, but a plurality of hollow portions may be present in the organic hollow particles.
  • the ratio of the inner hole to the outer hole of the organic hollow particles is calculated by the ratio (d1 / d2) between the inner hole diameter (d1) and the outer hole diameter (d2).
  • the ratio (d1 / d2) is more than 0.7 and not more than 0.999, preferably 0.75 to 0.995, more preferably 0.78 to 0.990, and still more preferably 0.80 to 0.985. Particularly preferred is 0.85 to 0.980.
  • the ratio (d1 / d2) is 0.7 or less, the effect of improving the cycle characteristics of the nonaqueous electrolyte secondary battery is lowered.
  • the ratio (d1 / d2) is more than 0.999, the organic hollow particles are destroyed during the preparation of the slurry composition for the non-aqueous electrolyte secondary battery negative electrode, and the effect of improving the cycle characteristics of the non-aqueous electrolyte secondary battery is achieved. May decrease.
  • the true specific gravity of the organic hollow particles is not particularly limited, but is preferably 0.01 to 0.5, more preferably 0.012 to 0.49, particularly preferably 0.04 to 0.48, and most preferably 0.31 to 0.47.
  • the true specific gravity of the organic hollow particles is less than 0.01, the strength of the organic hollow particles is reduced due to the thin outer shell, and the organic hollow particles are destroyed when adjusting the slurry composition for the negative electrode of the nonaqueous electrolyte secondary battery. The effect of improving the cycle characteristics of the nonaqueous electrolyte secondary battery may be reduced.
  • the true specific gravity of the organic hollow particles exceeds 0.5, the ratio of the volume of the outer shell to the volume of the organic hollow particles increases, and the cycle characteristics of the nonaqueous electrolyte secondary battery may be deteriorated.
  • the volume-based cumulative 50% particle diameter (D50) of the organic hollow particles is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 1.0 to 35 ⁇ m, still more preferably 2.0 to It is 20 ⁇ m, particularly preferably 2.5 to 15 ⁇ m, most preferably 3.0 to 10. If D50 is less than 0.1 ⁇ m, uniform dispersion may be difficult. On the other hand, when D50 exceeds 50 ⁇ m, the cycle characteristics of the nonaqueous electrolyte secondary battery may be deteriorated.
  • the volume-based cumulative particle size is a cumulative particle size obtained by laser diffraction scattering type particle size distribution measurement on a volume basis, and the measurement method will be described in detail in the following examples.
  • the organic hollow particles may further comprise fine particle fillers attached to the outer surface of the outer shell.
  • the organic hollow particles to which the fine particle filler is attached may be referred to as “organic hollow particles A” for simplicity.
  • the term “adhesion” used herein may simply mean that the fine particle fillers (11 and 12) are adsorbed on the outer surface of the outer shell (8) of the organic hollow particles A (10).
  • the thermoplastic resin constituting the nearby outer shell may be softened or melted by heating, and the fine particle filler may sink into the outer surface of the outer shell of the organic hollow particle A and be fixed (12). is there.
  • the particle shape of the fine particle filler may be indefinite or spherical.
  • the true specific gravity of the organic hollow particles A is not particularly limited, but is preferably 0.01 to 0.7, more preferably 0.03 to 0.6, particularly preferably 0.05 to 0.5, Most preferably, it is 0.07 to 0.30.
  • the true specific gravity of the organic hollow particles A is smaller than 0.01, the organic hollow particles A are destroyed during preparation of the slurry composition for the negative electrode of the nonaqueous electrolyte secondary battery, and the cycle characteristics of the nonaqueous electrolyte secondary battery using the organic hollow particles A May decrease.
  • the true specific gravity of the organic hollow particles A is greater than 0.7, the effect of improving the cycle characteristics of the non-aqueous electrolyte secondary battery is reduced.
  • the ratio between the average particle diameter of the fine particle filler and the average particle diameter of the organic hollow particles A is preferably from the viewpoint of the adhesion of the fine particle filler. 1 or less, more preferably 0.8 or less, particularly preferably 0.6 or less.
  • Various particles can be used as the fine particle filler, and any of inorganic and organic materials may be used.
  • the shape of the fine particle main body include a spherical shape, a needle shape, and a plate shape.
  • inorganic substances constituting the fine particle filler include limestone (heavy calcium carbonate), quartz, silica (silica), wollastonite, gypsum, apatite, magnetite, zeolite, clay (montmorillonite, saponite, hectorite, beidellite, and steven.
  • Minerals such as sight, nontronite, vermiculite, halloysite, talc, mica, mica, etc .; in the periodic table of elements, metal oxides of groups 1 to 16 (titanium oxide, zinc oxide, aluminum oxide, manganese oxide, Molybdenum oxide, tungsten oxide, vanadium oxide, tin oxide, iron oxide (including magnetic iron oxide, indium oxide, etc.), metal hydroxide (aluminum hydroxide, gold hydroxide, magnesium hydroxide, etc.), metal carbonate ( Calcium carbonate (light calcium carbonate), hydrogen carbonate Cium, sodium bicarbonate (bicarbonate), iron carbonate, etc., sulfate metal salts (aluminum sulfate, cobalt sulfate, sodium hydrogen sulfate, copper sulfate, nickel sulfate, barium sulfate, etc.), other metal salts (titanate (titanic acid) Barium, magnesium titanate, potassium titanate, etc
  • Inorganic substances constituting the fine particle filler are also synthetic calcium carbonate, ferrite, zeolite, silver ion supported zeolite, zirconia, alum, lead zirconate titanate, alumina fiber, cement, zonotlite, silicon oxide (silica, silicate, glass, (Including glass fiber), silicon nitride, silicon carbide, silicon sulfide; conductive carbon black such as furnace black, acetylene black and ketjen black; graphite such as natural graphite and artificial graphite; polyacrylonitrile carbon fiber, pitch carbon Carbon fibers such as fibers and vapor grown carbon fibers; carbon nanotubes, graphite, ketjen black, activated carbon, bamboo charcoal, charcoal, fullerene and the like may be used.
  • the inorganic material constituting the fine particle filler includes conductive carbon black such as furnace black, acetylene black, and ketjen black; graphite such as natural graphite and artificial graphite; polyacrylonitrile-based carbon fiber, pitch-based carbon fiber From the viewpoint of improving the performance of the nonaqueous electrolyte secondary battery, a particulate material having conductivity such as carbon fiber such as vapor grown carbon fiber;
  • Organic substances constituting the fine particle filler are sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, nitrocellulose, hydroxypropyl cellulose, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, ( Examples thereof include polyamide resins such as (meth) acrylic resins and nylon resins, silicone resins, urethane resins, polyethylene resins, polypropylene resins, and fluorine resins.
  • polyamide resins such as (meth) acrylic resins and nylon resins, silicone resins, urethane resins, polyethylene resins, polypropylene resins, and fluorine resins.
  • the inorganic substance or organic substance constituting the fine particle filler may be treated with a surface treatment agent such as a silane coupling agent, paraffin wax, fatty acid, resin acid, urethane compound, fatty acid ester, etc., or may be untreated.
  • a surface treatment agent such as a silane coupling agent, paraffin wax, fatty acid, resin acid, urethane compound, fatty acid ester, etc., or may be untreated.
  • An organic hollow particle is an expanded body of thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating, and the thermally expandable microspheres are heated and expanded. Can be obtained.
  • the thermoplastic resin is a polymer of a polymerizable component described later.
  • the maximum expansion temperature of the thermally expandable microspheres used as the raw material for the organic hollow particles is preferably 70 to 250 ° C., more preferably 80 to 200 ° C., and particularly preferably 90 to 150 ° C. If the maximum expansion temperature is outside the range of 70 to 250 ° C., the active material may be peeled off from the electrode, and the battery life may be shortened.
  • the ash content of the organic hollow particles is preferably 10% by weight or less, more preferably 9.5% by weight or less, further preferably 9.0% by weight or less, still more preferably 8.5% by weight or less, and particularly preferably 8.% by weight. 0 wt% or less, most preferably 7.5 wt% or less.
  • the battery life may be reduced in the non-aqueous electrolyte secondary battery containing organic hollow particles. It is considered that the ash content of the organic hollow particles is derived from a metal compound or the like. Moreover, the minimum with the preferable ash content of an organic hollow particle is 0 weight%.
  • the silicon content of the organic hollow particles is preferably 5% by weight or less, more preferably 4.5% by weight or less, further preferably 4% by weight or less, still more preferably 3.5% by weight or less, and particularly preferably 3. 0 wt% or less, most preferably 2.5 wt% or less. If the silicon content exceeds 5% by weight, the negative electrode of the nonaqueous electrolyte secondary battery in which the organic hollow particles are blended may swell with the electrolytic solution, and the active material may peel off. Moreover, the minimum with preferable silicon content of an organic hollow particle is 0 weight%.
  • Method for producing organic hollow particles for example, a step of thermally expanding thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating (expansion step) ). Prior to the expansion step, it is necessary to manufacture thermally expandable microspheres.
  • a method for manufacturing the thermally expandable microspheres for example, an oily mixture containing a polymerizable component and a foaming agent is dispersed.
  • a production method including a step (polymerization step) of polymerizing a polymerizable component using a polymerization initiator can be mentioned. Therefore, the organic hollow particles can be produced through a polymerization step and an expansion step in this order.
  • the foaming agent is not particularly limited as long as it is a substance that is vaporized by heating.
  • propane for example, propane, (iso) butane, (iso) pentane, (iso) hexane, (iso) heptane, (iso) octane, ( Hydrocarbons having 3 to 13 carbon atoms such as (iso) nonane, (iso) decane, (iso) undecane, (iso) dodecane, (iso) tridecane; (iso) hexadecane, (iso) eicosane and the like having more than 13 carbon atoms
  • Examples of the hydrocarbon include 20 or less.
  • the blowing agent is preferably a hydrocarbon having a boiling point of less than 60 ° C.
  • a hydrocarbon having a boiling point exceeding 60 ° C. is used, the active material may be peeled off from the electrode, and the battery life may be shortened.
  • the polymerizable component is a component that becomes a thermoplastic resin that forms the outer shell of the thermally expandable microsphere by polymerization.
  • the polymerizable component is a component which essentially includes a monomer component and may contain a crosslinking agent.
  • the monomer component generally includes a component called a (radical) polymerizable monomer having one polymerizable double bond.
  • nitrile monomers include acrylonitrile (AN), methacrylonitrile (MAN), and fumaronitrile.
  • the weight ratio of the nitrile monomer in the polymerizable component is not particularly limited, but is preferably 80% by weight or more, more preferably 93% by weight or more, and particularly preferably 98% by weight or more.
  • the upper limit of the weight ratio of the nitrile monomer is preferably 100% by weight. When the weight ratio of the nitrile monomer is less than 80% by weight, the retention of the foaming agent contained in the organic hollow particles is poor, and the foaming agent may be gradually released.
  • nitrile monomer is essentially acrylonitrile (AN) and / or methacrylonitrile (MAN), it has excellent retention of the foaming agent encapsulated in the thermally expanded microcapsules and the organic hollow particles that are the raw materials of the organic hollow particles. This is preferable.
  • the polymerizable component may contain a monomer other than the nitrile monomer as the monomer component.
  • the monomer other than the nitrile monomer is not particularly limited.
  • vinyl halide monomers such as vinyl chloride; vinylidene halide monomers such as vinylidene chloride; vinyl acetate, propionic acid Vinyl ester monomers such as vinyl and vinyl butyrate; carboxyl group-containing monomers such as (meth) acrylic acid, ethacrylic acid, crotonic acid and cinnamic acid; carboxylic anhydrides such as maleic acid, itaconic acid and fumaric acid Monomers: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meta ) Ac
  • Polymerizable components include (meth) acrylic acid ester monomers, carboxyl group-containing monomers, styrene monomers, vinyl ester monomers, acrylamide monomers, maleimide monomers, and vinylidene chloride. It is preferable that at least one selected from the group consisting of When the polymerizable component contains a nitrile monomer and a (meth) acrylic acid ester monomer, it is preferable from the viewpoints of retention of the foaming agent in the heat-expandable microsphere and heat resistance.
  • the polymerizable component may contain a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds in addition to the monomer component.
  • a polymerizable monomer crosslinking agent
  • crosslinking agent By polymerizing using a cross-linking agent, a decrease in the retention rate of the encapsulated foaming agent at the time of thermal expansion is suppressed, and thermal expansion can be effectively performed.
  • a polymerizable monomer having three or more polymerizable double bonds becomes brittle when the outer shell of the thermally expandable microsphere is too strong, and the elasticity of the organic hollow particles obtained by thermal expansion is weak. It may be damaged.
  • the crosslinking agent is not particularly limited.
  • aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, allyl methacrylate, triacryl formal, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trime Roll propane tri (meth) acrylate, EO-modified trimethylolprop
  • the amount of the crosslinking agent is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, particularly preferably 0. 3 to 0.9 parts by weight.
  • Polymerization of the polymerizable component may be performed using a polymerization initiator, and an oil-soluble polymerization initiator is preferable.
  • the oily mixture may further contain a chain transfer agent and the like.
  • the aqueous dispersion medium may further contain a dispersion stabilizer and the like.
  • the dispersion stabilizer is not particularly limited.
  • examples thereof include iron, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, calcium carbonate, barium carbonate, magnesium carbonate and the like.
  • These dispersion stabilizers may be used alone or in combination of two or more.
  • the amount of the dispersion stabilizer is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable component.
  • colloidal silica is preferable, and thermally expandable microspheres having a small particle diameter can be obtained stably.
  • Colloidal silica is widely marketed in the form of a dispersion containing colloidal silica, ie, a colloidal silica dispersion. “Quatron” manufactured by Fuso Chemical Industry Co., Ltd. “Adelite” manufactured by ADEKA Co., Ltd., Nippon Chemical Industry Co., Ltd. Various grades of physical properties such as average particle diameter and specific surface area of colloidal silica can be easily selected from commercially available products such as “Silica Doll” manufactured by Nissan Chemical Industries, “Snowtex” manufactured by Nissan Chemical Industries, Ltd., and “Ludox” manufactured by Dupont. Can be obtained.
  • the effective concentration of colloidal silica contained in the colloidal silica dispersion is not particularly limited, but is preferably 10 to 40% by weight, more preferably 13 to 30% by weight, still more preferably 14 to 25% by weight, and even more preferably. Is more than 15% by weight and less than 23% by weight, particularly preferably 16 to 22% by weight, most preferably 17 to 21% by weight. If the effective concentration of colloidal silica is outside the range of 10 to 40% by weight, the thermally expandable microspheres may not be obtained efficiently.
  • the average particle size of the colloidal silica is usually 1.0 to 20 nm, preferably 2.0 to 15 nm, more preferably 3.0 to 13 nm, and still more preferably 3.4 to 10 nm. More preferably, it is 3.6 to 6.0 nm, particularly preferably 3.8 to 5.5 nm, and most preferably 4.0 to 5.0 nm.
  • the average particle diameter of colloidal silica is less than 1.0 nm, the oil droplets of the oily mixture dispersed in the aqueous dispersion medium in the polymerization step may become unstable, and aggregates may be generated.
  • the average particle diameter of colloidal silica is more than 20 nm, it is necessary to add a large amount in order to stabilize the oil droplets of the oily mixture dispersed in the aqueous dispersion medium in the polymerization step.
  • the heat-expandable microspheres having a large ash content are used for paint applications, dispersion failure may occur.
  • the dispersion stabilizing aid is not particularly limited, and examples thereof include a polymer type dispersion stabilizing aid, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. An activator etc. can be mentioned. These dispersion stabilizing aids may be used alone or in combination of two or more.
  • dispersion stabilizing aid examples include, for example, a condensation product of diethanolamine and aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, a water-soluble nitrogen-containing compound, polyethylene oxide, tetramethylammonium hydroxide, gelatin, methylcellulose, polyvinyl Examples include alcohol, dioctyl sulfosuccinate, sorbitan ester, various emulsifiers, and the like.
  • water-soluble nitrogen-containing compounds examples include polyvinyl pyrrolidone, polyethyleneimine, polyoxyethylene alkylamine, polydialkylaminoalkyl (meth) acrylates such as polydimethylaminoethyl (meth) acrylate, and polydimethylaminopropyl methacrylamide.
  • examples include dialkylaminoalkyl (meth) acrylamide, polyacrylamide, polycationic acrylamide, polyamine sulfone, polyallylamine and the like.
  • polyvinylpyrrolidone is preferable.
  • the blending amount of the dispersion stabilizing aid used in the polymerization step is preferably 0.10 to 5 parts by weight, more preferably 0.15 to 4 parts by weight with respect to 100 parts by weight of the total of the polymerizable component and the foaming agent. More preferably, it is 0.20 to 3 parts by weight.
  • the blending amount of the dispersion stabilizing auxiliary is out of the range of 0.10 to 5 parts by weight with respect to 100 parts by weight of the total of the polymerizable component and the foaming agent, the oil of the oily mixture dispersed in the aqueous dispersion medium in the polymerization step Drops may become unstable and aggregates may be generated.
  • the oily mixture is emulsified and dispersed in an aqueous dispersion medium so that spherical oil droplets having a predetermined particle diameter are prepared.
  • the method for emulsifying and dispersing the oily mixture include, for example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like, and a static dispersion device such as a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.). And general dispersion methods such as a method using a film, a membrane emulsification method, and an ultrasonic dispersion method.
  • suspension polymerization is started by heating the dispersion in which the oily mixture is dispersed as spherical oil droplets in the aqueous dispersion medium.
  • the polymerization temperature is freely set depending on the kind of the polymerization initiator, but is preferably controlled in the range of 30 to 100 ° C., more preferably 40 to 90 ° C.
  • the time for maintaining the reaction temperature is preferably about 0.1 to 20 hours.
  • the initial polymerization pressure is not particularly limited, but is 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa in terms of gauge pressure.
  • the expansion step is not particularly limited as long as it is a step of heating and expanding the thermally expandable microspheres, and may be either a dry heating expansion method or a wet heating expansion method.
  • the dry heating expansion method include the method described in JP-A-2006-213930, particularly the internal injection method.
  • As another dry heating expansion method there is a method described in JP-A-2006-96963.
  • Examples of the wet heating expansion method include the method described in JP-A-62-201231.
  • a step of mixing thermally expandable microspheres and a fine particle filler for example, a step of mixing thermally expandable microspheres and a fine particle filler (mixing step), and a mixture obtained in the mixing step is used to exceed the softening point of the thermoplastic resin.
  • a production method including a step of heating to a temperature to expand the thermally expandable microspheres and attaching the fine particle filler to the outer surface of the outer shell (attachment step).
  • the mixing step is a step of mixing the thermally expandable microspheres and the fine particle filler.
  • the weight ratio of the fine particle filler and the thermally expandable microsphere in the mixing step is not particularly limited, but is preferably 90/10 to 60/40, more preferably 85. / 15 to 65/35, particularly preferably 80/20 to 70/30.
  • the fine particle filler / heat-expandable microsphere (weight ratio) is larger than 90/10, the true specific gravity of the organic hollow particles A is increased, and the effect of lowering the specific gravity may be reduced.
  • the fine particle filler / heat-expandable microsphere (weight ratio) is smaller than 60/40, the true specific gravity of the organic hollow particles A is lowered, and handling such as dusting may be deteriorated.
  • the apparatus used for the mixing step is not particularly limited, and can be performed using an apparatus having an extremely simple mechanism such as a container and a stirring blade. Moreover, you may use the powder mixer which can perform a general rocking
  • the mixture containing the thermally expandable microspheres and the fine particle filler obtained in the mixing step is heated to a temperature above the softening point of the thermoplastic resin constituting the outer shell of the thermally expandable microsphere. It is a process.
  • the thermally expandable microspheres are expanded and the fine particle filler is attached to the outer surface of the outer shell.
  • Heating may be performed using a general contact heat transfer type or direct heating type mixed drying apparatus.
  • the function of the mixing type drying apparatus is not particularly limited, but it is preferable to be able to adjust the temperature and disperse and mix the raw materials, and optionally equipped with a decompression device and a cooling device for speeding up drying.
  • a Ladige mixer made by Matsubo Co., Ltd.
  • solid air Hosokawa Micron Co., Ltd.
  • the heating temperature condition depends on the type of thermally expandable microspheres, but the optimum expansion temperature is good, preferably 60 to 250 ° C., more preferably 70 to 230 ° C., still more preferably 80 to 220 ° C. is there.
  • the positive electrode of the electrochemical element is formed by laminating a positive electrode active material layer on a current collector.
  • a positive electrode active material for the positive electrode of the electrochemical device, a positive electrode active material, a positive electrode binder, a solvent used for preparing the positive electrode, a water-soluble polymer used as necessary, and a positive electrode slurry composition containing other components such as a conductive additive. It can be obtained by applying to the surface of the electric body and drying. That is, the positive electrode active material layer is formed on the current collector by applying the slurry composition for the positive electrode to the surface of the current collector and drying it.
  • an active material that can be doped and dedoped with lithium ions is used, which is roughly classified into an inorganic compound and an organic compound.
  • 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.
  • 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.
  • 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.
  • a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
  • An iron-based oxide having poor electrical conductivity may be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
  • the positive electrode active material may be a mixture of the above inorganic compound and organic compound.
  • the positive electrode binder examples include resins such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, and polyacrylonitrile derivatives.
  • resins such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, and polyacrylonitrile derivatives.
  • a soft polymer such as an acrylic soft polymer, a diene soft polymer, an olefin soft polymer, a vinyl soft polymer, and the like.
  • the binder for positive electrodes may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the water-soluble polymer and conductive auxiliary used as necessary in the positive electrode slurry composition the water-soluble polymer and conductive auxiliary that can be used in the negative electrode slurry composition can be used. .
  • a solvent used for producing the positive electrode either water or an organic solvent may be used.
  • the organic solvent include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, and ⁇ -butyrolactone Esters such as ⁇ -caprolactone; Acylonitriles such as acetonitrile and propionitrile; Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether; N Amides such as -methylpyrrolidone and N, N-dimethylformamide; among them, N-methylpyrrolidone (NMP) is preferred.
  • NMP N-methyl
  • a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Of these, water is preferably used as the solvent.
  • the amount of the solvent may be adjusted so that the viscosity of the positive electrode slurry composition is suitable for application. Specifically, the solid content concentration of the positive electrode slurry is preferably adjusted to 30 to 90% by weight, more preferably 40 to 80% by weight.
  • the same current collector as the current collector used for the negative electrode of the non-aqueous electrolyte secondary battery can be used.
  • the method for applying the positive electrode slurry composition to the surface of 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.
  • Examples of the drying method include drying with warm air, hot air, and low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • the drying time is preferably 5 to 30 minutes, and the drying temperature is preferably 40 to 180 ° C.
  • the positive electrode active material layer after applying and drying the positive electrode slurry composition on the surface of the current collector, it is preferable to subject the positive electrode active material layer to a pressure treatment using, for example, a die press or a roll press, if necessary. .
  • the porosity of the positive electrode active material layer can be lowered.
  • the porosity is preferably 5% or more, more preferably 7% or more, preferably 30% or less, more preferably 20% or less.
  • the porosity is too small, it is difficult to obtain a high volume capacity, and the positive electrode active material layer is easily peeled off from the current collector.
  • the porosity when the porosity is too large, the charging efficiency and the discharging efficiency are lowered.
  • the positive electrode active material layer includes a curable polymer, it is preferable to cure the polymer after the positive electrode active material layer is formed.
  • An inorganic particle layer may be disposed between the positive electrode active material layer and the separator.
  • the inorganic particle layer is preferably disposed on the surface of the positive electrode active material layer.
  • the inorganic particle layer refers to a layer composed of inorganic particles, a binder, a dispersant, and the like.
  • the material constituting the inorganic particles include rutile type titanium oxide (rutile type titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia) and the like.
  • the inorganic particles are preferably aluminum oxide, rutile titanium oxide, and the like.
  • the content of inorganic particles in the inorganic particle layer is preferably 70 to 99.9% by weight, more preferably 90 to 99% by weight, and more preferably 95 to 99% by weight.
  • the average primary particle diameter of the inorganic particles is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less. A preferred lower limit of the average primary particle size is 0.1 ⁇ m.
  • the kind of binder contained in an inorganic particle layer is not specifically limited.
  • the binder contained in the inorganic particle layer is preferably a binder that satisfies at least one of the following properties (1) to (4).
  • (1) The dispersibility of the inorganic particles in the inorganic particle layer can be secured (pre-aggregation prevention).
  • the adhesion between the positive electrode active material layer and the inorganic particle layer can be secured.
  • the space between the inorganic particles due to swelling when the inorganic particle layer absorbs the nonaqueous electrolyte can be filled. (4) Suppressing elution of the non-aqueous electrolyte from the inorganic particle layer.
  • an aqueous binder is preferable.
  • the material constituting the binder include, for example, polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), modified products and derivatives thereof, copolymers containing acrylonitrile units, poly Examples include acrylic acid derivatives.
  • the binder may be composed of only one type, or may be composed of two or more types. For example, when it is desired to exhibit the characteristics (1) and (3) by adding a small amount of a binder to the inorganic particle layer, the binder is preferably a copolymer containing an acrylonitrile unit.
  • the amount of the binder contained in the inorganic particle layer is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the inorganic particles.
  • a preferable lower limit of the amount of the binder contained in the inorganic particle layer is 0.1 part by weight with respect to 100 parts by weight of the inorganic particles.
  • the thickness of the inorganic particle layer is not particularly limited, but is preferably 4 ⁇ m or less, more preferably 0.5 to 4 ⁇ m, and still more preferably 0.5 to 2 ⁇ m. When the thickness of the inorganic particle layer is more than 4 ⁇ m, the load characteristics of the nonaqueous electrolyte secondary battery may be lowered and the energy density may be lowered. When the thickness of the inorganic particle layer is less than 0.5 ⁇ m, the effect obtained by the inorganic particle layer may be insufficient.
  • Examples of the method of arranging the inorganic particle layer on the surface of the positive electrode active material layer include a method of applying a slurry made of inorganic particles, a binder, a solvent, and the like on the surface of the positive electrode active material and drying it.
  • Specific examples of the slurry application method include a die coating method, a gravure coating method, a dip coating method, a curtain coating method, and a spray coating method. Among these, gravure coating method, die coating method and the like are preferable.
  • the solid content concentration in the slurry is preferably in the range of 3 to 30% by weight.
  • the solid content concentration in the slurry is preferably in the range of 5 to 70% by weight.
  • the solvent contained in the slurry water is preferable.
  • the binder in the slurry is difficult to move into the positive electrode active material layer in the coating process. Therefore, expansion of the positive electrode active material layer by the binder can be suppressed. Thereby, the fall of the energy density of a nonaqueous electrolyte secondary battery can be suppressed. Water is also preferable in terms of reducing the environmental load.
  • the separator is not particularly limited as long as it can suppress a short circuit due to contact between the negative electrode and the positive electrode and can impregnate a nonaqueous electrolyte to obtain lithium ion conductivity.
  • a polyolefin resin such as polyethylene or polypropylene, a microporous film or nonwoven fabric containing an aromatic polyamide resin, a porous resin coat containing an inorganic ceramic powder, or the like can be used.
  • microporous membranes made of polyolefin resins (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as mixtures or copolymers thereof; polyethylene terephthalate, polycycloolefin, polyether sulfone, polyamide, Examples thereof include a microporous film made of a resin such as polyimide, polyimide amide, polyaramid, polycycloolefin, nylon, and polytetrafluoroethylene; a polyolefin fiber woven or non-woven fabric thereof; an aggregate of insulating substance particles, and the like.
  • the microporous membrane made of polyolefin resin Is preferred.
  • Nonaqueous electrolyte for example, a known non-aqueous electrolyte can be used.
  • the non-aqueous electrolyte includes a solute, a non-aqueous solvent, and the like.
  • LiXF y As the solute of the nonaqueous electrolyte, for example, LiXF y (wherein X is P, As, Sb, B, Bi, Al, Ga or In, and y is 6 when X is P, As or Sb) , when X is B, Bi, Al, Ga or an in, y is 4), lithium perfluoroalkyl sulfonic acid imide LiN (C m F 2m + 1 SO 2) (CnF 2n + 1 SO2) (wherein, m and n each independently is an integer of 1-4), lithium perfluoroalkyl sulfonic acid methide LiC (C p F2 q + 1 SO 2) (C r F 2r + 1 SO 2) ( wherein, p, q and r each independently LiCF 3 SO 3 , LiClO 4 , Li 2 B 10 Cl 10 , and Li 2 B 12 Cl 12 .
  • LiPF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 and the like are preferable because they are easily soluble in non-aqueous solvents and exhibit a high degree of dissociation.
  • the non-aqueous electrolyte may contain one type of solute or may contain a plurality of types of solutes. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the concentration of the supporting electrolyte in the electrolytic solution is preferably 0.5 to 2.5 M depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity may decrease.
  • the nonaqueous solvent for the nonaqueous electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte.
  • non-aqueous solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC).
  • Esters such as ⁇ -butyrolactone and methyl formate
  • ethers such as 1,2-dimethoxyethane and tetrahydrofuran
  • sulfur-containing compounds such as sulfolane and dimethyl sulfoxide.
  • a mixed solvent of a cyclic carbonate and a chain carbonate is preferably used as a non-aqueous solvent having a low viscosity, a low melting point, and a high lithium ion conductivity.
  • the mixing ratio of cyclic carbonate to chain carbonate may be in the range of 1: 9 to 5: 5 by volume ratio.
  • the non-aqueous solvent may be a mixed solvent of cyclic carbonate and ethers such as 1,2-dimetaxethane and 1,2-diethoxyethane.
  • an ionic liquid can be used as a nonaqueous solvent for the nonaqueous electrolyte.
  • the cation species and anion species of the ionic liquid are not particularly limited. From the viewpoint of low viscosity, electrochemical stability, and hydrophobicity, for example, a pyridinium cation, an imidazolium cation, or a quaternary ammonium cation is preferably used as the cation.
  • an ionic liquid containing a fluorine-containing imide anion is preferably used as the anion.
  • the non-aqueous electrolyte may be a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide or polyacrylonitrile with an electrolytic solution, or an inorganic solid electrolyte such as LiI or Li 3 N.
  • a polymer electrolyte such as polyethylene oxide or polyacrylonitrile
  • an inorganic solid electrolyte such as LiI or Li 3 N.
  • the non-aqueous solvent may be used in combination or in whole or in whole or in part of which hydrogen is replaced with fluorine.
  • additives to the electrolyte.
  • examples of the additive include carbonates such as vinylene carbonate (VC); sulfur-containing compounds such as ethylene sulfite (ES); and fluorine-containing compounds such as fluoroethylene carbonate (FEC).
  • An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the amount of the nonaqueous electrolyte in the nonaqueous electrolyte secondary battery is preferably 1.0 g / Ah or more and 3.0 g / Ah or less with respect to the design capacity.
  • the amount of the nonaqueous electrolyte with respect to the design capacity of the nonaqueous electrolyte secondary battery is within this range, high charge / discharge cycle characteristics can be obtained.
  • the amount of the nonaqueous electrolyte relative to the design capacity of the nonaqueous electrolyte secondary battery is too small, it is difficult to sufficiently supply the nonaqueous electrolyte into the negative electrode and the positive electrode, and the charge / discharge cycle characteristics may be deteriorated.
  • the nonaqueous electrolyte when the amount of the nonaqueous electrolyte with respect to the design capacity of the nonaqueous electrolyte secondary battery 1 is too large, the nonaqueous electrolyte is excessively held in the negative electrode and the positive electrode, and the ratio of the nonaqueous electrolyte in the negative electrode and the positive electrode is controlled. Can be difficult. Furthermore, when the amount of the nonaqueous electrolyte with respect to the design capacity of the nonaqueous electrolyte secondary battery 1 is too large, the amount of gas generated due to decomposition of the nonaqueous electrolyte increases, and the storage characteristics of the nonaqueous electrolyte secondary battery 1 and the high temperature are increased. Cycle characteristics may be degraded.
  • Non-aqueous electrolyte secondary battery As a specific method for producing a non-aqueous electrolyte secondary battery, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is wound in accordance with the shape of the battery, folded into a battery container, and put into a battery container. The method of inject
  • the shape of the nonaqueous electrolyte secondary battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
  • the material of the battery container is not particularly limited as long as it inhibits the penetration of moisture into the battery, and is not particularly limited, such as a metal or a laminate such as aluminum.
  • the nonaqueous electrolyte secondary battery according to the present embodiment can provide a nonaqueous electrolyte secondary battery excellent in cycle characteristics.
  • a laser diffraction particle size distribution analyzer (HEROS & RODOS manufactured by SYMPATEC) was used.
  • the dispersion pressure of the dry dispersion unit was 5.0 bar and the degree of vacuum was 5.0 mbar, which was measured by a dry measurement method.
  • the volume-based cumulative particle diameter means the diameter of a particle with respect to a predetermined ratio of a distribution obtained by accumulating all particles from the smaller side in the volume order.
  • the laser diffraction particle size distribution measuring device measures the distribution of the volume-based cumulative particle size, and the measured value of the volume-based cumulative 50% particle size (D50) can be confirmed with the software of the measuring device.
  • the volume-based cumulative 50% particle size (D50) is taken as the average particle size.
  • the cumulative particle diameter based on the number means the diameter of particles having a predetermined number ratio in a distribution in which all particles are arranged in order of particles and accumulated from the smaller side.
  • the number-based cumulative particle size can be converted from the volume-based cumulative particle size by software of the measuring device.
  • the organic hollow particles A if there is a fine particle filler that is adsorbed and not immobilized on the organic hollow particles, the value of the volume-based cumulative particle diameter becomes small, which is greatly different from the value of the actual organic hollow particles. End up.
  • the particle diameter of the organic hollow particles A was measured after performing a pretreatment for removing the adsorbed fine particle filler.
  • a pretreatment 1 part by weight of the organic hollow particles A is dispersed in 100 parts by weight of isopropanol and allowed to stand for 2 hours. The floated particles are collected and dried.
  • the ash content of thermally expandable microspheres and organic hollow particles The dried thermally expandable microspheres or organic hollow particles W p (g) are put in a crucible, heated with an electric heater, ignited by igniting at 700 ° C. for 30 minutes, and the obtained ash product W q (g ) Is weighed.
  • the ash content C A (% by weight) of the thermally expandable microspheres or organic hollow particles is calculated by the following calculation formula (D) from W p (g) and W q (g).
  • C A (W q / W p ) ⁇ 100 (D)
  • the displacement start temperature in the positive direction is defined as the expansion start temperature (T s ), and the temperature when the maximum displacement is indicated is defined as the maximum expansion temperature (T max ).
  • the true specific gravity of the organic hollow particles is measured by the following measuring method.
  • the true specific gravity is measured by an immersion method (Archimedes method) using isopropyl alcohol in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50%.
  • the volumetric flask having a capacity of 100 cc was emptied and dried, and the weight of the volumetric flask (WB 1 ) was weighed.
  • the weight (WB 2 ) of the measuring flask filled with 100 cc of isopropyl alcohol is weighed.
  • volumetric flask with a capacity of 100 cc was emptied and dried, and the weight of the volumetric flask (WS 1 ) was weighed.
  • the weighed volumetric flask is filled with about 50 cc of particles, and the weight (WS 2 ) of the volumetric flask filled with organic hollow particles is weighed.
  • the weight (WS 3 ) after accurately filling the meniscus with isopropyl alcohol to prevent bubbles from entering the volumetric flask filled with particles is weighed.
  • the WB 1, WB 2, WS 1 , WS 2 and WS 3 obtained by introducing the following expression to calculate the true specific gravity (d c) of the organic hollow particles.
  • d c ⁇ (WS 2 ⁇ WS 1 ) ⁇ (WB 2 ⁇ WB 1 ) / 100 ⁇ / ⁇ (WB 2 ⁇ WB 1 ) ⁇ (WS 3 ⁇ WS 2 ) ⁇
  • a flat box with a bottom of 12 cm in length, 13 cm in width, and 9 cm in height is made of aluminum foil, and 1.0 g of thermally expandable microspheres are uniformly placed therein, and obtained by measuring the expansion start temperature. The temperature is increased by 5 ° C. from the starting temperature of expansion, heated at each temperature for 1 minute, and then the true specific gravity of the expanded thermally expandable microspheres (hollow particles) is measured according to the above measurement method. Among them, the one showing the lowest true specific gravity is the true specific gravity at the time of maximum expansion.
  • the true specific gravity d p of the outer shell resin (thermoplastic resin constituting the outer shell) is measured by dispersing 10 g of thermally expandable microspheres in 200 ml of N, N-dimethylformamide and then treating with an ultrasonic disperser for 30 minutes. After immersing for 24 hours at room temperature, vacuum drying was performed at 120 ° C. for 5 hours to isolate the outer shell resin. The true specific gravity of the outer shell resin was measured for the obtained outer shell resin in the same manner as the method for measuring the true specific gravity.
  • monomer components acrylonitrile 180 g, methacrylonitrile 105 g, methyl methacrylate 15 g
  • cross-linking agent A trimethylolpropane trimethacrylate 1.5 g
  • blowing agent isobutane 30 g, isopentane 30 g
  • Polymerization initiator A (2,2′-azobis (2.4-dimethylvaleronitrile) 2.0 g
  • organic hollow particles can be produced by the wet heating expansion method described in JP-A-62-201231 as follows.
  • Example A1 Production of organic hollow particles by wet heating expansion method
  • this slurry is fed from a slurry introduction tube to a foaming tube (diameter 16 mm, volume 120 ml, made of SUS304TP) at a flow rate of 5 L / min, and further steam ( (Temperature: 147 ° C., pressure: 0.3 MPa) was supplied from the steam introduction pipe, mixed with the slurry, and wet-heated and expanded.
  • the slurry temperature (foaming temperature) after mixing was adjusted to 115 ° C.
  • the obtained slurry containing the hollow organic particles was allowed to flow out from the protruding portion of the foamed tube, mixed with cooling water (water temperature 15 ° C.), and cooled to 50-60 ° C.
  • the cooled slurry liquid was dehydrated with a centrifugal dehydrator to obtain an organic hollow particle composition 1 (water contained 90% by weight) containing 10% by weight of the wet organic hollow particles 1.
  • the obtained organic hollow particles were isolated and the physical properties were evaluated. The results are shown in Table 3.
  • Example A2 Wet organic hollow particles in the same manner except that the thermally expandable microspheres obtained in Production Example 1 were changed to the thermally expandable microspheres obtained in Production Example 2 in the wet heating expansion method described in Example A1.
  • the obtained organic hollow particles were isolated and the physical properties were evaluated. The results are shown in Table 3.
  • Example A3 20 parts by weight of the thermally expandable microspheres obtained in Production Example 3 and 80 parts by weight of Ketjen Black (manufactured by Lion Corporation, carbon ECP600JD: primary particle diameter 34 nm) were added to and mixed with the separable flask. Next, the temperature was raised to 140 ° C. over 5 minutes with stirring to obtain fine particle-attached organic hollow particles 3. The obtained organic hollow particles were isolated and the physical properties were evaluated. The results are shown in Table 3.
  • Example A4 Wet organic hollow particles in the same manner except that the thermally expandable microspheres obtained in Production Example 1 were changed to the thermally expandable microspheres obtained in Production Example 4 in the wet heating expansion method described in Example A1. An organic hollow particle composition 4 containing 10% by weight of 4 (water containing 90% by weight) was obtained. The obtained organic hollow particles were isolated and the physical properties were evaluated. The results are shown in Table 3.
  • a slurry composition for a lithium secondary battery negative electrode is prepared using the organic hollow particles obtained above, and the life characteristics of the nonaqueous electrolyte secondary battery are evaluated.
  • a slurry composition for negative electrode comprising 15 parts by weight) and 50 parts by weight of ion exchange water was prepared.
  • LiCoO 2 having a volume average particle diameter of 12 ⁇ m as a positive electrode active material
  • 2 parts by weight of acetylene black manufactured by Denki Kagaku Kogyo, HS-100
  • a polyvinylidene fluoride binder manufactured by Kureha, # 7208
  • An N-methylpyrrolidone solution having an effective concentration of 8% by weight was mixed with 25 parts by weight of N-methylpyrrolidone to obtain a positive electrode slurry composition having a total solid content of 70% by weight.
  • This positive electrode slurry composition was applied onto an aluminum foil having a thickness of 20 ⁇ m so that the film thickness after drying was 150 ⁇ m, dried at 60 ° C. for 2 minutes, and then heat-treated at 120 ° C. for 2 minutes. Created a sheet.
  • an aluminum packaging exterior was prepared as the battery exterior.
  • the positive electrode obtained above was cut into a 4 cm ⁇ 4 cm square and placed so that the slurry uncoated side was in contact with the aluminum packaging exterior.
  • a separator manufactured by Celgard, Cellguard 2500
  • the negative electrode sheet obtained above was cut into a square of 4.2 cm ⁇ 4.2 cm, and placed on the separator so that the negative electrode active material side was in contact with the separator.
  • laminate-type nonaqueous electrolyte secondary battery laminate-type nonaqueous electrolyte secondary battery
  • Example 1 Subsequently, 6 parts by weight of the organic hollow particles 1 obtained above were added to the negative electrode slurry composition described in Comparative Example 1 and mixed uniformly to prepare an organic hollow particle-containing negative electrode slurry composition.
  • a nonaqueous electrolyte secondary battery was prepared in the same manner except that the organic hollow particle-containing negative electrode slurry composition prepared above was used instead of the negative electrode slurry composition in Comparative Example 1.
  • the battery was repeatedly charged and discharged. A decrease in capacity retention rate (%) was suppressed, and improvement in cycle characteristics was confirmed.
  • Example 2 In Example 1, instead of the organic hollow particles 1, the organic hollow particles-containing negative electrode slurry composition and the nonaqueous electrolyte secondary battery were prepared in the same manner except that the organic hollow particles and the addition amount shown in Table 4 were changed. did. Table 4 shows the results of evaluating the cycle characteristics of the obtained nonaqueous electrolyte secondary battery.
  • Example 3 In Example 1, in place of the organic hollow particles 1, hollow silica (manufactured by Nittetsu Mining Co., Ltd., Silinax (registered trademark), primary particle diameter 80 to 130 nm) was used in the same manner except that 0.5 parts by weight was used. Thus, a hollow particle-containing negative electrode slurry and a non-aqueous electrolyte secondary battery were prepared. Table 4 shows the results of evaluating the cycle characteristics of the obtained nonaqueous electrolyte secondary battery.
  • the non-aqueous electrolyte secondary batteries of Examples 1 to 4 using the organic hollow particles of the present invention and the slurry composition for negative electrode are Comparative Examples 1 to 3 not including the organic hollow particles of the present invention. Compared to the above, it has excellent cycle characteristics.
  • the slurry composition for a nonaqueous electrolyte secondary battery negative electrode of the present invention can be used for a nonaqueous electrolyte secondary battery negative electrode.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'objectif de la présente invention est de proposer : une composition de suspension destinée à une électrode négative de batterie secondaire à électrolyte non aqueux ayant des caractéristiques de cycle améliorées ; une électrode négative de batterie secondaire à électrolyte non aqueux qui est obtenue en appliquant cette composition de suspension à un collecteur ; une batterie secondaire à électrolyte non aqueux qui est munie de cette électrode négative ; et des particules organiques creuses qui sont utilisées dans une composition de suspension destinée à des électrodes négatives de batterie secondaire à électrolyte non aqueux. Selon la présente invention, une composition de suspension destinée à des électrodes négatives de batterie secondaire à électrolyte non aqueux contient : des particules organiques creuses, dont chacune possède une enveloppe externe formée à partir d'une résine thermoplastique ; un liant destiné à des électrodes négatives ; et un matériau actif d'électrode négative. Le rapport du diamètre de pore interne (d1) au diamètre de pore externe (d2) des particules organiques creuses, c'est-à-dire (d1)/(d2) est supérieur à 0.7 mais égal à 0.999 ou moins.
PCT/JP2016/067888 2015-06-26 2016-06-16 Composition de suspension destinée à des électrodes négatives de batterie secondaire à électrolyte non aqueux et son utilisation Ceased WO2016208480A1 (fr)

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CN113725407A (zh) * 2020-05-25 2021-11-30 住友橡胶工业株式会社 硫类活性物质、电极、非水电解质二次电池及制造方法
JP2022510820A (ja) * 2018-12-06 2022-01-28 ネダーランゼ・オルガニサティ・フォーア・トゥーゲパスト－ナトゥールヴェテンシャッペリーク・オンデルゾエク・ティーエヌオー 伸縮性があり圧縮性のある機能層を含むバッテリーセル及び製造プロセス
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CN119725677A (zh) * 2023-09-28 2025-03-28 宁德时代新能源科技股份有限公司 电池单体、二次电池和用电装置
JP2025516905A (ja) * 2022-11-15 2025-05-30 香港時代新能源科技有限公司 負極シート、その製造方法、二次電池及び電力消費装置
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EP3783700B1 (fr) * 2018-03-30 2024-05-01 Mitsui Chemicals, Inc. Électrode positive équipée d'une sous-couche contenant des microcapsules, et batterie secondaire au lithium-ion
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CN112279675B (zh) * 2020-09-30 2022-05-27 青岛理工大学 一种基于高稳定性发泡剂的泡沫混凝土及其制备方法
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CN113725407A (zh) * 2020-05-25 2021-11-30 住友橡胶工业株式会社 硫类活性物质、电极、非水电解质二次电池及制造方法
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