WO2014196436A1 - Composition de bouillie pour membrane poreuse pour batterie secondaire au lithium-ion, séparateur pour batterie secondaire au lithium-ion, électrode pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion - Google Patents

Composition de bouillie pour membrane poreuse pour batterie secondaire au lithium-ion, séparateur pour batterie secondaire au lithium-ion, électrode pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion Download PDF

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Publication number
WO2014196436A1
WO2014196436A1 PCT/JP2014/064175 JP2014064175W WO2014196436A1 WO 2014196436 A1 WO2014196436 A1 WO 2014196436A1 JP 2014064175 W JP2014064175 W JP 2014064175W WO 2014196436 A1 WO2014196436 A1 WO 2014196436A1
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lithium ion
ion secondary
secondary battery
slurry composition
porous membrane
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PCT/JP2014/064175
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English (en)
Japanese (ja)
Inventor
智一 佐々木
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日本ゼオン株式会社
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Priority to JP2015521409A priority Critical patent/JP6327251B2/ja
Publication of WO2014196436A1 publication Critical patent/WO2014196436A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • 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 porous membrane slurry composition for lithium ion secondary batteries, and a separator for lithium ion secondary batteries, an electrode for lithium ion secondary batteries, and a lithium ion secondary battery using the same.
  • Lithium ion secondary batteries are frequently used as secondary batteries used as power sources for these portable terminals.
  • a separator is generally provided in order to prevent a short circuit between the positive electrode and the negative electrode.
  • the separator may be provided with a porous film as necessary.
  • the porous film By providing the separator with a porous film, it is possible to prevent the separator from being damaged by a foreign substance, so that the safety of the secondary battery can be improved. It has also been proposed to provide the porous film on an electrode plate. When an electrode is provided with a porous film, it can prevent that the electrode active material which fell from the electrode becomes a foreign material, and damages a separator.
  • Patent Documents 1 to 4 Furthermore, techniques such as Patent Documents 1 to 4 are also known.
  • gas When using lithium ion secondary batteries, gas may be generated. There are various causes for this gas, and an example thereof is halide ions in the electrolyte.
  • the electrolytic solution may be decomposed, or SEI (Solid Electrolyte Interface) on the electrode surface may be decomposed to generate gas.
  • the present invention was devised in view of the above problems, and a porous membrane slurry composition for a lithium ion secondary battery capable of producing a lithium ion secondary battery capable of suppressing gas generation, a separator for a lithium ion secondary battery, and
  • An object of the present invention is to provide an electrode for a lithium ion secondary battery; and a lithium ion secondary battery capable of suppressing gas generation.
  • the slurry composition for forming a porous film in a lithium ion secondary battery includes a water-soluble polymer containing a combination of acid group-containing monomer units and amide monomer units in a predetermined ratio, thereby providing a gas.
  • the inventors have found that the occurrence of the occurrence can be suppressed and completed the present invention. That is, the present invention is as follows.
  • a porous membrane slurry composition for a lithium ion secondary battery comprising non-conductive particles, a water-soluble polymer, a particulate polymer, and water
  • a porous membrane slurry composition for a lithium ion secondary battery wherein the water-soluble polymer contains 20 wt% to 80 wt% of acid group-containing monomer units and 0.1 wt% to 10 wt% of amide monomer units.
  • the nonconductive particles are organic particles.
  • a lithium ion secondary comprising: a porous film obtained by applying the porous film slurry composition for a lithium ion secondary battery according to any one of [1] to [7] on the separator substrate and drying the composition. Battery separator.
  • a lithium ion secondary battery comprising: a porous film obtained by applying and drying the porous film slurry composition for a lithium ion secondary battery according to any one of [1] to [7] on the electrode plate Electrode.
  • a lithium ion secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, A lithium ion secondary battery, wherein the separator is the lithium ion secondary battery separator according to [8].
  • a lithium ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte solution, A lithium ion secondary battery, wherein at least one of the positive electrode and the negative electrode is an electrode for a lithium ion secondary battery according to [9].
  • a lithium ion secondary battery capable of suppressing gas generation can be produced.
  • the lithium ion secondary battery of the present invention can suppress the generation of gas.
  • (meth) acrylic acid includes acrylic acid and methacrylic acid.
  • the (meth) acrylate includes acrylate and methacrylate.
  • (meth) acrylonitrile includes acrylonitrile and methacrylonitrile.
  • a certain substance is water-soluble means that when 0.5 g of the substance is dissolved in 100 g of water at 25 ° C., the insoluble content is 0 wt% or more and less than 1.0 wt%. Further, that a certain substance is water-insoluble means that an insoluble content is 90% by weight or more and 100% by weight or less when 0.5 g of the substance is dissolved in 100 g of water at 25 ° C.
  • the proportion of the structural unit formed by polymerizing a certain monomer in the polymer is usually that unless otherwise specified. This coincides with the ratio (preparation ratio) of the certain monomer in the total monomers used for polymerization of the polymer.
  • electrode plate includes not only a rigid plate member but also a flexible sheet and film.
  • porous membrane slurry composition for lithium ion secondary battery comprises non-conductive particles, a water-soluble polymer, a particulate polymer and water. Including.
  • Non-conductive particles are components filled in the porous film, and the gaps between the non-conductive particles can form pores of the porous film. Since the non-conductive particles have non-conductivity, the porous film can be made insulative, and therefore a short circuit in the secondary battery can be prevented. In general, non-conductive particles have high rigidity, which can increase the mechanical strength of the porous membrane. Therefore, even when a stress that tends to shrink is generated in the separator base material due to heat, the porous film can resist the stress, and therefore it is possible to prevent the occurrence of a short circuit due to the shrinkage of the separator base material. As the non-conductive particles, inorganic particles or organic particles may be used.
  • the inorganic particles are usually excellent in dispersion stability in water, hardly settled in the porous membrane slurry composition, and can maintain a uniform slurry state for a long time.
  • the heat resistance of the porous film can usually be increased.
  • an electrochemically stable material is preferable.
  • inorganic materials for non-conductive particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al (OH) 3 ), silicon oxide, Oxide particles such as magnesium oxide (magnesia), magnesium hydroxide, calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; silicon, diamond And the like; Covalent crystal particles such as barium sulfate, calcium fluoride, barium fluoride, and the like; Clay fine particles such as talc and montmorillonite;
  • oxide particles are preferable from the viewpoints of stability in an electrolytic solution and potential stability, and titanium oxide and aluminum oxide are particularly preferable from the viewpoint of low water absorption and excellent heat resistance (for example, resistance to high temperature of 180 ° C. or higher).
  • Aluminum oxide hydrate, magnesium oxide and magnesium hydroxide are more preferable, aluminum oxide, aluminum oxide hydrate, magnesium oxide and magnesium hydroxide are more preferable, and aluminum oxide is particularly preferable.
  • Polymer particles are usually used as the organic particles.
  • the organic particles can control the affinity for water by adjusting the type and amount of the functional group on the surface of the organic particles, and thus can control the amount of water contained in the porous film.
  • Organic particles are excellent in that they usually have less metal ion elution.
  • Examples of the polymer forming the nonconductive particles include various polymer compounds such as polystyrene, polyethylene, melamine resin, and phenol resin.
  • the polymer compound forming the particles may be used, for example, as a mixture, a modified product, a derivative, a random copolymer, an alternating copolymer, a graft copolymer, a block copolymer, a crosslinked product, or the like.
  • the organic particles may be formed of a mixture of two or more polymer compounds.
  • the polymer that forms the non-conductive particles is preferably a polymer containing an amide monomer unit.
  • An amide monomer unit is a structural unit having a structure formed by polymerizing an amide monomer.
  • the amide monomer is a monomer having an amide group and includes not only an amide compound but also an imide compound.
  • amide monomer examples include a carboxylic acid amide monomer, a sulfonic acid amide monomer, and a phosphoric acid amide monomer.
  • the carboxylic acid amide monomer is a monomer having an amide group bonded to a carboxylic acid group.
  • the carboxylic acid amide monomer include (meth) acrylamide, ⁇ -chloroacrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, N-hydroxymethyl (meta) ) Acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, N-3-hydroxypropyl (meth) acrylamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, diacetone Unsaturated carboxylic acid amide compounds such as acrylamide; N-dimethylaminomethyl (meth) acrylamide, N-2-aminoethyl (meth) acrylamide, N-2-methylaminoethyl (meth) acrylamide, N-2-ethylamino
  • the sulfonic acid amide monomer is a monomer having an amide group bonded to a sulfonic acid group.
  • examples of the sulfonic acid amide monomer include 2-acrylamido-2-methylpropanesulfonic acid and Nt-butylacrylamidesulfonic acid.
  • the phosphoric acid amide monomer is a monomer having an amide group bonded to a phosphoric acid group.
  • Examples of the phosphoric acid amide monomer include acrylamide phosphonic acid and acrylamide phosphonic acid derivatives.
  • carboxylic acid amide monomers are preferable, unsaturated carboxylic acid amide compounds are more preferable, and (meth) acrylamide and N-hydroxymethyl (meth) acrylamide are particularly preferable.
  • an amide monomer and an amide monomer unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the amide monomer unit in the polymer forming the non-conductive particles is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, particularly preferably 0.5% by weight or more, Preferably it is 50 weight% or less, More preferably, it is 45 weight% or less, Most preferably, it is 40 weight% or less.
  • the organic particles may not have a glass transition temperature, but when the polymer compound forming the organic particles has a glass transition temperature, the glass transition temperature is preferably Is 150 ° C. or higher, more preferably 200 ° C. or higher, particularly preferably 250 ° C. or higher, and preferably 500 ° C. or lower.
  • the method for producing organic particles as non-conductive particles is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method may be used.
  • the emulsion polymerization method and the suspension polymerization method are preferable because they can be polymerized in water and used as they are as the material for the porous membrane slurry composition.
  • the organic particles are generally composed of a polymer that substantially constitutes the organic particles, but may be accompanied by any component such as an additive added during the polymerization.
  • Non-conductive particles may be subjected to, for example, element substitution, surface treatment, solid solution, and the like as necessary. Further, the non-conductive particles may include one kind of the above materials alone in one particle, or may contain two or more kinds in combination at an arbitrary ratio. . Further, the non-conductive particles may be used in combination of two or more kinds of particles formed of different materials.
  • Examples of the shape of the nonconductive particles include a spherical shape, an elliptical spherical shape, a polygonal shape, a tetrapod (registered trademark) shape, a plate shape, and a scale shape.
  • tetrapod (registered trademark) shape, plate shape, and scale shape are preferable from the viewpoint of increasing the porosity of the porous membrane and suppressing the decrease in ion conductivity due to the porous membrane separator.
  • the volume average particle diameter of the non-conductive particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the BET specific surface area of the non-conductive particles is, for example, preferably 0.9 m 2 / g or more, more preferably 1.5 m 2 / g or more. Further, from the viewpoint of suppressing aggregation of non-conductive particles and optimizing the fluidity of the porous membrane slurry composition, the BET specific surface area is preferably not too large, for example, 150 m 2 / g or less.
  • the amount of non-conductive particles in the porous membrane is preferably 60% by weight or more, more preferably 65% by weight or more, and preferably 95% by weight or less.
  • the porous membrane slurry composition of the present invention contains a water-soluble polymer.
  • a part of the water-soluble polymer is released in water, while another part is adsorbed on the surface of the non-conductive particles to form a stable layer covering the non-conductive particles.
  • the water-soluble polymer has a function of binding non-conductive particles by interposing between non-conductive particles in the porous film, and between the non-conductive particles and the separator substrate or the electrode plate. By intervening, the effect of binding the porous film and the separator substrate or the electrode plate can be achieved.
  • the water-soluble polymer contains an acid group-containing monomer unit.
  • the acid group-containing monomer unit refers to a structural unit having a structure formed by polymerizing an acid group-containing monomer.
  • an acid group containing monomer shows the monomer containing an acid group. Therefore, the water-soluble polymer having an acid group-containing monomer unit also contains an acid group. Since the affinity of the water-soluble polymer to water is increased by the action of the acid group, the water-soluble polymer is soluble in water.
  • the water-soluble polymer has high adsorptivity to non-conductive particles because it has a highly polar acid group, the water-soluble polymer containing an acid group-containing monomer unit is a water-soluble polymer. As described above, a part of the layer easily forms a stable layer on the surface of the non-conductive particles. Therefore, in the porous membrane slurry composition, it is possible to effectively increase the dispersibility of the nonconductive particles.
  • Examples of the acid group include —COOH group (carboxylic acid group); —SO 3 H group (sulfonic acid group); —PO 3 H 2 group and —PO (OH) (OR) group (R represents a hydrocarbon group).
  • a phosphoric acid group such as Accordingly, examples of the acid group-containing monomer include monomers having these acid groups.
  • a monomer capable of generating the acid group by hydrolysis is also exemplified as the acid group-containing monomer.
  • Specific examples of such acid group-containing monomers include acid anhydrides that can generate carboxylic acid groups by hydrolysis.
  • Examples of the monomer having a carboxylic acid group include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and derivatives thereof.
  • Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, and isocrotonic acid.
  • Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and methylmaleic acid.
  • Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride and the like. Among these, monocarboxylic acid is preferable, and acrylic acid and methacrylic acid are more preferable.
  • Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, and (meth) acrylic acid-2-sulfonic acid.
  • examples thereof include ethyl, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2- (N-acryloyl) amino-2-methyl-1,3-propane-disulfonic acid, and the like. Of these, 2-acrylamido-2-methylpropanesulfonic acid is preferred.
  • Examples of the monomer having a phosphoric acid group include phosphoric acid-2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl phosphate- ( And (meth) acryloyloxyethyl.
  • the above-described monomer salt may be used as the acid group-containing monomer.
  • examples of such a salt include sodium salt of styrene sulfonic acid such as p-styrene sulfonic acid.
  • the acid group-containing monomer unit preferably has at least one group selected from the group consisting of a carboxylic acid group and a sulfonic acid group.
  • acid group-containing monomer and the acid group-containing monomer unit may be used alone or in combination of two or more at any ratio.
  • the ratio of the acid group-containing monomer unit in the water-soluble polymer is usually 20% by weight or more, preferably 25% by weight or more, more preferably 30% by weight or more, and usually 80% by weight or less, preferably 75% by weight. Hereinafter, it is more preferably 70% by weight or less.
  • the water-soluble polymer contains an amide monomer unit in combination with an acid group-containing monomer unit.
  • production of gas can be prevented in a lithium ion secondary battery because a water-soluble polymer contains an amide monomer unit.
  • this effect can be enhanced by combining the amide monomer unit and the acid group-containing monomer unit.
  • the water-soluble polymer is dissolved in the porous membrane slurry composition and spreads uniformly, it can effectively contribute to the prevention of gas generation in the formed porous membrane.
  • Examples of the amide monomer include the same examples as those exemplified in the description of the non-conductive particles. Among these, from the viewpoint of enhancing the durability of the porous membrane, a carboxylic acid amide monomer is preferable, an unsaturated carboxylic acid amide compound is more preferable, and (meth) acrylamide and N-hydroxymethyl (meth) acrylamide are particularly preferable. Moreover, an amide monomer and an amide monomer unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the amide monomer unit in the water-soluble polymer is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and usually 10% by weight or less, preferably Is 8% by weight or less, more preferably 5% by weight or less.
  • the ratio of the amide monomer in the water-soluble polymer is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and usually 10% by weight or less, preferably Is 8% by weight or less, more preferably 5% by weight or less.
  • the water-soluble polymer preferably contains a crosslinkable monomer unit in combination with an acid group-containing monomer unit and an amide monomer unit.
  • the crosslinkable monomer unit is a structural unit having a structure obtained by polymerizing a crosslinkable monomer.
  • the crosslinkable monomer is a monomer that can form a crosslinked structure during or after polymerization by heating or irradiation with energy rays.
  • the water-soluble polymer can be cross-linked, so that the strength and stability of the porous membrane can be increased. Thereby, it is possible to stably exhibit the action of the water-soluble polymer.
  • the degree of swelling of the water-soluble polymer by the electrolytic solution can be prevented from becoming excessively high, the low-temperature output characteristics of the lithium ion secondary battery can usually be improved.
  • crosslinkable monomer a monomer capable of forming a crosslinked structure upon polymerization can be used.
  • the crosslinkable monomer include monomers having two or more reactive groups per molecule. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule. Ionic monomers.
  • thermally crosslinkable groups contained in the monofunctional monomer include epoxy groups, oxetanyl groups, oxazoline groups, and combinations thereof.
  • an epoxy group is more preferable in terms of easy adjustment of crosslinking and crosslinking density.
  • crosslinkable monomer having an epoxy group as a thermally crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl.
  • Unsaturated glycidyl ethers such as ether; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, Glycidyl crotonate, glycy Unsaturated carboxylic acids such as ru-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidy
  • crosslinkable monomer having an oxetanyl group as a thermally crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl) ) -4-trifluoromethyloxetane.
  • crosslinkable monomer having an oxazoline group as a heat crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and And 2-isopropenyl-5-ethyl-2-oxazoline.
  • multifunctional monomers having two or more olefinic double bonds include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl
  • Examples include ethers, allyls or vinyl ethers of polyfunctional alcohols other than those described above, triallylamine, and divinylbenzene.
  • a crosslinkable monomer ethylene dimethacrylate, allyl glycidyl ether, glycidyl methacrylate, and ethylene glycol dimethacrylate are preferable, and ethylene dimethacrylate, allyl glycidyl ether, and glycidyl methacrylate are more preferable.
  • crosslinked monomer unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the proportion of the crosslinkable monomer unit in the water-soluble polymer is preferably 0.1% by weight or more, more preferably 0.15% by weight or more, particularly preferably 0.2% by weight or more, preferably 2. It is 0 wt% or less, more preferably 1.5 wt% or less, and particularly preferably 1.0 wt% or less. Since the mechanical strength of the water-soluble polymer can be increased by setting the ratio of the crosslinkable monomer unit in the water-soluble polymer to be equal to or higher than the lower limit of the above range, the connection between the porous membrane and the separator substrate or the electrode plate can be increased. Wearability can be improved. Moreover, durability of a porous film can be improved by making it into an upper limit or less.
  • the water-soluble polymer can contain a fluorine-containing monomer unit.
  • the fluorine-containing monomer unit is a structural unit having a structure formed by polymerizing a fluorine-containing monomer. Since the fluorine-containing monomer unit usually has high ionic conductivity, the ionic conductivity of the water-soluble polymer may be increased to reduce the internal resistance of the lithium ion secondary battery.
  • fluorine-containing monomer examples include a fluorine-containing (meth) acrylic acid ester monomer and a fluorine-containing aromatic diene monomer, and among them, a fluorine-containing (meth) acrylic acid ester monomer is preferable.
  • fluorine-containing (meth) acrylic acid ester monomer examples include monomers represented by the following formula (I).
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrocarbon group containing a fluorine atom.
  • the carbon number of the hydrocarbon group is preferably 1 or more, and preferably 18 or less.
  • the number of fluorine atoms contained in R 2 may be one or two or more.
  • fluorine-containing (meth) acrylic acid ester monomers represented by formula (I) include (meth) acrylic acid alkyl fluoride, (meth) acrylic acid fluoride aryl, and (meth) acrylic acid fluoride.
  • Aralkyl is mentioned. Of these, alkyl fluoride (meth) acrylate is preferred.
  • Such monomers include 2,2,2-trifluoroethyl (meth) acrylate; ⁇ - (perfluorooctyl) ethyl (meth) acrylate; 2,2, (meth) acrylic acid 3,3-tetrafluoropropyl; (meth) acrylic acid 2,2,3,4,4,4-hexafluorobutyl; (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [ Bis (trifluoromethyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl; (meth) acrylic acid 1H, 1H, 9H-perfluoro-1-nonyl, (meth) acrylic acid 1H, 1H, 11H-perfluoro (Medec) such as undecyl, perfluorooctyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, etc
  • the proportion of fluorine-containing monomer units in the water-soluble polymer is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. .
  • the ratio of the fluorine-containing monomer unit is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
  • the ratio of the fluorine-containing monomer unit in the water-soluble polymer is less than 0.1% by weight, it becomes easy to form a porous film on the substrate with a uniform thickness, and the durability of the porous film is increased.
  • the sex can be increased.
  • the water-soluble polymer may contain an arbitrary structural unit in addition to the acid group-containing monomer unit, amide monomer unit, crosslinkable monomer unit, and fluorine-containing monomer unit described above.
  • the water-soluble polymer can contain (meth) acrylic acid ester monomer units.
  • the (meth) acrylic acid ester monomer unit is a structural unit having a structure formed by polymerizing a (meth) acrylic acid ester monomer.
  • those containing fluorine are distinguished from (meth) acrylate monomers as fluorine-containing (meth) acrylate monomers.
  • Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t -Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl
  • the proportion of the (meth) acrylic acid ester monomer unit in the water-soluble polymer is preferably 25% by weight or more, more preferably 30% by weight or more, particularly preferably 35% by weight or more, and preferably 75% by weight. % Or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less.
  • arbitrary structural units that can be contained in the water-soluble polymer include structural units having a structure formed by polymerizing the following monomers. That is, aromatic vinyl monomers such as styrene, chlorostyrene, vinyltoluene, t-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, ⁇ -methylstyrene, divinylbenzene, etc.
  • aromatic vinyl monomers such as styrene, chlorostyrene, vinyltoluene, t-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, ⁇ -methylstyrene, divinylbenzene, etc.
  • ⁇ , ⁇ -unsaturated nitrile compound monomers such as acrylonitrile and methacrylonitrile; Olefin monomers such as ethylene and propylene; Halogen-containing monomers such as vinyl chloride and vinylidene chloride; Vinyl acetate and vinyl propionate Vinyl ester monomers such as vinyl butyrate and vinyl benzoate; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropyl And a structural unit having a structure formed by polymerizing one or more of vinyl ketone monomers such as nil vinyl ketone; and heterocyclic compound-containing vinyl compound monomers such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole. . Moreover, these may be used individually by 1 type and may be used combining two or more types
  • the weight average molecular weight of the water-soluble polymer is preferably 5,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 1,000,000 or less, more preferably 750,000 or less, Particularly preferably, it is 500,000 or less.
  • the weight average molecular weight of the water-soluble polymer can be determined by GPC as a value in terms of polystyrene using, as a developing solvent, a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide.
  • the amount of the water-soluble polymer in the porous membrane slurry composition is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 10 parts by weight with respect to 100 parts by weight of the non-conductive particles. Part or less, more preferably 5 parts by weight or less.
  • the water-soluble polymer can be produced, for example, by polymerizing a monomer composition containing the above-described monomer in an aqueous solvent. At this time, the ratio of each monomer in the monomer composition is usually the same as the ratio of structural units in the water-soluble polymer.
  • the aqueous solvent a solvent capable of dispersing a water-soluble polymer can be used.
  • the boiling point at normal pressure is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
  • the aqueous solvent will be given below.
  • the number in parentheses after the solvent name is the boiling point (unit: ° C) at normal pressure, and the value after the decimal point is a value rounded off or rounded down.
  • aqueous solvents examples include water (100); ketones such as diacetone alcohol (169) and ⁇ -butyrolactone (204); ethyl alcohol (78), isopropyl alcohol (82), and normal propyl alcohol (97).
  • Alcohols propylene glycol monomethyl ether (120), methyl cellosolve (124), ethyl cellosolve (136), ethylene glycol tertiary butyl ether (152), butyl cellosolve (171), 3-methoxy-3-methyl-1-butanol (174) ), Ethylene glycol monopropyl ether (150), diethylene glycol monobutyl ether (230), triethylene glycol monobutyl ether (271), dipropylene glycol monomethyl ether (188) Glycol ethers; and 1,3-dioxolane (75), 1,4-dioxolane (101), ethers such as tetrahydrofuran (66) and the like.
  • water is particularly preferable from the viewpoint that it is not flammable and a polymer dispersion can be easily obtained.
  • water may be used as the main solvent, and an aqueous solvent other than the above-described water may be mixed and used within a range in which the dispersion state of the polymer can be ensured.
  • the polymerization method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
  • the polymerization method any method such as ion polymerization, radical polymerization, and living radical polymerization can be used. Manufacturing efficiency, such as easy to obtain a high molecular weight, and no need for redispersion treatment because the polymer is obtained in a state of being dispersed in water as it is, and can be used for the production of a porous membrane slurry composition. From the viewpoint of the above, the emulsion polymerization method is particularly preferable.
  • the emulsion polymerization method is usually performed by a conventional method.
  • the method is described in “Experimental Chemistry Course” Vol. 28, (Publisher: Maruzen Co., Ltd., edited by The Chemical Society of Japan). That is, water, an additive such as a dispersant, an emulsifier, a crosslinking agent, a polymerization initiator, and a monomer are added to a sealed container equipped with a stirrer and a heating device so as to have a predetermined composition.
  • the composition is stirred to emulsify monomers and the like in water, and the temperature is increased while stirring to initiate polymerization. Or after emulsifying the said composition, it is the method of putting into a sealed container and starting reaction similarly.
  • polymerization initiators examples include organic compounds such as lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like. Peroxides; azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile; ammonium persulfate; and potassium persulfate.
  • a polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Additives such as emulsifiers, dispersants, polymerization initiators and the like are generally used in these polymerization methods, and the amount of use is usually the amount generally used.
  • the polymerization temperature and polymerization time can be arbitrarily selected depending on the polymerization method and the type of polymerization initiator. Usually, the polymerization temperature is about 30 ° C. or more, and the polymerization time is about 0.5 to 30 hours. Further, an additive such as amine may be used as a polymerization aid.
  • Examples of the method for adjusting the molecular weight of the polymer include adjusting the molecular weight of the polymer by controlling the amount of the emulsifier, the amount of the molecular weight modifier such as a crosslinkable monomer, the amount of the polymerization initiator, and the reaction temperature. it can.
  • a reaction liquid usually containing a water-soluble polymer is obtained.
  • the obtained reaction solution is usually acidic, and the water-soluble polymer is often dispersed in an aqueous solvent.
  • the water-soluble polymer dispersed in the water-soluble solvent as described above can usually be made soluble in an aqueous solvent by adjusting the pH of the reaction solution to, for example, 7 to 13. You may take out a water-soluble polymer from the reaction liquid obtained in this way.
  • water is used as an aqueous medium, and the porous membrane slurry composition of the present invention is produced using a water-soluble polymer dissolved in water.
  • Examples of the method for alkalizing the reaction solution to pH 7 to pH 13 include alkaline metal aqueous solutions such as lithium hydroxide aqueous solution, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution; alkaline earth such as calcium hydroxide aqueous solution and magnesium hydroxide aqueous solution.
  • Metal aqueous solution A method of mixing an alkaline aqueous solution such as an aqueous ammonia solution.
  • One kind of the alkaline aqueous solution may be used alone, or two or more kinds may be used in combination at any ratio.
  • the particulate polymer is a polymer particle.
  • the following advantages are usually obtained. That is, the binding property of the porous film is improved, and the separator for lithium ion secondary battery of the present invention (hereinafter sometimes referred to as “separator” as appropriate) or the lithium ion secondary during handling such as winding and transportation.
  • the strength against mechanical force applied to the battery electrode hereinafter sometimes referred to as “electrode” as appropriate
  • the shape of the particulate polymer is particulate, the particulate polymer can be bound to the non-conductive particles by a point instead of a surface. For this reason, since the hole in a porous film can be enlarged, the internal resistance of a lithium ion secondary battery can be made small.
  • the polymer constituting the particulate polymer various polymers can be used, but usually a water-insoluble polymer is used.
  • the polymer that forms the particulate polymer include polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, A polyacrylonitrile derivative or the like may be used.
  • the soft polymer particles exemplified below may be used as the particulate polymer.
  • a soft polymer for example, (I) Polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymer, butyl acrylate / acrylonitrile copolymer, butyl acrylate / acrylonitrile / glycidyl methacrylate copolymer, etc.
  • An acrylic soft polymer which is a homopolymer of acrylic acid or a methacrylic acid derivative or a copolymer thereof with a monomer copolymerizable therewith;
  • isobutylene-based soft polymers such as polyisobutylene, isobutylene-isoprene rubber, isobutylene-styrene copolymer;
  • a diene soft polymer and an acrylic soft polymer are preferable.
  • these soft polymers may have a cross-linked structure or may have a functional group introduced by modification.
  • a particulate polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the weight average molecular weight of the polymer constituting the particulate polymer is preferably 10,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, more preferably 500,000 or less. .
  • the weight average molecular weight of the polymer constituting the particulate polymer can be determined by gel permeation chromatography (GPC) as a value in terms of polystyrene using tetrahydrofuran as a developing solvent.
  • the glass transition temperature of the particulate polymer is preferably ⁇ 75 ° C. or higher, more preferably ⁇ 55 ° C. or higher, particularly preferably ⁇ 35 ° C. or higher, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and even more. Preferably it is 20 degrees C or less, Most preferably, it is 15 degrees C or less.
  • the glass transition temperature of the particulate polymer can be adjusted, for example, by combining various monomers.
  • the volume average particle diameter of the particulate polymer is preferably 50 nm or more, more preferably 70 nm or more, preferably 500 nm or less, more preferably 400 nm or less.
  • the amount of the particulate polymer is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 10 parts by weight or less, more preferably 100 parts by weight of non-conductive particles. 5 parts by weight or less.
  • the amount of the particulate polymer in the above range usually has a high binding property between the non-conductive particles and the binding property between the porous membrane and the separator substrate or the electrode plate, It is also significant in that the flexibility of the porous membrane can be increased and the ion conductivity of the porous membrane can be increased.
  • the weight ratio of the water-soluble polymer to the particulate polymer is preferably within a predetermined range. Specifically, the weight ratio is preferably 0.01 or more, more preferably 0.1 or more, and is preferably 1.5 or less, more preferably 1.0 or less.
  • the weight ratio is preferably 0.01 or more, more preferably 0.1 or more, and is preferably 1.5 or less, more preferably 1.0 or less.
  • the production method of the particulate polymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method may be used.
  • the emulsion polymerization method and the suspension polymerization method are preferable because they can be polymerized in water and used as they are as the material for the porous membrane slurry composition.
  • the particulate polymer is usually composed of a polymer substantially constituting it, but may be accompanied by any component such as an additive added during the polymerization.
  • the porous membrane slurry composition of the present invention contains water.
  • Water functions as a solvent or dispersion medium in the porous membrane slurry composition.
  • the water-soluble polymer is dissolved in water, and the particulate polymer is dispersed in water.
  • a solvent other than water may be used in combination with water.
  • the solvent that can be used in combination with water 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 and acetic acid Esters such as butyl, ⁇ -butyrolactone, ⁇ -caprolactone; nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran and ethylene glycol diethyl ether: methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether, etc. Alcohols; amides such as N-methylpyrrolidone (NMP) and N, N-dimethylformamide; and the like. One of these may be used alone,
  • the amount of the solvent in the porous membrane slurry composition is preferably set so that the solid content concentration of the porous membrane slurry composition falls within a desired range.
  • the solid content concentration of the specific porous membrane slurry composition is preferably 10% by weight or more, more preferably 15% by weight or more, particularly preferably 20% by weight or more, preferably 80% by weight or less, more preferably 75%. % By weight or less, particularly preferably 70% by weight or less.
  • solid content means the substance which remains after drying of a porous membrane slurry composition.
  • the porous membrane slurry composition may contain an optional component in addition to the above-described non-conductive particles, water-soluble polymer, particulate polymer and water.
  • optional components those which do not exert an excessively unfavorable influence on the battery reaction can be used.
  • Arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the porous membrane slurry composition preferably contains a carboxymethyl cellulose salt.
  • Carboxymethylcellulose salt acts as a thickener in the porous membrane slurry composition. Therefore, since the viscosity of the porous membrane slurry composition can be increased by the carboxymethyl cellulose salt, the applicability of the porous membrane slurry composition can be improved.
  • the carboxymethyl cellulose salt can usually increase the dispersion stability of the nonconductive particles in the porous membrane slurry composition, and can improve the binding property between the porous membrane and the separator substrate or the electrode plate. Examples of the carboxymethyl cellulose salt include a sodium salt and an ammonium salt.
  • carboxymethylcellulose salt may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the amount of the carboxymethyl cellulose salt is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 10 parts by weight or less, more preferably 7 parts by weight with respect to 100 parts by weight of the non-conductive particles. It is at most 5 parts by weight, particularly preferably at most 5 parts by weight.
  • carboxymethyl cellulose salt is also contained in the porous membrane.
  • strength of a porous film can be made high by making the quantity of a carboxymethylcellulose salt more than the lower limit of the said range.
  • flexibility of a porous film can be made favorable by setting it as below an upper limit.
  • the porous membrane slurry composition is, for example, an isothiazoline-based compound, a chelate compound, a pyrithione compound, a dispersant, a leveling agent, an antioxidant, a thickener, an antifoaming agent, a wetting agent, and a function of inhibiting electrolyte decomposition. It may contain an electrolyte solution additive and the like.
  • the porous membrane slurry composition of the present invention is usually excellent in dispersibility of each component contained in the composition. Therefore, the viscosity of the porous membrane slurry composition of the present invention can usually be easily lowered.
  • the specific viscosity of the porous membrane slurry composition is preferably 10 mPa ⁇ s to 2000 mPa ⁇ s from the viewpoint of improving the applicability when producing the porous membrane.
  • the said viscosity is a value when it measures at 25 degreeC and rotation speed 60rpm using an E-type viscosity meter.
  • the porous membrane slurry composition of the present invention is usually excellent in dispersion stability.
  • the dispersion stability of the porous membrane slurry composition means that the dispersibility of the composition does not easily change over time, and specifically, the viscosity of the composition does not easily change over time. Represents. Therefore, even when a porous membrane slurry composition stored for a long time is used, a high-quality porous membrane can be obtained.
  • the disperser is preferably an apparatus capable of uniformly dispersing and mixing the above components.
  • examples include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer.
  • a high dispersion apparatus such as a bead mill, a roll mill, or a fill mix is particularly preferable because a high dispersion share can be added.
  • Porous membrane for secondary battery By applying the porous membrane slurry composition of the present invention on a suitable substrate and drying, a porous membrane can be produced as a membrane formed by the solid content of the porous membrane slurry composition. That is, a porous membrane is produced by a production method including a step of applying a porous membrane slurry composition onto a substrate to obtain a membrane of the porous membrane slurry composition, and a step of removing a solvent such as water from the membrane by drying. Can be manufactured.
  • This porous film has an action of suppressing gas generation in a lithium ion secondary battery including the porous film.
  • the base material is a member that is a target for forming a film of the porous film slurry composition.
  • a base material There is no restriction
  • membrane of a porous film slurry composition is formed in the surface of a peeling film, a solvent is removed from the film
  • the constituent elements of the battery are used as the base material. Examples of such battery components include separator substrates and electrode plates.
  • Examples of the coating 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.
  • the dip method and the gravure method are preferable in that a uniform porous film can be obtained.
  • drying method examples include drying with winds such as warm air, hot air, and low-humidity air; vacuum drying; drying method by irradiation with infrared rays, far infrared rays, and electron beams.
  • the temperature during drying is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, particularly preferably 50 ° C. or higher, preferably 90 ° C. or lower, more preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower. .
  • the drying time is preferably 5 seconds or more, more preferably 10 seconds or more, particularly preferably 15 seconds or more, preferably 3 minutes or less, more preferably 2 minutes or less, and particularly preferably 1 minute or less.
  • the porous film may be subjected to pressure treatment by a pressing method such as a mold press and a roll press.
  • a pressing method such as a mold press and a roll press.
  • the pressure treatment By performing the pressure treatment, the binding property between the substrate and the porous film can be improved.
  • it is preferable to appropriately control the pressure and the pressurization time so as not to become excessively large.
  • heat treatment is also preferable, whereby the thermal crosslinking group contained in the polymer component can be crosslinked to increase the binding force.
  • the thickness of the porous membrane is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, particularly preferably 0.3 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the separator of the present invention includes a separator substrate and a porous membrane.
  • the provision of the porous film makes it possible to prevent the separator base material from being damaged by foreign substances and the separator base material from being contracted by heat. Therefore, the internal short circuit of a lithium ion secondary battery provided with this separator can be prevented, and the safety of the battery can be improved.
  • the separator of this invention is equipped with the porous film which concerns on this invention, generation
  • separator substrate for example, a porous substrate having fine pores can be used.
  • a separator base material By using such a separator base material, it is possible to prevent a short circuit without interfering with charge / discharge of the battery in the secondary battery.
  • the microporous film or nonwoven fabric containing polyolefin resin such as polyethylene resin and a polypropylene resin, an aromatic polyamide resin, etc. are mentioned.
  • the thickness of the separator substrate is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Within this range, the resistance due to the separator substrate in the secondary battery is reduced, and the workability during battery production is excellent.
  • the separator of this invention is equipped with the porous film mentioned above on the separator base material. That is, the separator of this invention is equipped with a separator base material and the porous film obtained by apply
  • a separator can be manufactured, for example, by performing the above-described method for manufacturing a porous film using a separator base material as a base material. At this time, the porous film may be provided on only one surface of the separator base material, or may be provided on both surfaces.
  • the electrode of the present invention includes an electrode plate and a porous film. Further, the electrode plate usually includes a current collector and an electrode active material layer. In the electrode of the present invention, the provision of the porous film prevents detachment of particles such as electrode active material from the electrode active material layer, separation of the electrode active material layer from the current collector, and internal short circuit of the battery. Can be prevented. Moreover, since the electrode of this invention is equipped with the porous film which concerns on this invention, generation
  • the current collector may be made of a material having electrical conductivity and electrochemical durability.
  • a metal material is used as the material of the current collector. Examples thereof include iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum and the like.
  • the current collector used for the positive electrode is preferably aluminum
  • the current collector used for the negative electrode is preferably copper.
  • the said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the shape of the current collector is not particularly limited, but a sheet having a thickness of about 0.001 mm to 0.5 mm is preferable.
  • the current collector is used after the surface has been roughened.
  • the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • the mechanical polishing method for example, an abrasive cloth paper to which abrasive particles are fixed, a grindstone, an emery buff, a wire brush provided with a steel wire, or the like is used.
  • an intermediate layer may be formed on the surface of the current collector.
  • Electrode active material layer is a layer provided on the current collector and includes an electrode active material.
  • an electrode active material of the lithium ion secondary battery a material capable of reversibly inserting or releasing lithium ions by applying a potential in an electrolytic solution can be used.
  • an inorganic compound or an organic compound may be used.
  • the positive electrode active material is roughly classified into those made of inorganic compounds and those made of organic compounds.
  • Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, composite oxides of lithium and transition metals, and transition metal sulfides.
  • Examples of the transition metal include Fe, Co, Ni, and Mn.
  • inorganic compounds used for the positive electrode active material include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiFeVO 4, and other lithium-containing composite metal oxides; TiS 2 , TiS 3 , non- Transition metal sulfides such as crystalline MoS 2 ; transition metal oxides such as Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13, etc. Can be mentioned.
  • examples of the positive electrode active material made of an organic compound include conductive polymers such as polyacetylene and poly-p-phenylene.
  • the positive electrode active material which consists of a composite material which combined the inorganic compound and the organic compound.
  • a composite material covered with a carbon material may be produced by reducing and firing an iron-based oxide in the presence of a carbon source material, and the composite material may be used as a positive electrode active material.
  • Iron-based oxides tend to have poor electrical conductivity, but can be used as a high-performance positive electrode active material by using a composite material as described above.
  • you may use as a positive electrode active material what carried out the element substitution of the said compound partially.
  • These positive electrode active materials may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the particle size of the positive electrode active material can be selected in consideration of other constituent requirements of the lithium ion secondary battery.
  • the volume average particle diameter of the positive electrode active material is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less. It is. When the volume average particle size of the positive electrode active material is within this range, a battery having a large charge / discharge capacity can be obtained, and handling of the electrode slurry composition and the electrode is easy.
  • the ratio of the positive electrode active material in the electrode active material layer is preferably 90% by weight or more, more preferably 95% by weight or more, and preferably 99.9% by weight or less, more preferably 99% by weight or less.
  • the negative electrode active material examples include carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads, and pitch-based carbon fibers; and conductive polymers such as polyacene.
  • metals such as silicon, tin, zinc, manganese, iron and nickel, and alloys thereof; oxides of the metals or alloys; sulfates of the metals or alloys; Further, metallic lithium; lithium alloys such as Li—Al, Li—Bi—Cd, and Li—Sn—Cd; lithium transition metal nitride; silicon and the like may be used.
  • an electrode active material having a conductive material attached to the surface by a mechanical modification method may be used. These negative electrode active materials may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the particle size of the negative electrode active material is appropriately selected in consideration of other constituent requirements of the lithium ion secondary battery.
  • the volume average particle diameter of the negative electrode active material is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and even more preferably 5 ⁇ m or more. Is 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 20 ⁇ m or less.
  • the specific surface area of the negative electrode active material, the output from the viewpoint of improving the density preferably 2m 2 / g or more, more preferably 3m 2 / g or more, more preferably 5 m 2 / g or more, and preferably 20 m 2 / g or less, more preferably 15 m 2 / g or less, and further preferably 10 m 2 / g or less.
  • the specific surface area of the negative electrode active material can be measured by, for example, the BET method.
  • the proportion of the negative electrode active material in the electrode active material layer is preferably 85% by weight or more, more preferably 88% by weight or more, and preferably 99% by weight or less, more preferably 97% by weight or less.
  • the electrode active material layer preferably contains an electrode binder in addition to the electrode active material.
  • an electrode binder in addition to the electrode active material.
  • the binding property of the electrode active material layer is improved, and the strength against the mechanical force applied in the process of winding the electrode is increased.
  • the electrode active material layer is less likely to be peeled off from the current collector and the porous film, the risk of short-circuiting due to the detached desorbed material is reduced.
  • the binder for the electrode for example, a polymer can be used.
  • the polymer that can be used as the electrode binder include the same examples as those exemplified as examples of the particulate polymer in the description of the porous membrane slurry composition of the present invention.
  • the binder for electrodes may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the amount of the binder for the electrode in the electrode active material layer is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, particularly preferably 0.5 parts by weight or more with respect to 100 parts by weight of the electrode active material. It is preferably 5 parts by weight or less, more preferably 3 parts by weight or less. When the amount of the electrode binder is within the above range, it is possible to prevent the electrode active material from dropping from the electrode without inhibiting the battery reaction.
  • the electrode active material layer may contain any component other than the electrode active material and the electrode binder as long as the effects of the present invention are not significantly impaired. Examples thereof include a conductive material and a reinforcing material. Moreover, arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Examples of the conductive material include conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube; carbon powder such as graphite; fiber and foil of various metals; .
  • conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube
  • carbon powder such as graphite
  • fiber and foil of various metals .
  • the specific surface area of the conductive material is preferably 50 m 2 / g or more, more preferably 60 m 2 / g or more, particularly preferably 70 m 2 / g or more, preferably 1500 m 2 / g or less, more preferably 1200 m 2 / g. Hereinafter, it is particularly preferably 1000 m 2 / g or less.
  • the reinforcing material for example, various inorganic and organic spherical, plate, rod or fiber fillers can be used. By using the reinforcing material, a tough and flexible electrode can be obtained, and excellent long-term cycle characteristics can be obtained.
  • the amount of the conductive material and the reinforcing agent used is usually 0 part by weight or more, preferably 1 part by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight, with respect to 100 parts by weight of the electrode active material. It is as follows.
  • the thickness of the electrode active material layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, preferably 300 ⁇ m or less, more preferably 250 ⁇ m or less for both the positive electrode and the negative electrode.
  • the method for producing the electrode active material layer is not particularly limited.
  • the electrode active material layer can be produced, for example, by applying an electrode active material, a solvent, and, if necessary, an electrode slurry composition containing an electrode binder and optional components onto a current collector and drying it.
  • the solvent either water or an organic solvent can be used.
  • the electrode of the present invention includes the porous film described above on the electrode plate. That is, the electrode of the present invention includes an electrode plate and a porous film obtained by applying a porous film slurry composition on the electrode plate and drying it. Such an electrode can be manufactured, for example, by performing the above-described porous film manufacturing method using an electrode plate as a substrate. At this time, the porous film may be provided on only one surface of the electrode plate, or may be provided on both surfaces. However, since the porous film is usually provided on the electrode active material layer, the electrode of the present invention includes a current collector, an electrode active material layer, and a porous film in this order.
  • the lithium ion secondary battery of this invention is equipped with a positive electrode, a negative electrode, and electrolyte solution.
  • the secondary battery of the present invention satisfies the following requirement (A), satisfies the requirement (B), or satisfies both the requirements (A) and (B).
  • the lithium ion secondary battery of the present invention includes a separator, and the separator is the separator of the present invention.
  • the water-soluble polymer contained in the porous film can trap halide ions in the electrolytic solution. It is inferred that the generation of the cause gas is suppressed. If halide ions are contained in the battery, the electrolyte and SEI may be decomposed along with charge and discharge, and gas may be generated. On the other hand, in the lithium ion secondary battery of the present invention, since the water-soluble polymer traps halide ions, the amount of halide ions in the electrolytic solution is reduced, so the amount of gas generated can be reduced. It is thought that.
  • the lithium ion secondary battery of the present invention usually has good cycle characteristics.
  • the reason why such a good cycle characteristic can be realized is not necessarily clear, but according to the study of the present inventor, it is presumed as follows. That is, firstly, since the generation of gas is suppressed as described above, it is possible to suppress a decrease in battery capacity due to the gas. Second, since the water-soluble polymer can trap halide ions in the electrolyte, corrosion of the current collector caused by halide ions can be prevented. If corrosion of the current collector can be prevented, an increase in resistance of the electrode due to the progress of corrosion can be suppressed.
  • the corrosion of the current collector can be prevented, a decrease in the binding force between the current collector and the electrode active material layer can be suppressed.
  • the water-soluble polymer according to the present invention is excellent in the ability to bind the porous film and the separator substrate or electrode plate, the porous film is peeled off from the separator substrate or electrode plate by repeated charge and discharge. hard. Therefore, the increase in the distance between the positive electrode and the negative electrode due to charge / discharge can be suppressed. And it is inferred that excellent cycle characteristics can be realized by combining these factors.
  • the lithium ion secondary battery of the present invention includes the electrode of the present invention as one or both of a positive electrode and a negative electrode.
  • the lithium ion secondary battery of the present invention includes the separator of the present invention as a separator, an electrode other than the electrode of the present invention may be provided as both the positive electrode and the negative electrode.
  • the lithium ion secondary battery of the present invention includes the separator of the present invention as a separator.
  • a separator other than the separator of the present invention may be provided as a separator.
  • the porous film with which the electrode of this invention is provided has a function as a separator, you may abbreviate
  • Electrolyte As the electrolytic solution, for example, a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the amount of the supporting electrolyte is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less, as the concentration in the electrolytic solution.
  • a solvent capable of dissolving the supporting electrolyte can be used.
  • alkyl carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), 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;
  • dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferred because high ion conductivity is easily obtained and the use temperature range is wide.
  • a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the electrolytic solution may contain an additive as necessary.
  • an additive for example, carbonate compounds such as vinylene carbonate (VC) are preferable.
  • An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the sources of fluoride ions include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi,
  • Examples include supporting electrolytes for electrolytic solutions such as CF 3 SO 2 ) 2 NLi and (C 2 F 5 SO 2 ) NLi; binders for electrodes such as polyvinylidene fluoride.
  • a source of chloride ions there may be mentioned a supporting electrolyte of an electrolytic solution such as LiAlCl 4 and LiClO 4 ; an additive such as a carboxymethyl cellulose salt; a residual HCl of an electrode active material, and the like.
  • the lithium ion secondary battery of the present invention is significant in that it can suppress deterioration of battery performance due to halide ions, even if it includes a component that can generate halide ions as described above.
  • the manufacturing method of the lithium ion secondary battery of the present invention is not particularly limited.
  • the above-described negative electrode and positive electrode may be overlapped via a separator, and this may be wound or folded in accordance with the shape of the battery and placed in the battery container, and the electrolyte may be injected into the battery container and sealed.
  • an expanded metal; an overcurrent prevention element such as a fuse or a PTC element; a lead plate or the like may be inserted to prevent an increase in pressure inside the battery or overcharge / discharge.
  • the shape of the battery may be any of, for example, a laminate cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, and a flat type.
  • the lithium ion secondary battery of the 800 mAh wound type cell manufactured by the Example and the comparative example was left still for 24 hours in 25 degreeC environment. Thereafter, under an environment of 25 ° C., a charge / discharge operation of charging up to 4.35 V at 0.1 C and discharging to 2.75 V at 0.1 C was performed, and the initial capacity C0 was measured.
  • the charge / discharge operation was repeated 1000 cycles under the same conditions as described above, and the capacity C1 after 1000 cycles was measured.
  • lithium ion secondary batteries (Examples 1 to 18, 20 and 21 and comparisons) Examples 1 to 4) were dismantled.
  • the dried separator was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece.
  • a cellophane tape was affixed to the surface of the porous membrane with the test piece facing down.
  • a cellophane tape defined in JIS Z1522 was used.
  • the cellophane tape was fixed on a horizontal test bench. Thereafter, the stress was measured when one end of the separator substrate was pulled vertically upward and pulled at a pulling speed of 50 mm / min. This measurement was performed 3 times, the average value of stress was calculated
  • the lithium ion secondary battery (Example 19) of the wound cell was disassembled.
  • the dried negative electrode was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece.
  • a cellophane tape was affixed to the surface of the porous membrane with the test piece facing down. At this time, a cellophane tape defined in JIS Z1522 was used.
  • the cellophane tape was fixed on a horizontal test bench. Then, the stress when one end of the current collector was pulled vertically upward at a pulling speed of 50 mm / min and peeled was measured. This measurement was performed 3 times, the average value of stress was calculated
  • Example 1 (1-1. Production of water-soluble polymer) In a 5 MPa pressure vessel with a stirrer, 1 part of acrylamide (carboxylic amide monomer), 35 parts of methacrylic acid (acid group-containing monomer), 2,2,2-trifluoroethyl methacrylate (fluorine-containing (meth) acrylic acid) 3 parts of ester monomer), 60 parts of ethyl acrylate (arbitrary monomer), 1 part of ethylene dimethacrylate (crosslinkable monomer), 0.6 part of t-dodecyl mercaptan, 150 parts of ion-exchanged water, After adding 1.0 part of potassium sulfate (polymerization initiator) and stirring sufficiently, the polymerization was started by heating to 60 ° C.
  • acrylamide carboxylic amide monomer
  • methacrylic acid acid group-containing monomer
  • 2,2,2-trifluoroethyl methacrylate fluorine-containing (meth) acrylic acid
  • the reaction was stopped by cooling to obtain a mixture containing a water-soluble polymer.
  • 10% ammonia water was added to the mixture containing the water-soluble polymer and adjusting the pH to 8, the water-soluble polymer was dissolved in water to obtain an aqueous solution containing the desired water-soluble polymer.
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the particulate polymer to adjust the pH to 8. Thereafter, unreacted monomers were removed from the mixture by heating under reduced pressure, and then cooled to 30 ° C. or lower to obtain an aqueous dispersion containing a desired particulate polymer.
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the non-conductive particles to adjust the pH to 8. Then, after removing unreacted monomer from the mixture by heating under reduced pressure, the mixture was cooled to 30 ° C. or lower to obtain an aqueous dispersion containing desired non-conductive particles.
  • the aqueous dispersion containing the non-conductive particles obtained in the step (1-3) is 100 parts in terms of solid content
  • the aqueous solution containing the water-soluble polymer obtained in the step (1-1) is 2 in terms of solid content.
  • 2 parts of carboxymethylcellulose sodium salt (“1220” manufactured by Daicel) and an aqueous dispersion containing the particulate polymer obtained in the step (1-2) were taken to be 2 parts corresponding to the solid content.
  • water was further mixed to adjust the solid content concentration to 40% by weight to produce a porous membrane slurry composition.
  • a part of the porous film slurry composition thus obtained was taken out and the viscosity change rate was measured in the manner described above.
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the particulate binder to adjust the pH to 8. Thereafter, the unreacted monomer was removed from the mixture by distillation under reduced pressure, followed by cooling to 30 ° C. or lower to obtain an aqueous dispersion containing a desired particulate binder.
  • aqueous dispersion containing the particulate binder obtained in the step (1-6) is added in an amount corresponding to the solid content, and ion-exchanged water is further added to obtain a final solid content concentration.
  • the mixture was adjusted to 52% and further mixed for 10 minutes. This was defoamed under reduced pressure to obtain a negative electrode slurry composition having good fluidity.
  • the negative electrode slurry composition obtained in the step (1-7) was applied onto a 20 ⁇ m thick copper foil as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m. Dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material before pressing. The negative electrode raw material before pressing was rolled with a roll press to obtain a negative electrode after pressing with a negative electrode active material layer having a thickness of 80 ⁇ m.
  • the positive electrode slurry composition obtained in the step (1-9) was applied on a 20 ⁇ m thick aluminum foil as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m. Dried. This drying was performed by conveying the aluminum foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Then, it heat-processed for 2 minutes at 120 degreeC, and obtained the positive electrode.
  • the positive electrode obtained in the step (1-10) was cut into a square of 4.6 ⁇ 4.6 cm 2 and arranged so that the surface on the current collector side was in contact with the aluminum packaging exterior.
  • the separator with the porous film obtained in the step (1-5) was cut into a square of 5 ⁇ 5 cm 2 , and this was cut on the surface of the positive electrode active material layer of the positive electrode, and the surface on the separator substrate side became the positive electrode Arranged to face each other.
  • the pressed negative electrode obtained in the step (1-8) was cut into a square of 5 ⁇ 5 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faces the separator.
  • Example 2 In the step (1-3), the amount of styrene was changed to 98 parts, and acrylamide was not used. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 3 In the step (1-3), the amount of styrene was changed to 97.85 parts, and the amount of acrylamide was changed to 0.15 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 4 In the step (1-3), the amount of styrene was changed to 53 parts, and the amount of acrylamide was changed to 45 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 5 In the step (1-3), the amount of sodium dodecylbenzenesulfonate was changed to 1.2 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 6 In the step (1-3), the amount of sodium dodecylbenzenesulfonate was changed to 0.1 part. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 7 In the step (1-1), the amount of methacrylic acid was changed to 22 parts, and the amount of ethyl acrylate was changed to 73 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 8 In the step (1-1), the amount of methacrylic acid was changed to 78 parts, and the amount of ethyl acrylate was changed to 17 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 9 In the step (1-1), vinyl sulfonic acid (VSA) was used instead of methacrylic acid. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • VSA vinyl sulfonic acid
  • Example 10 In the step (1-1), instead of using 35 parts of methacrylic acid, 25 parts of methacrylic acid and 10 parts of vinyl sulfonic acid were used in combination. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 11 In the step (1-1), the amount of acrylamide was changed to 0.2 parts, and the amount of ethyl acrylate was changed to 60.8 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 12 In the step (1-1), the amount of acrylamide was changed to 9 parts, and the amount of ethyl acrylate was changed to 52 parts. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 13 In the step (1-1), N-methylolacrylamide was used instead of acrylamide. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 14 In the step (1-1), methacrylamide was used instead of acrylamide. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 15 In the step (1-1), N, N-dimethylaminoethylacrylamide was used instead of acrylamide. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 16 In the step (1-1), N, N-dimethylaminopropylacrylamide was used instead of acrylamide. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 17 In the step (1-3), the amount of styrene was changed to 90 parts, and ethylene glycol dimethacrylate was not used. In the step (1-2), butyl acrylate, acrylonitrile, methacrylic acid and allyl methacrylate are not used, but instead 62.5 parts of styrene, 33.0 parts of 1,3-butadiene, 3.5 parts of itaconic acid And 1.0 part of 2-hydroxyethyl acrylate was used in combination. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 18 In the step (1-4), instead of the aqueous dispersion containing non-conductive particles obtained in the step (1-3), 100 parts of Al 2 O 3 particles (volume average particle diameter of 0.5 ⁇ m) were added. Using. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 19 On the negative electrode active material layer of the negative electrode after the press manufactured in the step (1-8), the porous film slurry composition manufactured in the step (1-4) is applied in a gravure coater to a coating amount of 6 mg after drying. / Cm ⁇ 2 > was applied and dried. This drying was performed by conveying the negative electrode in an oven at 100 ° C. at a speed of 20 m / min for 1 minute. This obtained the negative electrode provided with the electrode plate provided with an electrical power collector and a negative electrode active material layer, and a porous film.
  • a single-layer polypropylene separator base material (“Celguard 2500” manufactured by Celgard) was used, and the porous membrane produced in Example 19 as a negative electrode. An attached negative electrode was used.
  • a lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 20 In the step (1-1), the amount of methacrylic acid was changed to 22 parts, the amount of acrylamide was changed to 9 parts, ethyl acrylate was changed to 68 parts, and 2,2,2-trifluoroethyl methacrylate was changed to Not used.
  • a lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 21 In the step (1-1), the amount of methacrylic acid was changed to 78 parts, the amount of acrylamide was changed to 0.5 parts, ethyl acrylate was changed to 20.5 parts, and 2,2,2-trimethyl was added. Fluoroethyl methacrylate was not used. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • step (1-1) the amount of methacrylic acid was changed to 15 parts, the amount of ethyl acrylate was changed to 85 parts, and acrylamide, 2,2,2-trifluoroethyl methacrylate and ethylene dimethacrylate were not used. It was.
  • step (1-4) 100 parts of Al 2 O 3 particles (volume average particle diameter of 2 ⁇ m) are used instead of the aqueous dispersion containing non-conductive particles obtained in the step (1-3). Using. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • step (1-1) the amount of acrylamide was changed to 15 parts, the amount of ethyl acrylate was changed to 50 parts, and 2,2,2-trifluoroethyl methacrylate and ethylene dimethacrylate were not used.
  • step (1-4) 100 parts of Al 2 O 3 particles (volume average particle diameter of 2 ⁇ m) are used instead of the aqueous dispersion containing non-conductive particles obtained in the step (1-3). Using. A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • the viscosity change rate of the porous membrane slurry composition is smaller in the example than in the comparative example. From this, it was confirmed that the porous membrane slurry composition according to the present invention is usually excellent in dispersion stability.
  • the porous membrane produced using the porous membrane slurry composition having excellent dispersion stability has a small compositional bias and a uniform composition even when the porous membrane slurry composition after long-term storage is used. Therefore, there is no local brittle part, and the overall mechanical strength is excellent. Therefore, the safety of the lithium ion secondary battery can be improved.
  • the capacity retention rate ⁇ C of the battery is larger in the example than in the comparative example. From this, it was confirmed that a battery excellent in high-temperature cycle characteristics is usually obtained by the present invention. For this reason, it can be expected that the lifetime of the lithium ion secondary battery is extended by the present invention.
  • the peel strength after the cycle test is greater in the example than in the comparative example. From this, it was confirmed that the porous film according to the present invention can maintain a high binding force to the separator substrate and the electrode plate even when charging and discharging are repeated. If the porous film is peeled off from the separator substrate or the electrode plate, the distance between the positive electrode and the negative electrode is increased, the resistance is increased, and the battery performance may be lowered. Therefore, the porous film excellent in the binding force to the separator substrate and the electrode plate has an advantage that the battery performance can be prevented from deteriorating.

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Abstract

L'invention a pour objectif de fournir une batterie secondaire au lithium-ion permettant d'inhiber une génération de gaz. Plus précisément, l'invention concerne une composition de bouillie pour membrane poreuse pour batterie secondaire au lithium-ion, qui contient des particules non conductrices, un polymère soluble dans l'eau, un polymère sous forme particulaire et de l'eau. Le polymère soluble dans l'eau contient 20 à 80% en masse d'une unité polymère comprenant un groupe acide, et 0,1 à 10% en masse d'une unité monomère amide.
PCT/JP2014/064175 2013-06-04 2014-05-28 Composition de bouillie pour membrane poreuse pour batterie secondaire au lithium-ion, séparateur pour batterie secondaire au lithium-ion, électrode pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion WO2014196436A1 (fr)

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KR20190005154A (ko) * 2016-05-10 2019-01-15 니폰 제온 가부시키가이샤 비수계 2차 전지 기능층용 조성물, 비수계 2차 전지용 기능층, 및 비수계 2차 전지
WO2019039560A1 (fr) * 2017-08-24 2019-02-28 日本ゼオン株式会社 Composition de liant pour batteries secondaires non aqueuses, composition de bouillie pour couches fonctionnelles de batterie secondaire non aqueuse, couche fonctionnelle pour batteries secondaires non aqueuses, élément de batterie pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
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CN111208041A (zh) * 2020-01-10 2020-05-29 万邦德制药集团有限公司 一种银杏叶滴丸的制备方法
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WO2023189442A1 (fr) * 2022-03-31 2023-10-05 日本ゼオン株式会社 Composition de suspension pour couches fonctionnelles de batterie secondaire non aqueuse, séparateur pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
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KR20180044892A (ko) 2015-08-20 2018-05-03 니폰 제온 가부시키가이샤 비수계 2차 전지용 바인더 조성물, 비수계 2차 전지 기능층용 조성물, 비수계 2차 전지용 기능층 및 비수계 2차 전지
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