WO2014024823A1 - Bouillie et électrode négative pour batteries lithium-ion - Google Patents

Bouillie et électrode négative pour batteries lithium-ion Download PDF

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WO2014024823A1
WO2014024823A1 PCT/JP2013/071116 JP2013071116W WO2014024823A1 WO 2014024823 A1 WO2014024823 A1 WO 2014024823A1 JP 2013071116 W JP2013071116 W JP 2013071116W WO 2014024823 A1 WO2014024823 A1 WO 2014024823A1
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ethylenically unsaturated
negative electrode
lithium ion
ion battery
particles
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PCT/JP2013/071116
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English (en)
Japanese (ja)
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村田　浩一
石井　伸晃
武内　正隆
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昭和電工株式会社
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Priority to JP2013548654A priority Critical patent/JPWO2014024823A1/ja
Publication of WO2014024823A1 publication Critical patent/WO2014024823A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a slurry. More specifically, the present invention relates to a slurry capable of obtaining a lithium ion battery having a large charge / discharge capacity and good charge / discharge cycle characteristics, a negative electrode formed by applying the slurry, and a lithium ion battery having the negative electrode.
  • This application claims priority based on Japanese Patent Application No. 2012-176401 for which it applied to Japan on August 8, 2012, and uses the content here.
  • the power consumption of portable electronic devices is increasing because the multifunction of portable electronic devices is progressing faster than the power saving of electronic components. Therefore, higher capacity and smaller size of the lithium ion battery, which is the main power source of portable electronic devices, are more strongly demanded than ever. In addition, the demand for electric vehicles is increasing, and the lithium-ion batteries used there are also strongly required to have a high capacity.
  • the theoretical capacity of a lithium ion battery when Si-containing particles are used as the negative electrode material is 4200 mAh / g. Since the theoretical capacity of a lithium battery using metal lithium is 3900 mAh / g, if Si or the like can be used as a negative electrode material, it is expected that a lithium ion battery having a smaller size and higher capacity than a metal lithium battery can be obtained.
  • a negative electrode material such as Si has a large expansion coefficient and contraction coefficient associated with insertion / extraction (occlusion / release) of lithium ions.
  • the organic solvent N-methyl-pyrrolidone (NMP) is used as a binder for binding the active material to the current collector, and the resin itself has high swelling resistance to the electrolyte solution.
  • Vinylidene chloride (PVDF) has been used.
  • this organic solvent-based binder has a low binding property between active materials and between an active material and a current collector, and a large amount of binder is required to obtain an effective binding force, resulting in the capacity of a lithium ion battery.
  • the energy density is lowered.
  • the organic solvent-based binder uses NMP, which is an expensive organic solvent, in the solvent, so that the price of the final product is high.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • Patent Document 1 As a binder for an anode of an alloy containing Si or the like, which is expected to have a large capacity, it is known that the cycle characteristics of a binder using an aqueous binder are remarkably improved as compared with the case of using PVDF (for example, non-binding).
  • PVDF for example, non-binding
  • the object of the present invention is to use a water-dispersed binder, have good binding properties between active materials and between an active material and a current collector, have a large charge / discharge capacity, high charge / discharge efficiency, and charge / discharge cycle characteristics. It is an object to provide an alloy-based slurry, a negative electrode obtained using the slurry, and a lithium ion battery having the negative electrode, which can provide a lithium ion battery to be improved.
  • a negative electrode material for a lithium ion battery containing, as an active material, particles A containing at least one element selected from the group consisting of Si, Sn, Ge, and In, Obtained by polymerizing an ethylenically unsaturated monomer containing styrene, an ethylenically unsaturated carboxylic acid ester, an ethylenically unsaturated carboxylic acid, and a crosslinking agent having at least one ethylenically unsaturated group as essential components
  • a negative electrode material for a lithium ion battery containing, as an active material, particles A containing at least one element selected from the group consisting of Si, Sn, Ge, and In; Obtained by polymerizing an ethylenically unsaturated monomer containing styrene, an ethylenically unsaturated carboxylic acid ester, an ethylenically unsaturated carboxylic acid, and a crosslinking agent having at least one ethylenically unsaturated group as essential components
  • a negative electrode material for a lithium ion battery containing, as an active material, particles A containing at least one element selected from the group consisting of Si, Sn, Ge, and In; Presence of surfactant with ethylenically unsaturated monomer containing styrene, ethylenically unsaturated carboxylic acid ester, ethylenically unsaturated carboxylic acid, and crosslinking agent having at least one ethylenically unsaturated group as essential components
  • the manufacturing method of a slurry including the process of mixing below with the aqueous emulsion containing the polymer B obtained by superposition
  • the slurry of the present invention By using the slurry of the present invention, it is possible to obtain a lithium ion battery having good binding properties between the active materials and between the active material and the current collector and improving the charge / discharge cycle characteristics using the water dispersion binder. Moreover, the lithium ion battery obtained using the slurry for lithium ion battery negative electrodes of this invention has a large charge / discharge capacity compared with what was produced using the conventional aqueous binder, and is excellent in charge / discharge efficiency.
  • Example 1 shows the cycle characteristics in Example 1 and Comparative Example 1. It is a schematic diagram which shows the lithium ion battery which concerns on one Embodiment of this invention.
  • the negative electrode material used for the slurry according to one embodiment of the present invention includes, as an active material, particles A containing at least one element selected from the group consisting of Si, Sn, Ge, and In.
  • the particle A which is one of the constituent materials of the negative electrode material according to one embodiment of the present invention contains at least one element selected from the group consisting of Si, Sn, Ge and In. Of these elements, Si or Sn is preferable.
  • the particle A may be composed of a simple substance of these elements or a compound containing these elements, or may be composed of a compound, a mixture, a eutectic or a solid solution containing at least two of these elements. Good.
  • the particle A may be a particle in which a plurality of particles are aggregated. Examples of the shape of the particle A include a block shape, a scale shape, a spherical shape, and a fibrous shape. Of these, spherical or lump shape is preferable.
  • the particles A may be secondary particles.
  • the substance containing Si element include an alloy of Si element and alkaline earth metal; an alloy of Si and transition metal; an alloy of Si and metalloid; Si, Be, Ag, Al, Au, Cd. , Ga, In, Sb or Zn solid solution alloy or eutectic alloy; CaSi, CaSi 2 , Mg 2 Si, BaSi 2 , Cu 5 Si, FeSi, FeSi 2 , CoSi 2 , Ni 2 Si, NiSi 2 , MnSi, MnSi 2, MoSi 2, CrSi 2, Cr 3 Si, TiSi 2, Ti5Si 3, NbSi 2, NdSi 2, CeSi 2, WSi 2, W 5 Si 3, TaSi 2, Ta 5 Si 3, PtSi, V 3 Silicides such as Si, VSi 2 , PdSi, RuSi, RhSi; SiO 2 , SiC, Si 3 N 4 and the like can be mentioned.
  • Examples of the substance containing Sn element include tin alone, tin alloy, tin oxide, tin sulfide, tin halide, and stannate.
  • Specific examples of the substance containing the Sn element include an alloy of Sn and Zn, an alloy of Sn and Cd, an alloy of Sn and In, an alloy of Sn and Pb; SnO, SnO 2 , Mb 4 SnO 4 (Mb Represents a metal element other than Sn.)
  • Tin tin sulfide such as SnS, SnS 2 , Mb 2 SnS 3 ; SnX 2 , SnX 4 , MbSnX 4 (Mb represents a metal element other than Sn.
  • X Tin halides such as MgSn, Mg 2 Sn, FeSn, FeSn 2 , MoSn, and MoSn 2 .
  • the particle A has a 90% particle diameter (D 90 ) in a volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution analyzer, preferably 500 nm or less, more preferably 450 nm or less. In the measurement of the particle size distribution, the particle size of secondary particles is also included.
  • the particles A preferably have a particle size distribution that does not substantially contain particles having a size of 1 ⁇ m or more. The larger the particle size, the more easily the particles A are crushed due to contraction and expansion during charge / discharge, and an increase in internal resistance and a decrease in charge / discharge cycle characteristics are likely to occur.
  • the particle A has a 10% particle diameter (D 10 ) in a volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution analyzer, preferably 80 nm or more, more preferably 100 nm or more.
  • the particle A has a 50% particle size (D 50 ) in a volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution analyzer, preferably 100 to 400 nm, more preferably 200 to 300 nm.
  • pulverizer examples include a hammer mill, a jaw crusher, and a collision pulverizer.
  • classification can be performed by airflow classification and / or sieving.
  • airflow classifier examples include a turbo cryfire and a turboplex.
  • the negative electrode material preferably further includes carbon particles C containing a graphite material in addition to the particles A described above.
  • the carbon particles C are contained in an amount of preferably 250 to 2000 parts by mass, more preferably 250 to 500 parts by mass with respect to 100 parts by mass of the particles A.
  • the carbon particles C have a 50% particle diameter (D 50 ) in a volume-based cumulative particle size distribution of preferably 2 to 40 ⁇ m, more preferably 2 to 15 ⁇ m.
  • D 50 particle diameter
  • the particle size of secondary particles is also included.
  • the volume-based cumulative particle size distribution can be measured by a laser diffraction particle size distribution measuring machine.
  • the carbon particles C preferably have a particle size distribution in which 90% or more of particles having a particle diameter in the range of 1 to 50 ⁇ m are present on a number basis, and 90% or more of particles having a particle diameter in the range of 5 to 50 ⁇ m on the number basis It is preferable that the particle size distribution exists.
  • the carbon particles C have a 10% particle diameter (D 10 ) in a volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution analyzer, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
  • the carbon particles C may be particles composed only of graphite material (that is, graphite particles), or particles composed of graphite particles and a carbonaceous layer existing on the surface thereof (that is, carbon-coated graphite particles).
  • carbon-coated graphite particles or particles obtained by attaching carbon fibers to graphite particles may be used.
  • the graphite material examples include artificial graphite, pyrolytic graphite, expanded graphite, natural graphite, scaly graphite, and scaly graphite. Of these, artificial graphite is preferred.
  • the carbonaceous layer on the surface of the carbon-coated graphite particles has a peak intensity (I D ) derived from an amorphous component in the range of 1300 to 1400 cm ⁇ 1 and a range of 1580 to 1620 cm ⁇ 1 as measured by Raman spectroscopy.
  • the ratio I D / I G (R value) with the peak intensity (I G ) derived from the graphite component is preferably 0.1 or more, more preferably 0.2 or more.
  • Carbon-coated graphite particles can be produced according to a known method.
  • the graphite particles are agitated while spraying an organic compound such as an isotropic pitch, an anisotropic pitch, a resin, a resin precursor, or a monomer to the finely divided graphite particles.
  • the graphite particles and an organic compound such as pitch or phenol resin are mixed and mechanochemical treatment is performed using a device such as a hybridizer.
  • the adhesion amount of the organic compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the graphite particles.
  • the graphite particles to which the organic compound is adhered are preferably heat-treated at 200 ° C. or higher and 2000 ° C. or lower, more preferably 500 ° C. or higher and 1500 ° C. or lower. Carbon-coated graphite particles are obtained by this heat treatment.
  • the carbon fiber examples include vapor grown carbon fiber, petroleum pitch-based carbon fiber, coal pitch-based carbon fiber, and PAN-based carbon fiber. Of these, vapor grown carbon fiber is preferred.
  • the method for binding (adhering) the carbon fibers to the surface of the graphite particles or carbon-coated graphite particles For example, by mixing carbon fiber with an organic compound, attaching it to graphite particles or carbon-coated graphite particles, and then performing a heat treatment, the carbon fiber can be bound to the carbonaceous layer in the process of forming the carbonaceous layer. it can.
  • the amount of the carbon fiber is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the graphite particles.
  • the binder used in the slurry according to one embodiment of the present invention is ethylene containing, as essential components, a styrene, an ethylenically unsaturated carboxylic acid ester, an ethylenically unsaturated carboxylic acid, and a crosslinking agent having at least one ethylenically unsaturated group.
  • the binder is contained in an amount of preferably 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the negative electrode material.
  • the reason why styrene is an essential component in the polymer B is to develop binding properties between the negative electrode materials.
  • the amount of styrene used is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on the total ethylenically unsaturated monomer.
  • the glass transition temperature (Tg) of the polymer B falls within an appropriate range, and cracking is unlikely to occur in the negative electrode obtained from application of the slurry for negative electrode.
  • the total ethylenically unsaturated monomer does not include a surfactant having an ethylenically unsaturated group described later.
  • the ethylenically unsaturated carboxylic acid ester used as the raw material of the polymer B preferably contains an ethylenically unsaturated carboxylic acid ester having a polar group such as a hydroxy group or a glycidyl group.
  • a polar group such as a hydroxy group or a glycidyl group.
  • Specific examples include 2-hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, glycidyl acrylate, and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferred.
  • the amount of the ethylenically unsaturated carboxylic acid ester having a polar group is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total ethylenically unsaturated monomers. It is.
  • the ethylenically unsaturated carboxylic acid having a polar group in an amount of 0.1% by mass or more, the polymerization stability or mechanical stability is improved, and the swelling resistance of the dry film against the electrolytic solution is improved.
  • the content is 10% by mass or less, the binding property between the negative electrode materials and between the negative electrode material and the current collector tends to be improved.
  • the ethylenically unsaturated carboxylic acid ester may include those other than the above (referred to as other ethylenically unsaturated carboxylic acid ester).
  • n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and isobornyl (meth) acrylate are preferred from the viewpoint of ease of emulsion polymerization and durability.
  • the amount of other ethylenically unsaturated carboxylic acid ester used is preferably 25 to 85% by mass, more preferably 30 to 80% by mass, based on the total ethylenically unsaturated monomer.
  • amount of the ethylenically unsaturated carboxylic acid ester used is 25% by mass or more, flexibility and heat resistance of the obtained negative electrode tend to be improved, and when it is 85% by mass or less, the negative electrode materials and the negative electrode material and the current collector are collected. There is a tendency to improve the binding with the body.
  • ethylenically unsaturated carboxylic acid Specific examples of the ethylenically unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, or unsaturated dicarboxylic acids thereof. Of these, and among them, acrylic acid and itaconic acid are preferable. These ethylenically unsaturated carboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the ethylenically unsaturated carboxylic acid used is such that the acid value of the polymer B is preferably 6 to 100, more preferably 6 to 50.
  • the acid value is 6 or more, emulsion polymerization stability or mechanical stability is improved, and the heat resistance of the obtained negative electrode tends to be improved. Further, lithium ion, which is a negative electrode material, is occluded / released. Affinity and binding force with particles A other than carbon containing possible elements are improved.
  • the acid value is 100 or less, particularly when a material containing carbon particles C is used as the negative electrode material, the binding properties between the negative electrode materials and between the negative electrode material and the current collector tend to be improved.
  • the acid value is the number of mg of potassium hydroxide necessary to neutralize the carboxylic acid present in 1 g of resin. The acid value is measured according to JIS K5601-2-1 and can be obtained by the following formula (1).
  • Acid value (valence of carboxylic acid) ⁇ (mass% of ethylenically unsaturated carboxylic acid) ⁇ (molecular weight of ethylenically unsaturated carboxylic acid) ⁇ 56.1 ⁇ 1000 (1)
  • the amount of the ethylenically unsaturated carboxylic acid that provides the desired acid value varies depending on the type and ratio of the ethylenically unsaturated monomer used in the production of the polymer B.
  • the amount is preferably 1 to 10% by mass, more preferably 1 to 5% by mass based on the body.
  • Cross-linking agent Furthermore, in order to further improve the swelling resistance of the obtained lithium ion battery negative electrode with respect to the electrolyte solvent, a cross-linking agent having at least one ethylenically unsaturated bond is used in the production of the polymer B.
  • the cross-linking agent may be one having a group that reacts with a carboxyl group or one having two or more ethylenically unsaturated groups.
  • crosslinking agent monomers having two or more ethylenically unsaturated groups such as divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, triallyl cyanurate, vinyltrimethoxysilane
  • examples thereof include silane coupling agents having an ethylenically unsaturated group such as vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltriethoxysilane.
  • divinylbenzene is preferable.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the amount of the crosslinking agent used is preferably 0.1 to 5% by mass and more preferably 0.1 to 3% by mass with respect to the total ethylenically unsaturated monomer.
  • the amount of the crosslinking agent used is 0.1% by mass or more, the swelling resistance of the dry film to the electrolytic solution tends to be improved, and when it is 5% by mass or less, the emulsion polymerization stability is improved. The adhesion between the negative electrode material and the current collector tends to be improved.
  • a compound having at least one polymerizable ethylenically unsaturated group may be used as the ethylenically unsaturated monomer as long as the object of the present invention is not impaired.
  • the compound having a polar group such as an amide group and a nitrile group include (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylonitrile, N-vinylpyrrolidone and the like. Vinyl acetate and vinyl propionate can also be used.
  • a compound having a mercapto group, thioglycolic acid and its ester, ⁇ -mercaptopropionic acid and its ester may be used for adjusting the molecular weight.
  • the Tg of the polymer B is preferably 30 ° C. or lower.
  • Tg is 30 ° C. or lower, cracks occur in the negative electrode obtained from the application of the slurry for negative electrode, which is not preferable.
  • the above polymer B has a dry film swelling ratio of preferably 300% or less, more preferably 5% to 200%, with respect to a solvent of propylene carbonate / diethyl carbonate electrolyte at 60 ° C. It is preferable that the swelling resistance of the dry film with respect to the electrolytic solution at 60 ° C. is 300% or less because charge / discharge high temperature cycle characteristics at high temperatures are lowered.
  • the polymer B used for the slurry is obtained by polymerizing the above ethylenically unsaturated monomer. Usually, the polymerization is carried out by emulsion polymerization using water as a dispersion medium in the presence of a surfactant to obtain an aqueous emulsion containing the polymer B.
  • the reactive surfactant used in the polymerization is not particularly limited as long as it is a normal anionic surfactant or nonionic surfactant.
  • the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid salt, and the like.
  • Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Examples thereof include oxyethylene alkyl phenyl ether, polyoxyethylene polycyclic finyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • Preferred surfactants include those having an ethylenically unsaturated group, and more preferred are those represented by the following formulas (2) to (5).
  • R is an alkyl group, and n is an integer of 10 to 40
  • n is an integer of 10 to 12
  • m is an integer of 10 to 40
  • R is an alkyl group, M is NH 4 or Na
  • the amount of the surfactant used is not particularly limited.
  • a surfactant having an ethylenically unsaturated group it is preferably 0.3 to 3% by mass based on the total ethylenically unsaturated monomer.
  • the amount of the surfactant used is 0.3% by mass or more, the polymerization stability is improved, and since the particle system of the obtained aqueous emulsion is small, the resin emulsion does not easily precipitate.
  • the amount of the surfactant used is 3% by mass or less, the adhesion between the negative electrode material and the current collector is improved, which is preferable.
  • the radical polymerization initiator used in the polymerization may be a known and conventional one, and examples thereof include persulfate and peroxide.
  • examples of the persulfate include ammonium persulfate and potassium persulfate
  • examples of the peroxide include hydrogen peroxide and organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide.
  • these polymerization initiators may be used in combination with a reducing agent such as sodium bisulfite, Rongalite, and ascorbic acid for redox polymerization.
  • the polymerization method As the polymerization method, a polymerization method charged in a batch, a polymerization method while continuously supplying each component, and the like are applied.
  • the polymerization is usually carried out at a temperature of 30 to 90 ° C. with stirring.
  • the pH of the aqueous emulsion is adjusted to improve the polymerization stability, mechanical stability, and chemical stability during polymerization. be able to.
  • ammonia triethylamine, ethanolamine, caustic soda and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the binder may contain components other than the polymer B described above.
  • other components include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, and casein.
  • the amount of these other binder components used is preferably 5 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the polymer B.
  • the slurry contains a dispersion medium containing water.
  • the water contained in the dispersion medium is usually derived from the aqueous emulsion containing the above-mentioned polymer B, but is not limited thereto, and the amount can be appropriately adjusted depending on the viscosity of the slurry.
  • the dispersion medium may contain an organic solvent miscible with water as long as the object of the present invention is not impaired. Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, methanol, isopropyl alcohol, butanol, acetone, 2-butanone and cyclohexanone. When these organic solvents are used, the amount used is preferably 1 to 50% by mass, more preferably 1 to 20% by mass in the dispersion medium, and may not be used.
  • the slurry may contain a conductive aid.
  • the conductive auxiliary agent is not particularly limited as long as it has a function of imparting conductivity and electrode stability to the negative electrode (buffering action against volume change in insertion / extraction of lithium ions).
  • vapor grown carbon fiber for example, “VGCF” (registered trademark) manufactured by Showa Denko KK
  • conductive carbon for example, “Denka Black” (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd., “Super C65” manufactured by TIMCAL, “Super C45” TIMCAL And “KS6L” manufactured by TIMCAL).
  • the amount of the conductive auxiliary is preferably 10 to 150 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the negative electrode material.
  • the slurry for a lithium ion battery electrode according to an embodiment of the present invention is obtained by mixing the above-described components.
  • the well-known method used for manufacture of a lithium ion battery can be used.
  • a method of adding a negative electrode material and a conductive additive to the above-described aqueous emulsion containing the polymer B and further dispersing, dissolving, or kneading can be mentioned.
  • a negative electrode for a lithium ion battery includes a current collector and a negative electrode mixture layer.
  • the thickness of the negative electrode for a lithium ion battery is usually 50 to 200 ⁇ m.
  • the current collector for example, a metal foil made of nickel, copper, aluminum, or an alloy thereof can be used.
  • the metal foil may be a normal foil without holes, or a foil with holes such as a punching metal foil, a metal mesh, or a porous foil.
  • a known conductive layer for example, Japanese Patent Application Laid-Open No. 2006-32902, Japanese Patent Application Laid-Open No. 2008-60060, Japanese Patent Application Laid-Open No.
  • the negative electrode mixture layer includes the above-described negative electrode material, a binder, and, if necessary, a conductive additive.
  • the composition ratio is preferably 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, and preferably 10 to 150 parts by weight, more preferably 50 to 100 parts by weight of the conductive auxiliary, with respect to 100 parts by weight of the negative electrode material. Part by mass.
  • the negative electrode for a lithium ion battery has other layers such as a protective layer (see, for example, JP-A-2008-226666, JP-A-2009-181756, and JP-A-2010-244818) as necessary. You may do it.
  • the negative electrode for a lithium ion battery can be obtained, for example, by applying the above slurry to a current collector and drying it.
  • the method for applying the slurry is not particularly limited.
  • the thickness of the negative electrode for a lithium ion battery described above can be adjusted by the amount of slurry applied.
  • after drying the slurry for negative electrodes it can also adjust by carrying out pressure molding.
  • the pressure molding method include molding methods such as roll pressing and press pressing.
  • the pressure during pressure molding is preferably about 100 MPa to about 300 MPa (about 1 to 3 ton / cm 2 ).
  • a lithium ion battery according to an embodiment of the present invention has at least one selected from the group consisting of a non-aqueous electrolyte and a non-aqueous polymer electrolyte, a positive electrode, and the above-described negative electrode.
  • a sheet conventionally used for lithium ion batteries specifically, a sheet containing a positive electrode active material can be used.
  • the positive electrode active material include LiNiO 2 , LiCoO 2 , LiMn 2 O 4 , LiNi 0.34 Mn 0.33 Co 0.33 O 2 , and LiFePO 4 .
  • the non-aqueous electrolyte and non-aqueous polymer electrolyte used for the lithium ion battery are not particularly limited.
  • a lithium salt such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , CH 3 SO 3 Li, CF 3 SO 3 Li, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene Organic electrolytes dissolved in non-aqueous solvents such as carbonate, butylene carbonate, acetonitrile, propyronitrile, dimethoxyethane, tetrahydrofuran, and ⁇ -butyrolactone; polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, etc.
  • examples thereof include a gel polymer electrolyte and a solid polymer electrolyte containing a polymer having an ethylene oxide bond.
  • a small amount of a substance that causes a decomposition reaction when the lithium ion battery is initially charged may be added to the electrolytic solution.
  • the substance include vinylene carbonate, biphenyl, propane sultone, and the like.
  • the addition amount is preferably 0.01 to 5% by mass.
  • a lithium ion battery can be provided with a separator between the positive electrode and the negative electrode.
  • the separator include non-woven fabrics, cloths, microporous films, or a combination thereof, mainly composed of polyolefins such as polyethylene and polypropylene.
  • a known inorganic particle layer (see, for example, Japanese Patent Application Laid-Open No. 2001-319634, International Publication Pamphlet WO 2007/066768, Japanese Patent Application Laid-Open No. 2008-126996, Japanese Patent Application Laid-Open No. 2008-123988) is provided on the surface of the separator. It may be.
  • FIG. 2 shows a lithium ion battery according to an embodiment of the present invention.
  • a lithium ion battery 10 shown here is a separator that separates a negative electrode 1, a positive electrode 2 opposite to the negative electrode 1, and the negative electrode 1 and the positive electrode 2. 3 and a container 4 for housing them.
  • the negative electrode 1 includes a current collector 5 and a negative electrode mixture layer 6 provided on the surface of the current collector 5.
  • Reference numeral 7 denotes an electrolyte injected into the container 4.
  • the container 4 includes a main body 4a that houses the negative electrode 1, the positive electrode 2, and the separator 3, and a lid 4b that closes the main body 4a.
  • aqueous emulsion had a non-volatile content of 45.5%, a viscosity of 3000 mPa ⁇ s, a pH of 6.5, and the acid value of the polymer B was 18.95.
  • Si fine particles Alfa Aesar, CAS7440-21-3, product number 44384, primary particle size of 50 nm or less
  • carbon particles C carbon-coated graphite particles were prepared by the following procedure. Petroleum coke was pulverized to an average particle size of 5 ⁇ m. This was heat-treated at 3000 ° C. in an Atchison furnace to obtain graphite particles. Next, petroleum pitch was mixed with the graphite particles at a mass ratio of 1%, and the petroleum pitch was adhered to the surface of the graphite particles. Then, it carbonized at 1100 degreeC by inert atmosphere.
  • BET specific surface area is 2.6 m 2 / g
  • d002 is 0.3361 nm
  • LC is 59 nm
  • 10% particle diameter (D10) is 2.3 ⁇ m
  • 50% particle diameter (D50) is 5.7 ⁇ m
  • Carbon-coated graphite particles having a 90% particle diameter (D90) of 11.8 ⁇ m and I D / I G (R value) of 0.77 were obtained.
  • 0.375 g of Si fine particles and 1.125 g of carbon-coated graphite particles C were taken and mixed in a mortar to obtain a negative electrode material in which Si fine particles and graphite particles were combined.
  • a binder mixture was prepared by adding carboxymethyl cellulose (manufactured by Daicel, product number: 1380) to the aqueous emulsion so that the solid mass ratio was 1: 1, and mixing them.
  • TIMCAL carbon black (SUPER C45) was prepared as a conductive aid.
  • the obtained slurry for a lithium ion battery negative electrode was applied on a copper foil such that the negative electrode mixture layer had a thickness of 120 ⁇ m. This was dried at 70 ° C. for 3 hours. A sheet piece having a diameter of 16 mm was punched out from the obtained sheet, and pressed at 1.5 ton / cm 2 with a POWER SAMPLE HYDRAULIC PRESS / BRE-3 manufactured by Maekawa Tester, Ltd., to obtain a negative electrode. There was no transfer on the negative electrode after pressing.
  • a 2320 type coin cell (diameter 23 mm, thickness 2.0 mm) was prepared. A foil piece having a diameter of 20 mm was punched from a lithium foil having a thickness of 0.1 mm. This was used as a positive electrode. The positive electrode was lightly pressure-bonded to a SUS spacer with a punch. This was put in a coin cell cap. Next, an electrolytic solution was injected into the coin cell.
  • the electrolytic solution was obtained by dissolving electrolyte LiPF 6 at a concentration of 1 mol / L in a solvent in which ethylene carbonate, methyl ethyl carbonate, and diethyl carbonate were mixed at a volume ratio of 3: 5: 2. It is.
  • aqueous emulsion In the synthesis of the aqueous emulsion, the same operation as in the synthesis of the aqueous emulsion described in Example 1 was performed except that 250 parts of styrene and 220 parts of 2-ethylhexyl acrylate were changed to 320 parts of styrene and 150 parts of 2-ethylhexyl acrylate. It was.
  • the obtained aqueous emulsion had a nonvolatile content of 44.9%, a viscosity of 2900 mPa ⁇ s, a pH of 6.5, and the acid value of the polymer B was 18.95.
  • the preparation of the Si-graphite composite negative electrode material, the production of the negative electrode, the production of the evaluation battery, and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 A negative electrode was produced in the same manner as in Example 1 except that the aqueous emulsion was changed to SBR (manufactured by Zeon Corporation, product number: BM400B) in Example 1, and an evaluation battery was produced and a charge / discharge test was performed. The results are shown in Table 1 and FIG. After pressing, the negative electrode sheet adhered to the press plate, and the negative electrode mixture layer was slightly transferred.
  • SBR manufactured by Zeon Corporation, product number: BM400B
  • the binders in Examples 1 and 2 also show good binding properties with respect to the alloy-based negative electrode.
  • the evaluation batteries using the binders in Example 1 and Example 2 have high initial charge / discharge amounts and high initial efficiency, and excellent cycle characteristics at the 50th cycle.

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Abstract

L'invention porte sur une bouillie qui contient : un matériau d'électrode négative pour batteries lithium-ion, qui contient, en tant que matériau actif, des particules (A) qui contiennent au moins un élément sélectionné parmi le groupe contenant Si, Sn, Ge et In ; un liant qui contient un polymère (B) qui est obtenu par polymérisation d'un monomère à insaturation éthylénique en présence d'un agent de surface réactif, ledit monomère à insaturation éthylénique contenant du styrène, un ester d'acide carboxylique à insaturation éthylénique, un acide carboxylique à insaturation éthylénique et un agent de réticulation en tant qu'ingrédients essentiels ; et un support de dispersion qui contient de l'eau.
PCT/JP2013/071116 2012-08-08 2013-08-05 Bouillie et électrode négative pour batteries lithium-ion WO2014024823A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014112618A1 (fr) * 2013-01-21 2014-07-24 昭和電工株式会社 Liant pour électrodes de batterie secondaire au lithium-ion, bouillie, électrode, et batterie secondaire au lithium-ion
WO2015045522A1 (fr) * 2013-09-27 2015-04-02 昭和電工株式会社 Composition de liant pour des électrodes de batterie non aqueuse, boue pour électrodes de batterie non aqueuse, électrode de batterie non aqueuse, batterie non aqueuse
WO2017056984A1 (fr) * 2015-09-28 2017-04-06 Ｎｅｃエナジーデバイス株式会社 Procédé de fabrication d'électrode négative pour piles rechargeables lithium-ion
WO2017094712A1 (fr) * 2015-11-30 2017-06-08 日本電気株式会社 Batterie rechargeable au lithium-ion
CN109860596A (zh) * 2018-12-27 2019-06-07 上海三瑞高分子材料股份有限公司 一种锂电池用硅基负极浆料及其制备方法
US10707519B2 (en) 2015-11-30 2020-07-07 Nec Corporation Lithium ion secondary battery
JP2021153060A (ja) * 2017-03-28 2021-09-30 東亞合成株式会社 非水電解質二次電池電極用バインダー
JP2022169616A (ja) * 2017-05-24 2022-11-09 昭和電工株式会社 水系バインダー樹脂組成物、非水系電池用スラリー、非水系電池電極、非水系電池セパレータ、及び非水系電池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004214182A (ja) * 2002-12-17 2004-07-29 Mitsubishi Chemicals Corp 非水系電解液二次電池用負極およびそれを用いた非水系電解液二次電池
JP2007115671A (ja) * 2005-09-22 2007-05-10 Matsushita Electric Ind Co Ltd リチウムイオン二次電池用負極およびそれを用いたリチウムイオン二次電池
JP2010287470A (ja) * 2009-06-12 2010-12-24 Panasonic Corp 非水二次電池およびその製造方法
JP2011243464A (ja) * 2010-05-19 2011-12-01 Showa Denko Kk リチウムイオン二次電池電極用バインダー、これら電極用バインダーを用いて得られるスラリー、これらスラリーを用いて得られる電極およびこれら電極を用いて得られるリチウムイオン二次電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3744462B2 (ja) * 2002-05-08 2006-02-08 ソニー株式会社 非水電解質電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004214182A (ja) * 2002-12-17 2004-07-29 Mitsubishi Chemicals Corp 非水系電解液二次電池用負極およびそれを用いた非水系電解液二次電池
JP2007115671A (ja) * 2005-09-22 2007-05-10 Matsushita Electric Ind Co Ltd リチウムイオン二次電池用負極およびそれを用いたリチウムイオン二次電池
JP2010287470A (ja) * 2009-06-12 2010-12-24 Panasonic Corp 非水二次電池およびその製造方法
JP2011243464A (ja) * 2010-05-19 2011-12-01 Showa Denko Kk リチウムイオン二次電池電極用バインダー、これら電極用バインダーを用いて得られるスラリー、これらスラリーを用いて得られる電極およびこれら電極を用いて得られるリチウムイオン二次電池

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6007263B2 (ja) * 2013-01-21 2016-10-12 昭和電工株式会社 リチウムイオン二次電池電極用バインダー、スラリー、電極、及びリチウムイオン二次電池
JPWO2014112618A1 (ja) * 2013-01-21 2017-01-19 昭和電工株式会社 リチウムイオン二次電池電極用バインダー、スラリー、電極、及びリチウムイオン二次電池
WO2014112618A1 (fr) * 2013-01-21 2014-07-24 昭和電工株式会社 Liant pour électrodes de batterie secondaire au lithium-ion, bouillie, électrode, et batterie secondaire au lithium-ion
US9947929B2 (en) 2013-09-27 2018-04-17 Showa Denko K.K. Binder composition for nonaqueous battery electrodes, slurry for nonaqueous battery electrodes, nonaqueous battery electrode, and nonaqueous battery
WO2015045522A1 (fr) * 2013-09-27 2015-04-02 昭和電工株式会社 Composition de liant pour des électrodes de batterie non aqueuse, boue pour électrodes de batterie non aqueuse, électrode de batterie non aqueuse, batterie non aqueuse
JPWO2015045522A1 (ja) * 2013-09-27 2017-03-09 昭和電工株式会社 非水系電池電極用バインダー組成物、非水系電池電極用スラリー、非水系電池電極及び非水系電池
CN108028365A (zh) * 2015-09-28 2018-05-11 Nec能源元器件株式会社 用于制备锂离子二次电池用负极的方法
WO2017056984A1 (fr) * 2015-09-28 2017-04-06 Ｎｅｃエナジーデバイス株式会社 Procédé de fabrication d'électrode négative pour piles rechargeables lithium-ion
JPWO2017056984A1 (ja) * 2015-09-28 2018-07-12 Ｎｅｃエナジーデバイス株式会社 リチウムイオン二次電池用負極の製造方法
US20180233735A1 (en) * 2015-09-28 2018-08-16 Nec Energy Devices, Ltd. Method for producing negative electrode for lithium ion secondary batteries
WO2017094712A1 (fr) * 2015-11-30 2017-06-08 日本電気株式会社 Batterie rechargeable au lithium-ion
CN108292779A (zh) * 2015-11-30 2018-07-17 日本电气株式会社 锂离子二次电池
JPWO2017094712A1 (ja) * 2015-11-30 2018-09-13 日本電気株式会社 リチウムイオン二次電池
US10707519B2 (en) 2015-11-30 2020-07-07 Nec Corporation Lithium ion secondary battery
US10756337B2 (en) 2015-11-30 2020-08-25 Nec Corporation Lithium ion secondary battery
JP2021153060A (ja) * 2017-03-28 2021-09-30 東亞合成株式会社 非水電解質二次電池電極用バインダー
JP2022169616A (ja) * 2017-05-24 2022-11-09 昭和電工株式会社 水系バインダー樹脂組成物、非水系電池用スラリー、非水系電池電極、非水系電池セパレータ、及び非水系電池
JP7444206B2 (ja) 2017-05-24 2024-03-06 株式会社レゾナック 非水系電池セパレータ用スラリーおよび非水系電池セパレータ
CN109860596A (zh) * 2018-12-27 2019-06-07 上海三瑞高分子材料股份有限公司 一种锂电池用硅基负极浆料及其制备方法

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