WO2015133154A1 - Composition de liant pour batterie secondaire lithium-ion, composition de bouillie pour électrode de batterie secondaire lithium-ion, composition de bouillie pour film poreux de batterie secondaire lithium-ion, électrode pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion - Google Patents

Composition de liant pour batterie secondaire lithium-ion, composition de bouillie pour électrode de batterie secondaire lithium-ion, composition de bouillie pour film poreux de batterie secondaire lithium-ion, électrode pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion Download PDF

Info

Publication number
WO2015133154A1
WO2015133154A1 PCT/JP2015/001247 JP2015001247W WO2015133154A1 WO 2015133154 A1 WO2015133154 A1 WO 2015133154A1 JP 2015001247 W JP2015001247 W JP 2015001247W WO 2015133154 A1 WO2015133154 A1 WO 2015133154A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium ion
ion secondary
secondary battery
slurry composition
electrode
Prior art date
Application number
PCT/JP2015/001247
Other languages
English (en)
Japanese (ja)
Inventor
園部　健矢
豊 丸橋
順一 浅野
政憲 渋谷
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2016506152A priority Critical patent/JP6536564B2/ja
Publication of WO2015133154A1 publication Critical patent/WO2015133154A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a binder composition for a lithium ion secondary battery, and particularly to a binder composition that can be suitably used for forming a negative electrode of a lithium ion secondary battery.
  • Lithium ion secondary batteries are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. Therefore, in recent years, improvement of battery members such as electrodes and separators has been studied for the purpose of further improving the performance of lithium ion secondary batteries.
  • an electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer is formed, for example, by applying a slurry composition obtained by dispersing an electrode active material and a binder composition containing a binder in a dispersion medium on a current collector and drying it. Is done.
  • the battery capacity of the lithium ion secondary battery can be increased by adopting a silicon-based negative electrode active material as an electrode active material (negative electrode active material) for the negative electrode.
  • a silicon-based negative electrode active material as an electrode active material (negative electrode active material) for the negative electrode.
  • the silicon-based negative electrode active material has a high theoretical capacity and can increase the battery capacity of the lithium ion secondary battery, it greatly expands and contracts with charge and discharge. Accordingly, in a negative electrode using a silicon-based negative electrode active material, deterioration of the silicon-based negative electrode active material itself (that is, structural destruction of the silicon-based negative electrode active material) due to expansion and contraction of the silicon-based negative electrode active material due to repeated charge / discharge. Miniaturization) and / or the electrode plate structure is broken, and the conductive path in the electrode is broken. That is, a lithium ion secondary battery including a negative electrode using a silicon-based negative electrode active material has a problem that cycle characteristics are deteriorated due to expansion and contraction of the silicon-based negative electrode active material.
  • a binder composition containing a predetermined non-crosslinked polyacrylic acid as a binder is used to absorb and relax the expansion and contraction of the silicon-based negative electrode active material.
  • a technique for suppressing a decrease in cycle characteristics of an ion secondary battery has been proposed (see, for example, Patent Document 1).
  • the conventional binder composition containing a predetermined non-crosslinked polyacrylic acid as a binder cannot sufficiently absorb and relax the expansion and contraction of the negative electrode active material, and the cycle characteristics of the lithium ion secondary battery It was not possible to sufficiently suppress the decrease in the above.
  • the slurry composition prepared using the binder composition There is a possibility that the stability of the product may be lowered and the productivity of the negative electrode may be lowered.
  • a binder having high rigidity is used, cracking of the binder and peeling from the negative electrode active material are likely to occur in the negative electrode prepared using the binder composition, and as a result, the negative electrode is provided.
  • gas generation that is presumed to be caused by cracking and peeling of the binder may increase, and the high temperature storage characteristics of the lithium ion secondary battery may deteriorate.
  • the present invention ensures the stability of the slurry composition and the productivity of the electrode even when used in combination with an electrode active material that expands and contracts greatly with charge and discharge of a silicon-based negative electrode active material.
  • it aims at providing the binder composition for lithium ion secondary batteries which can exhibit the cycling characteristics and high temperature storage characteristic which were excellent in the lithium ion secondary battery.
  • the present inventor has intensively studied for the purpose of solving the above problems. Then, the inventor obtained by copolymerizing an ethylenically unsaturated carboxylic acid and / or a salt thereof and a polyfunctional compound having a polyoxyalkylene structure and two or more ethylenically unsaturated bonds at a predetermined ratio.
  • a binder composition containing a copolymer as a binder, excellent cycle characteristics and high-temperature storage characteristics are ensured for lithium ion secondary batteries while ensuring the stability of the slurry composition and the productivity of the electrodes. It was found that it can be demonstrated.
  • the binder composition containing the copolymer as a binder is a protective layer (referred to as a “heat-resistant layer”) comprising a porous film for a lithium ion secondary battery on a substrate such as an electrode or a separator. It has been found that it can also be suitably used in the formation. And this inventor completed this invention based on the said new knowledge.
  • the binder composition for a lithium ion secondary battery of the present invention comprises at least one of an ethylenically unsaturated carboxylic acid and a salt thereof.
  • a copolymer obtained by polymerizing a monomer composition comprising an ethylenically unsaturated carboxylic acid compound and a polyfunctional compound having a polyoxyalkylene structure and two or more ethylenically unsaturated bonds In the monomer composition, the ratio of the ethylenically unsaturated carboxylic acid compound in all monomers is 70.0% by mass or more and 99.9% by mass or less, and the ratio of the polyfunctional compound in all monomers.
  • Such a binder composition containing, as a binder, a copolymer obtained by polymerizing a monomer composition containing an ethylenically unsaturated carboxylic acid compound and a polyfunctional compound in a predetermined ratio is charged and discharged. Even when used in combination with an electrode active material that expands and contracts, the cycle characteristics and high-temperature storage of lithium ion secondary batteries are ensured while ensuring the stability of the slurry composition and the productivity of the electrode. The characteristics can be exhibited. Moreover, if the binder composition containing the above-mentioned copolymer as a binder is used, a porous membrane for a lithium ion secondary battery having excellent heat shrinkage can also be obtained.
  • the copolymer preferably contains a lithium carboxylate base. This is because when the copolymer contains a carboxylate lithium base (—COOLi), the stability of the slurry composition prepared using the binder composition is further improved. In addition, the battery characteristics (for example, initial coulomb efficiency, cycle characteristics, and high-temperature storage characteristics) of the lithium ion secondary battery produced using the binder composition are further improved.
  • the electrolyte solution swelling degree of the said copolymer is 5 mass% or more and 50 mass% or less of the binder composition for lithium ion secondary batteries of this invention. This is because if the degree of swelling of the electrolyte solution in the copolymer is 5 to 50% by mass, the cycle characteristics and high-temperature storage characteristics of a lithium ion secondary battery produced using the binder composition can be sufficiently improved.
  • the “electrolyte swelling degree” can be measured by using the measuring method described in the examples of the present specification.
  • the slurry composition for lithium ion secondary battery electrodes of this invention is either binder composition for lithium ion secondary batteries mentioned above. Materials and electrode active materials.
  • any of the above-described lithium ion secondary battery binder composition and electrode slurry containing a lithium ion secondary battery electrode slurry composition is used for forming an electrode mixture layer, electrode productivity is improved.
  • a lithium ion secondary battery that exhibits excellent cycle characteristics and high-temperature storage characteristics while ensuring is obtained.
  • the electrode active material is preferably a Si-containing material.
  • a Si-containing material As the electrode active material, a high-capacity lithium ion secondary battery can be obtained.
  • the slurry composition for lithium ion secondary battery porous films of this invention is the binder for lithium ion secondary batteries mentioned above. Including a composition and non-conductive particles.
  • the electrode for lithium ion secondary batteries of this invention is the slurry composition for lithium ion secondary battery electrodes mentioned above.
  • the electrode mixture layer prepared by using is provided on a current collector.
  • the present invention aims to advantageously solve the above-mentioned problems, and the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and at least one of the positive electrode and the negative electrode Is the electrode for a lithium ion secondary battery described above.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and at least one of the positive electrode and the negative electrode Is the electrode for a lithium ion secondary battery described above.
  • the lithium ion secondary battery of this invention is equipped with a positive electrode, a negative electrode, electrolyte solution, and a separator,
  • the said positive electrode, negative electrode, and separator At least one of them is provided with a porous film formed using the slurry composition for a lithium ion secondary battery porous film described above.
  • the positive electrode, the negative electrode, and the separator is provided with the porous film formed using the above-described slurry composition for a lithium ion secondary battery porous film, excellent cycle characteristics and high temperature storage are provided. A lithium ion secondary battery exhibiting characteristics can be obtained.
  • the lithium ion secondary battery exhibits excellent cycle characteristics and high temperature storage characteristics while ensuring the stability of the slurry composition and the productivity of the electrode. Can do.
  • the binder composition for lithium ion secondary batteries of this invention the porous film for lithium ion secondary batteries which is excellent in heat-resistant shrinkage can be provided.
  • the slurry composition for lithium ion secondary battery electrodes which exhibits the outstanding cycling characteristics and high temperature storage characteristic can be provided, ensuring the productivity of an electrode.
  • the present invention it is possible to provide a slurry composition for a porous membrane of a lithium ion secondary battery that exhibits excellent cycle characteristics and high temperature storage characteristics. Furthermore, according to this invention, the electrode for lithium ion secondary batteries which exhibits the outstanding cycling characteristics and high temperature storage characteristic can be provided. And according to this invention, the lithium ion secondary battery which is excellent in cycling characteristics and high temperature storage characteristics can be provided.
  • the binder composition for a lithium ion secondary battery of the present invention can be used when preparing a slurry composition for a lithium ion secondary battery electrode.
  • the slurry composition for lithium ion secondary battery electrodes of the present invention prepared using the binder composition for lithium ion secondary batteries of the present invention can be used when forming an electrode of a lithium ion secondary battery. it can.
  • the binder composition for lithium ion secondary batteries of this invention can be used when preparing the slurry composition for lithium ion secondary battery porous films.
  • the slurry composition for lithium ion secondary battery porous films of this invention prepared using the binder composition for lithium ion secondary batteries of this invention is a porous film on the electrode and separator of a lithium ion secondary battery. Can be used to produce a substrate with a porous membrane.
  • the binder composition for lithium ion secondary batteries of this invention contains a binder and a solvent.
  • the binder composition for a lithium ion secondary battery of the present invention comprises an ethylenically unsaturated carboxylic acid compound comprising at least one of an ethylenically unsaturated carboxylic acid and a salt thereof, a polyoxyalkylene structure and two or more ethylenic acids. It contains a copolymer obtained by polymerizing a monomer composition containing a polyfunctional compound having an unsaturated bond in a predetermined ratio as a binder.
  • the binder is formed by forming an electrode mixture layer on the current collector using the slurry composition for lithium ion secondary battery electrodes prepared using the binder composition for lithium ion secondary batteries of the present invention.
  • the component contained in the electrode mixture layer is a component that can be held so as not to be detached from the electrode mixture layer.
  • the binder was formed on a substrate such as an electrode or a separator using the slurry composition for a lithium ion secondary battery porous film prepared using the binder composition for a lithium ion secondary battery of the present invention.
  • the component contained in the porous membrane can be held so as not to be detached from the porous membrane.
  • the binder used for the binder composition for lithium ion secondary batteries of this invention is obtained by superposing
  • the binder composition for lithium ion secondary batteries of this invention may contain further polymers other than the said copolymer as a binder arbitrarily.
  • the binder composition for a lithium ion secondary battery of the present invention is a copolymer obtained by polymerizing a monomer composition containing a predetermined proportion of an ethylenically unsaturated carboxylic acid compound and a polyfunctional compound. Even if it is used for the production of an electrode slurry composition, an electrode and a lithium ion secondary battery in combination with an electrode active material that expands and contracts greatly with charge and discharge, it is contained.
  • the lithium ion secondary battery can exhibit excellent cycle characteristics and high-temperature storage characteristics while ensuring the stability of the product and the productivity of the electrodes.
  • the binder composition for a lithium ion secondary battery of the present invention contains the above copolymer, while ensuring the stability of the slurry composition for the porous film and the productivity of the substrate with the porous film, It is possible to provide a porous membrane for a lithium ion secondary battery having excellent heat shrinkage resistance.
  • the stability of the slurry composition for an electrode of the present invention, the productivity of the electrode, and the cycle characteristics and high-temperature storage characteristics of the lithium ion secondary battery are improved.
  • the reason for this is not clear, but is presumed to be due to the following reasons. That is, a copolymer obtained by polymerizing a monomer composition containing a predetermined proportion of an ethylenically unsaturated carboxylic acid compound and a polyfunctional compound is obtained by polymerizing only an ethylenically unsaturated carboxylic acid compound. Compared to polymers, it exhibits tough polymer properties.
  • the copolymer has a reasonably high rigidity due to the use of a predetermined amount of an ethylenically unsaturated carboxylic acid compound and the formation of a crosslinked structure via the ethylenically unsaturated bond of the polyfunctional compound, Appropriate flexibility is exhibited by the polyoxyalkylene structure of the polyfunctional compound. Therefore, according to the copolymer having a reasonably high rigidity, expansion and contraction of the electrode active material can be suppressed and deterioration of cycle characteristics can be suppressed.
  • the electrode slurry composition is secured while ensuring the stability of the electrode slurry composition by the interaction between the polymer chains such as the formation of a crosslinked structure via the ethylenically unsaturated bond of the polyfunctional compound.
  • the productivity of the electrode can be increased by increasing the solid content concentration of the slurry composition.
  • the binder composition for a lithium ion secondary battery of the present invention is used for the preparation of a slurry composition for a porous film and the formation of a porous film, the development of the tough polymer properties and the formation of a crosslinked structure, etc. It is surmised that the interaction between the polymer chains achieves improvement in the heat shrinkage resistance of the porous film, as well as ensuring the stability of the slurry composition for the porous film and the productivity of the substrate with the porous film.
  • the lithium ion secondary battery binder composition of the present invention is prepared as a porous film slurry composition and a porous film. It is presumed that the battery characteristics of the lithium ion secondary battery can be improved also when used for forming the battery.
  • the copolymer used as the binder of the binder composition for a lithium ion secondary battery of the present invention is obtained by polymerizing a monomer composition described in detail below. And this copolymer usually has a structural unit derived from a monomer contained in the monomer composition at a ratio similar to the abundance ratio of each monomer in the monomer composition. Contains.
  • the monomer composition used for preparing the copolymer contains, for example, a monomer, an additive such as a polymerization initiator, and a polymerization solvent. And a monomer composition contains an ethylenically unsaturated carboxylic acid compound and a polyfunctional compound in a predetermined ratio as a monomer. Specifically, the monomer composition has an ethylenic content of 70.0% by mass or more and 99.9% by mass or less when the amount of all monomers in the monomer composition is 100% by mass. A saturated carboxylic acid compound and a polyfunctional compound of 0.1% by mass or more and 30.0% by mass or less are contained. The monomer composition may optionally further contain, as a monomer, an ethylenically unsaturated carboxylic acid compound and another compound copolymerizable with the polyfunctional compound.
  • ethylenically unsaturated carboxylic acid compounds As the ethylenically unsaturated carboxylic acid compound, at least one of an ethylenically unsaturated carboxylic acid and a salt thereof can be used.
  • the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
  • the ethylenically unsaturated carboxylate include sodium salts, potassium salts and lithium salts of ethylenically unsaturated carboxylic acids.
  • ethylenically unsaturated carboxylic acid and its salt may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • examples of the ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic. Acid, ⁇ -diaminoacrylic acid and the like.
  • examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, diacrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, and the like.
  • examples of ethylenically unsaturated dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, diphenyl maleate, nonyl maleate, decyl maleate , Dodecyl maleate, octadecyl maleate, fluoroalkyl maleate and the like.
  • an ethylenically unsaturated carboxylic acid compound preferably a lithium salt of an ethylenically unsaturated carboxylic acid can be used as the ethylenically unsaturated carboxylic acid compound.
  • an ethylenically unsaturated carboxylate is used, the water solubility of the resulting copolymer can be increased, so when preparing the copolymer using water as the polymerization solvent, the monomer composition contains Even when the monomer concentration is high, it is possible to prevent inhomogeneous progress of polymerization due to precipitation of the copolymer.
  • the polymerization can be progressed uniformly while increasing the productivity by using the monomer composition having a high monomer concentration.
  • lithium carboxylate base —COOLi
  • the stability of the slurry composition is further improved, and lithium ion This is because the battery characteristics (for example, initial coulomb efficiency, cycle characteristics, and high-temperature storage characteristics) of the secondary battery are further improved.
  • the ethylenically unsaturated carboxylic acid compound may be acrylic. It is preferable to use acid, methacrylic acid or a salt thereof, and it is more preferable to use acrylic acid or acrylate.
  • the monomer which the monomer composition used for preparation of a copolymer needs for the ratio which the ethylenically unsaturated carboxylic acid compound mentioned above occupies is 70.0 mass% or more and 99.9 mass% or less.
  • the proportion of the ethylenically unsaturated carboxylic acid compound in the monomer is preferably 80.0% by mass or more, more preferably 90.0% by mass or more, and 99.5% by mass or less. It is preferable that it is 99.0 mass% or less.
  • the proportion of the ethylenically unsaturated carboxylic acid compound in the monomer is less than 70.0% by mass, the rigidity of the copolymer is lowered, and is produced using the binder composition for a lithium ion secondary battery of the present invention.
  • the cycle characteristics of the lithium ion secondary battery deteriorated.
  • the proportion of the ethylenically unsaturated carboxylic acid compound in the monomer is more than 99.9% by mass, the rigidity of the copolymer becomes excessively high and becomes brittle.
  • the high-temperature storage characteristic of the lithium ion secondary battery produced using the binder composition for secondary batteries falls.
  • m is an integer of 1 or more
  • n is an integer of 2 or more
  • a compound having two or more ethylenically unsaturated bonds can be used.
  • the compound which has a polyoxyalkylene structure and two or more ethylenically unsaturated bonds may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polyfunctional compound As a polyfunctional compound, the poly (meth) acrylate of the polyol which has a polyoxyalkylene structure etc. are mentioned, for example.
  • the polyfunctional compound is not particularly limited, and examples thereof include the following compounds (I) to (V).
  • “(meth) acrylate” refers to acrylate and / or methacrylate.
  • the number (functional number) of ethylenically unsaturated bonds of the polyfunctional compound is preferably 2 or more and 6 or less, and more preferably 2 or more and 4 or less.
  • the polyfunctional compound is preferably a bi- to hexa-functional polyacrylate, more preferably a bi- to tetra-functional polyacrylate. .
  • the polyoxyalkylene possessed by the polyfunctional compound is preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less, and preferably 2 or more. preferable. This is because if the integer m is too large, the stability of the slurry composition may decrease. Moreover, when the integer m is too small, the rigidity of the copolymer becomes high, and the high-temperature storage characteristics of the lithium ion secondary battery may be deteriorated.
  • the integer n of the polyoxyalkylene structure (— (C m H 2m O) n —) of the polyfunctional compound is preferably 20 or less, more preferably 15 or less, It is particularly preferably 10 or less, more preferably 2 or more, further preferably 3 or more, and particularly preferably 4 or more. This is because if the integer n is too large, the stability of the slurry composition may decrease. Moreover, when the integer n is too small, the rigidity of a copolymer becomes high and there exists a possibility that the high temperature storage characteristic of a lithium ion secondary battery may fall.
  • the polyfunctional compound has a plurality of polyoxyalkylene structures (— (C m H 2m O) n —) in the molecule
  • the average value of the integers n of the plurality of polyoxyalkylene structures is within the above range. It is preferable that the integer n of all the polyoxyalkylene structures is included in the above range.
  • the proportion of the polyfunctional compound in the body is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and preferably 20.0% by mass or less. More preferably, it is 0 mass% or less.
  • the proportion of the polyfunctional compound in the monomer is less than 0.1% by mass, the rigidity of the copolymer becomes excessively high, and lithium produced using the binder composition for a lithium ion secondary battery of the present invention The high temperature storage characteristics of the ion secondary battery are degraded.
  • the proportion of the polyfunctional compound in the monomer is more than 30.0% by mass, precipitation of the electrode active material or the like in the slurry composition prepared using the binder composition for a lithium ion secondary battery of the present invention As a result, the productivity of the electrode and the substrate with the porous film is lowered, the rigidity of the copolymer is lowered, and the cycle characteristics of the lithium ion secondary battery produced using the binder composition are lowered.
  • the other compound which is a monomer arbitrarily blended known compounds copolymerizable with the above-mentioned ethylenically unsaturated carboxylic acid compound and polyfunctional compound can be used.
  • the other compound is not particularly limited, and is a compound having two or more ethylenically unsaturated bonds and not having a polyoxyalkylene structure, or a solubility parameter (SP value) of a copolymer. ) Can be adjusted.
  • examples of the compound having two or more ethylenically unsaturated bonds and not having a polyoxyalkylene structure include 1,6-hexanediol diacrylate and 1,9-nonanediol diester.
  • examples thereof include poly (meth) acrylates of polyols having no polyoxyalkylene structure, such as acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.
  • the electrolyte solution normally used for a lithium ion secondary battery a compound close
  • the proportion of the compound having two or more ethylenically unsaturated bonds and not having a polyoxyalkylene structure in the monomer is preferably 5% by mass or less. This is because if the proportion of the monomer in the monomer exceeds 5% by mass, the stability of the slurry composition prepared using the binder composition for a lithium ion secondary battery may be lowered. Moreover, it is preferable that the ratio which the compound which can adjust the magnitude
  • SP value solubility parameter
  • additives to be added to the monomer composition include known additives that can be used for a polymerization reaction such as a polymerization initiator such as potassium persulfate and a polymerization accelerator such as tetramethylethylenediamine.
  • a polymerization initiator such as potassium persulfate
  • a polymerization accelerator such as tetramethylethylenediamine.
  • the kind and compounding quantity of an additive can be arbitrarily selected according to a polymerization method etc.
  • a polymerization solvent blended in the monomer composition a known solvent capable of dissolving or dispersing the above-described monomer can be used depending on the polymerization method and the like.
  • water is preferably used as the polymerization solvent.
  • the polymerization solvent an aqueous solution of an arbitrary compound or a mixed solution of a small amount of an organic medium and water may be used.
  • the copolymer used as a binder for the binder composition for lithium ion secondary batteries of the present invention is a monomer composition obtained by mixing the above-described monomers, additives and polymerization solvent by a known method. Can be obtained, for example, by radical polymerization.
  • the solution containing the copolymer and the polymerization solvent obtained by polymerizing the monomer composition may be used as a binder composition as it is, or may be subjected to solvent substitution or addition of optional components. After that, it may be used as a binder composition.
  • examples of the polymerization method include known polymerization methods such as aqueous solution polymerization, slurry polymerization, suspension polymerization, and emulsion polymerization.
  • aqueous solution polymerization using water as a polymerization solvent is preferable.
  • the monomer composition is adjusted to a predetermined concentration, and the dissolved oxygen in the reaction system is sufficiently replaced with an inert gas.
  • a radical polymerization initiator is added, and if necessary, heating or ultraviolet rays are added. It is a method of performing a polymerization reaction by irradiating light.
  • the pH of the aqueous solution should be adjusted to 7 or more and 12 or less after polymerization. Is preferred. This is because the stability of the slurry composition and the high-temperature storage characteristics of the lithium ion secondary battery can be further improved by neutralizing the resulting aqueous solution and adjusting the pH to 7-12.
  • a monomer composition containing an ethylenically unsaturated carboxylic acid is used as the ethylenically unsaturated carboxylic acid compound
  • a basic lithium compound should be used when neutralizing the aqueous solution. Is preferred.
  • the carboxylic acid group in the copolymer becomes a carboxylic acid lithium base (—COOLi), and the stability of the slurry composition is further improved, and the battery characteristics of the lithium ion secondary battery ( This is because, for example, initial coulomb efficiency, cycle characteristics, and high-temperature storage characteristics are further improved.
  • the basic lithium compound lithium carbonate (Li 2 CO 3 ) or lithium hydroxide (LiOH) can be used, and lithium hydroxide is preferably used.
  • the copolymer prepared as described above and used as a binder of the binder composition for a lithium ion secondary battery of the present invention preferably has an electrolyte swelling degree of 5% by mass or more. More preferably, it is more preferably 10% by mass or more, particularly preferably 15% by mass or more, more preferably 120% by mass or less, and 70% by mass or less. Is more preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 38% by mass or less, particularly preferably 35% by mass or less, and 30% by mass. It is more particularly preferable that the content is not more than mass%.
  • the degree of swelling of the electrolytic solution is 5% by mass or more, the flexibility of the copolymer can be secured, cracking and peeling of the copolymer can be suppressed, and the high-temperature storage characteristics of the lithium ion secondary battery can be improved.
  • the degree of swelling of the electrolytic solution is 120% by mass or less, the rigidity of the copolymer can be secured, the expansion and contraction of the electrode active material can be suppressed, and the cycle characteristics of the lithium ion secondary battery can be improved.
  • the electrolyte solution swelling degree of a copolymer can be adjusted by changing the kind and quantity of a monomer in a monomer composition. Specifically, for example, by increasing the blending amount of the polyfunctional compound, the degree of electrolyte solution swelling can be increased.
  • the binder composition for a lithium ion secondary battery of the present invention containing the above-described copolymer as a binder may further contain a polymer other than the above-described copolymer as a binder.
  • polymers other than the copolymer mentioned above known polymers, such as a particulate polymer dispersible in the solvent of a binder composition, are mentioned.
  • the particulate polymer include diene polymers such as styrene-butadiene copolymer and acrylonitrile-butadiene copolymer, acrylic polymers, fluorine polymers, and silicon polymers.
  • the polymer other than the copolymer is As described above, it may be mixed with a copolymer in advance as a binder composition and then used for preparing a slurry composition, or without being mixed with the copolymer in advance, You may mix with a copolymer with a substance etc. (namely, preparation of the binder composition which also contains polymers other than a copolymer as a binder, and preparation of a slurry composition may be implemented simultaneously).
  • the solvent of the binder composition for a lithium ion secondary battery of the present invention a known solvent that can dissolve or disperse the binder described above can be used. Among these, water is preferably used as the solvent. In addition, at least one part of the solvent of a binder composition can be made into the polymerization solvent contained in the monomer composition used when preparing a copolymer, without being specifically limited.
  • the binder composition for a lithium ion secondary battery of the present invention may contain a thickener as a known component that can be optionally blended in the binder composition.
  • the binder composition includes, as other components optionally blended, natural thickeners such as carboxymethylcellulose, thickening polysaccharides, alginic acid, and starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and the like.
  • the synthetic thickener (except for those corresponding to the above-mentioned copolymer) may be contained.
  • the other components are previously mixed with a copolymer as described above.
  • the binder composition may be used for preparing the slurry composition, or may be mixed with the copolymer together with the electrode active material and the like at the time of preparing the slurry composition without being previously mixed with the copolymer ( That is, the preparation of the binder composition containing other components and the preparation of the slurry composition may be performed simultaneously.
  • the slurry composition for lithium ion secondary battery electrodes of the present invention includes the above-described binder composition for lithium ion secondary batteries of the present invention and an electrode active material. And the slurry composition for lithium ion secondary battery electrodes of this invention can be preferably used as a slurry composition for lithium ion secondary battery negative electrodes.
  • the slurry composition for a negative electrode of a lithium ion secondary battery that can be prepared using the binder composition for a lithium ion secondary battery of the present invention includes the above-described binder composition, a negative electrode active material, and a dispersion medium such as water. And other components added as necessary. That is, a slurry composition for a negative electrode of a lithium ion secondary battery includes at least the above-described copolymer, a negative electrode active material, and a dispersion medium such as water, and optionally, other polymers such as a particulate polymer, And further contains other components such as thickeners.
  • the binder composition for a lithium ion secondary battery of the present invention is a slurry composition, a negative electrode, and a lithium ion secondary battery manufactured in combination with a negative electrode active material that greatly expands and contracts with charge and discharge. Even when it is used, the lithium ion secondary battery can exhibit excellent cycle characteristics and high temperature storage characteristics while ensuring the stability of the slurry composition and the productivity of the negative electrode. Therefore, in the slurry composition for a negative electrode of a lithium ion secondary battery, from the viewpoint of increasing the capacity of the lithium ion secondary battery, a silicon-based negative electrode active material and optionally other negative electrode active materials are used as the negative electrode active material. It is preferable.
  • the silicon-based negative electrode active material is an active material containing silicon.
  • silicon (Si) an alloy containing silicon, SiO, SiO x , a Si-containing material formed by coating or compounding a Si-containing material with conductive carbon, and conductive carbon. Examples include composites.
  • these silicon type negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 types.
  • the alloy containing silicon examples include an alloy composition containing silicon and at least one element selected from the group consisting of titanium, iron, cobalt, nickel, and copper.
  • the alloy containing silicon examples include an alloy composition containing silicon, aluminum, and a transition metal such as iron, and further containing a rare earth element such as tin and yttrium.
  • SiO x is a compound containing at least one of SiO and SiO 2 and Si, and x is usually 0.01 or more and less than 2. Then, SiO x, for example, can be formed by using a disproportionation reaction of silicon monoxide (SiO). Specifically, SiO x can be prepared by heat-treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to produce silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher, in an atmosphere containing an organic gas and / or vapor after grinding and mixing SiO and optionally a polymer.
  • SiO x can be prepared by heat-treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to produce silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher, in an atmosphere containing an organic gas and / or
  • a composite of Si-containing material and conductive carbon for example, a pulverized mixture of SiO, a polymer such as polyvinyl alcohol, and optionally a carbon material is heat-treated in an atmosphere containing, for example, an organic gas and / or steam.
  • the composite material is a method in which the surface of SiO particles is coated by a chemical vapor deposition method using an organic gas, etc., and SiO particles and graphite or artificial graphite are formed into composite particles (granulated by a mechanochemical method). ) Can also be obtained by a known method such as a method.
  • the silicon-based negative electrode active material is preferably an alloy containing silicon and SiO x .
  • Examples of the negative electrode active material used in combination with the silicon negative electrode active material in the slurry composition for a negative electrode of a lithium ion secondary battery include a carbon negative electrode active material and a metal negative electrode active material.
  • the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton capable of inserting lithium (also referred to as “dope”).
  • examples of the carbon-based negative electrode active material include carbonaceous materials and graphite. Quality materials.
  • the carbonaceous material is a material having a low degree of graphitization (ie, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or lower.
  • the minimum of the heat processing temperature at the time of carbonizing is not specifically limited, For example, it can be 500 degreeC or more.
  • the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
  • the graphitizable carbon for example, a carbon material using tar pitch obtained from petroleum or coal as a raw material can be mentioned.
  • examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.
  • the graphite material is a material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher.
  • the upper limit of heat processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
  • the graphite material include natural graphite and artificial graphite.
  • the artificial graphite for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. Examples thereof include graphitized mesophase pitch-based carbon fibers that have been heat-treated.
  • the metal-based negative electrode active material is an active material containing a metal, and usually includes an element capable of inserting lithium in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh / The active material which is more than g.
  • the metal-based negative electrode active material include simple metals other than Si that can form lithium metal and lithium alloys (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, and Sb). , Sn, Sr, Zn, Ti, etc.) and alloys thereof, and oxides, sulfides, nitrides, carbides, phosphides, and the like thereof.
  • the negative electrode active material is preferably a mixture of a silicon-based negative electrode active material and a carbon-based negative electrode active material such as artificial graphite.
  • the dispersion medium for the slurry composition for a lithium ion secondary battery negative electrode is not particularly limited, and a known dispersion medium can be used. Among these, water is preferably used as the dispersion medium. In addition, at least one part of the dispersion medium of a slurry composition can be made into the solvent which the binder composition used for preparation of a slurry composition contained, without being specifically limited.
  • the said slurry composition for lithium ion secondary battery negative electrodes may contain components, such as a electrically conductive material, a reinforcing material, a leveling agent, and electrolyte solution additive other than the said component. These are not particularly limited as long as they do not affect the battery reaction, and known ones such as those described in International Publication No. 2012/115096 can be used. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the said slurry composition for lithium ion secondary battery negative electrodes can be prepared by disperse
  • the above components and the dispersion medium are mixed using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crushed crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a fill mix, etc.
  • a slurry composition can be prepared.
  • water is usually used as the dispersion medium, but an aqueous solution of an arbitrary compound or a mixed solution of a small amount of an organic medium and water may be used.
  • the ratio of each said component in a slurry composition can be adjusted suitably.
  • the content ratio of the copolymer in the slurry composition is 100 parts by mass of the negative electrode active material. It is preferable that it is 0.5 mass part or more and 10 mass parts or less.
  • the content ratio of the other polymer in the slurry composition is: The amount is preferably 0.05 parts by mass or more and 2 parts by mass or less per 100 parts by mass of the negative electrode active material.
  • the content ratio of the other polymer in the slurry composition is 0.5 mass per 100 parts by mass of the negative electrode active material. It is more preferable that the amount is not more than parts.
  • it is desirable that the content of the other polymer is less than that normally used from the viewpoint of suppressing expansion.
  • the content of the thickener in the slurry composition is 0.3 per 100 parts by mass of the negative electrode active material from the viewpoint of improving the stability of the slurry composition. It is preferable that it is not less than 5.0 parts by mass.
  • the ratio of the thickener to the copolymer is preferably 2: 1 to 1: 2 and more preferably 3: 2 to 2: 3.
  • a slurry composition for a positive electrode of a lithium ion secondary battery that can be prepared using the binder composition for a lithium ion secondary battery of the present invention includes the binder composition described above, a positive electrode active material, a dispersion medium such as water, and the like. And other components such as a conductive material and a thickener added depending on the content. That is, a slurry composition for a lithium ion secondary battery positive electrode includes at least the above-described copolymer, a positive electrode active material, and a dispersion medium such as water, and optionally, other polymers such as a particulate polymer, Furthermore, it contains other components such as a conductive material and a thickener.
  • the slurry composition for a lithium ion secondary battery positive electrode prepared using the binder composition for a lithium ion secondary battery of the present invention further includes a particulate polymer as a binder, and as a thickener. It preferably contains carboxymethylcellulose.
  • a particulate polymer as a binder, and as a thickener. It preferably contains carboxymethylcellulose.
  • a compound containing a transition metal for example, a transition metal oxide, a transition metal sulfide, a composite metal oxide of lithium and a transition metal, or the like can be used.
  • a transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc. are mentioned, for example.
  • transition metal oxide for example, MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , amorphous Examples include MoO 3 , amorphous V 2 O 5 , and amorphous V 6 O 13 .
  • the composite metal oxide of lithium and transition metal include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure. It is done.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn lithium-containing composite oxide (Li (Co Mn Ni) O 2 ), Ni—Mn—Al lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, and solid solution of LiMaO 2 and Li 2 MbO 3 .
  • examples of the Co—Ni—Mn lithium-containing composite oxide include Li [Ni 0.5 Co 0.2 Mn 0.3 ] O 2 and Li [Ni 1/3 Co 1/3 Mn 1/3 ] O 2 .
  • Examples of the solid solution of LiMaO 2 and Li 2 MbO 3 include xLiMaO 2. (1-x) Li 2 MbO 3 .
  • x represents a number satisfying 0 ⁇ x ⁇ 1
  • Ma represents one or more transition metals having an average oxidation state of 3+
  • Mb represents one or more transition metals having an average oxidation state of 4+.
  • Examples of such a solid solution include Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 .
  • the “average oxidation state” indicates an average oxidation state of the “one or more transition metals”, and is calculated from the molar amount and valence of the transition metal.
  • lithium-containing composite metal oxide having a spinel structure examples include lithium manganate (LiMn 2 O 4 ) and compounds in which a part of Mn of lithium manganate (LiMn 2 O 4 ) is substituted with another transition metal.
  • LiMn 2 O 4 lithium manganate
  • Specific examples include Li s [Mn 2-t Mc t] O 4 , such as LiNi 0.5 Mn 1.5 O 4.
  • Mc represents one or more transition metals having an average oxidation state of 4+.
  • Mc include Ni, Co, Fe, Cu, and Cr.
  • T represents a number satisfying 0 ⁇ t ⁇ 1, and s represents a number satisfying 0 ⁇ s ⁇ 1.
  • a lithium-excess spinel compound represented by Li 1 + x Mn 2 ⁇ x O 4 (0 ⁇ X ⁇ 2) can also be used.
  • Examples of the lithium-containing composite metal oxide having an olivine type structure include olivine type phosphorus represented by Li y MdPO 4 such as olivine type lithium iron phosphate (LiFePO 4 ) and olivine type lithium manganese phosphate (LiMnPO 4 ).
  • An acid lithium compound is mentioned.
  • Md represents one or more transition metals having an average oxidation state of 3+, and examples thereof include Mn, Fe, and Co.
  • Y represents a number satisfying 0 ⁇ y ⁇ 2.
  • Md may be partially substituted with another metal. Examples of the metal that can be substituted include Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B, and Mo.
  • the said slurry composition for lithium ion secondary battery positive electrodes can be prepared by disperse
  • the ratio of each said component in a slurry composition can be adjusted suitably.
  • the electrode for lithium ion secondary batteries of this invention equips a collector with the electrode compound-material layer prepared using the slurry composition for lithium ion secondary battery electrodes (negative electrode and positive electrode) mentioned above.
  • the electrode mixture layer of the electrode for a lithium ion secondary battery of the present invention contains at least an electrode active material and a copolymer as a binder.
  • each component contained in the electrode mixture layer was contained in the above-mentioned slurry composition for lithium ion secondary battery electrodes, and a suitable abundance ratio of each of these components is the electrode slurry. It is the same as the preferred abundance ratio of each component in the composition.
  • the electrode for lithium ion secondary batteries of this invention is prepared using the binder composition for lithium ion secondary batteries of this invention, it is high in productivity, and the cycle of a lithium ion secondary battery The deterioration of the characteristics and the high temperature storage characteristics can be suppressed.
  • the lithium ion secondary battery electrode of the present invention is applied, for example, to a step of applying the slurry composition for a lithium ion secondary battery electrode of the present invention onto a current collector (coating step) and a current collector.
  • the lithium ion secondary battery electrode slurry composition is dried to form an electrode mixture layer on the current collector (drying step).
  • the electrode for a lithium ion secondary battery of the present invention is prepared by dry granulating the slurry composition for a lithium ion secondary battery electrode described above to prepare composite particles, and using the composite particles, an electrode is formed on the current collector. It can also be manufactured by a method of forming a composite material layer.
  • a method for applying the slurry composition for a lithium ion secondary battery electrode of the present invention on a current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the electrode slurry composition may be applied to only one surface of the current collector, or may be applied to both surfaces. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the electrode mixture layer obtained by drying.
  • the current collector to which the electrode slurry composition is applied a material having electrical conductivity and electrochemical durability is used.
  • a current collector for example, a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used.
  • a copper foil is particularly preferable as the current collector used for the negative electrode.
  • the current collector used for the positive electrode is particularly preferably an aluminum foil.
  • the said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the method for drying the electrode slurry composition on the current collector is not particularly limited, and a known method can be used. For example, drying with hot air, hot air, low-humidity air, vacuum drying, infrared rays, electron beam, etc. The drying method by irradiation is mentioned. Thus, by drying the slurry composition for electrodes on the current collector, an electrode mixture layer is formed on the current collector, and the electrode for a lithium ion secondary battery comprising the current collector and the electrode mixture layer Can be obtained.
  • the electrode mixture layer may be subjected to pressure treatment using a die press or a roll press.
  • the adhesion between the electrode mixture layer and the current collector can be improved by the pressure treatment.
  • the electrode mixture layer includes a curable polymer, it is preferable to cure the polymer after the electrode mixture layer is formed.
  • the slurry composition for a porous membrane of a lithium ion secondary battery of the present invention includes the above-described binder composition for a lithium ion secondary battery of the present invention and non-conductive particles.
  • the slurry composition for a lithium ion secondary battery porous membrane of the present invention includes the above-described binder composition, non-conductive particles, a dispersion medium such as water, and others added as necessary. Containing. That is, the slurry composition for a lithium ion secondary battery porous membrane includes at least the above-described copolymer, non-conductive particles, and a dispersion medium such as water, and optionally other heavy components such as a particulate polymer. It further contains other components such as coalescence and thickener. In addition, it is preferable that the slurry composition for lithium ion secondary battery porous films of this invention further contains a particulate polymer as a binder, and contains carboxymethylcellulose as a thickener.
  • Non-conductive particles both inorganic fine particles and organic fine particles can be used, but usually inorganic fine particles are used.
  • a material of nonelectroconductive particle the material which exists stably in the use environment of a lithium ion secondary battery, and is electrochemically stable is preferable.
  • preferable examples of the non-conductive particle material include aluminum oxide (alumina), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO 3 , ZrO, alumina-silica.
  • Oxide particles such as complex oxides; Nitride particles such as aluminum nitride and boron nitride; Covalent crystal particles such as silicon and diamond; Slightly soluble ionic crystal particles such as barium sulfate, calcium fluoride and barium fluoride; Talc And clay fine particles such as montmorillonite.
  • these particles may be subjected to element substitution, surface treatment, solid solution, and the like as necessary.
  • the non-conductive particles may contain one kind of the above materials alone in one particle, or may contain two or more kinds in combination at any ratio. . Further, as the non-conductive particles, two or more kinds of particles formed of different materials may be used in combination.
  • an oxide is used. Particles are preferable, and titanium oxide, magnesium oxide, and aluminum oxide are more preferable, and aluminum oxide is particularly preferable from the viewpoint of low water absorption and excellent heat resistance (for example, resistance to high temperature of 180 ° C. or higher).
  • the dispersion medium of the slurry composition for a lithium ion secondary battery porous membrane of the present invention is not particularly limited, and a known dispersion medium can be used. Among these, water is preferably used as the dispersion medium. In addition, at least one part of the dispersion medium of a slurry composition can be made into the solvent which the binder composition used for preparation of a slurry composition contained, without being specifically limited.
  • the slurry composition for a porous membrane of a lithium ion secondary battery of the present invention may contain components such as a reinforcing material, a leveling agent, and an electrolytic solution additive in addition to the above components. These are not particularly limited as long as they do not affect the function of the porous membrane, and known ones such as those described in International Publication No. 2012/115096 can be used. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the slurry composition for a porous membrane of a lithium ion secondary battery of the present invention disperses the above components in a dispersion medium, similarly to the slurry composition for a negative electrode of a lithium ion secondary battery and the slurry composition for a positive electrode of a lithium ion secondary battery. Can be prepared. In addition, the ratio of each said component in a slurry composition can be adjusted suitably.
  • the slurry composition for a porous membrane of a lithium ion secondary battery of the present invention can be used for producing a substrate with a porous membrane for a lithium ion secondary battery.
  • the substrate with a porous film for a lithium ion secondary battery includes a substrate made of an electrode or a separator and a porous film formed on the substrate, and the porous film includes at least non-conductive particles. And a copolymer as a binder.
  • each component contained in the electrode mixture layer was contained in the slurry composition for a lithium ion secondary battery porous membrane, and a suitable abundance ratio of each of these components is a porous membrane.
  • the said base material with a porous film for lithium ion secondary batteries is prepared using the binder composition for lithium ion secondary batteries of this invention, productivity is high and it is excellent in heat-resistant shrinkage. ing. In addition, the battery characteristics of the lithium ion secondary battery can be improved.
  • the said base material with a porous film for lithium ion secondary batteries is a process (application
  • the manufactured slurry composition for a lithium ion secondary battery porous film is dried to form a porous film on a substrate (drying process).
  • the coating process and the drying process when manufacturing the substrate with a porous film for a lithium ion secondary battery are performed by applying the slurry composition for the porous film on the substrate instead of applying the electrode slurry composition on the current collector. Since it can carry out similarly to manufacture of the electrode for lithium ion secondary batteries mentioned above except the point which apply
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and at least one of the positive electrode and the negative electrode is the above-described electrode for a lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and at least one of the positive electrode, the negative electrode, and the separator (that is, at least one base material) is the lithium ion described above.
  • a porous film formed using the slurry composition for a secondary battery porous film is provided.
  • the lithium ion secondary battery of the present invention uses a porous film formed by using the electrode for a lithium ion secondary battery of the present invention or the slurry composition for a porous film of a lithium ion secondary battery of the present invention, Excellent cycle characteristics and high temperature storage characteristics.
  • a lithium ion secondary battery using the above negative electrode for a lithium ion secondary battery will be described.
  • the lithium ion secondary battery of the present invention lithium using the above positive electrode for a lithium ion secondary battery as a positive electrode is described.
  • An ion secondary battery is also included.
  • a known positive electrode used as a positive electrode for a lithium ion secondary battery can be used.
  • the positive electrode for example, a positive electrode formed by forming a positive electrode mixture layer on a current collector can be used.
  • the current collector one made of a metal material such as aluminum can be used.
  • the positive electrode mixture layer a layer containing a known positive electrode active material, a conductive material, and a binder can be used.
  • an electrolytic solution in which an electrolyte is dissolved in a solvent can be used.
  • the solvent an organic solvent capable of dissolving the electrolyte can be used.
  • the solvent include alkyl carbonate solvents such as ethylene carbonate, propylene carbonate, and ⁇ -butyrolactone, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, methyl acetate, dimethoxyethane. , Dioxolane, methyl propionate, methyl formate and the like can be used.
  • a lithium salt can be used as the electrolyte.
  • the lithium salt for example, those described in JP 2012-204303 A can be used.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable as the electrolyte because they are easily dissolved in an organic solvent and exhibit a high degree of dissociation.
  • ⁇ Separator> As the separator, for example, those described in JP 2012-204303 A can be used. Among these, the thickness of the separator as a whole can be reduced, thereby increasing the ratio of the electrode active material in the lithium ion secondary battery and increasing the capacity per volume.
  • a microporous film made of a series resin polyethylene, polypropylene, polybutene, polyvinyl chloride is preferred.
  • a positive electrode and a negative electrode are overlapped via a separator, and this is wound into a battery container according to the shape of the battery as necessary. It can be manufactured by injecting and sealing the liquid.
  • an overcurrent prevention element such as a fuse or a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary.
  • the shape of the lithium ion secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
  • ⁇ Electrolytic solution swelling> The aqueous solution containing the copolymer was dried in an environment of 50% humidity and a temperature of 23 to 25 ° C. to form a film having a thickness of 1 ⁇ 0.3 mm.
  • the film formed was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours, then cut and weighed approximately 1 g.
  • the mass of the obtained film piece is defined as W0.
  • Electrolyte swelling degree (mass%) ⁇ (W1-W0) / W0 ⁇ ⁇ 100 ⁇ Glass transition temperature>
  • the aqueous dispersion containing the particulate polymer was dried for 3 days in an environment of 50% humidity and a temperature of 23 to 26 ° C. to form a film having a thickness of 1 ⁇ 0.3 mm.
  • the formed film was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours. Then, using the dried film as a sample, a differential scanning calorimeter (DSC6220SII, manufactured by Nanotechnology Co., Ltd.) under the conditions of a measurement temperature of ⁇ 100 ° C. to 180 ° C. and a heating rate of 5 ° C./min in accordance with JIS K7121. Was used to measure the glass transition temperature Tg (° C.).
  • Tg glass transition temperature
  • the formed film was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours. Thereafter, the dried film was cut into 3 to 5 mm square, and about 1 g was precisely weighed. The mass of the film piece obtained by cutting is defined as w0.
  • This piece of film was immersed in 50 g of tetrahydrofuran (THF) for 24 hours. Then, the film piece pulled up from THF was vacuum-dried at 105 degreeC for 3 hours, and the mass w1 of insoluble matter was measured. And gel content was computed using the following formulas.
  • the prepared lithium ion secondary battery was allowed to stand at a temperature of 25 ° C. for 5 hours after electrolyte injection. Next, the cell voltage was charged to 3.65 V by a constant current method at a temperature of 25 ° C. and 0.2 C, and then an aging treatment was performed at a temperature of 60 ° C. for 12 hours.
  • ⁇ C ′ is 85% or more
  • B: ⁇ C ′ is 83% or more and less than 85%
  • C: ⁇ C ′ is 80% or more and less than 83%
  • D: ⁇ C ′ is less than 80% ⁇ Storage stability of lithium ion secondary battery>
  • the prepared lithium ion secondary battery was allowed to stand at a temperature of 25 ° C. for 5 hours after electrolyte injection.
  • the cell voltage was charged to 3.65 V by a constant current method at a temperature of 25 ° C. and 0.2 C, and then an aging treatment was performed at a temperature of 60 ° C. for 12 hours. And it discharged to cell voltage 2.75V by the constant current method of temperature 25 degreeC and 0.2C.
  • CC-CV charging upper limit cell voltage 4.20 V
  • CC discharge was performed to a cell voltage of 3.00 V by a constant current method of 0.2 C.
  • the cell volume (V0) of the lithium ion secondary battery was calculated by the Archimedes method.
  • the cell voltage is charged to 4.20 V by a constant current method at a temperature of 25 ° C. and 0.2 C, and left for 3 days under the condition of a temperature of 80 ⁇ 2 ° C.
  • a constant current method at a temperature of 25 ° C. and 0.2 C
  • the cell voltage was discharged to 2.75V.
  • Gas generation amount (mL) V1 (mL) ⁇ V0 (mL)
  • Example 1 Preparation of aqueous solution containing copolymer> 720 g of ion-exchanged water was charged into a 1 L flask with a septum, heated to a temperature of 40 ° C., and the inside of the flask was replaced with nitrogen gas at a flow rate of 100 mL / min.
  • the slurry composition for a negative electrode of a lithium ion secondary battery is applied to the surface of a copper foil having a thickness of 20 ⁇ m as a current collector with a comma coater so that the coating amount is 8.8 to 9.2 mg / cm 2. Applied.
  • the copper foil coated with the lithium ion secondary battery negative electrode slurry composition is conveyed at a rate of 200 mm / min for 2 minutes in an oven at a temperature of 80 ° C. and further for 2 minutes in an oven at a temperature of 120 ° C. By this, the slurry composition on copper foil was dried and the negative electrode original fabric was obtained.
  • the obtained negative electrode raw material was pressed with a roll press so that the density was 1.63 to 1.67 g / cm 3, and further, under vacuum conditions for the purpose of removing moisture and further promoting crosslinking.
  • the negative electrode was obtained by placing in an environment of 105 ° C. for 4 hours.
  • the obtained slurry composition for a positive electrode of a lithium ion secondary battery is applied on an aluminum foil having a thickness of 20 ⁇ m, which is a current collector, with a comma coater so that the coating amount becomes 25.3 to 25.8 mg / cm 2. It was applied to. Thereafter, the aluminum foil coated with the slurry composition for a positive electrode of a lithium ion secondary battery was dried by conveying it in an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material.
  • the obtained positive electrode raw material was pressed with a roll press machine so that the density was 3.40 to 3.50 g / cm 3, and for the purpose of removing moisture, the temperature was 120 ° C. under vacuum conditions.
  • a positive electrode was obtained after 3 hours in the environment.
  • a wound cell was prepared using a single-layer polypropylene separator, the negative electrode and the positive electrode, and placed in an aluminum packaging material.
  • vinylene carbonate as an additive is 2% by volume (solvent. Ratio) containing
  • Example 2 Except having used the monomer shown in Table 1 in the quantity shown in Table 1, it carried out similarly to Example 1 except having used the aqueous solution containing the copolymer prepared like the copolymer A as a binder composition.
  • a slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced.
  • the methyl methacrylate used in Example 2 is corresponded to the compound (other compound) which can adjust the magnitude
  • SP value solubility parameter
  • Example 5 In the same manner as in Example 3 except that a 5% aqueous solution of sodium hydroxide was used instead of the 10% aqueous solution of lithium hydroxide when preparing the aqueous solution containing the copolymer, an aqueous solution containing the copolymer, lithium ion A slurry composition for a secondary battery negative electrode, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced.
  • Example 6 Except having used the monomer shown in Table 1 in the quantity shown in Table 1, it carried out similarly to Example 1 except having used the aqueous solution containing the copolymer prepared like the copolymer A as a binder composition.
  • a slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced. Then, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • Example 10 An aqueous solution containing the copolymer B was prepared in the same manner as the copolymer A except that the monomers shown in Table 1 were used in the amounts shown in Table 1. Further, an aqueous dispersion of a particulate polymer made of a styrene-butadiene copolymer was prepared as follows.
  • the slurry composition for lithium ion secondary battery negative electrodes replaces with the aqueous solution containing the copolymer A, and the aqueous solution containing the copolymer B (solid content concentration: 4.5%) is solid content equivalent 3
  • Slurry compositions, negative electrodes for lithium ion secondary batteries, positive electrodes for lithium ion secondary batteries, and lithium ion secondary batteries were produced.
  • Example 1 Further, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • ⁇ Preparation of aqueous dispersion of particulate polymer comprising styrene-butadiene copolymer> In a 5 MPa pressure vessel with a stirrer, 65 parts of styrene, 35 parts of 1,3-butadiene, 2 parts of itaconic acid, 1 part of 2-hydroxyethyl acrylate, 0.3 part of t-dodecyl mercaptan as a molecular weight regulator, dodecyl as an emulsifier 5 parts of sodium benzenesulfonate, 150 parts of ion-exchanged water as a solvent, and 1 part of potassium persulfate as a polymerization initiator were added, and after stirring sufficiently, the temperature was raised to 55 ° C.
  • styrene-butadiene copolymer had a gel content of 92% by mass and a glass transition temperature (Tg) of 10 ° C.
  • Example 11 Example except that an aqueous dispersion of a particulate polymer made of a styrene butadiene acrylonitrile copolymer prepared as follows was used instead of the aqueous dispersion of a particulate polymer made of a styrene-butadiene copolymer.
  • a slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced.
  • Example 1 Further, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • the polymer serving as a shell portion was polymerized, and the reaction was stopped by cooling when the total amount of monomer consumption reached 95.0%.
  • a 5% aqueous sodium hydroxide solution was added to the aqueous dispersion containing the polymer thus obtained to adjust the pH to 8.
  • the unreacted monomer was removed by heating under reduced pressure. Thereafter, the mixture was cooled to a temperature of 30 ° C. or lower to obtain an aqueous dispersion containing a particulate polymer made of a styrene butadiene acrylonitrile copolymer.
  • the gel content of the styrene butadiene acrylonitrile copolymer was 75% by mass, the glass transition temperature (Tg) of the core part was ⁇ 37 ° C., and the glass transition temperature (Tg) of the shell part was 35 ° C. .
  • Example 12 Similar to Example 10 except that an aqueous dispersion of a particulate polymer made of an acrylic polymer prepared as follows was used instead of the aqueous dispersion of a particulate polymer made of a styrene-butadiene copolymer.
  • a slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced.
  • Example 1 Further, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • ⁇ Preparation of aqueous dispersion of particulate polymer made of acrylic polymer> In a 5 MPa pressure vessel equipped with a stirrer, 82 parts of butyl acrylate, 2 parts of acrylonitrile, 2 parts of methacrylic acid, 1 part of N-methylolacrylamide, 1 part of allyl glycidyl ether, 4 parts of sodium lauryl sulfate as an emulsifier, ion-exchanged water 150 as a solvent And 0.5 part of ammonium persulfate as a polymerization initiator were added and sufficiently stirred, and then heated to a temperature of 80 ° C. to initiate polymerization.
  • the reaction was stopped by cooling.
  • the aqueous dispersion containing the acrylic polymer thus obtained was adjusted to pH 7 by adding a 5% aqueous sodium hydroxide solution.
  • the unreacted monomer was removed by heating under reduced pressure. Furthermore, it cooled to the temperature of 30 degrees C or less after that, and obtained the water dispersion liquid containing the particulate polymer which consists of an acrylic polymer.
  • the acrylic polymer had a gel content of 90% by mass and a glass transition temperature (Tg) of ⁇ 50 ° C.
  • Example 13 A slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, lithium, except that an aqueous solution containing a copolymer A was used instead of the aqueous solution containing the copolymer B A positive electrode for an ion secondary battery and a lithium ion secondary battery were produced. Further, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • Example 14 When preparing the slurry composition for the negative electrode of the lithium ion secondary battery, the blending amount of the aqueous solution containing the copolymer A (solid content concentration: 4.5%) is 1.5 parts corresponding to the solid content, and carboxy is used as the thickener.
  • a positive electrode for a lithium ion secondary battery and a lithium ion secondary battery were produced.
  • Example 1 Further, in the same manner as in Example 1, the degree of swelling of the electrolyte solution of the copolymer, the stability of the slurry composition, the productivity of the electrode, and the cycle characteristics and storage stability of the lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • Comparative Example 2 Except having used the monomer shown in Table 1 in the quantity shown in Table 1, it carried out similarly to Example 1 except having used the aqueous solution containing the copolymer prepared like the copolymer A as a binder composition.
  • a slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced.
  • the pentaerythritol tetraacrylate used in Comparative Example 2 corresponds to a compound having two or more ethylenically unsaturated bonds and not having a polyoxyalkylene structure.
  • AA indicates acrylic acid
  • PEGDA refers to polyethylene glycol diacrylate
  • EPETA refers to ethoxylated pentaerythritol tetraacrylate
  • MMA indicates methyl methacrylate
  • PETA refers to pentaerythritol tetraacrylate.
  • Examples 1 to 14 and Comparative Examples 1 to 4 in Table 1 in Examples 1 to 14, excellent cycle characteristics and excellent lithium ion secondary battery while ensuring the stability of the slurry composition and the productivity of the electrode It can be seen that the high temperature storage characteristics can be exhibited.
  • the stability of the slurry composition can be stabilized by adjusting the amount of the monomer and the degree of electrolyte swelling of the copolymer when preparing the copolymer. It can be seen that the characteristics, electrode productivity, and cycle characteristics and high-temperature storage characteristics of the lithium ion secondary battery can be aligned at a high level.
  • the lithium ion secondary battery Furthermore, from Examples 3 and 5 in Table 1, by using a lithium hydroxide aqueous solution at the time of neutralization of the aqueous solution containing the copolymer to obtain a copolymer having a lithium carboxylate base, the lithium ion secondary battery It can be seen that the high temperature storage characteristics can be improved. Further, from Examples 2 and 10 to 13 in Table 1, it can be seen that the cycle characteristics and high-temperature storage characteristics of the lithium ion secondary battery can be improved by using the copolymer and the particulate polymer in combination.
  • Example 14 is an example in which carboxymethylcellulose, which has high thixotropy and can improve the stability of the slurry composition at low cost, is used in combination with a copolymer. From Table 1, it can be seen that the lithium ion secondary battery can exhibit high performance by using the copolymer and carboxymethyl cellulose in combination when the slurry composition needs high stability.
  • the lithium ion secondary battery exhibits excellent cycle characteristics and high temperature storage characteristics while ensuring the stability of the slurry composition and the productivity of the electrode. Can do.
  • excellent cycle characteristics and high temperature storage characteristics can be exhibited in the lithium ion secondary battery while ensuring the productivity of the electrodes.
  • excellent cycle characteristics and high temperature storage characteristics can be exhibited in a lithium ion secondary battery.
  • the electrode for a lithium ion secondary battery of the present invention excellent cycle characteristics and high temperature storage characteristics can be exhibited in the lithium ion secondary battery. And according to this invention, the lithium ion secondary battery which is excellent in cycling characteristics and high temperature storage characteristics can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention a pour objectif de fournir une composition de liant pour batterie secondaire lithium-ion qui tout en garantissant la stabilité d'une composition de bouillie et la productivité d'une électrode, permet de développer d'excellentes caractéristiques de cycle et de conservation à haute température d'une batterie secondaire lithium-ion. Ladite composition de liant contient un copolymère obtenu par polymérisation d'une composition de monomère qui contient un composé carboxylique éthyléniquement insaturé constitué d'un acide carboxylique éthyléniquement insaturé et/ou d'un sel de celui-ci, et un composé multifonction qui possède une structure de polyoxyalkylène et au moins deux liaisons éthyléniquement insaturées.
PCT/JP2015/001247 2014-03-07 2015-03-06 Composition de liant pour batterie secondaire lithium-ion, composition de bouillie pour électrode de batterie secondaire lithium-ion, composition de bouillie pour film poreux de batterie secondaire lithium-ion, électrode pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion WO2015133154A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016506152A JP6536564B2 (ja) 2014-03-07 2015-03-06 リチウムイオン二次電池用バインダー組成物、リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池多孔膜用スラリー組成物、リチウムイオン二次電池用電極、及びリチウムイオン二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014045454 2014-03-07
JP2014-045454 2014-03-07

Publications (1)

Publication Number Publication Date
WO2015133154A1 true WO2015133154A1 (fr) 2015-09-11

Family

ID=54054966

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/001247 WO2015133154A1 (fr) 2014-03-07 2015-03-06 Composition de liant pour batterie secondaire lithium-ion, composition de bouillie pour électrode de batterie secondaire lithium-ion, composition de bouillie pour film poreux de batterie secondaire lithium-ion, électrode pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion

Country Status (2)

Country Link
JP (1) JP6536564B2 (fr)
WO (1) WO2015133154A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152056A1 (fr) * 2015-03-24 2016-09-29 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
JP2017103206A (ja) * 2015-11-19 2017-06-08 旭化成株式会社 蓄電デバイス用セパレータ及びそれを用いた積層体、捲回体、リチウムイオン二次電池又は蓄電デバイス
JP2017191777A (ja) * 2016-04-14 2017-10-19 三星エスディアイ株式会社Samsung SDI Co., Ltd. 多孔性耐熱層組成物、多孔性耐熱層を含む分離膜、および該分離膜を用いた電気化学電池
WO2018180232A1 (fr) * 2017-03-28 2018-10-04 東亞合成株式会社 Liant pour électrode de batterie secondaire à électrolyte non aqueux
WO2019021810A1 (fr) * 2017-07-24 2019-01-31 株式会社クラレ Membrane de séparation pour des batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant
CN110183584A (zh) * 2019-05-05 2019-08-30 欣旺达惠州动力新能源有限公司 一种丙烯腈聚合物乳液粘结剂及其制备方法
US10468710B2 (en) * 2017-03-06 2019-11-05 Toyota Jidosha Kabushiki Kaisha Nonaqueous secondary battery
JPWO2018180405A1 (ja) * 2017-03-27 2020-02-06 日本ゼオン株式会社 電極構成体固定用接着剤及び電気化学素子
CN113363437A (zh) * 2021-05-18 2021-09-07 恒大新能源技术(深圳)有限公司 硅基负极材料及其制备方法、负极片、二次电池
CN114094102A (zh) * 2021-11-03 2022-02-25 珠海冠宇电池股份有限公司 一种二次电池
WO2024024772A1 (fr) * 2022-07-27 2024-02-01 東亞合成株式会社 Liant pour électrode de batterie secondaire à électrolyte non aqueux

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268053A (ja) * 2002-03-13 2003-09-25 Hitachi Chem Co Ltd 電池用バインダ樹脂、これを含有する電極及び電池
JP2006210208A (ja) * 2005-01-31 2006-08-10 Matsushita Electric Ind Co Ltd 非水電解質二次電池
JP2014011067A (ja) * 2012-06-29 2014-01-20 Toyota Motor Corp 非水電解質二次電池
JP2014029850A (ja) * 2012-06-28 2014-02-13 Nippon Zeon Co Ltd リチウムイオン二次電池負極用スラリー組成物、二次電池用負極および二次電池
WO2014196547A1 (fr) * 2013-06-04 2014-12-11 日本ゼオン株式会社 Composition de liant pour électrode de batterie secondaire au lithium-ion, composition de bouillie pour électrode de batterie secondaire au lithium-ion, électrode pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268053A (ja) * 2002-03-13 2003-09-25 Hitachi Chem Co Ltd 電池用バインダ樹脂、これを含有する電極及び電池
JP2006210208A (ja) * 2005-01-31 2006-08-10 Matsushita Electric Ind Co Ltd 非水電解質二次電池
JP2014029850A (ja) * 2012-06-28 2014-02-13 Nippon Zeon Co Ltd リチウムイオン二次電池負極用スラリー組成物、二次電池用負極および二次電池
JP2014011067A (ja) * 2012-06-29 2014-01-20 Toyota Motor Corp 非水電解質二次電池
WO2014196547A1 (fr) * 2013-06-04 2014-12-11 日本ゼオン株式会社 Composition de liant pour électrode de batterie secondaire au lithium-ion, composition de bouillie pour électrode de batterie secondaire au lithium-ion, électrode pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152056A1 (fr) * 2015-03-24 2016-09-29 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
JP2017103206A (ja) * 2015-11-19 2017-06-08 旭化成株式会社 蓄電デバイス用セパレータ及びそれを用いた積層体、捲回体、リチウムイオン二次電池又は蓄電デバイス
JP2017191777A (ja) * 2016-04-14 2017-10-19 三星エスディアイ株式会社Samsung SDI Co., Ltd. 多孔性耐熱層組成物、多孔性耐熱層を含む分離膜、および該分離膜を用いた電気化学電池
US10468710B2 (en) * 2017-03-06 2019-11-05 Toyota Jidosha Kabushiki Kaisha Nonaqueous secondary battery
JP7003989B2 (ja) 2017-03-27 2022-02-10 日本ゼオン株式会社 電極構成体固定用接着剤及び電気化学素子
JPWO2018180405A1 (ja) * 2017-03-27 2020-02-06 日本ゼオン株式会社 電極構成体固定用接着剤及び電気化学素子
WO2018180232A1 (fr) * 2017-03-28 2018-10-04 東亞合成株式会社 Liant pour électrode de batterie secondaire à électrolyte non aqueux
US11773246B2 (en) 2017-03-28 2023-10-03 Toagosei Co. Ltd. Binder for nonaqueous electrolyte secondary battery electrode
CN110462900A (zh) * 2017-03-28 2019-11-15 东亚合成株式会社 非水电解质二次电池电极用粘合剂
JPWO2018180232A1 (ja) * 2017-03-28 2020-01-23 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
CN110462900B (zh) * 2017-03-28 2023-05-09 东亚合成株式会社 非水电解质二次电池电极用粘合剂
WO2019021810A1 (fr) * 2017-07-24 2019-01-31 株式会社クラレ Membrane de séparation pour des batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant
CN110183584B (zh) * 2019-05-05 2023-05-05 欣旺达惠州动力新能源有限公司 一种丙烯腈聚合物乳液粘结剂及其制备方法
CN110183584A (zh) * 2019-05-05 2019-08-30 欣旺达惠州动力新能源有限公司 一种丙烯腈聚合物乳液粘结剂及其制备方法
CN113363437A (zh) * 2021-05-18 2021-09-07 恒大新能源技术(深圳)有限公司 硅基负极材料及其制备方法、负极片、二次电池
CN114094102A (zh) * 2021-11-03 2022-02-25 珠海冠宇电池股份有限公司 一种二次电池
WO2024024772A1 (fr) * 2022-07-27 2024-02-01 東亞合成株式会社 Liant pour électrode de batterie secondaire à électrolyte non aqueux

Also Published As

Publication number Publication date
JPWO2015133154A1 (ja) 2017-04-06
JP6536564B2 (ja) 2019-07-03

Similar Documents

Publication Publication Date Title
JP6988948B2 (ja) リチウムイオン二次電池電極用バインダー組成物、リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
CN107078299B (zh) 锂离子二次电池及其所用负极、负极用糊组合物、负极用复合颗粒、以及负极用浆料组合物
JP6536564B2 (ja) リチウムイオン二次電池用バインダー組成物、リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池多孔膜用スラリー組成物、リチウムイオン二次電池用電極、及びリチウムイオン二次電池
JP7020118B2 (ja) 非水系二次電池電極用バインダー組成物、非水系二次電池電極用スラリー組成物、非水系二次電池用電極、及び非水系二次電池
JP6627763B2 (ja) 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
JP6398995B2 (ja) 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
JP6855681B2 (ja) リチウムイオン二次電池電極用バインダー組成物、リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
JP6645430B2 (ja) 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
JP6428342B2 (ja) リチウムイオン二次電池電極用バインダー組成物、リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
JP6601413B2 (ja) 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
JP6528497B2 (ja) リチウムイオン二次電池シリコン系負極用バインダー組成物およびリチウムイオン二次電池シリコン系負極用スラリー組成物
JP6477503B2 (ja) リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池
US10249879B2 (en) Binder composition for secondary battery electrode-use, slurry composition for secondary battery electrode-use, electrode for secondary battery-use and production method therefor, and secondary battery
JP7276135B2 (ja) 二次電池用バインダー組成物、二次電池用スラリー組成物、二次電池用機能層、二次電池用電極層および二次電池
EP3306709B1 (fr) Composition de suspension destinée à une électrode négative de batterie rechargeable, électrode négative destinée à une batterie rechargeable et batterie rechargeable
JP6455015B2 (ja) 二次電池用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
JP6579250B2 (ja) 二次電池用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池
WO2020090927A1 (fr) Composition de liant pour batterie secondaire et son procédé de fabrication, composition de bouillie pour batterie secondaire, couche fonctionnelle pour batterie secondaire et son procédé de fabrication, couche d'électrode pour batterie secondaire et batterie secondaire

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15758623

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016506152

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15758623

Country of ref document: EP

Kind code of ref document: A1