WO2016185925A1 - Électrode pour batterie secondaire et batterie secondaire li-ion l'utilisant - Google Patents

Électrode pour batterie secondaire et batterie secondaire li-ion l'utilisant Download PDF

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WO2016185925A1
WO2016185925A1 PCT/JP2016/063729 JP2016063729W WO2016185925A1 WO 2016185925 A1 WO2016185925 A1 WO 2016185925A1 JP 2016063729 W JP2016063729 W JP 2016063729W WO 2016185925 A1 WO2016185925 A1 WO 2016185925A1
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electrode
binder
active material
maleimide
secondary battery
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PCT/JP2016/063729
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English (en)
Japanese (ja)
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井上　和彦
乙幡　牧宏
恵美子 藤井
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日本電気株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode for a secondary battery, a secondary battery using the electrode, and a method for producing the same. More specifically, the present invention relates to an electrode for a secondary battery whose safety and energy density are improved by containing a maleimide resin and a predetermined binder, a lithium ion secondary battery using the same, and a method for producing the same.
  • Secondary batteries such as lithium-ion secondary batteries have advantages such as high energy density, low self-discharge, and excellent long-term reliability, so they are being put to practical use in notebook computers and mobile phones. ing. Furthermore, in recent years, in addition to higher functionality of electronic devices, the market expansion of motor-driven vehicles such as electric vehicles and hybrid vehicles, and the acceleration of the development of household and industrial power storage systems, excellent battery characteristics such as cycle characteristics, In addition, development of a high-performance secondary battery with further improved capacity and energy density is required.
  • an electrode of a secondary battery has a structure in which an electrode mixture layer is formed on a current collector, and the electrode mixture layer includes an active material, a binder, and a conductive auxiliary material if necessary.
  • the binder has a function of adhering between the active material particles and between the active material and the current collector.
  • the binder since it has excellent basic characteristics as a battery binder such as oxidation resistance, adhesiveness, and electrolyte resistance, polyvinylidene fluoride (PVdF) is widely used, and more favorable characteristics are obtained. Development of a binder is being carried out.
  • Patent Document 1 as a binder, a fluorine-containing polymer represented by (B1) (VDF) m (TFE) n (HFP) 1 and (B2) polyvinylidene fluoride or polyacrylic acid
  • a slurry for an electrode mixture containing at least one selected from the group consisting of a polymer, a polymethacrylic acid polymer, polyimide, polyamide and polyamideimide it has excellent adhesion to the current collector and is flexible It is described that an electrode rich in properties can be obtained.
  • Patent Document 2 discloses a lithium battery that includes a positive electrode plate, a negative electrode plate, and a heat insulating layer disposed on the charge / discharge surface of the electrode plate, and that can lower the conductivity when the temperature of the lithium battery increases. Is described.
  • Patent Document 3 a thermal operation protection film is provided on the material surface of the positive electrode plate or the negative electrode plate, and when the temperature of the lithium battery rises to the heat operation temperature of the heat operation protection film, the heat operation protection film is crosslinked.
  • a lithium battery is described that reacts to prevent thermal runaway.
  • the heat-insulating layer (Patent Document 2) and the thermal operation protective film (Patent Document 3) are made of a nitrogen-containing polymer formed by the reaction of a bismaleimide monomer and barbituric acid.
  • the polymer when the temperature of the battery rises, the polymer is converted into a crosslinked polymer, which inhibits lithium ion diffusion and lowers the conductivity of the battery. That is, these batteries use the thermal reactivity of the maleimide group of the polymer to stop the battery function when the temperature rises.
  • an object of the present invention is to provide a secondary battery electrode having high safety and high energy density.
  • One embodiment of the present invention relates to an electrode including an active material, a maleimide resin, and a binder, wherein the content of vinylidene fluoride monomer units in the binder is 2.9% by mass or less of the total mass of the electrode mixture layer.
  • an electrode for a secondary battery having high safety and high energy density can be provided.
  • FIG. 1 is a schematic cross-sectional view of a lithium ion secondary battery using a secondary battery electrode according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view showing a structure of a laminated laminate type secondary battery according to an embodiment of the present invention. It is a disassembled perspective view which shows the basic structure of a film-clad battery. It is sectional drawing which shows the cross section of the battery of FIG. 3 typically.
  • VdF monomer vinylidene fluoride monomer
  • VdF-containing polymer When a polymer containing a VdF monomer unit (hereinafter also referred to as “VdF-containing polymer”) is used as a binder of an electrode containing a maleimide resin, the resilience of the binder is increased, and a high electrode density may not be obtained. This is because HF is eliminated from the VdF monomer unit in the polymer constituting the binder to form a carbon-carbon double bond, and this double bond reacts with the maleimide group of the maleimide resin to form a crosslink (gel) This is considered to be because the flexibility of the binder and thus the electrode mixture layer is impaired.
  • VdF-containing polymer a polymer containing a VdF monomer unit
  • Possible causes of the carbon-carbon double bond from the VdF monomer unit include a basic component derived from the active material, moisture in the slurry used for manufacturing the electrode, and the like.
  • a basic component derived from the active material moisture in the slurry used for manufacturing the electrode, and the like.
  • a high electrode density cannot be obtained even by rolling, and that the compressed electrode mixture layer is restored over time.
  • the high energy density may not be achieved, or the binding force of the electrode mixture layer and the cycle characteristics of the battery (capacity maintenance ratio after repeated charge / discharge) may decrease.
  • the content of the VdF monomer unit in the binder is 2.9% by mass or less of the total mass of the electrode mixture layer, thereby cross-linking the maleimide resin and the binder component. And the flexibility of the electrode mixture layer is secured, and as a result, a high electrode density can be obtained. Note that the above mechanism is inference and does not limit the present invention.
  • the electrode of this embodiment can be made into the structure by which the electrode mixture layer containing an active material, maleimide resin, a binder, and a conductive auxiliary material etc. as needed was formed in the single side
  • the electrode mixture layer may be referred to as “positive electrode active material layer” or “negative electrode active material layer”.
  • the binder of this embodiment is characterized in that the content of vinylidene fluoride (VdF) monomer units is 2.9% by mass or less of the total mass of the electrode mixture layer.
  • the content of the VdF monomer unit is more preferably 2.6% by mass or less, still more preferably 2.3% by mass or less, and may be 0% by mass.
  • VdF-containing polymer As a polymer containing a VdF monomer unit that can be used as a binder (hereinafter also referred to as “VdF-containing polymer”), in addition to polyvinylidene fluoride (PVdF), a copolymer containing a VdF monomer unit (hereinafter referred to as “VdF monomer unit”). (Also referred to as “VdF-containing copolymer”).
  • the monomer other than the VdF monomer constituting the VdF-containing copolymer is not particularly limited as long as it can be polymerized with the VdF monomer.
  • fluorine-containing olefin monomers such as trifluoroethylene chloride (CTFE) and perfluoroalkoxyfluoroethylene.
  • CTFE trifluoroethylene chloride
  • the copolymer may be a binary or ternary or higher copolymer, and may be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or a combination thereof. There may be.
  • VdF-containing copolymer examples include, but are not limited to, a VdF-HFP copolymer, a VdF-TFE copolymer, and a VdF-HFP-TFE copolymer.
  • the ratio of the VdF monomer unit to the other monomer units in the VdF-containing polymer is not particularly limited, and can be 100: 0 to 1:99, preferably 100: 0 to 50:50.
  • the mass average molecular weight of the VdF-containing polymer is not particularly limited, but is preferably in the range of 20,000 to 2,000,000, and more preferably in the range of 200,000 to 1,000,000.
  • the VdF-containing polymer contains fluorine, it has high oxidation resistance and has an advantage that it has an excellent balance of various properties such as heat resistance, adhesiveness, and electrolytic solution resistance.
  • the content of the VdF monomer unit is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more of the total mass of the electrode mixture layer. It is preferable to use it.
  • only a polymer that does not contain a VdF monomer unit may be used as the binder.
  • Polymers that do not contain VdF monomer units include fluorine-containing monomers such as acrylic resin, polyimide, polyamide, styrene-butadiene copolymer rubber, polytetrafluoroethylene (eg, TFE, HFP, CTFE, perfluoroalkoxyalkane, etc.).
  • Fluorine-based resin, polypropylene, polyethylene, polyacrylic acid, polyethersulfone, polyamideimide, and the like are exemplified, but not limited thereto.
  • Only one type of binder may be used, or two or more types of components may be used in combination.
  • the combination of two or more types was either a combination of two or more VdF-containing polymers, a combination of a VdF-containing polymer and a polymer not containing VdF monomer units, or a combination of polymers not containing two or more VdF monomer units. May be.
  • the “vinylidene fluoride (VdF) monomer unit” means a monomer unit represented by (—CH 2 —CF 2 —), and a part of the monomer unit is the above-mentioned HF in the electrode. When it is converted to a structure represented by (—CH ⁇ CF—) by elimination (dehydrofluoric acid reaction), it may further form a crosslink with the maleimide resin.
  • the content of the VdF monomer unit in the present specification means a mass corresponding to (—CH 2 —CF 2 —) before undergoing the dehydrofluorination reaction.
  • content of a VdF monomer unit can also be determined by analyzing an electrode mixture layer individually or in combination of various analysis methods.
  • VdF component which occupies in a mixture layer can be quantified by quantifying the pyrolysis gas derived from VdF by Py / GC / MS (pyrolysis gas mass).
  • the positive electrode binder contains at least one fluorine-containing polymer such as a VdF-containing polymer or tetrafluoroethylene from the viewpoint of oxidation resistance. More preferably, the negative electrode binder contains a water-dispersed polymer such as styrene-butadiene copolymer rubber or polyacrylic acid.
  • the binder content is not particularly limited, but from the viewpoints of “sufficient binding force” and “higher energy” which are in a trade-off relationship, preferably 0.1% by mass or more and 25% by mass of the total mass of the electrode mixture layer. % Or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 1.0% by mass or more and 8.0% by mass or less.
  • the maleimide resin includes compounds having a crosslinking formation temperature of preferably 80 to 250 ° C., more preferably 130 ° C. to 250 ° C., further preferably 150 ° C. to 230 ° C., and particularly preferably 180 ° C. to 200 ° C. . It is preferable that the maleimide resin has a cross-linking temperature of 80 ° C.
  • the crosslinking formation temperature is 250 ° C. or lower because the shutdown function can be exhibited before the secondary battery becomes too hot.
  • the maleimide resin of this embodiment is not particularly limited as long as it has at least one terminal maleimide group, but is preferably a polyfunctional maleimide resin.
  • the polyfunctional maleimide resin has 2 or more, preferably 3 or more, more preferably 4 or more terminal maleimide groups in the molecule. The greater the number of terminal maleimide groups in the molecule, the easier it is to crosslink and form a network when the temperature rises, so that an excellent shutdown function can be given to the battery.
  • maleimide resins examples include maleimide monomers, oligomers, prepolymers and polymers formed using maleimide monomers. Moreover, the polymer which introduce
  • maleimide resin As a preferred embodiment of the maleimide resin, maleimide resins formed using maleimide monomers as exemplified in [1] and [2] below can be mentioned.
  • the maleimide resin may be a homopolymer or a copolymer.
  • hyperbranched polymer having a highly branched structure As a preferred example of maleimide resin, a hyperbranched polymer having a highly branched structure will be described. Since the hyperbranched polymer has a large number of terminal maleimide groups, it can exhibit an excellent shutdown function. Examples of such hyperbranched polymers include hyperbranched polymers formed from a maleimide monomer and a dione compound as described in Japanese Patent No. 5432619.
  • maleimide monomer for forming the hyperbranched polymer a monomaleimide monomer, a bismaleimide monomer, a trimaleimide monomer, and a tetrafunctional or higher functional maleimide monomer can be used in combination.
  • Examples of the bismaleimide monomer include compounds represented by the following formula (1) or (2).
  • R 1 is —R—, —R—NH 2 —R—, —C (O) —, —R—C (O) —R—, —R—C (O) —, —O—, —O—O—, —S—, —S—S—, —S (O) —, —R—S (O) —R—, —SO 2 —, — (C 6 H 4 ) -, -R- (C 6 H 4 ) -R-, -R- (C 6 H 4 ) -O-,-(C 6 H 4 )-(C 6 H 4 )-, -R- (C 6 H 4 ) — (C 6 H 4 ) —R—, or —R— (C 6 H 4 ) — (C 6 H 4 ) —O—, wherein R is an alkylene group having 1 to 8 carbon atoms, -(C 6 H 4 )-represents
  • Y is an alkylene group having 1 to 8 carbon atoms, —C (O) —, —O—, —O—O—, —S—, —S—S—, —S (O)).
  • —, Or —SO 2 —, and X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are each independently halogen, hydrogen, alkyl having 1 to 8 carbons Group, a cycloalkyl group having 1 to 8 carbon atoms, or a silylalkyl group having 1 to 8 carbon atoms.
  • bismaleimide monomer examples are not particularly limited, but N, N′-bismaleimide-4,4′-diphenylmethane, 1,1 ′-(methylenedi-4,1-phenylene) bismaleimide, N, N ′-(1,1′-biphenyl-4,4′-diyl) bismaleimide, N, N ′-(4-methyl-1,3-phenylene) bismaleimide, 1,1 ′-(3 3'-dimethyl-1,1'-biphenyl-4,4'-diyl) bismaleimide, N, N'-ethylenedimaleimide, N, N '-(1,2-phenylene) dimaleimide, N, N'- (1,3-phenylene) dimaleimide, N, N′-thiodimaleimide, N, N′-dithiodimaleimide, N, N′-ketone dimaleimide, N, N′-methylene-bismaleimide, bis-
  • Examples of the monomaleimide monomer, trimaleimide monomer, and tetrafunctional or more maleimide monomer include compounds represented by the following formulas (3) to (6).
  • R 2 is a phenyl group, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
  • each R 3 independently represents a phenylene group, an alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.
  • each R 4 independently represents a phenylene group, an alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.
  • n is 1 to 1000, preferably 1 to 500, and more preferably 5 to 200.
  • the bismaleimide monomer is preferably in the range of 50 to 99 mol% of the total maleimide monomer. The range of 66 to 99 mol% is more preferable.
  • Examples of the dione compound include barbituric acid represented by the following formulas (7) to (10) or derivatives thereof, and acetylacetone represented by the following formula (11) or derivatives thereof.
  • the dione compound does not include a compound having a maleimide group.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently —H, —CH 3 , —C 2 H 5 , —C 6 H 5 , —CH (CH 3 ) 2 , —CH 2 CH (CH 3 ) 2 , —CH 2 CH 2 CH (CH 3 ) 2 , or —CH (CH 3 ) CH 2 CH 2 CH 3. )
  • barbituric acid in which R 5 , R 6 , R 7 and R 8 in the above formulas (7) and (8) are all hydrogen is preferable.
  • R 13 and R 14 are each independently an aliphatic group, an aromatic group, or a heterocyclic group.
  • the compound represented by the above formula (11) is acetylacetone.
  • the aliphatic group is a linear or branched alkyl group having 1 to 6 carbon atoms;
  • the aromatic group is a phenyl group, naphthyl group, benzyl group, phenethyl group, or the like;
  • a heterocyclic group Includes a 4- to 6-membered saturated heterocyclic group or an unsaturated heterocyclic group having at least one selected from O, N, and S as a hetero atom.
  • a hyperbranched polymer can be formed by polymerizing the maleimide monomer, preferably a maleimide monomer containing a bismaleimide monomer, and a dione compound in a solvent containing a Bronsted base.
  • the molar ratio of dione compound to maleimide monomer is 1:20 to 4: 1. More preferably, the molar ratio is from 1: 5 to 2: 1. More preferably, the molar ratio is 1: 3 to 1: 1.
  • the solvent containing a Bronsted base for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), pyrrolidone, N-dodecylpyrrolidone, or a combination thereof can be used.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • pyrrolidone N-dodecylpyrrolidone
  • a Bronsted base for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), pyrrolidone, N-dodecylpyrrolidone, or a combination thereof can be used.
  • another Bronsted neutral solvent such as ⁇ -butyrolactone (GBL) may be added to the Bronsted base.
  • GBL ⁇ -butyrolactone
  • the reaction temperature may be set low, which is preferable.
  • the reaction temperature is, for example, 20 to 150 ° C, preferably 20 to 100 ° C.
  • the branching degree, polymerization degree, structure, etc. of the hyperbranched polymer can be adjusted by adding dione to the reaction in a batch system.
  • the molecular weight (mass average molecular weight) of the hyperbranched polymer is not particularly limited, but is preferably 400 to 100,000, more preferably 800 to 20,000, and 1,000 to 10,000. More preferably, it is 000.
  • the mass average molecular weight is determined by converting the molecular weight using a calibration curve using a monodisperse molecular weight polystyrene as a standard substance using gel permeation chromatography (GPC).
  • the degree of branching (%) of the hyperbranched polymer is not particularly limited, but is preferably 30 to 100%, more preferably 40 to 90%, and still more preferably 50 to 80%. .
  • the degree of branching of the polymer is as follows: T is the number of terminal portions of the polymer, D is the number of branched portions, and L is the number of unbranched portions. (D + T) / (D + T + L) ⁇ 100 (%) It is represented by
  • the hyperbranched polymer preferably has three or more terminal maleimide groups in one molecule.
  • the number of terminal maleimide groups is more preferably 4 or more per molecule, and still more preferably 5 or more.
  • the maleimide resin according to the present embodiment include a prepolymer obtained by reacting bismaleimide and diamine, and a polyaminobismaleimide resin formed using the prepolymer.
  • a prepolymer formed from a bismaleimide compound and an alicyclic diamine is rich in solvent solubility as compared with a prepolymer formed from a bismaleimide compound and a linear aliphatic diamine or aromatic diamine.
  • high temperature is not required for hardening for a long time, it can be used suitably in this embodiment.
  • the molecular weight (mass average molecular weight) of the prepolymer or the resin compound formed using the prepolymer is not particularly limited, but is preferably 400 to 100,000, preferably 800 to It is more preferably 20,000, and even more preferably 1,000 to 10,000.
  • the bismaleimide compound is not particularly limited, and the bismaleimide exemplified in the production of the hyperbranched polymer described above can be used.
  • alicyclic diamines include 4,4′-methylenebiscyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, and 1,3-bis (aminomethyl) cyclohexane. 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, norbornenediamine, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decanediamine, etc. It is done.
  • Each of the bismaleimide compound and the alicyclic diamine can be used alone or in combination of two or more.
  • the reaction solvent is not particularly limited, and 1,4-dioxane, tetrahydrofuran, chloroform, methylene chloride, methyl ethyl ketone and the like can be used.
  • the reaction conditions can be set as appropriate, for example, at 10 to 60 ° C. for 10 minutes to 2 hours.
  • another preferred embodiment of the maleimide resin includes a compound having a structure in which a terminal maleimide group is introduced into an arbitrary polymer structure.
  • the position at which the terminal maleimide group is introduced is not particularly limited, and may be the molecular chain terminal of the polymer structure, may be inside other than the molecular chain terminal, or both.
  • X represents a residue excluding the hydroxyl group of the polyhydric alcohol
  • n is the number of hydroxyl groups of the polyhydric alcohol
  • R each independently has a molecular weight of 100 to 5000 having a maleimide group at the end of the molecular chain.
  • examples of the polyhydric alcohol that gives a residue represented by X include dihydric to tetrahydric alcohols, pentahydric alcohols, cycloalkane polyols, sugar alcohols, and sugars.
  • polyhydric alcohols examples include dihydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol; glycerin, trimethylolpropane, trimethylol Trivalent alcohols such as ethane and hexanetriol; tetrahydric alcohols such as pentaerythritol, methylglycoside, and diglycerin; polyglycerin (eg, triglycerin, tetraglycerin, etc.), polypentaerythritol (eg, dipentaerythritol, tripentaerythritol, etc.) And other alcohols; cycloalkane polyols such as tetrakis (hydroxymethyl) cyclohexanol; adonitol, arabitol, xylitol, sorbitol Manni
  • n is an integer of 2 to 20. From the viewpoint of forming a bridge when the temperature of the secondary battery rises, n is more preferably 3 or more. That is, it is preferable that the polymer having a maleimide group at the molecular chain end represented by the above formula (12) is a branched polymer and has a maleimide group at least at a part of the molecular chain end.
  • R has a structure in which a maleimide group is introduced at an arbitrary polymer terminal.
  • the polymer structure is not particularly limited and can be selected according to the application. Examples thereof include acrylic, polyether, polycarbonate, polyurethane, epoxy, alkyd, and polyester structures having a molecular weight of 100 to 5000.
  • the affinity of the secondary battery with the electrolytic solution can be adjusted by the density of these functional groups. Since carbonates and ethers are widely used as the electrolytic solution, it is preferable to have at least one of a polyether, polycarbonate, polyurethane, and polyester structure having a high affinity as a partial structure.
  • the polymer structure and the maleimide group may be bonded via a linking group.
  • linking group examples include —O—, —CO—, —CO—O—, —Y—, and —O—Y—.
  • -CO-Y- wherein Y is a linear or branched alkylene group having 1 to 20 carbon atoms
  • the branched polymer having a polyester structure as R in the above formula (12) is obtained by transesterifying a polyester resin using a compound having three or more hydroxyl groups as described in, for example, JP-A-2007-284463. It can obtain by making the hydroxyl-terminated polyester resin obtained by reacting with maleimide carboxylic acid.
  • Examples of the branched polymer having a polyester structure include a compound formed from polylactic acid represented by the following formula (13).
  • m is an integer from 1 to 10
  • R ′ each independently represents the following formula:
  • p is an integer of 1 to 50, and Y is a linear or branched alkylene group having 1 to 20 carbon atoms).
  • the molecular weight (mass average molecular weight) of the polymer having a maleimide group of the present embodiment is not particularly limited, but is preferably 400 to 100,000, more preferably 800 to 20,000, More preferably, it is 1000 to 10,000.
  • the content of the maleimide resin is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.0% by mass or less, based on the total mass of the electrode mixture layer. More preferably, it is 0.1 mass% or more and 3.0 mass% or less.
  • the configuration other than the binder and the maleimide resin is not particularly limited. Examples of each component will be described below.
  • the positive electrode active material is not particularly limited as long as it is a material capable of occluding and releasing lithium, but it is preferable to include a high-capacity compound from the viewpoint of increasing the energy density.
  • the high-capacity compound include lithium nickel oxide (LiNiO 2 ) or a lithium nickel composite oxide obtained by substituting a part of Ni of lithium nickelate with another metal element.
  • the layered structure is represented by the following formula (A) Lithium nickel composite oxide is preferred.
  • the Ni content is high, that is, in the formula (A), x is preferably less than 0.5, and more preferably 0.4 or less.
  • x is preferably less than 0.5, and more preferably 0.4 or less.
  • LiNi ⁇ Co ⁇ Mn ⁇ O 2 (0.75 ⁇ ⁇ ⁇ 0.85, 0.05 ⁇ ⁇ ⁇ 0.15, 0.10 ⁇ ⁇ ⁇ 0.20) may be mentioned. More specifically, for example, LiNi 0.8 Co 0.05 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2, LiNi 0.8 Co 0.1 Al can be preferably used 0.1 O 2 or the like.
  • the Ni content does not exceed 0.5, that is, in the formula (A), x is 0.5 or more. It is also preferred that the number of specific transition metals does not exceed half.
  • LiNi 0.4 Co 0.3 Mn 0.3 O 2 (abbreviated as NCM433), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 (abbreviated as NCM523), LiNi 0.5 Co 0.3 Mn 0.2 O 2 (abbreviated as NCM532), etc. (however, the content of each transition metal in these compounds varies by about 10%) Can also be included).
  • two or more compounds represented by the formula (A) may be used as a mixture.
  • NCM532 or NCM523 and NCM433 range from 9: 1 to 1: 9 (typically 2 It is also preferable to use a mixture in 1).
  • a material having a high Ni content (x is 0.4 or less) and a material having a Ni content not exceeding 0.5 (x is 0.5 or more, for example, NCM433) are mixed. As a result, a battery having a high capacity and high thermal stability can be formed.
  • the positive electrode active material for example, LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2), Li 2 MnO 3 , Li x Mn 1.5 Ni 0.5 O 4 (0 ⁇ x ⁇ 2) Lithium manganate having a layered structure or spinel structure such as LiCoO 2 or a part of these transition metals replaced with another metal; Li in these lithium transition metal oxides more than the stoichiometric composition And those having an olivine structure such as LiFePO 4 .
  • any of the positive electrode active materials described above can be used alone or in combination of two or more.
  • content of a positive electrode active material is not specifically limited, In an electrode mixture layer, Preferably it is 70 to 98 mass%, More preferably, it is 80 to 97 mass%, More preferably, it is 85 mass%. The mass is 97% by mass or more.
  • the lithium nickel composite oxide in which x is less than 0.5 in the above formula (A) is preferably contained in the positive electrode active material by 50% by mass or more, and more preferably by 60% by mass or more. 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass. While these active materials having a high Ni content have a high capacity, the energy released during pyrolysis tends to increase, and safety may be required.
  • the electrode containing the maleimide resin according to the present embodiment is applied to the positive electrode, it is possible to provide a shutdown function when the battery temperature rises, so that both high safety and high capacity can be achieved.
  • a negative electrode active material Although it does not restrict
  • a negative electrode active material can be used individually by 1 type or in combination of 2 or more types. In one embodiment, it is preferable to include at least a carbon material.
  • Examples of the carbon material include carbon, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof.
  • carbon with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a negative electrode current collector made of a metal such as copper.
  • amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
  • metals that can be alloyed with lithium include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and alloys of two or more thereof. Is mentioned. Two or more of these metals or alloys may be used in combination. These metals or alloys may contain one or more non-metallic elements. Among these, it is preferable to use silicon, tin, or an alloy thereof as the negative electrode active material. By using silicon or tin as the negative electrode active material, a lithium secondary battery excellent in weight energy density and volume energy density can be provided.
  • the metal oxide that can occlude and release lithium ions examples include silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof. Among these, it is preferable to use silicon oxide as the negative electrode active material.
  • the metal oxide (b) can contain one or more elements selected from nitrogen, boron and sulfur in a range of, for example, 0.1 to 5% by mass.
  • the above-described positive electrode active material and / or negative electrode active material is coated with a maleimide resin.
  • the active material an active material previously coated with a maleimide resin may be used. Or you may coat
  • the method for coating the active material is not particularly limited, and a method of stirring and mixing the active material and the maleimide resin in a solution can be mentioned.
  • the mixing ratio of the active material and the maleimide resin is such that the maleimide resin is 0.05% by mass or more, preferably 0.1% by mass or more and 10% by mass or less, preferably 7% by mass or less with respect to the active material.
  • the mixing ratio may be outside the above range.
  • the solvent used is not particularly limited as long as it can dissolve or disperse the maleimide resin without dissolving the active material.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • Pyrrolidone N-dodecylpyrrolidone, chloroform and the like
  • the step of stirring and mixing can be usually performed at room temperature, and is preferably performed for 15 minutes or more, preferably 30 minutes or more, and preferably within 3 days in consideration of the production process.
  • the coated active material can be obtained by drying under reduced pressure or the like. Moreover, it is also preferable to refine
  • the maleimide resin preferably covers 60% or more of the active material surface, and more preferably covers 70% or more.
  • the surface coverage of the active material is preferably 95% or less. Note that the surface coverage of the active material can be measured by mapping of nitrogen molecules by SEM-EDS (scanning electron microscope / energy dispersive X-ray spectroscopy) capable of light element analysis.
  • a conductive auxiliary material may be added to the electrode mixture layer of the positive electrode and the negative electrode for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as carbon black, acetylene black, and carbon nanotube.
  • the content of the conductive auxiliary material is preferably 0.1 to 10% by mass in the electrode mixture layer, more preferably 0.5 to 5% by mass.
  • a thickener may be added to the electrode mixture layer of the positive electrode and the negative electrode.
  • the thickener include carboxymethyl cellulose, polypropylene oxide, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, hydroxyethyl polyacrylate, ammonium polyacrylate, and sodium polyacrylate.
  • an aqueous dispersion polymer such as SBR is used in the negative electrode, it may be preferable to use a thickener together.
  • the positive electrode and negative electrode current collectors aluminum, nickel, stainless steel, chromium, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • the shape include foil, flat plate, and mesh.
  • the electrode comprises a slurry containing an active material, a maleimide resin, and a binder having a VdF monomer unit content of 2.9% by mass or less of the total mass of the electrode mixture layer on the current collector. It can be manufactured by coating.
  • the slurry can be prepared by kneading an active material, a maleimide resin, a binder, and a conductive auxiliary material, if necessary, using an organic solvent such as N-methylpyrrolidone.
  • an organic solvent such as N-methylpyrrolidone.
  • the maleimide resin, an uncoated active material, and a binder can be directly added to the slurry and kneaded to coat the maleimide resin with the active material.
  • This method is preferable because the reduced-pressure drying step in the above-described active material coating step can be omitted.
  • the slurry obtained as described above is applied on one side or both sides of the current collector, leaving an extension connected to the terminal of the electrode, and dried to form an electrode mixture layer.
  • the temperature of a drying process becomes like this.
  • it is 50 to 200 degreeC, More preferably, it is 80 to 180 degreeC.
  • the temperature of the drying process is too high, a part of the maleimide group reacts, so that the charge / discharge characteristics of the battery may be deteriorated.
  • the obtained electrode mixture layer so as to obtain a desired electrode density.
  • the method for rolling the electrode mixture layer include a uniaxial press and a roll press.
  • a roll press is preferable from the viewpoint of improving productivity, but the method is not limited thereto, and a known method is appropriately adopted. Good.
  • the density can be improved by using a press device provided with a heating device.
  • the resilience of the binder increases due to the reaction between the maleimide resin and the binder. As a result, a desired electrode density may not be obtained even by rolling.
  • the compressed electrode is restored over time, the reliability of the battery is reduced.
  • the adhesive strength of the electrode is reduced, or the electrode is loosened after the electrode is manufactured and / or during the charge / discharge cycle.
  • the cycle characteristics may deteriorate.
  • Such a problem is particularly remarkable when rolling is performed by a roll press.
  • the rebound of the binder can be reduced by setting the content of the VdF monomer unit to 2.9% by mass or less, the energy density and reliability are not affected by the rolling method. Can be improved.
  • the electrode density after rolling is not particularly limited, from the viewpoint of high energy density, the electrode density of the positive 2.90 g / cm 3 or higher, preferably 3.00 g / cm 3 or more, the electrode density of the negative electrode 1 .40g / cm 3 or more, preferably a 1.45 g / cm 3 or more.
  • the electrode density can be appropriately set in consideration of the required energy density and the battery configuration.
  • the electrode which concerns on this embodiment may be used for any one of a positive electrode and a negative electrode, and may be used for both. That is, either the positive electrode or the negative electrode may have a structure not containing a maleimide resin, or may have a structure containing more than 2.9% by mass of the VdF monomer unit in the electrode mixture layer. .
  • the electrode according to this embodiment is used for at least the positive electrode, safety can be improved even when a high-capacity positive electrode active material having a large release energy during pyrolysis is used, and the base derived from the active material raw material In the case where an organic component is also included, a decrease in the flexibility of the binder can be suppressed, which is more preferable.
  • ⁇ Basic structure of secondary battery> There are various types of secondary batteries, such as a cylindrical type, a flat wound square type, a laminated square type, a coin type, a flat wound laminate type, and a laminated laminate type, depending on the structure and shape of the electrode.
  • the present invention is applicable to any of these types.
  • FIG. 1 shows a cross-sectional view of a laminated lithium ion secondary battery according to this embodiment.
  • the lithium ion secondary battery according to the present embodiment includes a positive electrode current collector 3 made of a metal such as an aluminum foil, and a positive electrode active material layer 1 containing a positive electrode active material provided thereon.
  • a negative electrode current collector 4 made of a metal such as copper foil and a negative electrode active material layer 2 containing a negative electrode active material provided thereon.
  • the positive electrode and the negative electrode are laminated via a separator 5 made of a nonwoven fabric or a polypropylene microporous film so that the positive electrode active material layer 1 and the negative electrode active material layer 2 face each other.
  • the electrode element (also referred to as “battery element” or “electrode stack”) preferably has a configuration in which a plurality of positive electrodes and a plurality of negative electrodes are stacked via a separator, as shown in FIG.
  • the secondary battery includes a battery element 20, a film outer package 10 that houses the battery element 20 together with an electrolyte, and a positive electrode tab 51 and a negative electrode tab 52 (hereinafter also simply referred to as “electrode tabs”). .
  • the battery element 20 is formed by alternately stacking a plurality of positive electrodes 30 and a plurality of negative electrodes 40 with a separator 25 interposed therebetween.
  • the electrode material 32 is applied to both surfaces of the metal foil 31.
  • the electrode material 42 is applied to both surfaces of the metal foil 41. Note that the present invention is not limited to a stacked battery, and can be applied to a battery of a wound type.
  • the secondary battery of FIG. 1 has electrode tabs pulled out on both sides of the outer package, but the secondary battery to which the present invention can be applied has the electrode tab pulled out on one side of the outer package as shown in FIG. It may be a configuration.
  • each of the positive and negative metal foils has an extension on a part of the outer periphery.
  • the extensions of the negative electrode metal foil are collected together and connected to the negative electrode tab 52, and the extensions of the positive electrode metal foil are collected together and connected to the positive electrode tab 51 (see FIG. 4).
  • the portions gathered together in the stacking direction between the extension portions in this way are also called “current collecting portions”.
  • the film outer package 10 is composed of two films 10-1 and 10-2 in this example.
  • the films 10-1 and 10-2 are heat sealed to each other at the periphery of the battery element 20 and sealed.
  • the positive electrode tab 51 and the negative electrode tab 52 are drawn out in the same direction from one short side of the film outer package 10 sealed in this way.
  • FIGS. 3 and 4 show examples in which the cup portion is formed on one film 10-1 and the cup portion is not formed on the other film 10-2.
  • a configuration in which a cup portion is formed on both films (not shown) or a configuration in which neither cup portion is formed (not shown) may be employed.
  • a non-aqueous electrolytic solution containing a lithium salt (supporting salt) and a non-aqueous solvent that dissolves the supporting salt can be used.
  • an aprotic organic solvent such as carbonate ester (chain or cyclic carbonate), carboxylic acid ester (chain or cyclic carboxylic acid ester), and phosphate ester can be used.
  • carbonate solvents examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate. (EMC), chain carbonates such as dipropyl carbonate (DPC); and propylene carbonate derivatives.
  • PC propylene carbonate
  • EC ethylene carbonate
  • BC butylene carbonate
  • VVC vinylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DPC dipropyl carbonate
  • propylene carbonate derivatives examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate
  • carboxylic acid ester solvent examples include aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate; and lactones such as ⁇ -butyrolactone.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like.
  • solvents that can be contained in the non-aqueous electrolyte include, for example, ethylene sulfite (ES), propane sultone (PS), butane sultone (BS), dioxathilane-2,2-dioxide (DD), and sulfolene.
  • ES ethylene sulfite
  • PS propane sultone
  • BS butane sultone
  • DD dioxathilane-2,2-dioxide
  • sulfolene sulfolene
  • a non-aqueous solvent can be used individually by 1 type or in combination of 2 or more types.
  • LiPF 6 LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN ( CF 3 SO 2) 2 normal lithium salt which can be used in lithium ion batteries or the like can be used.
  • the supporting salt can be used alone or in combination of two or more.
  • Porous films and nonwoven fabrics such as a polypropylene, polyethylene, fluorine resin, aliphatic polyamide, aromatic polyamide, polyimide, polyester, polyphenylene sulfide, and these as a base material
  • What adhered or joined inorganic substances, such as a silica, an alumina, and glass, and what processed independently as a nonwoven fabric or cloth can be used.
  • stacked them can also be used as a separator.
  • the exterior body can be appropriately selected as long as it is stable to the electrolyte and has a sufficient water vapor barrier property.
  • a laminated laminate type secondary battery a laminate film made of aluminum, silica-coated polypropylene, polyethylene, or the like can be used as the outer package.
  • An exterior body may be comprised with a single member and may be comprised combining several members.
  • the secondary battery according to the present embodiment can be manufactured according to a normal method.
  • a laminated laminate type lithium ion secondary battery can be manufactured as follows. First, according to the above, a positive electrode and a negative electrode in which an electrode mixture layer is provided on a current collector are prepared.
  • the positive electrode and the negative electrode are arranged to face each other via a separator to form an electrode pair, and an electrode stack having the number of layers corresponding to a predetermined capacity is formed.
  • This electrode laminated body has a positive electrode terminal connected to the positive electrode current collector and a negative electrode terminal connected to the negative electrode current collector.
  • this electrode laminated body is accommodated in an exterior body (container), a nonaqueous electrolytic solution is injected, and the electrode is impregnated with the electrolytic solution. Then, the opening part of an exterior body is sealed and a secondary battery is completed.
  • a plurality of lithium ion secondary batteries provided with the secondary battery electrode of the present embodiment on the positive electrode and / or the negative electrode can be combined to form a battery pack (assembled battery).
  • the battery pack may have a configuration in which two or more secondary batteries are connected in series, in parallel, or both in accordance with the battery capacity and output.
  • the secondary battery or its battery pack of this embodiment can be used for a vehicle.
  • the vehicle include a hybrid vehicle, a fuel cell vehicle, and an electric vehicle (all include four-wheeled vehicles (passenger cars, commercial vehicles such as trucks and buses, light vehicles, etc.), two-wheeled vehicles (motorcycles), and three-wheeled vehicles). Since these vehicles include the secondary battery according to the present embodiment, they are excellent in safety and reliability.
  • the vehicle according to the present embodiment is not limited to an automobile, and may be various power sources for other vehicles, for example, a moving body such as a train.
  • the secondary battery or the assembled battery according to this embodiment can be used for a power storage device.
  • a power storage device for example, a power source connected to a commercial power source supplied to a general household and a load such as a home appliance, and used as a backup power source or auxiliary power at the time of a power failure, Examples include photovoltaic power generation, which is also used for large-scale power storage for stabilizing power output with large time fluctuation due to renewable energy.
  • each p is independently an integer of 1 to 50 with respect to R.
  • Example 2 Synthesis of Maleimide Resin Compound (Resin B) (1) 4.5 g of 4,4′-bismaleimide di-phenylmethane was placed in a 250 mL three-necked round bottom flask, 60 g of NMP solvent was added, and heated to 70 ° C. With sufficient agitation, 4,4′-bismaleimide di-phenylmethane was completely dissolved in the NMP solvent (R5).
  • BTA barbituric acid
  • Resin (A) was added to a slurry of a metal oxide (lithium nickel composite oxide (NCA: LiNi 0.80 Co 0.15 Al 0.05 O 2 )) and chloroform of the same mass with respect to the metal oxide. The mixture was added at a ratio of 11% by mass, mixed and stirred for 60 minutes, and then dried under reduced pressure to prepare a coated body (MA) -1 of a metal oxide resin (A).
  • a metal oxide lithium nickel composite oxide (NCA: LiNi 0.80 Co 0.15 Al 0.05 O 2 )
  • Example 3-2 A coating (MA) -2 was obtained in the same manner as in Example 3-1, except that the ratio of the resin (A) was changed to 0.54% by mass.
  • Example 3-3 A coating (MA) -3 was obtained in the same manner as in Example 3-1, except that the proportion of the resin (A) was 1.1% by mass.
  • Example 3-4 A coating (MA) -4 was obtained in the same manner as in Example 3-1, except that the ratio of the resin (A) was 3.4% by mass.
  • Example 3-5 A coating (MB) -1 was obtained in the same manner as in Example 3-1, except that the maleimide resin was changed to resin (B).
  • the amount of the resin (B) added is a value corresponding to the weight of the resin (B) excluding the solvent in the solution (R7).
  • Example 3-6 A coating (MB) -2 was obtained in the same manner as in Example 3-3 except that the maleimide resin was changed to resin (B).
  • Example 3-7 A coating (MB) -3 was obtained in the same manner as in Example 3-4 except that the maleimide resin was changed to resin (B).
  • Example 3-8 A slurry was prepared in the same manner as in Example 3-3 except that the metal oxide of the slurry was (lithium nickel composite oxide (NMC: LiNi 0.80 Mn 0.15 Co 0.05 O 2 )). C) -1 was obtained.
  • NMC lithium nickel composite oxide
  • NMP N-methyl-2-pyrrolidone
  • Natural graphite, sodium carboxymethyl methylcellulose as a thickener, and styrene-butadiene rubber as a binder are mixed in an aqueous solution at a weight ratio of 98.0: 1.0: 1.0 to prepare a slurry, and copper
  • the negative electrode active material layer was formed by coating on a current collector foil and drying. Similarly, after forming an active material layer on the back surface of the current collector foil made of copper, a negative electrode plate was obtained by rolling.
  • Electrode As the non-aqueous solvent of the electrolytic solution, a non-aqueous solvent in which EC and DEC were mixed at a volume ratio of 30:70 (EC: DEC) was used. LiPF 6 was dissolved as a supporting salt to a concentration of 1M.
  • the positive electrode plate was cut to 30 mm ⁇ 30 mm without the current extraction portion, and the negative electrode plate was cut to 32 mm ⁇ 32 mm without the current extraction portion, and laminated via a separator.
  • the electrode laminate in which the electrode and the separator were laminated was connected to the electrode tab and housed in a film outer package made of a laminate film of an aluminum film and a resin film. After injecting the electrolytic solution, the outer package made of a laminate film was sealed under a reduced pressure atmosphere to produce a battery. The operation of discharging the produced secondary battery to 4.3 V at 1 C and then discharging to 3 V at 1 C was repeated 500 times. Table 2 shows the capacity retention after 500 times.
  • PVdF polyvinylidene fluoride
  • Example 4-3 A positive electrode using a covering (MA) -3 as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 94.0: 4.0: 2.0.
  • a battery was fabricated and evaluated in the same manner as in Example 4-1, except that was fabricated.
  • (PVdF / PAA) was used at a weight ratio of 93.0: 4.0: 3.0 to produce a positive electrode.
  • a battery was produced and evaluated in the same manner as in Example 4-1, except that (PVdF / PES) was used at a weight ratio of 93.0: 4.0: 3.0 to produce a positive electrode.
  • a battery was produced and evaluated in the same manner as in Example 4-1, except that a positive electrode was produced using a weight ratio of 93.0: 4.0: 3.0.
  • Example 4-7 Except that a positive electrode was produced using a covering (MA) -1 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder in a weight ratio of 92.1: 4.0: 3.9. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • a covering (MA) -1 as an active material
  • carbon black as a carbon conductive agent
  • PVdF-HFP as a binder in a weight ratio of 92.1: 4.0: 3.9.
  • a battery was prepared and evaluated in the same manner as in Example 4-1.
  • Example 4-8 Except that a positive electrode was produced using a covering (MA) -4 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder at a weight ratio of 92.1: 4.0: 3.9. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • Example 4-9 Except that a positive electrode was produced using a covering (MB) -1 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder in a weight ratio of 92.1: 4.0: 3.9. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • MB covering
  • PVdF-HFP PVdF-HFP
  • Example 4-10 Except that a positive electrode was produced using a covering (MB) -3 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder at a weight ratio of 92.1: 4.0: 3.9. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • Example 4-11 Except that a positive electrode was produced using a covering (MC) -1 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder in a weight ratio of 92.1: 4.0: 3.9. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • MC covering
  • PVdF-HFP PVdF-HFP
  • Example 4-1 A positive electrode using a covering (MA) -3 as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 92.0: 4.0: 4.0.
  • a battery was fabricated and evaluated in the same manner as in Example 4-1, except that was fabricated.
  • Example 4-2 A positive electrode using a covering (MB) -2 as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 92.0: 4.0: 4.0 A battery was fabricated and evaluated in the same manner as in Example 4-1, except that was fabricated.
  • MB covering
  • PVdF polyvinylidene fluoride
  • Example 4-3 An uncoated metal oxide (NCA) as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder are used at a weight ratio of 92.0: 4.0: 4.0.
  • NCA uncoated metal oxide
  • PVdF polyvinylidene fluoride
  • Example 4-5 A positive electrode using a covering (MA) -2 as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 93.0: 4.0: 3.0 A battery was fabricated and evaluated in the same manner as in Example 4-1, except that was fabricated.
  • MA covering
  • PVdF polyvinylidene fluoride
  • Example 4-6 A positive electrode using a covering (MA) -3 as an active material, carbon black as a carbon conductive agent, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 93.0: 4.0: 3.0 A battery was fabricated and evaluated in the same manner as in Example 4-1, except that was fabricated.
  • MA covering
  • PVdF polyvinylidene fluoride
  • Example 4-7 Except that a positive electrode was produced using a covering (MA) -3 as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder at a weight ratio of 92.0: 4.0: 4.0. A battery was prepared and evaluated in the same manner as in Example 4-1.
  • a positive electrode was prepared using metal oxide (NCA) not coated as an active material, carbon black as a carbon conductive agent, and PVdF-HFP as a binder at a weight ratio of 92.0: 4.0: 4.0.
  • NCA metal oxide
  • PVdF-HFP as a binder
  • the battery according to the present invention can be used in, for example, all industrial fields that require a power source and industrial fields related to transportation, storage, and supply of electrical energy.
  • power supplies for mobile devices such as mobile phones and notebook computers
  • power supplies for transportation and transportation media such as trains, satellites, and submarines, including electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
  • a backup power source such as a UPS
  • a power storage facility for storing power generated by solar power generation, wind power generation, etc .
  • power storage facility for storing power generated by solar power generation, wind power generation, etc .

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Abstract

La présente invention concerne une électrode comprenant une substance active, une résine de maléimide, et un liant. La teneur d'une unité monomère de fluorure de vinylidène dans le liant est de 2,9% en masse ou moins de la masse totale d'une couche de mélange d'électrode.
PCT/JP2016/063729 2015-05-15 2016-05-09 Électrode pour batterie secondaire et batterie secondaire li-ion l'utilisant WO2016185925A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018128139A1 (fr) * 2017-01-06 2018-07-12 三井化学株式会社 Batterie rechargeable à électrolyte non aqueux et matériau s'utilisant dans celle-ci
WO2019176553A1 (fr) * 2018-03-15 2019-09-19 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux et son procédé de production
CN115986056A (zh) * 2023-03-17 2023-04-18 宁德新能源科技有限公司 二次电池及电子装置

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JPWO2018128139A1 (ja) * 2017-01-06 2019-11-14 三井化学株式会社 非水電解質二次電池及びそれに用いる材料
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