WO2010098380A1 - Électrode pour pile secondaire au lithium-ion - Google Patents

Électrode pour pile secondaire au lithium-ion Download PDF

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Publication number
WO2010098380A1
WO2010098380A1 PCT/JP2010/052946 JP2010052946W WO2010098380A1 WO 2010098380 A1 WO2010098380 A1 WO 2010098380A1 JP 2010052946 W JP2010052946 W JP 2010052946W WO 2010098380 A1 WO2010098380 A1 WO 2010098380A1
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electrode
meth
group
binder
active material
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PCT/JP2010/052946
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English (en)
Japanese (ja)
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康尋 脇坂
真弓 福峯
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日本ゼオン株式会社
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Priority to JP2011501634A priority Critical patent/JP5569515B2/ja
Priority to KR1020117019672A priority patent/KR101529758B1/ko
Publication of WO2010098380A1 publication Critical patent/WO2010098380A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 lithium ion secondary battery having a porous film, and more particularly to an electrode for a lithium ion secondary battery having a porous film layer having high flexibility and rate characteristics. Moreover, this invention relates to the lithium ion secondary battery provided with the electrode which has this porous membrane layer.
  • lithium ion secondary batteries exhibit the highest energy density and are often used especially for small electronics applications. In addition to small electronics applications, it is also expected to be used in automotive applications. Among them, there is a demand for improved safety while further improving the high rate, high capacity, and long life of lithium ion secondary batteries.
  • a lithium ion secondary battery generally includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte including an electrode active material layer carried on a current collector.
  • the electrode active material layer includes an electrode active material having an average particle size of about 5 to 50 ⁇ m and a binder.
  • the electrode is produced by applying an active material layer forming slurry containing a powdered electrode active material on a current collector to form an electrode active material layer.
  • a separator for separating the positive electrode and the negative electrode a very thin separator made of stretched polyethylene resin or the like having a thickness of about 10 to 50 ⁇ m is used.
  • a lithium ion secondary battery is manufactured through a lamination process of an electrode and a separator, a cutting process of cutting into a predetermined electrode shape, and the like.
  • the active material may fall off from the electrode active material layer, and a part of the dropped active material may be included in the battery as foreign matter.
  • Such a foreign substance has a particle size of about 5 to 50 ⁇ m and is approximately the same as the thickness of the separator, so that it causes a problem of penetrating the separator in the assembled battery and causing a short circuit. Further, heat is generated when the battery is operated. As a result, the separator made of stretched polyethylene resin or the like is also heated. In general, a separator made of stretched polyethylene resin or the like tends to shrink even at a temperature of 150 ° C. or less, and easily leads to a short circuit of the battery. Further, when a sharply shaped protrusion such as a nail penetrates the battery (for example, during a nail penetration test), a short circuit occurs instantaneously, reaction heat is generated, and the short circuit part expands.
  • non-conductive particles on or in the separator Inclusion of inorganic particles such as alumina as non-conductive particles increases the strength of the separator and improves safety. Also, by coating the electrode with a porous film layer containing non-conductive particles rather than coating the non-conductive particles on the separator, the porous film layer does not shrink at all, so there is a risk of short circuit. Are much less likely, and significant safety improvements are expected. Furthermore, by providing a porous membrane layer, it is possible to prevent the active material from dropping off during the battery production process. In addition to improving safety by introducing these porous membrane layers, there is a need for material development that meets the demands for higher capacity, longer life, and higher rate characteristics. In addition, various studies have been made to coat a separator and an electrode with a porous film layer containing titanium oxide or zinc oxide having a high dielectric constant instead of alumina having a low dielectric constant.
  • Patent Document 1 discloses a porous protective film formed on an electrode using fine particles such as titanium oxide and PVDF or polyethylene as a binder.
  • Patent Document 2 studies are also being made to form a protective film on an electrode by using a heat-crosslinking resin containing acrylonitrile in an inorganic filler such as titanium oxide, zirconium oxide or magnesium oxide.
  • JP 2000-149906 A JP-A-2005-353584 (corresponding US Patent Application Publication No. 2008/44733)
  • the present invention has been made in view of the prior art as described above, and in an electrode having a porous film used for a lithium ion secondary battery, a porous film that can contribute to flexibility, rate characteristics, and cycle characteristics is provided. It aims at providing the electrode for lithium ion secondary batteries which has.
  • the porous film contains a specific copolymer as a binder and specific non-conductive particles.
  • the non-conductive particles in the porous film can be reduced during winding, and the electrolyte retention in the binder in the battery is improved. It has been found that it exhibits cycle characteristics, and the present invention has been completed.
  • the present invention for solving the above-mentioned problems includes the following matters as a gist.
  • a gist On the current collector, an electrode active material layer and a porous film containing a non-conductive particle having a dielectric constant of 10 or more and a binder are laminated in this order.
  • Lithium ion comprising a copolymer comprising) an acrylonitrile monomer unit and a (meth) acrylic acid ester monomer unit, and the content ratio of the (meth) acrylonitrile monomer unit is less than 50% by mass.
  • Secondary battery electrode On the current collector, an electrode active material layer and a porous film containing a non-conductive particle having a dielectric constant of 10 or more and a binder are laminated in this order.
  • Lithium ion comprising a copolymer comprising) an acrylonitrile monomer unit and a (meth) acrylic acid ester monomer unit, and the content ratio of the (meth) acrylonitrile
  • the copolymer contained in the binder contains a heat crosslinkable crosslinkable group, and the heat crosslinkable crosslinkable group is composed of an epoxy group, an N-methylolamide group, and an oxazoline group.
  • the electrode for a lithium ion secondary battery according to (2) which is at least one selected from:
  • the copolymer contained in the binder further comprises at least one hydrophilic group selected from the group consisting of a carboxylic acid group, a hydroxyl group and a sulfonic acid group.
  • the electrode for lithium ion secondary batteries in any one.
  • Non-conductive particles having a dielectric constant of 10 or more, a binder and a solvent, wherein the binder includes a (meth) acrylonitrile monomer unit and a (meth) acrylate monomer unit, And the slurry for porous films which contains the copolymer whose content rate of the said (meth) acrylonitrile monomer unit is less than 50 weight%.
  • a method for producing an electrode for a lithium ion secondary battery comprising applying the slurry for a porous membrane according to (6) above onto an electrode active material layer and then drying the slurry.
  • a lithium ion secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the electrode according to (1) above.
  • a porous membrane that can suppress the dropping of the porous membrane layer during winding.
  • a porous membrane is formed on the surface of the secondary battery electrode, functions as a protective film for the electrode, has a high non-conductive particle retention in the porous membrane surface layer portion, and can be prevented from falling off during winding.
  • the present invention is described in detail below.
  • the electrode for a lithium ion secondary battery of the present invention is formed by laminating an electrode active material layer and a porous film containing non-conductive particles having a dielectric constant of 10 or more and a binder in this order on a current collector. .
  • Non-conductive particles It is desired that the nonconductive particles having a dielectric constant of 10 or more used in the present invention exist stably in the usage environment of the lithium ion secondary battery and are also stable electrochemically. Various non-conductive inorganic particles can be used.
  • oxide particles such as magnesium oxide, zirconium oxide, zinc oxide and titanium oxide, and covalently bonded crystal particles such as diamond are used. These particles may be subjected to element substitution, surface treatment, or solid solution as necessary, and may be used alone or in combination of two or more. Among these, oxide particles are preferable from the viewpoints of stability in an electrolytic solution and potential stability.
  • the dielectric constant is preferably 20 or more and less than 500, more preferably 30 or more and less than 500, and particularly preferably 50 or more and less than 200.
  • the dielectric constant of the nonconductive particles is within the above range, the dispersibility of the nonconductive particles and the strength of the porous film are excellent.
  • the dielectric constant of the non-conductive particles is less than 10
  • the dispersibility of the non-conductive particles and the strength of the porous film become insufficient, and the non-conductive particles easily fall off from the porous film.
  • non-conductive metal such as carbon black, graphite, SnO 2 , ITO, metal powder, and fine powder of conductive compounds and oxides
  • electrical insulation can be achieved. It can also be used.
  • non-conductive particles may be used in combination of two or more thereof.
  • the average particle diameter (volume average D50 average particle diameter) of the non-conductive particles used in the present invention is preferably 5 nm or more and 10 ⁇ m or less, more preferably 10 nm or more and 5 ⁇ m or less.
  • the average particle diameter of the non-conductive particles be in the range of 50 nm or more and 2 ⁇ m or less because dispersibility, ease of application, and control of voids are excellent.
  • the BET specific surface area of these particles is preferably 0.9 to 200 m 2 / g from the viewpoint of suppressing the aggregation of the particles and optimizing the fluidity of the slurry. More preferably, it is ⁇ 150 m 2 / g.
  • the shape of the non-conductive powder used in the present invention is not particularly limited, such as a spherical shape, a needle shape, a rod shape, a conical shape, and a plate shape. Porous particles can also be used.
  • the content ratio of non-conductive particles in the porous membrane is preferably 5 to 99% by mass, more preferably 50 to 98% by mass.
  • the binder used in the present invention comprises a copolymer containing a (meth) acrylonitrile monomer unit and a (meth) acrylic acid ester monomer unit.
  • This copolymer is obtained by copolymerizing at least a monomer that provides a (meth) acrylonitrile monomer unit and a monomer that provides a (meth) acrylic acid ester monomer unit.
  • (meth) acrylic acid means acrylic acid and methacrylic acid
  • (meth) acrylo” means acrylo and methacrylo.
  • Examples of the monomer that gives the (meth) acrylic acid ester monomer unit include (meth) acrylic acid alkyl ester, (meth) acrylic acid perfluoroalkyl ester, and (meth) acrylic acid ester having a functional group in the side chain. Can be mentioned. Of these, (meth) acrylic acid alkyl esters are preferred, and they exhibit lithium ion conductivity due to swelling in the electrolyte, and are difficult to cause bridging and aggregation due to the polymer in a small particle size dispersion.
  • the number of carbon atoms of the alkyl group or perfluoroalkyl group bonded to the non-carbonyl oxygen atom of the ester or (meth) acrylic acid perfluoroalkyl ester is preferably 1 to 14, more preferably 1 to 5.
  • Examples of (meth) acrylic acid alkyl esters in which the alkyl group or perfluoroalkyl group bonded to the non-carbonyl oxygen atom has 1 to 5 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid Alkyl acrylates such as isopropyl, n-butyl acrylate and t-butyl acrylate; 2- (perfluorobutyl) ethyl acrylate, 2- (perfluoropentyl) ethyl acrylate and the like Fluoroalkyl) ethyl; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate; and 2- (par Fluorobuty ) Ethyl methacrylate,
  • acrylic acid alkyl esters include non-carbonyl oxygen such as n-hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, and isobornyl acrylate
  • Examples of the monomer giving the (meth) acrylonitrile monomer unit used in the present invention include acrylonitrile and methacrylonitrile.
  • the content ratio of the (meth) acrylonitrile monomer unit in the copolymer needs to be less than 50% by mass.
  • the content ratio of the (meth) acrylonitrile monomer unit in the copolymer is 50% by mass or more, the flexibility of the binder is lowered, and the porous film is powdered off.
  • the content rate of the (meth) acrylonitrile monomer unit in a copolymer becomes like this.
  • they are 5 mass% or more and 40 mass% or less, More preferably, they are 10 mass% or more and 20 mass% or less.
  • the body unit) is in a mass ratio of preferably 5/95 to 50/50, more preferably 5/95 to 30/70, and still more preferably 10/90 to 20/80.
  • the total content of (meth) acrylonitrile monomer units and (meth) acrylic acid ester monomer units in the copolymer is preferably 50% by mass or more, and 60% by mass or more. It is more preferable, and it is especially preferable that it is 75 mass or more.
  • flexibility of a porous film are made by making the content rate of the (meth) acrylonitrile monomer unit and the (meth) acrylic acid ester monomer unit in a copolymer into the said range. Can be improved together.
  • the binder used in the present invention is preferably crosslinkable by heating or energy ray irradiation.
  • the crosslinking density can be adjusted by the intensity of heating or energy beam irradiation.
  • the degree of swelling decreases as the crosslink density increases, the degree of swelling can be adjusted by changing the crosslink density.
  • a binder that can be cross-linked by heating or energy ray irradiation can be obtained by containing a cross-linking agent in the binder and / or by containing a cross-linkable group in the copolymer constituting the binder. it can.
  • the binder contains a crosslinking agent containing a thermally crosslinkable group in addition to the copolymer constituting the binder, and / or in the copolymer constituting the binder.
  • a heat-crosslinkable crosslinkable group is contained in the porous film, the porous film can be cross-linked by heat treatment after the porous film is formed, and further, the dissolution in the electrolyte can be suppressed. It is preferable because a porous film can be obtained.
  • the crosslinking agent to be used is not particularly limited, but may be an organic peroxide, heat or A cross-linking agent that exhibits an effect by light is used.
  • an organic peroxide or a crosslinking agent that exhibits an effect by heat is preferable in that it contains a thermally crosslinkable group.
  • organic peroxide examples include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis ( peroxyketals such as t-butylperoxy) butane; hydroperoxides such as t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide; dicumyl peroxide, 2, Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, ⁇ , ⁇ 'bis (t-butylperoxy-m-isopropyl) benzene: octanoyl peroxide, iso Diacyl peroxides such as butyryl peroxide; peroxydicarbonate And peroxyesters. Among these, dialkyl
  • the cross-linking agent (curing agent) that exhibits an effect by heat is not particularly limited as long as it can be cross-linked by heating, but diamine, triamine or higher aliphatic polyamine, alicyclic polyamine, aromatic polyamine bisazide. , Acid anhydrides, dicarboxylic acids, diols, polyhydric phenols, polyamides, diisocyanates, polyisocyanates and the like.
  • aliphatic polyamines such as hexamethylenediamine, triethylenetetraamine, diethylenetriamine, and tetraethylenepentamine; diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 2,6 ] decane; 1,3- (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis Alicyclic polyamines such as (4-aminocyclohexyl) methane; 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, ⁇ , ⁇ '-bis (4-aminophenyl) -1,3-diisopropylbenzene , ⁇ , ⁇ '-bis (4-aminophene,
  • aromatic polyamines, acid anhydrides, polyhydric phenols and polyhydric alcohols are preferred for reasons such as excellent strength and adhesion of the porous membrane, and among them, 4,4-diaminodiphenylmethane (aromatic Polyamines), maleic anhydride-modified norbornene resins (acid anhydrides), polyhydric phenols and the like are particularly preferable.
  • the crosslinking agent that exhibits an effect by light reacts with the copolymer of the present invention by irradiation with actinic rays such as g rays, h rays and i rays, far ultraviolet rays, x rays and electron rays.
  • actinic rays such as g rays, h rays and i rays, far ultraviolet rays, x rays and electron rays.
  • it is not particularly limited as long as it is a photoreactive substance that forms a crosslinking compound, and examples thereof include an aromatic bisazide compound, a photoamine generator, and a photoacid generator.
  • aromatic bisazide compound examples include 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) 4-methylcyclohexanone, Representative examples include 4'-diazidodiphenylsulfone, 4,4'-diazidobenzophenone, 4,4'-diazidodiphenyl, 2,7-diazidofluorene, 4,4'-diazidophenylmethane, and the like. . These can be used singly or in combination of two or more.
  • the photoamine generator examples include o-nitrobenzyloxycarbonyl carbamate, 2,6-dinitrobenzyloxycarbonyl carbamate or ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyloxycarbonyl of aromatic amine or aliphatic amine.
  • examples thereof include carbamate bodies. More specifically, o-nitrobenzyloxycarbonyl carbamates such as aniline, cyclohexylamine, piperidine and the like can be mentioned. These can be used singly or in combination of two or more.
  • the photoacid generator is a substance that generates Bronsted acid or Lewis acid upon irradiation with actinic rays.
  • onium salts halogenated organic compounds, quinonediazide compounds, ⁇ , ⁇ -bis (sulfonyl) diazomethane series Compounds, ⁇ -carbonyl- ⁇ -sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and the like.
  • These compounds that can be cleaved by irradiation with actinic rays to generate an acid may be used alone or in combination of two or more.
  • cross-linking agents can be used alone or in combination of two or more.
  • the amount of the crosslinking agent is usually in the range of 0.001 to 30 parts by weight, preferably 0.01 to 25 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer used in the present invention. It is. When the amount of these cross-linking agents is within this range, the crosslinkability and the properties of the cross-linked product such as lithium conductivity in the electrolytic solution, solubility in the electrolytic solution, and strength of the porous membrane are highly balanced, which is preferable.
  • cross-linking aid when a cross-linking agent is used, it is preferable to further use a cross-linking aid (curing aid) because the cross-linking property and the dispersibility of the compounding agent can be further improved.
  • the crosslinking aid used in the present invention is not particularly limited, but may be a known one disclosed in JP-A No. 62-34924, for example, quinone dioxime, benzoquinone dioxime, p.
  • Oxime / nitroso crosslinking aids such as nitrosophenol; maleimide crosslinking aids such as N, Nm-phenylenebismaleimide; allylic crosslinking aids such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate; Examples thereof include methacrylate-based crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; vinyl-based crosslinking aids such as vinyltoluene, ethylvinylbenzene and divinylbenzene; Among these, allylic crosslinking auxiliaries and methacrylate crosslinking auxiliaries are preferable because they are easily dispersed uniformly.
  • the addition amount of the crosslinking aid is appropriately selected depending on the type of the crosslinking agent, but is usually 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 1 part by mass of the crosslinking agent. If the addition amount of the crosslinking aid is too small, crosslinking is difficult to occur. Conversely, if the addition amount is too large, the lithium conductivity and water resistance of the crosslinked binder may be lowered.
  • the heat-crosslinkable crosslinkable group is selected from the group consisting of an epoxy group, an N-methylolamide group, and an oxazoline group. At least one selected from the above is preferable, and an epoxy group is more preferable because it is easy to adjust the crosslinkability and the crosslink density.
  • the thermally crosslinkable crosslinkable group is a monomer that provides a (meth) acrylonitrile monomer unit and a monomer that provides a (meth) acrylic acid ester monomer unit.
  • a monomer containing a thermally crosslinkable crosslinking group is added, and if necessary, it can be introduced into the copolymer by copolymerizing with other monomers copolymerizable therewith.
  • Examples of the monomer containing an epoxy group include a monomer containing a carbon-carbon double bond and an epoxy group, and a monomer containing a halogen atom and an epoxy group.
  • Examples of the monomer containing a carbon-carbon double bond and an epoxy group include unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether; butadiene monoepoxide, Diene or polyene monoepoxides such as chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene; -Alkenyl epoxides such as epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl
  • Examples of the monomer having a halogen atom and an epoxy group include epihalohydrins such as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, ⁇ -methylepichlorohydrin; p-chlorostyrene oxide; dibromo Phenyl glycidyl ether;
  • Examples of the monomer containing an N-methylolamide group include (meth) acrylamides having a methylol group such as N-methylol (meth) acrylamide.
  • Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Examples thereof include oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like.
  • the content ratio of the heat-crosslinkable crosslinkable group in the copolymer is preferably 0 with respect to 100% by mass of the total amount of monomers as the amount of the monomer containing the heat-crosslinkable crosslinkable group at the time of polymerization.
  • the range is from 1 to 10% by mass, more preferably from 0.1 to 5% by mass.
  • the content ratio of the heat-crosslinkable crosslinkable group in the copolymer can be controlled by the monomer charge ratio at the time of producing the copolymer constituting the binder.
  • the copolymer used as the binder further includes at least one hydrophilic group selected from the group consisting of a carboxylic acid group, a hydroxyl group and a sulfonic acid group.
  • the copolymer contains the hydrophilic group, both the dispersion stability of the nonconductive particles and the binding property between the nonconductive particles can be improved.
  • the binder contains the hydrophilic group, so that the binder is easily adsorbed on the surface of the non-conductive particles, and the non-conductive The dispersibility of the particles is high, and a smooth porous film can be formed on the electrode.
  • the hydrophilic group is at least one selected from the group consisting of a carboxylic acid group, a hydroxyl group, and a sulfonic acid group.
  • a sulfonic acid group or a carboxylic acid group is preferable from the viewpoint of further improving dispersibility and binding properties of the nonconductive particles.
  • the hydrophilic group contains a monomer that gives a (meth) acrylonitrile monomer unit, a monomer that gives a (meth) acrylic acid ester monomer unit, and a hydrophilic group when producing the copolymer. It can introduce
  • Examples of the monomer containing a carboxylic acid group include monocarboxylic acid and derivatives thereof, dicarboxylic acid, acid anhydrides thereof, and derivatives thereof.
  • monocarboxylic acids examples include acrylic acid, methacrylic acid, crotonic acid and the like.
  • Monocarboxylic acid derivatives include 2-ethylacrylic acid, 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, ⁇ -Diaminoacrylic acid and the like.
  • dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • Dicarboxylic acid derivatives include maleic acid derivatives such as methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, and fluoromaleic acid; methylallyl maleate, diphenyl maleate, nonyl maleate, decyl maleate And maleate esters such as dodecyl maleate, octadecyl maleate and fluoroalkyl maleate.
  • Monomers containing a hydroxyl group include ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol, 5-hexen-1-ol; 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate, di-2-hydroxypropyl itaconate, etc.
  • ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol, 5-hexen-1-ol
  • 2-hydroxyethyl acrylate acrylic acid- 2-hydroxypropyl
  • 2-hydroxyethyl methacrylate 2-hydroxypropyl methacrylate
  • di-2-hydroxyethyl maleate di-4-hydroxybutyl maleate
  • di-2-hydroxypropyl itaconate etc.
  • Alkanol esters of ethylenically unsaturated carboxylic acids general formula CH 2 ⁇ CR 1 —COO— (C n H 2n O) m —H (m is an integer from 2 to 9, n is an integer from 2 to 4, R 1 Represents a hydrogen or methyl group) and esters of polyalkylene glycol represented by (meth) acrylic acid; Mono (meth) acrylic acid esters of dihydroxy esters of dicarboxylic acids such as loxyethyl-2 ′-(meth) acryloyloxyphthalate, 2-hydroxyethyl-2 ′-(meth) acryloyloxysuccinate; 2-hydroxyethyl vinyl ether; Vinyl ethers such as 2-hydroxypropyl vinyl ether; (meth) allyl-2-hydroxyethyl ether, (meth) allyl-2-hydroxypropyl ether, (meth) allyl-3-hydroxypropyl ether, (meth) allyl-2- Mono (
  • Examples of the monomer containing a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide-2- Examples thereof include methylpropane sulfonic acid and 3-allyloxy-2-hydroxypropane sulfonic acid.
  • hydrophilic group a sulfonic acid group or a carboxylic acid group is preferable from the viewpoint of further improving the dispersibility and binding property of the nonconductive particles.
  • the content ratio of the hydrophilic group in the copolymer is preferably 0.1 to 40% by mass with respect to 100% by mass of the total amount of the monomer containing the hydrophilic group at the time of polymerization.
  • the range is preferably 0.5 to 20% by mass.
  • the content ratio of the hydrophilic group in the copolymer can be controlled by the monomer charge ratio when producing the copolymer constituting the binder. When the content ratio of the hydrophilic group in the copolymer is within the above range, the nonconductive particles can be more favorably dispersed.
  • the above-mentioned thermally crosslinkable crosslinkable group and hydrophilic group It is preferable to contain.
  • the copolymer contains a thermally crosslinkable crosslinkable group and a hydrophilic group, it becomes easier to increase the crosslink density and to obtain a high-strength film.
  • the copolymer used as the binder used in the present invention may contain other monomers copolymerizable with these in addition to the above monomers.
  • Other copolymerizable monomers include styrene monomers such as styrene, chlorostyrene, vinyl toluene, methyl t-butylstyrene vinyl benzoate, vinyl naphthalene, chloromethyl styrene, ⁇ -methyl styrene, and divinyl benzene.
  • Olefins such as ethylene and propylene; diene monomers such as butadiene and isoprene; halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; Vinyl ethers such as vinyl ether, ethyl vinyl ether, and butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, and isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinyl pyridine Heterocycle-containing vinyl compounds such as vinyl imidazole; acrylamide, methacrylamide, amide monomers such as acrylamide-2-methylpropane sulfonic acid; and the like.
  • the method for producing the copolymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
  • the polymerization method any method such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
  • the polymerization initiator used for the polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
  • Organic peroxides, azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like.
  • the glass transition temperature of the above copolymer used as a binder can give flexibility to the porous film at room temperature, cracks at the time of winding and winding, chipping of the porous film layer, etc. From the viewpoint of suppressing the above, it is preferably 15 ° C. or lower, more preferably 0 ° C. or lower.
  • the glass transition temperature of the copolymer can be adjusted by changing the use ratio of the monomer constituting the copolymer.
  • the content of the binder in the porous membrane is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and most preferably 0.5 to 3% by mass.
  • the content ratio of the binder in the porous film is in the above range, so that the non-conductive particles can be bound to each other, the binding property to the electrode, and the flexibility can be maintained while inhibiting the movement of Li. And it can suppress that resistance increases.
  • the porous film may further contain other components such as a dispersant, a leveling agent, an antifoaming agent, and an electrolytic solution additive having a function of inhibiting decomposition of the electrolytic solution. These are not particularly limited as long as they do not affect the battery reaction.
  • dispersant examples include anionic compounds, cationic compounds, nonionic compounds, and polymer compounds.
  • a dispersing agent is selected according to the nonelectroconductive particle to be used.
  • the content ratio of the dispersant in the porous film is preferably within a range that does not affect the battery characteristics, and specifically 10 mass% or less.
  • leveling agents examples include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants. By mixing the surfactant, it is possible to prevent the repelling that occurs during coating or to improve the smoothness of the electrode.
  • Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the slurry for forming a porous film can be controlled, and the leveling property of the porous film obtained thereby can be improved.
  • the content ratio of the leveling agent and nanoparticles in the porous film is preferably within a range that does not affect the battery characteristics, and is specifically 10% by mass or less.
  • the method for producing the porous film of the present invention includes 1) a non-conductive particle having a dielectric constant of 10 or more, a co-polymer containing a predetermined amount of a (meth) acrylonitrile monomer unit and a (meth) acrylate monomer unit.
  • On the release film Include; cloth, it is deposited, a method of transferring the resultant porous film on a given substrate.
  • the method for producing a porous film of the present invention is characterized in that the slurry for a porous film is applied on an electrode active material layer and then dried.
  • the slurry for porous film of the present invention is a binder comprising a non-conductive particle having a dielectric constant of 10 or more, a copolymer containing a (meth) acrylonitrile monomer unit and a (meth) acrylic acid ester monomer unit, And a solvent.
  • a non-conductive particle having a dielectric constant of 10 or more those exemplified for the porous film are used.
  • the solvent is not particularly limited as long as it can uniformly disperse the solid content (non-conductive particles and binder).
  • the solvent used for the slurry for the porous membrane either water or an organic solvent can be used.
  • the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorinated aliphatic hydrocarbons include methylene chloride, chloroform, and carbon tetrachloride.
  • Others include pyridine, acetone, dioxane, dimethylformamide, methyl ethyl ketone, diisopropyl ketone, cyclohexanone, tetrahydrofuran, n-butyl phthalate, methyl phthalate, ethyl phthalate, tetrahydrofurfuryl alcohol, ethyl acetate, butyl acetate, 1-nitropropane, disulfide Examples include carbon, tributyl phosphate, cyclohexane, cyclopentane, xylene, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone and the like. These solvents can be used alone or as a mixed solvent.
  • solvents may be used alone or as a mixed solvent by mixing two or more of them.
  • a solvent having excellent dispersibility of non-conductive particles and having a low boiling point and high volatility is preferable because the solvent can be removed at a low temperature in a short time.
  • acetone, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, water, N-methylpyrrolidone, or a mixed solvent thereof is preferable.
  • cyclohexanone, xylene, N-methylpyrrolidone, or a mixed solvent thereof is particularly preferable because it has low volatility and excellent workability during slurry coating.
  • the solid content concentration of the slurry for the porous membrane is not particularly limited as long as it can be applied and immersed and has a fluid viscosity, but is generally about 20 to 50% by mass.
  • the slurry for the porous film includes a non-conductive particle having a dielectric constant of 10 or more, a copolymer containing a (meth) acrylonitrile monomer unit and a (meth) acrylate monomer unit.
  • a dispersant and an electrolytic solution additive having a function of suppressing decomposition of the electrolytic solution may be included. These are not particularly limited as long as they do not affect the battery reaction.
  • the production method of the slurry for the porous membrane is not particularly limited, and the above-mentioned non-conductive particles having a dielectric constant of 10 or more, a predetermined amount of (meth) acrylonitrile monomer unit and (meth) acrylic acid ester monomer unit. It is obtained by mixing a binder comprising the copolymer to be contained, and a solvent and other components added as necessary.
  • the mixing device is not particularly limited as long as it can uniformly mix the above components, and a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and the like can be used.
  • a high dispersion apparatus such as a bead mill, a roll mill, or a fill mix that can add a high dispersion share.
  • the slurry viscosity in the slurry state for the porous membrane is preferably 50 mPa ⁇ s to 10,000 mPa ⁇ s, more preferably 50 to 500 mPa ⁇ s, from the viewpoint of uniform coating property and slurry aging stability.
  • the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
  • the substrate is not particularly limited, but the porous film of the present invention is particularly preferably formed on the surface of the secondary battery electrode, and particularly the surface of the electrode active material layer of the electrode. More preferably, it is formed.
  • the method for applying the slurry for the porous film onto the electrode active material layer is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method. Among them, the dip method and the gravure method are preferable in that a uniform porous film can be obtained.
  • the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. The drying temperature can be changed depending on the type of solvent used.
  • a low-volatility solvent such as N-methylpyrrolidone
  • it is preferably dried at a high temperature of 120 ° C. or more with a blower-type dryer.
  • a highly volatile solvent when used, it can be dried at a low temperature of 100 ° C. or lower.
  • the adhesion between the electrode active material layer and the porous film can be improved by a press treatment using a mold press or a roll press.
  • the pressure treatment is excessively performed, the porosity of the porous film may be impaired, so the pressure and the pressure time are controlled appropriately.
  • the film thickness of the porous film is not particularly limited and is appropriately set according to the use or application field of the porous film. If the film is too thin, a uniform film cannot be formed. Since the capacity per (mass) is reduced, 0.1 to 50 ⁇ m is preferable, 0.2 to 10 ⁇ m is more preferable, and 0.5 to 10 ⁇ m is particularly preferable.
  • the porous film formed on the electrode active material layer has a structure in which non-conductive particles are bound via a binder and voids between the non-conductive particles are formed. Since the electrolytic solution can penetrate into the voids, the battery reaction is not hindered.
  • the porous film of the present invention is formed on the surface of the secondary battery electrode and is particularly preferably used as a protective film or separator for the electrode active material layer.
  • the secondary battery electrode on which the porous film is formed is not particularly limited, and the porous film of the present invention can be formed on electrodes having various configurations.
  • the porous film may be formed on any surface of the positive electrode and the negative electrode of the secondary battery, or may be formed on both the positive electrode and the negative electrode.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, and an electrolytic solution, and at least one of the positive electrode and the negative electrode is the electrode for the lithium ion secondary battery of the present invention.
  • the positive electrode and the negative electrode are generally formed by attaching an electrode active material layer containing an electrode active material as an essential component to a current collector.
  • the electrode active material used for the electrode for the lithium ion secondary battery is not particularly limited as long as it can reversibly insert and release lithium ions by applying a potential in the electrolyte, and can be an inorganic compound or an organic compound.
  • Electrode active materials (positive electrode active materials) for lithium ion secondary battery positive electrodes are broadly classified into those made of inorganic compounds and those made of organic compounds.
  • Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, composite oxides of lithium and transition metals, and transition metal sulfides.
  • As the transition metal Fe, Co, Ni, Mn and the like are used.
  • the inorganic compound used for the positive electrode active material include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiFeVO 4, and other lithium-containing composite metal oxides; TiS 2 , TiS 3 , non- Transition metal sulfides such as crystalline MoS 2 ; transition metal oxides such as Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13 It is done. These compounds may be partially element-substituted.
  • the positive electrode active material made of an organic compound for example, a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
  • An iron-based oxide having poor electrical conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
  • the positive electrode active material for a lithium ion secondary battery may be a mixture of the above inorganic compound and organic compound.
  • the particle diameter of the positive electrode active material is appropriately selected in consideration of other constituent elements of the battery. From the viewpoint of improving battery characteristics such as load characteristics and cycle characteristics, the 50% volume cumulative diameter is usually 0.1. It is ⁇ 50 ⁇ m, preferably 1 to 20 ⁇ m. When the 50% volume cumulative diameter is within this range, a secondary battery having a large charge / discharge capacity can be obtained, and handling of the slurry for electrodes and the electrodes is easy.
  • the 50% volume cumulative diameter can be determined by measuring the particle size distribution by laser diffraction.
  • Examples of electrode active materials (negative electrode active materials) for negative electrodes of lithium ion secondary batteries include carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads, pitch-based carbon fibers, and high conductivity such as polyacene. Examples include molecules.
  • the negative electrode active material metals such as silicon, tin, zinc, manganese, iron, nickel, alloys thereof, oxides or sulfates of the metals or alloys are used.
  • lithium alloys such as lithium metal, Li—Al, Li—Bi—Cd, and Li—Sn—Cd, lithium transition metal nitride, silicon, and the like can be used.
  • the electrode active material a material obtained by attaching a conductivity imparting material to the surface by a mechanical modification method can also be used.
  • the particle diameter of the negative electrode active material is appropriately selected in consideration of other constituent elements of the battery. From the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics, a 50% volume cumulative diameter is usually The thickness is 1 to 50 ⁇ m, preferably 15 to 30 ⁇ m.
  • the electrode active material layer preferably contains a binder (hereinafter sometimes referred to as “binder for active material layer”) in addition to the electrode active material.
  • binder for active material layer a binder
  • the binding property of the electrode active material layer in the electrode is improved, the strength against mechanical force applied during the process of winding the electrode is increased, Since the electrode active material layer is less likely to be detached, the risk of a short circuit due to the desorbed material is reduced.
  • Various resin components can be used as the binder for the active material layer.
  • polyethylene polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives, and the like can be used. These may be used alone or in combination of two or more.
  • the soft polymer exemplified below can also be used as the binder for the active material layer.
  • Acrylic acid such as polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymer, butyl acrylate / acrylonitrile copolymer, butyl acrylate / acrylonitrile / glycidyl methacrylate copolymer
  • an acrylic soft polymer which is a homopolymer of a methacrylic acid derivative or a copolymer with a monomer copolymerizable therewith Isobutylene-based soft polymers such as polyisobutylene, isobutylene-isoprene rubber, isobutylene-styrene copolymer; Polybutadiene, polyisoprene, butadiene / styrene random cop
  • Olefinic soft polymers of Vinyl-based soft polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl acetate / styrene copolymer; Epoxy-based soft polymers such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber; Fluorine-containing soft polymers such as vinylidene fluoride rubber and tetrafluoroethylene-propylene rubber; Examples thereof include other soft polymers such as natural rubber, polypeptide, protein, polyester-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer. These soft polymers may have a cross-linked structure or may have a functional group introduced by modification.
  • the amount of the binder for the active material layer in the electrode active material layer is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, particularly preferably 100 parts by weight of the electrode active material. 0.5 to 3 parts by mass.
  • the amount of the binder for the active material layer in the electrode active material layer is in the above range, it is possible to prevent the active material from dropping from the electrode without inhibiting the battery reaction.
  • the binder for the active material layer is prepared as a solution or a dispersion to produce an electrode.
  • the viscosity at that time is usually in the range of 1 mPa ⁇ s to 300,000 mPa ⁇ s, preferably 50 mPa ⁇ s to 10,000 mPa ⁇ s.
  • the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
  • the electrode active material layer may contain a conductivity imparting material or a reinforcing material.
  • a conductivity imparting material conductive carbon such as acetylene black, ketjen black, carbon black, vapor-grown carbon fiber, and carbon nanotube can be used. Examples thereof include carbon powders such as graphite, and fibers and foils of various metals.
  • the reinforcing material various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used.
  • the amount of the conductivity-imparting material used is usually 0 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.
  • the electrode active material layer may be present alone, but is usually present in a form attached to the current collector.
  • the electrode active material layer can be formed by attaching a slurry containing an electrode active material and a solvent (hereinafter sometimes referred to as “active material layer forming slurry”) to a current collector.
  • any solvent can be used as long as it can be dissolved or dispersed in the form of particles.
  • a solvent that dissolves the binder for the active material layer is used, the dispersion of the electrode active material or the like is stabilized by the adsorption of the binder for the active material layer to the surface.
  • the slurry for forming the active material layer contains a solvent and disperses the electrode active material, the binder for the active material layer, and the conductivity-imparting material.
  • the solvent it is preferable to use a solvent capable of dissolving the binder because the dispersibility of the electrode active material and the conductivity-imparting material is excellent.
  • organic solvents include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ⁇ -butyrolactone, ⁇ -Esters such as caprolactone; Acylonitriles such as acetonitrile and propionitrile; Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol and ethylene glycol monomethyl ether; N-methyl Amides such as pyrrolidone and N, N-dimethylformamide are exemplified. These solvents may be used alone or in admix
  • the active material layer forming slurry may further contain additives that exhibit various functions such as a thickener.
  • a thickener a polymer soluble in an organic solvent used for the slurry for forming an active material layer is used. Specifically, acrylonitrile-butadiene copolymer hydride or the like is used.
  • the slurry for forming an active material layer includes trifluoropropylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxaspiro [4,4] nonane, in order to increase battery stability and life.
  • 2,7-dione, 12-crown-4-ether and the like can be used. These may be used by being contained in an electrolyte solution described later.
  • the amount of the solvent in the slurry for forming the active material layer is adjusted so as to have a viscosity suitable for coating according to the type of the electrode active material, the binder for the active material layer, and the like.
  • the solid content concentration of the electrode active material, the binder for the active material layer, and other additives is preferably 30 to 90% by mass, more preferably The amount is adjusted to 40 to 80% by mass.
  • the slurry for forming the active material layer is obtained by mixing the electrode active material, the binder for the active material layer added as necessary, the conductivity-imparting material, other additives, and the solvent using a mixer. . Mixing may be performed by supplying the above components all at once to a mixer. When using the electrode active material, the binder for the active material layer, the conductivity-imparting material and the thickener as the constituent components of the slurry for forming the active material layer, the conductivity-imparting material and the thickener are mixed in the solvent.
  • the conductive material is dispersed in the form of fine particles, and then the binder for the active material layer and the electrode active material are added and further mixed to improve the dispersibility of the slurry.
  • a mixer a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer, and the like can be used. It is preferable because aggregation of the resin can be suppressed.
  • the particle size of the slurry for forming an active material layer is preferably 35 ⁇ m or less, and more preferably 25 ⁇ m or less.
  • the conductive material is highly dispersible and a homogeneous electrode can be obtained.
  • the current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material. From the viewpoint of having heat resistance, for example, iron, copper, aluminum, nickel, stainless steel, etc. Metal materials such as titanium, tantalum, gold, and platinum are preferable. Among these, aluminum is particularly preferable for the positive electrode of the nonaqueous electrolyte lithium ion secondary battery, and copper is particularly preferable for the negative electrode.
  • the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable. In order to increase the adhesive strength of the electrode active material layer, the current collector is preferably used after roughening in advance.
  • Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • a mechanical polishing method an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
  • an intermediate layer may be formed on the surface of the current collector in order to increase the adhesive strength and conductivity of the electrode active material layer.
  • the method for producing the electrode active material layer may be any method in which the electrode active material layer is bound in layers on at least one side, preferably both sides of the current collector.
  • the active material layer forming slurry is applied to a current collector and dried, and then heated at 120 ° C. or higher for 1 hour or longer to form an electrode active material layer.
  • the method for applying the slurry for forming the active material layer to the current collector is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
  • the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • the porosity of the electrode active material layer of the electrode is preferably lower by pressure treatment using a die press or a roll press.
  • a preferable range of the porosity is 5% to 15%, more preferably 7% to 13%. If the porosity is too high, charging efficiency and discharging efficiency are deteriorated. When the porosity is too low, there are problems that it is difficult to obtain a high volume capacity, or that the electrode active material layer is easily peeled off and is likely to be defective. Further, when a curable polymer is used, it is preferably cured.
  • the thickness of the electrode active material layer is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m, for both the positive electrode and the negative electrode.
  • Electrode As the electrolytic solution, an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is used.
  • a lithium salt is used as the supporting electrolyte.
  • the lithium salt is not particularly limited, LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable. Two or more of these may be used in combination. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate.
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • Carbonates such as (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; Are preferably used. Moreover, you may use the liquid mixture of these solvents.
  • carbonates are preferable because they have a high dielectric constant and a wide stable potential region. Since the lithium ion conductivity increases as the viscosity of the solvent used decreases, the lithium ion conductivity can be adjusted depending on the type of the solvent.
  • the concentration of the supporting electrolyte in the electrolytic solution is usually 1 to 30% by mass, preferably 5 to 20% by mass.
  • the concentration is usually 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity tends to decrease. Since the degree of swelling of the polymer particles increases as the concentration of the electrolytic solution used decreases, the lithium ion conductivity can be adjusted by the concentration of the electrolytic solution.
  • a positive electrode with a porous film and a negative electrode with a porous film are overlapped via a separator, and this is wound into a battery container according to the shape of the battery.
  • an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
  • the shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
  • separator a known separator such as a polyolefin resin such as polyethylene or polypropylene or a separator containing an aromatic polyamide resin is used.
  • a separator can also be abbreviate
  • ⁇ Porous membrane electrode characteristics flexibility>
  • the electrode is cut into a rectangle having a width of 1 cm and a length of 5 cm to form a test piece. Place the test piece on the desk with the current collector side facing down, and lay a stainless steel rod with a diameter of 1 mm on the current collector side in the center in the length direction (2.5 cm from the end). Install.
  • the test piece is bent 180 degrees around the stainless steel bar so that the electrode active material layer with a porous film is on the outside.
  • Ten test pieces are tested, and the bent portion of the active material layer of each test piece is observed for cracking or peeling, and determined according to the following criteria. It shows that an electrode is excellent in a softness
  • B Cracking or peeling is observed in 1 to 3 of 10 sheets.
  • C Cracking or peeling is observed on 4 to 9 of 10 sheets.
  • D Cracking or peeling is observed in all 10 sheets
  • ⁇ Porous membrane slurry characteristics sedimentation> Put the slurry for porous membranes up to a height of 5 cm in a test tube with a diameter of 1 cm, and use 5 test samples each. The test sample is placed vertically on a desk. The state of the slurry is observed every other day for 10 days and judged according to the following criteria. It shows that it is excellent in sedimentation so that two-phase separation is not seen. A: Two-phase separation is not observed even after 10 days. B: Two-phase separation is observed after 5 to 10 days. C: Two-phase separation is observed after 2 to 5 days. D: Two-phase separation is observed after 1 day. E: Two-phase separation is observed within 3 hours.
  • Rate characteristics> A 10-cell full-cell coin type battery is charged to 4.3 V by a constant current method of 0.1 C, and then discharged to 3.0 V at 0.1 C to obtain a 0.1 C discharge capacity a. Thereafter, the battery is charged to 4.3 V at 0.1 C, and then discharged to 3.0 V at 4 C to obtain a 1 C discharge capacity b. Using an average value of 10 cells as a measurement value, a capacity retention ratio represented by a ratio (b / a (%)) of an electric capacity between 1C discharge capacity b and 0.1C discharge capacity a is obtained, and this is evaluated for rate characteristics. The standard. The higher this value, the better the rate characteristics. A: 90% or more B: 80% or more and less than 90% C: 50% or more and less than 80% D: less than 50%
  • High-temperature cycle characteristics A 10-cell full-cell coin-type battery was charged to 4.3 V by a constant current method of 0.2 C in an atmosphere of 50 ° C., and the electric capacity was repeatedly measured by charging and discharging to 3.0 V. Using the average value of 10 cells as a measured value, the charge / discharge capacity retention ratio represented by the ratio (%) of the electric capacity at the end of 50 cycles and the electric capacity at the end of 5 cycles was obtained, To do. The higher this value, the better the high-temperature cycle characteristics.
  • Example 1 ⁇ Production of polymer> In an autoclave equipped with a stirrer, 300 parts of ion-exchanged water, 41 parts of n-butyl acrylate, 41.5 parts of ethyl acrylate, 15 parts of acrylonitrile, 2.0 parts of glycidyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid 0.5 part, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator and 0.3 part of potassium persulfate as a polymerization initiator were added and stirred sufficiently, and then heated to 70 ° C. for polymerization. A coalesced particle aqueous dispersion was obtained.
  • the polymerization conversion rate determined from the solid content concentration was approximately 99%.
  • NMP N-methylpyrrolidone
  • the content ratio of the (meth) acrylonitrile monomer unit in the polymer A is 15%, and the content ratio of the heat crosslinkable crosslinkable group (epoxy group) is a monomer containing a heat crosslinkable crosslinkable group (glycidyl methacrylate).
  • 2% of the hydrophilic group (sulfonic acid group) content was 0.5% of the monomer containing the hydrophilic group (2-acrylamido-2-methylpropanesulfonic acid).
  • Non-conductive particles titanium oxide, average particle size 0.3 ⁇ m, dielectric constant 100
  • a solution of polymer A are mixed so as to have a content ratio of 100: 2 (solid content equivalent ratio).
  • Methylpyrrolidone was mixed so as to have a solid content concentration of 40% and dispersed using a bead mill to prepare slurry 1 for porous membrane. The sedimentation property of the obtained slurry for porous membrane was measured. The results are shown in Table 1.
  • negative electrode composition and negative electrode As a negative electrode active material, 95 parts of graphite having a particle size of 20 ⁇ m and a specific surface area of 4.2 m 2 / g, and PVDF (polyvinylidene fluoride) as a binder for an active material layer are mixed with 5 parts of solids, and NMP is further mixed. Was added and mixed with a planetary mixer to prepare a slurry-like electrode composition for negative electrode (slurry for forming a negative electrode active material layer). This negative electrode composition was applied to one side of a 10 ⁇ m thick copper foil, dried at 110 ° C. for 3 hours, and then roll pressed to obtain a negative electrode having a negative active material layer having a thickness of 60 ⁇ m.
  • PVDF polyvinylidene fluoride
  • Electrode composition for positive electrode and positive electrode Add 95 parts of LiCoO 2 as the positive electrode active material, 3 parts of PVDF (polyvinylidene fluoride) corresponding to the solid content as the binder for the active material layer, and further add 2 parts of acetylene black and 20 parts of N-methylpyrrolidone. Then, a slurry-like electrode composition for positive electrode (slurry for forming a positive electrode active material layer) was prepared by mixing with a planetary mixer. This positive electrode composition was applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 3 hours, and then roll pressed to obtain a positive electrode having a positive electrode active material layer having a thickness of 70 ⁇ m.
  • PVDF polyvinylidene fluoride
  • the obtained positive electrode was cut into a circle having a diameter of 13 mm and the negative electrode having a diameter of 14 mm ⁇ .
  • a separator made of a circular polypropylene porous membrane having a diameter of 18 mm and a thickness of 25 ⁇ m is interposed on the positive electrode active material layer surface side of the positive electrode so that the electrode active material layers face each other and the aluminum foil of the positive electrode is in contact with the bottom surface of the outer container
  • a stainless steel coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm) with expanded metal placed on the negative electrode copper foil and polypropylene packing Stowed.
  • Example 2 In an autoclave equipped with a stirrer, 300 parts of ion exchange water, 51 parts of n-butyl acrylate, 41.5 parts of ethyl acrylate, 5 parts of acrylonitrile, 2.0 parts of glycidyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid 0.5 part, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator and 0.3 part of potassium persulfate as a polymerization initiator were added and stirred sufficiently, and then heated to 70 ° C. for polymerization. A coalesced particle aqueous dispersion was obtained.
  • the polymerization conversion rate determined from the solid content concentration was approximately 99%.
  • 320 parts of NMP was added to 100 parts of this polymer particle aqueous dispersion, and water was evaporated under reduced pressure to obtain a copolymer (hereinafter referred to as “polymer B”) NMP solution.
  • the concentration of the polymer B solution was 8% by mass. Further, the glass transition temperature of this polymer B was ⁇ 25 ° C.
  • the content ratio of the (meth) acrylonitrile monomer unit in the polymer B is 5%, and the content ratio of the heat crosslinkable crosslinkable group (epoxy group) is the monomer containing the heat crosslinkable crosslinkable group (glycidyl methacrylate).
  • 2% of the hydrophilic group (sulfonic acid group) content was 0.5% of the monomer containing the hydrophilic group (2-acrylamido-2-methylpropanesulfonic acid). .
  • a slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 1 except that the polymer B was used instead of the polymer A as a binder. And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 3 In an autoclave equipped with a stirrer, 300 parts of ion-exchanged water, 83 parts of n-butyl acrylate, 15 parts of acrylonitrile, 2.0 parts of glycidyl methacrylate, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator, and as a polymerization initiator After adding 0.3 part of potassium persulfate and stirring sufficiently, it heated and polymerized at 70 degreeC and the polymer particle aqueous dispersion was obtained. The polymerization conversion rate determined from the solid content concentration was approximately 99%.
  • polymer C a copolymer
  • concentration of the polymer C solution was 9% by mass.
  • the glass transition temperature of polymer C was ⁇ 15 ° C.
  • the content ratio of the (meth) acrylonitrile monomer unit in the polymer C is 15%, and the content ratio of the heat crosslinkable crosslinkable group (epoxy group) is the monomer containing the heat crosslinkable crosslinkable group (glycidyl methacrylate). ) 2%, and the hydrophilic group content was 0%.
  • a slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 1 except that the polymer C was used instead of the polymer A as a binder. And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 4 In an autoclave equipped with a stirrer, 300 parts of ion-exchanged water, 84.5 parts of ethyl acrylate, 15 parts of acrylonitrile, 0.5 part of allyl glycidyl ether, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator, and a polymerization initiator After adding 0.3 parts of potassium persulfate and stirring sufficiently, it heated and polymerized at 70 degreeC and obtained the polymer particle aqueous dispersion. The polymerization conversion rate determined from the solid content concentration was approximately 99%.
  • polymer D a copolymer
  • the concentration of the polymer D solution was 10% by mass.
  • the glass transition temperature of the polymer D was 2 ° C.
  • the content ratio of the (meth) acrylonitrile monomer unit in the polymer D is 15%, and the content ratio of the heat crosslinkable crosslinkable group is the ratio of the monomer (allyl glycidyl ether) containing the heat crosslinkable crosslinkable group. 0.5%, and the content ratio of the hydrophilic group was 0%.
  • a slurry for a porous membrane, an electrode with a porous membrane, and a battery were prepared in the same manner as in Example 1 except that the polymer D was used instead of the polymer A as a binder. And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 5 In an autoclave equipped with a stirrer, 300 parts of ion-exchanged water, 59 parts of n-butyl acrylate, 40 parts of acrylonitrile, 1 part of glycidyl methacrylate, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator, and persulfuric acid as a polymerization initiator After adding 0.3 part of potassium and stirring sufficiently, it heated and polymerized at 70 degreeC and the polymer particle aqueous dispersion was obtained. The polymerization conversion rate determined from the solid content concentration was approximately 99%.
  • polymer E a copolymer
  • the concentration of the polymer E solution was 8% by mass.
  • the glass transition temperature of this polymer was 30 ° C.
  • the content ratio of the (meth) acrylonitrile monomer unit in the copolymer is 40%, and the content ratio of the heat crosslinkable crosslinkable group is the ratio of the monomer (glycidyl methacrylate) containing the heat crosslinkable crosslinkable group.
  • the content ratio of the hydrophilic group was 1.0%.
  • a slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 1 except that the polymer E was used instead of the polymer A as a binder. And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 6 A slurry for a porous film, an electrode with a porous film, and a battery were produced in the same manner as in Example 2 except that zinc oxide (average particle size 0.3 ⁇ m, dielectric constant 36) was used instead of titanium oxide as non-conductive particles. . And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 7 A slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 2 except that zirconium oxide (average particle size: 0.3 ⁇ m, dielectric constant: 27) was used instead of titanium oxide as non-conductive particles. . And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 8 A slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 2 except that magnesium oxide (average particle size: 0.3 ⁇ m, dielectric constant: 10) was used instead of titanium oxide as non-conductive particles. . And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • PBA represents polybutyl acrylate
  • PVDF represents polyvinylidene fluoride
  • PAN represents polyacrylonitrile
  • polymer F a copolymer
  • the concentration of the polymer F solution was 8% by mass.
  • the glass transition temperature of this polymer was 100 ° C.
  • the content ratio of the (meth) acrylonitrile monomer unit in the copolymer is 70%, and the content ratio of the heat crosslinkable crosslinkable group is the ratio of the monomer (glycidyl methacrylate) containing the heat crosslinkable crosslinkable group.
  • the content of hydrophilic groups was 0% and 0%.
  • a slurry for a porous membrane, an electrode with a porous membrane, and a battery were prepared in the same manner as in Example 1 except that the polymer F was used instead of the polymer A as a binder. And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • Example 5 A slurry for a porous film, an electrode with a porous film, and a battery were prepared in the same manner as in Example 2 except that aluminum oxide (average particle size: 0.3 ⁇ m, dielectric constant: 9) was used instead of titanium oxide as non-conductive particles. . And the sedimentation property in the produced slurry for porous films, the flexibility of the electrode with a porous film, the rate characteristics of the battery and the high temperature cycle characteristics were evaluated. The results are shown in Table 1.
  • the non-conductive particles used for the porous film are those having a dielectric constant of 10 or more, and the binder contains a (meth) acrylonitrile monomer unit and a (meth) acrylate monomer unit.
  • the flexibility of the electrode with a porous film is improved and no sedimentation of the slurry is observed.
  • Example 1 which further contains a crosslinkable group and a hydrophilic group, is most excellent in flexibility, sedimentation, high temperature life characteristics, and rate characteristics.

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Abstract

L'invention concerne une électrode pour piles secondaires au lithium-ion qui comprend une membrane poreuse qui peut contribuer à la flexibilité et aux caractéristiques de taux/caractéristiques de cycle, avec une électrode à membrane poreuse qui est utilisée pour les piles secondaires au lithium-ion. L'électrode pour piles secondaires au lithium-ion est fabriquée par stratification d'une couche de matériau actif d'électrode et d'une membrane poreuse qui contient des particules non conductrices ayant une constante diélectrique de 10 ou plus et un agent de liaison, sur un collecteur dans ledit ordre. L'agent de liaison susmentionné comprend une unité monomère (méth)acrylonitrile et une unité ester (méth)acrylique, et comprend également un copolymère contenant moins de 50 % en masse de l'unité monomère (méth)acrylonitrile susmentionnée.
PCT/JP2010/052946 2009-02-25 2010-02-25 Électrode pour pile secondaire au lithium-ion WO2010098380A1 (fr)

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