WO2019054350A1 - Electrode mixture for non-aqueous electrolyte secondary battery - Google Patents

Electrode mixture for non-aqueous electrolyte secondary battery Download PDF

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Publication number
WO2019054350A1
WO2019054350A1 PCT/JP2018/033553 JP2018033553W WO2019054350A1 WO 2019054350 A1 WO2019054350 A1 WO 2019054350A1 JP 2018033553 W JP2018033553 W JP 2018033553W WO 2019054350 A1 WO2019054350 A1 WO 2019054350A1
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Prior art keywords
mass
crosslinking agent
electrolyte secondary
electrode
copolymer
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PCT/JP2018/033553
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French (fr)
Japanese (ja)
Inventor
靖仁 牛島
隼一 藤重
藤田　浩司
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住友精化株式会社
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Application filed by 住友精化株式会社 filed Critical 住友精化株式会社
Priority to JP2019542053A priority Critical patent/JP7139342B2/en
Priority to KR1020197033363A priority patent/KR20200051521A/en
Priority to CN201880043053.8A priority patent/CN110832679B/en
Publication of WO2019054350A1 publication Critical patent/WO2019054350A1/en

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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
    • H01M4/62—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode mixture for non-aqueous electrolyte secondary batteries and the like.
  • a binder (binding agent) which is an electrode component is also one of the components that affect the performance of the secondary battery.
  • a binder is used to firmly fix the structure of the electrode, but by using a binder with higher binding strength and toughness, it is possible to prevent the electrode from collapsing at the time of battery charge / discharge and to improve cycle characteristics (that is, the life is long Become).
  • the binder which is one of the members constituting the electrode, has low conductivity and can be a cause of resistance during charge and discharge as compared with the electrode active material, the conductive additive and the like.
  • An electrode can not be formed only with an active material or a conductive support agent, and a binder is indispensable for bonding members. For this reason, in order to improve battery performance, development of an electrode having a small resistance while containing a binder is required.
  • the present invention has been made in view of the current state of the prior art, and its main object is to provide an electrode mixture having a small resistance while containing a binder, and from that, from the electrode mixture.
  • An object of the present invention is to manufacture an electrode and to provide an electrode mixture for a non-aqueous electrolyte secondary battery comprising the electrode.
  • the present inventors contain a specific binder, a specific crosslinker, and an electrode active material, and in particular, a specific ratio of the binder and the crosslinker. It has been found that an electrode having a low resistance value can be produced by using the electrode mixture for a non-aqueous electrolyte secondary battery, and the present invention has been completed by further improvement.
  • the present invention includes, for example, the subject matters described in the following sections.
  • Item 1 Containing an electrode active material, a crosslinking agent, and a binder,
  • the binder includes a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid
  • the crosslinker is a metal chelate complex compound
  • the crosslinking agent is contained in an amount of 0.2 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the binding agent and the crosslinking agent.
  • Electrode mixture for non-aqueous electrolyte secondary batteries Item 2.
  • the metal chelate complex compound is at least one selected from the group consisting of a titanium chelate complex compound and a zirconium chelate complex compound.
  • the crosslinking agent is a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group and / or a hydroxyl group.
  • Item 5 The non-aqueous electrolyte secondary battery according to any one of Items 1 to 4, wherein the ethylenically unsaturated carboxylic acid alkali metal neutralized product is an alkali metal acrylate neutralized product and / or an alkali metal methacrylate neutralized product. Electrode mix. Item 6.
  • Item 8. A non-aqueous electrolyte secondary battery comprising the electrode for a non-aqueous electrolyte secondary battery according to Item 6.
  • An electric device comprising the non-aqueous electrolyte secondary battery according to item 7.
  • the crosslinking agent is a metal chelate complex compound
  • the binding agent is a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, and the binding agent and the crosslinking agent may be used.
  • the crosslinking agent is mixed so as to be 0.2 parts by mass or more and less than 10 parts by mass with respect to a total amount of 100 parts by mass.
  • the electrode using the electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention has high cycleability and a relatively low resistance value after cycling. That is, by using the binding agent of the present invention for the electrode, it is possible to prevent the electrode from collapsing during battery charge and discharge and to improve the cycle characteristics (that is, the life becomes longer). The rate characteristic is improved to enable high output).
  • the outline is shown about one aspect of the electrode mixture for nonaqueous electrolyte secondary batteries included in the present invention.
  • An electrode mixture for a non-aqueous electrolyte secondary battery shown in FIG. 1 is coated on a metal foil, dried, pressed, and heated to prepare an outline of one embodiment when an electrode is prepared.
  • the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention contains an electrode active material (active material for positive electrode or negative electrode), a crosslinking agent, and a binder, and the binder is vinyl. And a copolymer of an alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, wherein the crosslinking agent is a metal chelate complex compound.
  • the binder and the crosslinking agent are contained in a specific ratio (0.2 parts by mass or more and less than 10 parts by mass of the crosslinking agent with respect to 100 parts by mass of the binder).
  • the said combination is a composition (mixture composition) containing said each component.
  • the mixture is preferably in the form of a slurry.
  • the electrode mixture may contain, for example, a liquid medium (preferably water). Furthermore, a conductive aid, a dispersion aid and the like may be contained.
  • the binder used in the present invention comprises a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid.
  • the said copolymer is obtained, for example, by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester, in a mixed solvent of an aqueous organic solvent and water in the presence of an alkali containing alkali metal. Can be obtained by saponification.
  • vinyl ester examples include vinyl acetate, vinyl propionate, and vinyl pivalate, but vinyl acetate is preferable because the saponification reaction easily proceeds.
  • vinyl esters may be used alone, or two or more thereof may be used in combination.
  • ethylenically unsaturated carboxylic acid ester examples include acrylic acid, methyl ester of methacrylic acid, ethyl ester, n-propyl ester, iso-propyl ester, n-butyl ester, and t-butyl ester.
  • Methyl acrylate and methyl methacrylate are preferred because the saponification reaction easily proceeds.
  • One of these ethylenically unsaturated carboxylic acid esters may be used alone, or two or more thereof may be used in combination.
  • vinyl esters and other ethylenically unsaturated monomers copolymerizable with ethylenic unsaturated carboxylic acid esters may be used in addition to vinyl esters and ethylenically unsaturated carboxylic acid esters. May be copolymerized.
  • the copolymer obtained by saponifying the copolymer thus obtained and obtained by polymerizing vinyl alcohol as a monomer can also be used as a binder in the present invention.
  • a crosslinking agent may also be combined and copolymerized.
  • the copolymer obtained by saponifying the copolymer thus obtained is also included in the copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, and a binder It can be preferably used as That is, the copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid may be an uncrosslinked resin or a crosslinked resin.
  • crosslink monomer in resin in the present specification
  • the electrode assembly for a non-aqueous electrolyte secondary battery according to the present invention It distinguishes conceptually from the "crosslinking agent” which an agent contains. That is, the electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention contains an electrode active material, a "crosslinking agent”, and a binder, and the binder contains a crosslinkable resin.
  • crosslinking agent which an agent contains. That is, the electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention contains an electrode active material, a "crosslinking agent", and a binder, and the binder contains a crosslinkable resin.
  • in-resin crosslinking monomers may be used for the preparation of the crosslinkable resin. However, only the concept is merely distinguished, and it does not prevent that the substance used as the "crosslinking agent” and the substance used as the "in-resin crosslinking monomer” are the same substance.
  • the intra-resin crosslinking monomer includes those having two or more reactive functional groups capable of copolymerization.
  • the said reactive functional group is a reactive functional group which can be copolymerized with the monomer which is the raw material of the copolymer of vinyl alcohol and an alkali metal neutralized ethylenically unsaturated carboxylic acid.
  • Each of the two or more reactive functional groups crosslinks by being incorporated (bonded) into the backbone of another copolymer.
  • a reactive functional group capable of copolymerization a vinyl group is preferably mentioned.
  • a monomer having two vinyl groups is preferably mentioned as the in-resin crosslinking monomer.
  • intra-resin crosslinking monomer for example, divinylbenzene is preferably mentioned.
  • divinylbenzene is preferably mentioned.
  • bifunctional acrylate, bifunctional methacrylate and the like for example, 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate and the like are preferably mentioned.
  • crosslinking agents having two or more vinyl sulfone groups can also be used as intra-resin crosslinking monomers, for example, CH 2 2CH—SO 2 —CH 2 —CO—NH— (CH 2 ) n —NH
  • a compound represented by —CO—CH 2 —SO 2 —CH CH 2 (wherein n is a natural number of 1 to 6, and 2 or 3 is particularly preferable).
  • Examples of commercially available products of such compounds include VS-B and VS-C manufactured by Fujifilm.
  • the electrode mixture for non-aqueous electrolyte secondary batteries included in the present invention contains an electrode active material, a crosslinking agent, and a binder.
  • the electrode mixture for a non-aqueous electrolyte secondary battery is different from, and distinguished from, the electrode mixture containing the crosslinkable resin and the electrode active material. That is, the "in-resin crosslinking monomer" -derived portion contained in the crosslinkable resin is not a "crosslinking agent".
  • the intra-resin crosslinking monomer is already used for crosslinking when preparing the crosslinkable resin and has no crosslinking ability (in other words, the intra-resin crosslinking monomer already constitutes the crosslinkable portion of the crosslinkable resin) It is.
  • a composition after heat treatment of the electrode mixture for non-aqueous electrolyte secondary batteries included in the present invention and crosslinking by a crosslinking agent for example, the mixture is applied to a metal plate or a metal foil and heat treated
  • the electrode mixture containing the binder containing the crosslinkable resin and the electrode active material is different and distinguished. Ru.
  • the crosslinking agent not only crosslinks the copolymers contained in the binder but can also crosslink the copolymer contained in the binder and the electrode active material, and It is because it can crosslink.
  • the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention is applied to a metal plate or a metal foil and then heat-treated to obtain the composition (for example, in the case of an electrode composition)
  • the crosslinking agent can also bond the metal plate or metal foil and the copolymer or electrode active material contained in the binder.
  • a crosslink portion derived from a crosslink monomer in the resin exists in the crosslinkable resin, but the crosslinkable resin and the electrode active material crosslink It has not been.
  • summary is shown in FIG. 1 about the one aspect
  • the said electrode mixture is coated to metal foil, it is made to dry, it presses, and it heats, and the outline
  • the binder containing the crosslinkable resin and the electrode mixture only containing the electrode active material are different from the electrode mixture for the non-aqueous electrolyte secondary battery of the present invention, a crosslinking agent is further added thereto.
  • An outline is shown in FIG. 3 about what can become an electrode mixture for non-aqueous electrolyte secondary batteries of this invention in the case.
  • the copolymer of the vinyl alcohol and the ethylenically unsaturated carboxylic acid alkali metal neutralized product randomly copolymerizes the vinyl ester and the ethylenically unsaturated carboxylic acid ester, It is a substance obtained by saponifying an ester moiety derived from a monomer, and the bond between the monomers is a C—C covalent bond. (Hereafter, it may be described as a saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer. Moreover, as is apparent from the above description, "/" in this case indicates that random copolymerization is performed. Show)
  • the molar ratio of vinyl ester to ethylenically unsaturated carboxylic acid ester is preferably 95/5 to 5/95. , 95/5 to 50/50 is more preferable, and 90/10 to 60/40 is further preferable. Within the range of 95/5 to 5/95, the polymer obtained after saponification has particularly preferably improved retention as a binder.
  • the copolymerization composition ratio is preferably 95/5 to 5/95 in molar ratio, and 95/5 to 50 / 50 is more preferable, and 90/10 to 60/40 is further preferable.
  • the ethylenically unsaturated carboxylic acid alkali metal neutralized product is preferably at least one selected from the group consisting of alkali metal acrylate neutralized products and alkali metal methacrylate neutralized products.
  • alkali metal of the ethylenically unsaturated carboxylic acid alkali metal neutralized material although lithium, sodium, potassium, rubidium, cesium etc. can be illustrated, Preferably they are potassium and sodium.
  • Particularly preferred ethylenically unsaturated carboxylic acid alkali metal neutralized products are selected from the group consisting of sodium acrylate neutralized products, potassium acrylate neutralized products, sodium methacrylate neutralized products, and potassium methacrylate neutralized products It is at least one kind.
  • a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer which is a precursor of a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, is a powdery form, from the viewpoint of obtaining the copolymer. Obtained by a suspension polymerization method in which a polymer particle is obtained by polymerizing in the state of suspending a monomer mainly composed of a vinyl ester and an ethylenically unsaturated carboxylic acid ester in a dispersant aqueous solution containing a polymerization catalyst. Is preferred.
  • polymerization catalyst examples include organic peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, with preference given to lauryl peroxide.
  • the addition amount of the polymerization catalyst is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 3% by mass, with respect to the total mass of the monomers.
  • the amount is less than 0.01% by mass, the polymerization reaction may not be completed, and when the amount is more than 5% by mass, binding of a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid finally obtained. The effect may not be enough.
  • An appropriate substance may be selected as the above-mentioned dispersant at the time of carrying out the polymerization, depending on the kind and amount of monomers to be used, but specifically, polyvinyl alcohol (partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol And water soluble polymers such as polyvinyl pyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; and water insoluble inorganic compounds such as calcium phosphate and magnesium silicate. These dispersants may be used alone or in combination of two or more.
  • the amount of the dispersing agent used is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total mass of the monomers, although it depends on the kind of monomers to be used, etc. .
  • water-soluble salts such as alkali metals and alkaline earth metals can also be added to adjust the surface active effect and the like of the dispersant.
  • examples thereof include sodium chloride, potassium chloride, calcium chloride, lithium chloride, anhydrous sodium sulfate, potassium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate and tripotassium phosphate, etc., and their water solubility
  • the salts may be used alone or in combination of two or more.
  • the amount of the water-soluble salt used is usually 0.01 to 10% by mass with respect to the mass of the aqueous dispersant solution, depending on the type, amount and the like of the dispersant used.
  • the temperature for polymerizing the monomer is preferably -20 to 20 ° C, more preferably -10 to 10 ° C, with respect to the 10 hour half-life temperature of the polymerization catalyst.
  • the 10 hour half-life temperature of lauryl peroxide is about 62 ° C.
  • the polymerization reaction may not be completed, and when the temperature exceeds 20 ° C, a copolymer of vinyl alcohol obtained and alkali metal neutralized with ethylenically unsaturated carboxylic acid is obtained.
  • the binding effect of may not be sufficient.
  • the time for polymerizing the monomers depends on the type and amount of the polymerization catalyst used, the polymerization temperature and the like, but is usually several hours to several tens of hours.
  • the copolymer After completion of the polymerization reaction, the copolymer is separated by a method such as centrifugation, filtration and the like, and is obtained as a water-containing cake.
  • the obtained water-containing cake-like copolymer can be used as it is or, if necessary, dried for saponification reaction.
  • the number average molecular weight of the polymer in the present specification is a value determined by a molecular weight measurement apparatus equipped with a GFC column (for example, OHpak manufactured by Shodex Corp.) using DMF as a solvent.
  • a molecular weight measuring device for example, 2695 manufactured by Waters, RI detector 2414 can be mentioned.
  • the number average molecular weight of the copolymer before saponification is preferably 10,000 to 1,000,000, and more preferably 50,000 to 800,000.
  • the binding power tends to be further improved as a binder. Therefore, even if the electrode mixture (particularly, the negative electrode mixture) is an aqueous slurry, thick coating of the slurry is facilitated.
  • the saponification reaction can be carried out, for example, in the presence of an alkali containing an alkali metal, in an aqueous organic solvent alone, or in a mixed solvent of an aqueous organic solvent and water.
  • an alkali containing an alkali metal used for the saponification reaction conventionally known ones can be used, but alkali metal hydroxide is preferable, and sodium hydroxide and potassium hydroxide are preferable from the viewpoint of high reactivity. Is particularly preferred.
  • the amount of the alkali is preferably 60 to 140% by mole, and more preferably 80 to 120% by mole, relative to the number of moles of the monomer. If the alkali amount is less than 60 mol%, saponification may be insufficient, and even if it is used more than 140 mol%, no further effect is obtained and it is not economical.
  • an aqueous organic solvent or a mixed solvent of an aqueous organic solvent and water examples include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol; ketones such as acetone and methyl ethyl ketone; and mixtures thereof
  • Lower alcohols are preferable, and in particular, a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid having excellent binding effect and excellent resistance to mechanical shear can be obtained, particularly methanol. And ethanol are preferred.
  • the mass ratio of the aqueous organic solvent / water in the mixed solvent of the aqueous organic solvent and water is preferably 30/70 to 85/15, more preferably 40/60 to 85/15, and further preferably 40/60 to 80/20. preferable. If it deviates from the range of 30/70 to 85/15, the solvent affinity of the copolymer before saponification or the solvent affinity of the copolymer after saponification is insufficient, and the saponification reaction is sufficiently advanced May not be When the ratio of the aqueous organic solvent is less than 30/70, not only the binding ability as a binder is lowered, but also the viscosity is significantly increased in the saponification reaction, so that vinyl ester / ethylenically unsaturated carboxylic acid is industrially It is difficult to obtain a saponified ester copolymer, and when the ratio of the aqueous organic solvent is more than 85/15, the water solubility of the resulting vinyl ester / ethylenically unsaturated carb
  • the temperature at which the vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer is saponified is, for example, preferably 20 to 60 ° C., more preferably 20 to 50 ° C., although it depends on the molar ratio of the monomers.
  • saponification is performed at a temperature lower than 20 ° C., there is a possibility that the saponification reaction may not be completed, and in the case of a temperature higher than 60 ° C., the inside of the reaction system may be thickened and stirring becomes impossible.
  • the time for the saponification reaction varies depending on the type and amount of alkali used, but the reaction is usually completed in about several hours.
  • a paste or slurry-like copolymer saponified dispersion is usually obtained.
  • Spherical single particles or spherical particles can be obtained by solid-liquid separation according to a conventionally known method such as centrifugation, filtration, and thoroughly washed with a lower alcohol such as methanol to obtain a saponified liquid-containing copolymer obtained. It is possible to obtain a saponified copolymer, that is, a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid as aggregated agglomerated particles.
  • the acid saponification of the saponified copolymer with an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; an organic acid such as formic acid, acetic acid, oxalic acid or citric acid;
  • an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid
  • an organic acid such as formic acid, acetic acid, oxalic acid or citric acid
  • Different alkali metals such as lithium oxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide and the like (that is, different alkali metals), vinyl alcohol and ethylenic unsaturated carbon Copolymers of acid alkali metal neutralized products can also be obtained.
  • the conditions for drying the liquid-containing copolymer saponified product are not particularly limited, but in general, it is preferable to dry at a temperature of 30 to 120 ° C. under normal pressure or reduced pressure.
  • the drying time is usually from several hours to several tens of hours, depending on the pressure and temperature at the time of drying.
  • the volume average particle diameter of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid is preferably 1 to 200 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • a binding effect can be obtained more preferably at 1 ⁇ m or more, and by making it 200 ⁇ m or less, the water-based thickening liquid becomes more uniform and a preferable binding effect can be obtained.
  • the volume average particle size of the copolymer is determined by installing a batch cell (for example, SALD-BC manufactured by Shimadzu Corporation, for example, SALD-BC manufactured by Shimadzu Corporation) and using 2 as the dispersion solvent. It is a value measured using propanol or methanol.
  • the saponified liquid-containing copolymer is dried, and when the volume-average particle diameter of the obtained saponified copolymer exceeds 100 ⁇ m, the volume-average particle is obtained by grinding using a conventionally known grinding method such as mechanical milling.
  • the diameter can be adjusted to, for example, 10 to 100 ⁇ m.
  • Mechanical milling is a method of applying to the saponified copolymer obtained with external force such as impact, tension, friction, compression, shear, etc., and a device for that purpose is a rolling mill, a vibration mill, a planetary mill, a rocking motion. Mills, horizontal mills, attritor mills, jet mills, grinders, homogenizers, fluidizers, paint shakers, mixers and the like.
  • a planetary mill saponified copolymer and balls are put together in a container, and the kinetic energy generated by rotating and revolving is used to grind or mix the saponified copolymer powder. According to this method, it is known to be crushed to nano order.
  • copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid is used.
  • the viscosity of the aqueous solution containing 1% by mass is preferably 30 mPa ⁇ s to 10000 mPa ⁇ s, and more preferably 40 to 5000 mPa ⁇ s.
  • the viscosity of the prepared slurry-like electrode mixture is preferably obtained, and when the composition is applied to a current collector, the mixture does not spread too much and coating may be facilitated, and The dispersibility of the active material and the conductive aid in the agent also becomes good. If the viscosity is 10000 mPa ⁇ s or less, the viscosity of the prepared mixture is not too high, and it becomes easier to thinly and uniformly coat the current collector.
  • the viscosity of the 1% by mass aqueous solution was measured using a rotational viscometer (model DV-I +) manufactured by BROOK FIELD, spindle No. 5 and 50 rpm (liquid temperature 25 ° C.).
  • a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid can function as a binder for a lithium ion secondary battery electrode which is excellent in binding ability and binding persistence.
  • a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid strengthens the current collector and the active material and the active material to each other.
  • binding durability such that the electrode mixture does not peel off from the current collector or the active material falls off due to the volume change of the active material caused by the repetition of charge and discharge. It is considered that this is because the capacity of the active material is not reduced.
  • the mixture for a lithium ion secondary battery electrode (preferably, electrode slurry) contains vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid as a binder, as long as the effects of the present invention are not impaired.
  • Other aqueous binders may be added to the copolymer of
  • the addition amount of the other water-based binder is 80% by mass based on the total mass of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid and the other water-based binder.
  • it is less than. More preferably, it is less than 70% by mass.
  • the content ratio of the copolymer of vinyl alcohol and the alkali metal neutralized product of ethylenic unsaturated carboxylic acid in the binder is preferably 20% by mass or more and 100% by mass or less. Preferably, it is 30% by mass or more and 100% by mass or less. Furthermore, the said minimum may be 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
  • water-based binder materials include, for example, carboxymethylcellulose (CMC), polyacrylic acid, sodium polyacrylate, acrylic resin such as polyacrylate, sodium alginate, polyimide (PI), polytetrafluoroethylene ( Materials such as PTFE), polyamide, polyamide imide, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), ethylene acetic acid copolymer (EVA) and the like can be mentioned. These may be used singly or in combination of two or more.
  • acrylic resins represented by sodium polyacrylate, sodium alginate, polyimide and the like are suitably used, and acrylic resins are particularly suitably used.
  • the crosslinking agent used in the present invention is a metal chelate complex compound having a crosslinking ability.
  • the metal chelate complex compound include titanium chelate complex compounds, zirconium chelate complex compounds, and aluminum chelate complex compounds. Among them, titanium chelate complex compounds and zirconium chelate complex compounds are preferable, and titanium chelate complex compounds are more preferable.
  • the said crosslinking agent is a crosslinking agent which has 2 or more (preferably 2, 3 or 4, preferably 2) functional groups capable of reacting with a carboxyl group and / or a hydroxyl group.
  • the crosslinking agent is preferably an aqueous crosslinking agent (water-soluble crosslinking agent).
  • the functional group capable of reacting with the carboxyl group and / or the hydroxyl group means a functional group that reacts with the carboxyl group and / or the hydroxyl group to form a chemical bond. Like an alkoxy group, even if oneself is eliminated by a reaction, if a bond is formed as a result, it is included in this.
  • the need for the catalyst and the need for heating are not particularly limited.
  • an alkoxy group, an acylate group, etc. are mentioned preferably.
  • the alkoxy group include, for example, 1 to 18 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18) And linear or branched alkoxy groups.
  • a lactate group, a stearate group, an isostearate group etc. are mentioned, for example.
  • the copolymer with the hydrate is crosslinked to improve the mechanical strength.
  • two or more (preferably two, three or four, and more preferably two) functional groups capable of reacting with the carboxyl group and / or the hydroxyl group are present in the crosslinker molecule. There is a need to.
  • the functional groups present in one molecule of crosslinker may be the same or different.
  • the crosslinking point increases and mechanical strength may be improved.
  • the number is too large, gelation may progress in the state of the electrode coating liquid, which may make coating difficult, and in this case, it is inconvenient. It is. Whether or not gelation occurs depends on the number of carboxyl groups and / or hydroxyl groups in the molecular chain of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid, the copolymer and the crosslinking agent Since it also depends on the mixing ratio, gelation can be avoided by appropriately adjusting these.
  • metal chelate complex compound As a crosslinking agent (metal chelate complex compound) which has an alkoxy group and / or an acylate group, metal chelate compounds, such as Matsumoto Fine Chemical Co., Ltd. product organics series, are illustrated.
  • titanium chelate complex compound examples include titanium lactate ammonium salt, titanium lactate, titanium triethanol aminate, titanium diethanol aminate, titanium aminoethyl aminoethanolate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium Preferred are ethyl acetoacetate, titanium dodecylbenzene sulfonate, titanium phosphate, titanium octyrene glycolate, titanium ethyl acetoacetate, etc. Among them, titanium lactate ammonium salt, titanium lactate, titanium triethanol aminate, titanium diethanol aminate And titanium aminoethyl aminoethanolate are more preferred.
  • titanium chelate complex compounds include, for example, Organics TC series manufactured by Matsumoto Fine Chemical Co., Ltd., more specifically, for example, organics TC-300, TC-310, TC-400, TC -315, TC-335, TC-500, and TC-510.
  • zirconium chelate complex compound a zirconyl chloride compound, a zirconium lactate ammonium salt, a zirconium ammonium carbonate etc. are mentioned preferably, for example. More specifically, for example, (HO) Zr [OCH (CH 3 ) COO ⁇ ] 3 (NH 4 + ) 3 and the like can be mentioned.
  • zirconium chelate complex compounds include, for example, Orgatics ZA series manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics ZC series (for example Organics ZC-126, ZC-300, etc.) and Sannopco Co., Ltd. AZ coat 5800 MT etc. are mentioned.
  • aluminum chelate complex compounds include aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate and the like, and more specifically, for example, Al (C 5 H 7 O 2 ) 3 And Al (C 5 H 7 O 2 ) (C 6 H 9 O 3 ) 2 and Al (C 6 H 9 O 3 ) 3 .
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the crosslinking agent is 0.2 parts by mass or more and less than 10 parts by mass, when the total mass of the crosslinking agent and the binder is 100 parts by mass.
  • the content is more preferably 0.3, 0.4, or 0.5 parts by mass or more, and still more preferably 0.6, 0.7, 0.8, 0.9, or 1 parts by mass or more.
  • the electrical resistance value of the electrode obtained in which the proportion of the active material is relatively high may be particularly preferably lowered.
  • the content ratio of the said crosslinking agent is 0.2 mass part or more, the crosslinking effect fully expresses and the mechanical strength of binder resin is high and preferable battery performance is obtained preferably.
  • the positive electrode active material used in this technical field can be used.
  • the negative electrode active material is not particularly limited, and examples thereof include silicon (Si) and tin (Sn) or materials containing these, carbon (especially carbon materials (eg, graphite, hard carbon, soft carbon)), lithium titanate and the like.
  • silicon Si
  • tin Sn
  • carbon especially carbon materials (eg, graphite, hard carbon, soft carbon)
  • lithium titanate lithium titanate
  • materials capable of absorbing and desorbing lithium ions in large quantities can be used. If it is such a material, it is possible to exhibit the effect of the present embodiment regardless of any one of a simple substance, an alloy, a compound, a solid solution, and a composite active material containing a silicon-containing material and a tin-containing material.
  • silicon-containing material in addition to Si (silicon), silicon oxide (preferably SiOx (0.05 ⁇ x ⁇ 1.95), more specifically, for example, SiO), or B or Mg in any of these At least one element selected from the group consisting of Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, W, Zn, C, N, Sn, and Si
  • Si silicon oxide
  • SiOx 0.05 ⁇ x ⁇ 1.95
  • B or Mg in any of these At least one element selected from the group consisting of Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, W, Zn, C, N, Sn, and Si
  • An alloy, a compound, a solid solution or the like in which a part is substituted can be used. These can be referred to as silicon compounds.
  • tin-containing materials include Ni 2 Sn 4 , Mg 2 Sn, SnO x (0 ⁇ x ⁇ 2), SnO 2 , SnSiO 3 , LiSnO, and the like.
  • a carbon material crystalline carbon, amorphous carbon, or these may be used together. These materials can be used singly or in combination of two or more. In particular, at least one selected from the group consisting of silicon, silicon compounds, and carbon materials is preferable.
  • the ratio of carbon material to silicon and / or silicon compound is 5/95 to 50 in mass ratio It is preferable that it is / 50.
  • the upper limit of the mass ratio may be 10/90 or 15/85.
  • the lower limit of the mass ratio may be 40/60, 35/65, 30/70, or 25/75.
  • the conductive aid is not particularly limited as long as it has conductivity.
  • powder of metal, carbon, conductive polymer, conductive glass and the like can be exemplified, and acetylene black (AB), ketjen black (KB), carbon black (for example, SuperP (SP)), graphite, thermal black, furnace Black, lamp black, channel black, roller black, disc black, soft carbon, hard carbon, graphene, amorphous carbon carbon nanotube (CNT), carbon nanofiber (for example, vapor grown carbon fiber named VGCF which is a registered trademark) Etc.
  • the conduction aid be contained in the electrode mixture, for example, about 0.01 to 5% by mass, and it is more preferable to contain about 0.02 to 3% by mass or about 0.05 to 2% by mass. preferable.
  • Dispersion aid When a dispersion aid is used, examples of the dispersion aid include glucuronic acid, humic acid, glycine, polyglycine, aspartic acid, glutamic acid and the like.
  • Electrode mix By adding a crosslinking agent, a binder and, if necessary, a liquid medium (preferably water) to an electrode active material (positive electrode active material or negative electrode active material) to form a paste-like slurry, an electrode mixture (positive electrode combination) Agent or negative electrode mixture) is obtained.
  • the binder may be dissolved in water in advance, and may be used, or the active material and the powder of the binder may be mixed in advance, and then water may be added and mixed. Moreover, also when adding other components, it can mix with the said slurry.
  • the use amount of the liquid medium is not particularly limited, but, for example, 40% by mass or more and 2000% by mass or less when the total of the active material, the crosslinking agent, and the binding agent is 100% by mass. Preferably, 50% by mass or more and 1000% by mass or less are more preferable, and 60% by mass or more and 500% by mass or less are more preferable.
  • the binder is used for the purpose of bonding the active materials to each other and the current collector. That is, it is used to form a good active material layer when the slurry is applied onto the current collectors of both electrodes and dried.
  • the amount of the binder used is also not particularly limited, but is preferably 0.5% by mass or more based on the total mass of the electrode active material, the crosslinking agent, and the binder, for example. % Or more is more preferable, and 2% by mass or more is more preferable.
  • the content is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less.
  • the electrode mixture may be a positive electrode mixture or a negative electrode mixture, and is particularly preferably a negative electrode mixture.
  • the content of the electrode active material is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more More preferable.
  • the total content of the crosslinking agent and the binder in the electrode mixture is preferably less than 20% by mass, more preferably less than 15% by mass, and less than 10% by mass More preferable.
  • the positive electrode can be made using techniques used in the art.
  • the current collector of the positive electrode is not particularly limited as long as it is a material having electron conductivity and capable of supplying a current to the held positive electrode material.
  • conductive materials such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, etc., alloys containing two or more of these conductive materials (for example, stainless steel) ) Can be used.
  • C, Al, stainless steel and the like are preferable as the current collector from the viewpoints of high electrical conductivity and stability in the electrolytic solution and oxidation resistance, and Al and the like are preferable from the viewpoint of material cost.
  • the shape of the current collector is not particularly limited, and a foil-like substrate, a three-dimensional substrate or the like can be used.
  • a three-dimensional substrate foil metal, mesh, woven fabric, non-woven fabric, expand, etc.
  • an electrode of high capacity density can be obtained even with a binder that lacks adhesion to the current collector. .
  • high rate charge and discharge characteristics are also improved.
  • the negative electrode can be made using techniques used in the art.
  • the current collector of the negative electrode is not particularly limited as long as it is a material having electron conductivity and capable of supplying a current to the held negative electrode material.
  • conductive materials such as C, Cu, Ni, Fe, V, Nb, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, etc., and two kinds of these conductive materials Alloys containing the above, such as stainless steel, may be used.
  • Fe may be plated with Cu. From the viewpoints of high electrical conductivity and good stability and oxidation resistance in the electrolyte, C, Ni, stainless steel and the like are preferable as the current collector, and Cu and Ni are more preferable from the viewpoint of material cost.
  • the shape of the current collector is not particularly limited, and a foil-like substrate, a three-dimensional substrate or the like can be used. Among them, when a three-dimensional substrate (foam metal, mesh, woven fabric, non-woven fabric, expanded substrate, etc.) is used, an electrode having a high capacity density even with a binder which lacks adhesion to the current collector. Is obtained. In addition, high rate charge and discharge characteristics are also improved.
  • the nonaqueous electrolyte secondary battery of the present embodiment can be obtained by using the electrode of the nonaqueous electrolyte secondary battery of the present embodiment.
  • a non-aqueous electrolyte secondary battery for example, a lithium ion secondary battery is preferable.
  • a lithium ion secondary battery needs to contain lithium ions, and therefore, a lithium salt is preferable as the electrolyte salt.
  • the lithium salt is not particularly limited, and specific examples thereof include lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, and the like. . These lithium salts can be used singly or in combination of two or more.
  • the above-mentioned lithium salt has high electronegativity and is easy to ionize, so it is excellent in charge and discharge cycle characteristics, and can improve the charge and discharge capacity of the secondary battery.
  • a solvent for the electrolyte for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone and the like can be used, and these solvents can be used singly or in combination of two or more.
  • propylene carbonate alone, a mixture of ethylene carbonate and diethyl carbonate, or ⁇ -butyrolactone alone is preferable.
  • the mixing ratio of the mixture of ethylene carbonate and diethyl carbonate can be arbitrarily adjusted in the range in which one component is 10% by volume or more and 90% by volume or less.
  • the electrolyte of the lithium secondary battery of the present embodiment may be a solid electrolyte or an ionic liquid.
  • the lithium secondary battery of the above-mentioned structure it can function as a lithium secondary battery excellent in the life characteristic.
  • lithium secondary battery Although it does not specifically limit as a structure of a lithium secondary battery, It can apply to the existing battery forms and structures, such as a lamination type battery and a wound type battery.
  • the non-aqueous electrolyte secondary battery provided with the negative electrode of the present embodiment has excellent life characteristics, and can be used as a power source for various electric devices (including vehicles using electricity).
  • Examples of the electric devices include portable TVs, laptops, tablets, smartphones, PC keyboards, displays for PCs, desktop PCs, CRT monitors, PC racks, printers, integrated PCs, wearable computers, word processors, word processors, mice, hard disks, PCs Peripheral equipment, Iron, Cooling equipment, Refrigerator, Hot air heater, Hot carpet, Clothes dryer, Futon dryer, Humidifier, Dehumidifier, Window fan, Blower, Ventilation fan, Toilet seat with cleaning function, Car navigation system, Flashlight, Lighting equipment , Mobile karaoke machine, microphone, air purifier, blood pressure monitor, coffee mill, coffee maker, Kotatsu, mobile phone, game machine, music recorder, music player, disc changer, radio, shaver, juicer, Guredder, water purifier, dish dryer, car component, stereo, speaker, headphone, transceiver, trouser press, vacuum cleaner, body fat scale, weight scale, health meter, movie player, electric kettle, electric razor, electric stand, electric pot, Electronic game machines,
  • Gr represents graphite
  • the volume average particle diameter of the saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer was 180 ⁇ m. The volume average particle size was measured by a laser diffraction type particle size distribution measuring apparatus (SALD-7100 manufactured by Shimadzu Corporation).
  • the particle diameter of the obtained saponified copolymer was measured by a laser diffraction type particle size distribution analyzer (SALD-7100 manufactured by Shimadzu Corporation), and the volume average particle diameter was 39 ⁇ m.
  • SALD-7100 laser diffraction type particle size distribution analyzer manufactured by Shimadzu Corporation
  • the saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer obtained in Production Example 3 was used as a copolymer [1] in the examination.
  • the viscosity of a 1% by mass aqueous solution of the copolymer [1] was 1,630 mPa ⁇ s, and the copolymerization composition ratio of vinyl ester to ethylenically unsaturated carboxylic acid ester was 6/4 in molar ratio.
  • the viscosity of the 1% by mass aqueous solution was measured using a rotational viscometer (model DV-I +) manufactured by BROOK FIELD, and spindle No. 1 was used. It measured on the conditions of 5 and 50 rpm (liquid temperature 25 degreeC).
  • Production Example 4 In Production Example 1, 25.9 g (0.301 mol) of methyl acrylate and 232.8 g (2.704 mol) of vinyl acetate are used instead of 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate. The same procedures as in Production Examples 1 to 3 were carried out except using, to obtain a saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer. The said vinyl ester / ethylenic unsaturated carboxylic acid ester copolymer saponification thing was made into copolymer [2].
  • the volume average particle diameter of the copolymer [2] was 34 ⁇ m. Further, the viscosity of a 1% by mass aqueous solution of the copolymer [2] was 50 mPa ⁇ s, and the copolymer composition ratio of the vinyl ester and the ethylenically unsaturated carboxylic acid ester was 9/1. The volume average particle diameter and the viscosity of the 1% by mass aqueous solution were measured in the same manner as in the copolymer [1].
  • the slurry-like negative electrode mixture was prepared by mixing .05 parts by mass and 100 parts by mass of water.
  • the obtained mixture is applied on an electrolytic copper foil having a thickness of 10 ⁇ m and dried, and then pressure is applied using a roll press (manufactured by Ono Roll Co., Ltd.) to closely bond the electrolytic copper foil and the coating film. Then, heat treatment (under reduced pressure, 120 ° C., 12 hours) was performed to fabricate a negative electrode.
  • the thickness of the active material layer (coated film) was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Example 2 In Example 1, 4.9 parts by mass of the copolymer [1] is used in place of 4.95 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.1 part by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • an organic titanium compound crosslinking agent TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • Example 3 In Example 1, in place of 4.95 parts by mass of the copolymer [1], 4.65 parts by mass of the copolymer [1] is used, and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.35 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • an organic titanium compound crosslinking agent TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • Example 1 is the same as Example 1 except that in place of 4.95 parts by mass of the copolymer [1], no crosslinking agent is added, and only 5.0 parts by mass of the copolymer [1] is mixed.
  • a negative electrode was produced.
  • the thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Example 1 In Example 1, 4.95 parts by mass of the copolymer [1] is replaced with 4.995 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.005 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • an organic titanium compound crosslinking agent TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • Example 2 (Reference Example 1) In Example 2, 4.5 parts by mass of the copolymer [1] is used in place of 4.95 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode slurry was prepared in the same manner as in Example 1 except that 0.5 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. And no slurry was obtained, which made it difficult to coat the electrodeposited copper foil.
  • an organic titanium compound crosslinking agent TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • Example 4 (Study of crosslinker species) (Example 4) In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., TC-300) is used. A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Example 5 In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., TC-315) A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Example 6 In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic zirconia compound crosslinking agent (manufactured by Sannopco, AZ-coated 5800 MT) is used. A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Example 2 In Example 2, in place of 0.1 part by mass of an organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of an epoxy-based crosslinking agent (Nagase Chemtech Co., Ltd., Denacol EX-810) A negative electrode was produced in the same manner as in Example 2 except for using.
  • the thickness of the active material layer was 50 ⁇ m, and the basis weight of the negative electrode was 10 mg / cm 2 .
  • Table 2 shows the composition of each negative electrode.
  • the aluminum foil and the coating film are closely bonded with a roll press machine (made by Ono Roll Co., Ltd.), and then heat treatment (under reduced pressure, 120 ° C. , 12 hours or more) to prepare a positive electrode.
  • the capacity density of the positive electrode was 1.6 mAh / cm 2 (average thickness of the active material layer: 50 ⁇ m).
  • the said positive electrode was used as a positive electrode also in any examination shown below.
  • LiPF 6 A small pouch cell of 20 mAh was prepared, which was provided with an EC / DEC (1/1 v / v%) + 1 mass% VC solution (manufactured by Kishida Chemical Co., Ltd.) containing 1 mol / L of electrolyte.
  • PP indicates polypropylene
  • LiPF6 indicates lithium hexafluorophosphate
  • EC indicates ethylene carbonate
  • DEC indicates diethyl carbonate
  • VC vinylene carbonate

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Abstract

Provided is an electrode mixture with a small resistance despite including a binding agent. Specifically provided is an electrode mixture for a non-aqueous electrolyte secondary battery, said electrode mixture including an electrode active material, a crosslinking agent, and a binding agent, wherein the binding agent includes a copolymer of a vinyl alcohol and an ethylenically unsaturated alkali metal carboxylate neutralization product, the crosslinking agent is a metal chelate complex compound, and the crosslinking agent is included at a rate of greater than or equal to 0.2 parts by mass and less than 10 parts by mass per 100 parts by mass of the total quantity of the binding agent and the crosslinking agent.

Description

非水電解質二次電池用電極合剤Electrode mixture for non-aqueous electrolyte secondary battery
　本発明は、非水電解質二次電池用電極合剤等に関する。 The present invention relates to an electrode mixture for non-aqueous electrolyte secondary batteries and the like.
　近年、ノートパソコン、スマートフォン、携帯ゲーム機器、ＰＤＡ等の携帯電子機器の普及に伴い、これらの機器をより軽量化し、且つ、長時間の使用を可能とするため、電源として使用される二次電池の小型化及び高容量化が要求されている。さらに最近では、電池の携帯性及び取扱性を重視して、大きな電流で短時間での充電が可能な急速充電特性も重要な要求特性となってきている。 In recent years, with the spread of portable electronic devices such as laptop computers, smartphones, portable game devices, PDAs, etc., secondary batteries used as a power source to reduce the weight of these devices and enable long-time use Needs to be miniaturized and to have a high capacity. Furthermore, in recent years, with an emphasis on battery portability and handleability, rapid charge characteristics capable of charging in a short time with a large current have also become important requirements.
　リチウム二次電池の急速充電特性を向上させる手段としては、主として電極構成部材の改良が挙げられる。 As a means for improving the rapid charge characteristics of the lithium secondary battery, mainly the improvement of electrode components can be mentioned.
　電極構成要素であるバインダー（結着剤）も二次電池の性能を左右する部品の一つである。電極の構造を強固に固定するためにバインダーが用いられるが、より結着力が高く強靭なバインダーを用いることで、電池充放電時の電極の崩壊を防ぎ、サイクル特性がよくなる（すなわち、寿命が長くなる）。ただ、一般に、電極を構成する部材の１つであるバインダーは、電極活物質や導電助剤などに比べて、導電性が低く充放電時の抵抗の要因となり得る。活物質や導電助剤だけでは電極は形成できず、部材の接着のためにはバインダーは欠かせない。このため、電池性能を向上させるために、バインダーを含有しつつも抵抗が小さい電極の開発が求められている。 A binder (binding agent) which is an electrode component is also one of the components that affect the performance of the secondary battery. A binder is used to firmly fix the structure of the electrode, but by using a binder with higher binding strength and toughness, it is possible to prevent the electrode from collapsing at the time of battery charge / discharge and to improve cycle characteristics (that is, the life is long Become). However, in general, the binder, which is one of the members constituting the electrode, has low conductivity and can be a cause of resistance during charge and discharge as compared with the electrode active material, the conductive additive and the like. An electrode can not be formed only with an active material or a conductive support agent, and a binder is indispensable for bonding members. For this reason, in order to improve battery performance, development of an electrode having a small resistance while containing a binder is required.
特開２０１２－２０４２０３号公報JP 2012-204203 A 特開２０００－３４８７３０号公報JP 2000-348730 A
　本発明は、上記従来技術の現状に鑑みてなされたものであり、その主な目的は、結着剤を含有しつつも抵抗が小さい電極合剤を提供すること、ひいては、当該電極合剤から電極を製造し、当該電極を備えた非水電解質二次電池用電極合剤を提供することにある。 The present invention has been made in view of the current state of the prior art, and its main object is to provide an electrode mixture having a small resistance while containing a binder, and from that, from the electrode mixture. An object of the present invention is to manufacture an electrode and to provide an electrode mixture for a non-aqueous electrolyte secondary battery comprising the electrode.
　本発明者らは、上記課題を解決するために鋭意検討した結果、特定の結着剤、特定の架橋剤、及び電極活物質を含み、特に当該結着剤と当該架橋剤とを特定の比率で含む、非水電解質二次電池用電極合剤を用いることで、抵抗値が低い電極を製造できること見出し、さらに改良を重ねて本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors contain a specific binder, a specific crosslinker, and an electrode active material, and in particular, a specific ratio of the binder and the crosslinker. It has been found that an electrode having a low resistance value can be produced by using the electrode mixture for a non-aqueous electrolyte secondary battery, and the present invention has been completed by further improvement.
　本発明は例えば以下の項に記載の主題を包含する。
項１．
電極活物質と、架橋剤と、結着剤とを含有し、
前記結着剤が、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を含み、
前記架橋剤が、金属キレート錯体化合物であり、
前記結着剤及び前記架橋剤の合計量１００質量部に対して前記架橋剤が０．２質量部以上１０質量部未満含有される、
非水電解質二次電池用電極合剤。
項２．
金属キレート錯体化合物が、チタンキレート錯体化合物及びジルコニウムキレート錯体化合物からなる群より選択される少なくとも１種である、項１に記載の非水電解質二次電池用電極合剤。
項３．
前記架橋剤は、カルボキシル基および／または水酸基と反応可能な官能基を２個以上有する架橋剤である、項１又は２に記載の非水電解質二次電池用電極合剤。
項４．
前記架橋剤は、アルコキシ基及びアシレート基からなる群より選択される官能基を、同一又は異なって２個以上有する架橋剤である、項１又は２に記載の非水電解質二次電池用電極合剤。
項５．
前記エチレン性不飽和カルボン酸アルカリ金属中和物が、アクリル酸アルカリ金属中和物および／またはメタクリル酸アルカリ金属中和物である、項１～４のいずれかに記載の非水電解質二次電池用電極合剤。
項６．
項１～５のいずれかに記載の非水電解質二次電池用電極合剤を用いた非水電解質二次電池用電極。
項７．
項６に記載の非水電解質二次電池用電極を備えた非水電解質二次電池。
項８．
項７に記載の非水電解質二次電池を備えた電気機器。
項９．
電極活物質、架橋剤、及び結着剤を混合する工程を含み、
ここで、前記架橋剤は金属キレート錯体化合物であり、前記結着剤はビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体であり、前記結着剤及び前記架橋剤の合計量１００質量部に対して前記架橋剤が０．２質量部以上１０質量部未満となるよう混合される、
非水電解質二次電池用電極合剤の製造方法。 The present invention includes, for example, the subject matters described in the following sections.
Item 1.
Containing an electrode active material, a crosslinking agent, and a binder,
The binder includes a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid,
The crosslinker is a metal chelate complex compound,
The crosslinking agent is contained in an amount of 0.2 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the binding agent and the crosslinking agent.
Electrode mixture for non-aqueous electrolyte secondary batteries.
Item 2.
The electrode mixture for a non-aqueous electrolyte secondary battery according to item 1, wherein the metal chelate complex compound is at least one selected from the group consisting of a titanium chelate complex compound and a zirconium chelate complex compound.
Item 3.
The electrode combination material for nonaqueous electrolyte secondary batteries according to Item 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group and / or a hydroxyl group.
Item 4.
The electrode combination for nonaqueous electrolyte secondary batteries according to item 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups selected from the group consisting of alkoxy groups and acylate groups, which may be the same or different. Agent.
Item 5.
The non-aqueous electrolyte secondary battery according to any one of Items 1 to 4, wherein the ethylenically unsaturated carboxylic acid alkali metal neutralized product is an alkali metal acrylate neutralized product and / or an alkali metal methacrylate neutralized product. Electrode mix.
Item 6.
An electrode for a non-aqueous electrolyte secondary battery using the electrode mixture for a non-aqueous electrolyte secondary battery according to any one of Items 1 to 5.
Item 7.
Item 8. A non-aqueous electrolyte secondary battery comprising the electrode for a non-aqueous electrolyte secondary battery according to Item 6.
Item 8.
Item 8. An electric device comprising the non-aqueous electrolyte secondary battery according to item 7.
Item 9.
Mixing the electrode active material, the crosslinking agent, and the binding agent,
Here, the crosslinking agent is a metal chelate complex compound, and the binding agent is a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, and the binding agent and the crosslinking agent may be used. The crosslinking agent is mixed so as to be 0.2 parts by mass or more and less than 10 parts by mass with respect to a total amount of 100 parts by mass.
The manufacturing method of the electrode mixture for nonaqueous electrolyte secondary batteries.
　本発明に係る非水電解質二次電池用電極合剤を用いた電極はサイクル性が高く、サイクル後の抵抗値が比較的低い。つまり、本発明の結着剤を電極に用いることで、電池充放電時の電極の崩壊を防ぎ、サイクル特性がよくなる（すなわち、寿命が長くなる）ため、充放電後の抵抗が低く（すなわち、レート特性が向上し高出力が可能と）なる。 The electrode using the electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention has high cycleability and a relatively low resistance value after cycling. That is, by using the binding agent of the present invention for the electrode, it is possible to prevent the electrode from collapsing during battery charge and discharge and to improve the cycle characteristics (that is, the life becomes longer). The rate characteristic is improved to enable high output).
本発明に包含される非水電解質二次電池用電極合剤の一態様について、その概要を示す。The outline is shown about one aspect of the electrode mixture for nonaqueous electrolyte secondary batteries included in the present invention. 図１に示す非水電解質二次電池用電極合剤を金属箔に塗工し、乾燥させ、プレスし、加熱して電極を調製した際の一態様の概要を示す。An electrode mixture for a non-aqueous electrolyte secondary battery shown in FIG. 1 is coated on a metal foil, dried, pressed, and heated to prepare an outline of one embodiment when an electrode is prepared. 架橋型樹脂を含む結着剤及び電極活物質を含有する電極合剤、並びに、これにさらに架橋剤を加えた場合には本発明の非水電解質二次電池用電極合剤となり得ることについて、概要を示す。An electrode mixture containing a binder and an electrode active material containing a crosslinkable resin, and when it is further added with a crosslinking agent, it can be an electrode mixture for a non-aqueous electrolyte secondary battery of the present invention, Give an overview.
　以下、本発明の各実施形態について、さらに詳細に説明する。 Hereinafter, each embodiment of the present invention will be described in more detail.
　本発明に包含される非水電解質二次電池用電極合剤は、電極活物質（正極または負極用活物質）と、架橋剤と、結着剤とを含有し、前記結着剤は、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を含み、前記架橋剤は金属キレート錯体化合物である。また、前記結着剤と前記架橋剤とは、特定の比率（前記結着剤１００質量部に対して前記架橋剤が０．２質量部以上１０質量部未満）で含有される。当該合剤は、前記各成分を含む組成物（合剤組成物）である。また、当該合剤は、スラリーの形態であることが好ましい。 The electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention contains an electrode active material (active material for positive electrode or negative electrode), a crosslinking agent, and a binder, and the binder is vinyl. And a copolymer of an alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, wherein the crosslinking agent is a metal chelate complex compound. The binder and the crosslinking agent are contained in a specific ratio (0.2 parts by mass or more and less than 10 parts by mass of the crosslinking agent with respect to 100 parts by mass of the binder). The said combination is a composition (mixture composition) containing said each component. The mixture is preferably in the form of a slurry.
　また、当該電極合剤には、電極活物質、架橋剤、及び結着剤の他にも、例えば液体媒体（好ましくは水）が含まれていてもよい。またさらに、導電助剤、分散助剤などが含まれていてもよい。 In addition to the electrode active material, the crosslinking agent, and the binder, the electrode mixture may contain, for example, a liquid medium (preferably water). Furthermore, a conductive aid, a dispersion aid and the like may be contained.
　（結着剤）
　本発明に用いられる結着剤は、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を含む。当該共重合体は、例えば、ビニルエステルとエチレン性不飽和カルボン酸エステルとを共重合させて得られた共重合体を、アルカリ金属を含むアルカリの存在下、水性有機溶媒と水の混合溶媒中でケン化することによって得ることができる。すなわち、ビニルアルコール自体は不安定であるため直接モノマーとして使用することはできないが、ビニルエステルをモノマーとして使用して得られた重合体をケン化することにより、生成された重合体は結果としてビニルアルコールをモノマーとして重合させた態様となる。 (Binding agent)
The binder used in the present invention comprises a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid. The said copolymer is obtained, for example, by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester, in a mixed solvent of an aqueous organic solvent and water in the presence of an alkali containing alkali metal. Can be obtained by saponification. That is, although vinyl alcohol itself is unstable and can not be used directly as a monomer, the polymer produced by saponifying a polymer obtained using a vinyl ester as a monomer results in vinyl as a result It becomes an aspect which polymerized alcohol as a monomer.
　前記ビニルエステルとしては、例えば酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニルなどが挙げられるが、ケン化反応が進行しやすいため酢酸ビニルが好ましい。これらのビニルエステルは、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the vinyl ester include vinyl acetate, vinyl propionate, and vinyl pivalate, but vinyl acetate is preferable because the saponification reaction easily proceeds. One of these vinyl esters may be used alone, or two or more thereof may be used in combination.
　前記エチレン性不飽和カルボン酸エステルとしては、例えばアクリル酸、メタクリル酸のメチルエステル、エチルエステル、ｎ－プロピルエステル、ｉｓｏ－プロピルエステル、ｎ－ブチルエステル、及びｔ－ブチルエステルなどが挙げられるが、ケン化反応が進行しやすいためアクリル酸メチル、及びメタクリル酸メチルが好ましい。これらのエチレン性不飽和カルボン酸エステルは、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the ethylenically unsaturated carboxylic acid ester include acrylic acid, methyl ester of methacrylic acid, ethyl ester, n-propyl ester, iso-propyl ester, n-butyl ester, and t-butyl ester. Methyl acrylate and methyl methacrylate are preferred because the saponification reaction easily proceeds. One of these ethylenically unsaturated carboxylic acid esters may be used alone, or two or more thereof may be used in combination.
　また、必要に応じて、ビニルエステル及びエチレン性不飽和カルボン酸エステルと共重合可能な他のエチレン性不飽和単量体を、ビニルエステル及びエチレン性不飽和カルボン酸エステルに加えて使用し、これらを共重合させてもよい。このようにして得られる共重合体をケン化して得られる、ビニルアルコールをモノマーとして重合させた態様の共重合体も、本発明において結着剤として用いることができる。 In addition, if necessary, vinyl esters and other ethylenically unsaturated monomers copolymerizable with ethylenic unsaturated carboxylic acid esters may be used in addition to vinyl esters and ethylenically unsaturated carboxylic acid esters. May be copolymerized. The copolymer obtained by saponifying the copolymer thus obtained and obtained by polymerizing vinyl alcohol as a monomer can also be used as a binder in the present invention.
　またさらに、ビニルエステル及びエチレン性不飽和カルボン酸エステル（並びに必要に応じて前記他のエチレン性不飽和単量体）を共重合する際、架橋剤をも組み合わせて共重合させてもよい。このようにして得られる共重合体をケン化して得られる共重合体も、本発明において、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体に包含され、結着剤として好ましく用いることができる。つまり、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体は、未架橋樹脂であっても架橋型樹脂であってもよい。 Furthermore, when copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester (and, if necessary, the other ethylenically unsaturated monomer), a crosslinking agent may also be combined and copolymerized. In the present invention, the copolymer obtained by saponifying the copolymer thus obtained is also included in the copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, and a binder It can be preferably used as That is, the copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid may be an uncrosslinked resin or a crosslinked resin.
　なお、このようにして得られる架橋型樹脂を調製するために用いられる架橋剤を、本明細書では「樹脂内架橋モノマー」と表記して、本発明に係る非水電解質二次電池用電極合剤が含有する「架橋剤」と概念上区別する。すなわち、本発明に係る非水電解質二次電池用電極合剤は、電極活物質と、「架橋剤」と、結着剤とを含有するところ、当該結着剤は架橋型樹脂を含んでいてもよく、当該架橋型樹脂の調製には「樹脂内架橋モノマー」が用いられ得る。ただし、概念上区別するだけであって、当該「架橋剤」として用いられる物質と、当該「樹脂内架橋モノマー」として用いられる物質とが、同一物質であることは妨げない。 The crosslinker used to prepare the crosslinkable resin thus obtained is referred to as "crosslink monomer in resin" in the present specification, and the electrode assembly for a non-aqueous electrolyte secondary battery according to the present invention It distinguishes conceptually from the "crosslinking agent" which an agent contains. That is, the electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention contains an electrode active material, a "crosslinking agent", and a binder, and the binder contains a crosslinkable resin. Also, "in-resin crosslinking monomers" may be used for the preparation of the crosslinkable resin. However, only the concept is merely distinguished, and it does not prevent that the substance used as the "crosslinking agent" and the substance used as the "in-resin crosslinking monomer" are the same substance.
　樹脂内架橋モノマーとしては、共重合が可能な反応性官能基を２つ又はそれ以上有するものが挙げられる。当該反応性官能基は、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の原料であるモノマーと、共重合が可能な反応性官能基である。２つ又はそれ以上の反応性官能基のそれぞれが別の共重合体の骨格中に取り込まれる（結合する）ことで架橋する。共重合が可能な反応性官能基としてはビニル基が好ましく挙げられる。樹脂内架橋モノマーとして、ビニル基を２個有するモノマーが好ましく挙げられる。より具体的には、当該樹脂内架橋モノマーとしては、例えばジビニルベンゼンが好ましく挙げられる。また例えば、２官能性アクリレート、２官能性メタクリレート等（例えば２－ヒドロキシ－３－アクリロイロキシプロピルメタクリレート、ポリエチレングリコールジアクリレート、等）が好ましく挙げられる。またさらに、ビニルスルホン基を２個又はそれ以上有する架橋剤も樹脂内架橋モノマーとして用いることができ、例えば、ＣＨ２＝ＣＨ－ＳＯ２－ＣＨ２－ＣＯ－ＮＨ－（ＣＨ２）ｎ－ＮＨ－ＣＯ－ＣＨ２－ＳＯ２－ＣＨ＝ＣＨ２（ここでｎは１～６の自然数を示し、２又は３が特に好ましい）で表される化合物が好ましく挙げられる。このような化合物の市販品として、例えば富士フイルム社製ＶＳ－Ｂ、ＶＳ－Ｃを挙げることができる。 The intra-resin crosslinking monomer includes those having two or more reactive functional groups capable of copolymerization. The said reactive functional group is a reactive functional group which can be copolymerized with the monomer which is the raw material of the copolymer of vinyl alcohol and an alkali metal neutralized ethylenically unsaturated carboxylic acid. Each of the two or more reactive functional groups crosslinks by being incorporated (bonded) into the backbone of another copolymer. As a reactive functional group capable of copolymerization, a vinyl group is preferably mentioned. A monomer having two vinyl groups is preferably mentioned as the in-resin crosslinking monomer. More specifically, as the intra-resin crosslinking monomer, for example, divinylbenzene is preferably mentioned. For example, bifunctional acrylate, bifunctional methacrylate and the like (for example, 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate and the like) are preferably mentioned. Furthermore, crosslinking agents having two or more vinyl sulfone groups can also be used as intra-resin crosslinking monomers, for example, CH 2 2CH—SO 2 —CH 2 —CO—NH— (CH 2 ) n —NH Preferred is a compound represented by —CO—CH 2 —SO 2 —CH = CH 2 (wherein n is a natural number of 1 to 6, and 2 or 3 is particularly preferable). Examples of commercially available products of such compounds include VS-B and VS-C manufactured by Fujifilm.
　上記の通り、本発明に包含される非水電解質二次電池用電極合剤は、電極活物質と、架橋剤と、結着剤とを含有する。ここで、当該非水電解質二次電池用電極合剤は、前記架橋型樹脂を含む結着剤及び電極活物質を含有する電極合剤とは異なるものであり、区別される。つまり、前記架橋型樹脂に含まれる「樹脂内架橋モノマー」由来部分は、「架橋剤」ではない。樹脂内架橋モノマーは架橋型樹脂調製時に既に架橋のために用いられており架橋能を有していない（換言すれば、樹脂内架橋モノマーは架橋型樹脂の架橋部分を既に構成している）からである。 As described above, the electrode mixture for non-aqueous electrolyte secondary batteries included in the present invention contains an electrode active material, a crosslinking agent, and a binder. Here, the electrode mixture for a non-aqueous electrolyte secondary battery is different from, and distinguished from, the electrode mixture containing the crosslinkable resin and the electrode active material. That is, the "in-resin crosslinking monomer" -derived portion contained in the crosslinkable resin is not a "crosslinking agent". The intra-resin crosslinking monomer is already used for crosslinking when preparing the crosslinkable resin and has no crosslinking ability (in other words, the intra-resin crosslinking monomer already constitutes the crosslinkable portion of the crosslinkable resin) It is.
　またさらに、本発明に包含される非水電解質二次電池用電極合剤を熱処理して架橋剤による架橋がなされた後の組成物（例えば、当該合剤を金属版もしくは金属箔に塗布及び熱処理して調製した非水電解質二次電池用電極が備える電極組成物）についても、前記架橋型樹脂を含む結着剤と電極活物質とを含有する電極合剤とは異なるものであり、区別される。当該組成物において、架橋剤は結着剤に含まれる共重合体どうしを架橋するのみならず、結着剤に含まれる共重合体と電極活物質とをも架橋し得、また電極活物質どうしを架橋し得るからである。さらには、本発明に包含される非水電解質二次電池用電極合剤が金属板若しくは金属箔に塗布された後熱処理されて当該組成物が得られた場合（例えば、電極組成物である場合）、架橋剤は、当該金属板若しくは金属箔と結着剤に含まれる共重合体又は電極活物質とをも結合し得る。前記架橋型樹脂を含む結着剤と電極活物質とを含有する電極合剤では、架橋型樹脂内に樹脂内架橋モノマー由来の架橋部分が存在するが、架橋型樹脂と電極活物質とは架橋されていない。 Furthermore, a composition after heat treatment of the electrode mixture for non-aqueous electrolyte secondary batteries included in the present invention and crosslinking by a crosslinking agent (for example, the mixture is applied to a metal plate or a metal foil and heat treated Also for the electrode composition provided in the electrode for the non-aqueous electrolyte secondary battery prepared in the above manner, the electrode mixture containing the binder containing the crosslinkable resin and the electrode active material is different and distinguished. Ru. In the composition, the crosslinking agent not only crosslinks the copolymers contained in the binder but can also crosslink the copolymer contained in the binder and the electrode active material, and It is because it can crosslink. Furthermore, when the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention is applied to a metal plate or a metal foil and then heat-treated to obtain the composition (for example, in the case of an electrode composition) The crosslinking agent can also bond the metal plate or metal foil and the copolymer or electrode active material contained in the binder. In the electrode mixture containing the binder containing the crosslinkable resin and the electrode active material, a crosslink portion derived from a crosslink monomer in the resin exists in the crosslinkable resin, but the crosslinkable resin and the electrode active material crosslink It has not been.
　本発明に包含される非水電解質二次電池用電極合剤の一態様について、その概要を図１に示す。また、当該電極合剤を金属箔に塗工し、乾燥させ、プレスし、加熱して電極を調製した際の一態様の概要を図２に示す。また、架橋型樹脂を含む結着剤及び電極活物質を含有するだけの電極合剤は、本発明の非水電解質二次電池用電極合剤とは異なるが、これにさらに架橋剤を加えた場合には本発明の非水電解質二次電池用電極合剤となり得ることについて、概要を図３に示す。 The outline | summary is shown in FIG. 1 about the one aspect | mode of the electrode mixture for nonaqueous electrolyte secondary batteries included in this invention. Moreover, the said electrode mixture is coated to metal foil, it is made to dry, it presses, and it heats, and the outline | summary of one aspect at the time of preparing an electrode is shown in FIG. Further, although the binder containing the crosslinkable resin and the electrode mixture only containing the electrode active material are different from the electrode mixture for the non-aqueous electrolyte secondary battery of the present invention, a crosslinking agent is further added thereto. An outline is shown in FIG. 3 about what can become an electrode mixture for non-aqueous electrolyte secondary batteries of this invention in the case.
　本実施形態におけるケン化反応の一例として、酢酸ビニル／アクリル酸メチル共重合体が水酸化カリウム（ＫＯＨ）により１００％ケン化されたときのケン化反応を以下に示す。 As an example of the saponification reaction in this embodiment, a saponification reaction when vinyl acetate / methyl acrylate copolymer is 100% saponified with potassium hydroxide (KOH) is shown below.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　なお、上に示すように本実施形態に係るビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体は、ビニルエステルとエチレン性不飽和カルボン酸エステルをランダム共重合させて、モノマー由来のエステル部分をケン化させた物質であり、モノマー同士の結合はＣ－Ｃ共有結合である。（以下、ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物と記載する場合がある。また、前記説明から明らかなように、ここでの「／」はランダム共重合していることを示す。） In addition, as shown above, the copolymer of the vinyl alcohol and the ethylenically unsaturated carboxylic acid alkali metal neutralized product according to the present embodiment randomly copolymerizes the vinyl ester and the ethylenically unsaturated carboxylic acid ester, It is a substance obtained by saponifying an ester moiety derived from a monomer, and the bond between the monomers is a C—C covalent bond. (Hereafter, it may be described as a saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer. Moreover, as is apparent from the above description, "/" in this case indicates that random copolymerization is performed. Show)
　本実施形態の共重合体においては、ビニルエステルとエチレン性不飽和カルボン酸エステルのモル比（ビニルアルコール／エチレン性不飽和カルボン酸アルカリ金属中和物）は、９５／５～５／９５が好ましく、９５／５～５０／５０がより好ましく、９０／１０～６０／４０が更に好ましい。９５／５～５／９５の範囲内であれば、ケン化後得られる重合体が、結着剤としての保持力が特に好ましく向上する。 In the copolymer of the present embodiment, the molar ratio of vinyl ester to ethylenically unsaturated carboxylic acid ester (vinyl alcohol / ethylenically unsaturated carboxylic acid alkali metal neutralized product) is preferably 95/5 to 5/95. , 95/5 to 50/50 is more preferable, and 90/10 to 60/40 is further preferable. Within the range of 95/5 to 5/95, the polymer obtained after saponification has particularly preferably improved retention as a binder.
　したがって、得られるビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との前記共重合体において、共重合組成比はモル比で９５／５～５／９５が好ましく、９５／５～５０／５０がより好ましく、９０／１０～６０／４０が更に好ましい。 Therefore, in the copolymer of vinyl alcohol obtained and the above-mentioned copolymer of an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, the copolymerization composition ratio is preferably 95/5 to 5/95 in molar ratio, and 95/5 to 50 / 50 is more preferable, and 90/10 to 60/40 is further preferable.
　エチレン性不飽和カルボン酸アルカリ金属中和物としては、アクリル酸アルカリ金属中和物及びメタクリル酸アルカリ金属中和物からなる群より選択される少なくとも１種が好ましい。また、エチレン性不飽和カルボン酸アルカリ金属中和物のアルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等が例示できるが、好ましくはカリウム及びナトリウムである。特に好ましいエチレン性不飽和カルボン酸アルカリ金属中和物は、アクリル酸ナトリウム中和物、アクリル酸カリウム中和物、メタクリル酸ナトリウム中和物、及びメタクリル酸カリウム中和物からなる群より選択される少なくとも１種である。 The ethylenically unsaturated carboxylic acid alkali metal neutralized product is preferably at least one selected from the group consisting of alkali metal acrylate neutralized products and alkali metal methacrylate neutralized products. Moreover, as an alkali metal of the ethylenically unsaturated carboxylic acid alkali metal neutralized material, although lithium, sodium, potassium, rubidium, cesium etc. can be illustrated, Preferably they are potassium and sodium. Particularly preferred ethylenically unsaturated carboxylic acid alkali metal neutralized products are selected from the group consisting of sodium acrylate neutralized products, potassium acrylate neutralized products, sodium methacrylate neutralized products, and potassium methacrylate neutralized products It is at least one kind.
　ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の前駆体であるビニルエステル／エチレン性不飽和カルボン酸エステル共重合体は、粉末状で共重合体が得られる観点から、重合触媒を含む分散剤水溶液中にビニルエステルおよびエチレン性不飽和カルボン酸エステルを主体とする単量体を懸濁させた状態で重合させて重合体粒子とする懸濁重合法により得られたものが好ましい。 A vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer, which is a precursor of a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, is a powdery form, from the viewpoint of obtaining the copolymer. Obtained by a suspension polymerization method in which a polymer particle is obtained by polymerizing in the state of suspending a monomer mainly composed of a vinyl ester and an ethylenically unsaturated carboxylic acid ester in a dispersant aqueous solution containing a polymerization catalyst. Is preferred.
　前記重合触媒としては、例えばベンゾイルパーオキシド、ラウリルパーオキシドなどの有機過酸化物、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルなどのアゾ化合物が挙げられるが、とりわけラウリルパーオキシドが好ましい。 Examples of the polymerization catalyst include organic peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, with preference given to lauryl peroxide.
　重合触媒の添加量は、単量体の総質量に対して、０．０１～５質量％が好ましく、０．０５～３質量％がより好ましく、０．１～３質量％がさらに好ましい。０．０１質量％未満では、重合反応が完結しない場合があり、５質量％を超えると最終的に得られるビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の結着効果が十分でない場合がある。 The addition amount of the polymerization catalyst is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 3% by mass, with respect to the total mass of the monomers. When the amount is less than 0.01% by mass, the polymerization reaction may not be completed, and when the amount is more than 5% by mass, binding of a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid finally obtained. The effect may not be enough.
　重合を行わせる際の前記分散剤は、使用する単量体の種類、量などにより適当な物質を選択すればよいが、具体的にはポリビニルアルコール（部分ケン化ポリビニルアルコール、完全ケン化ポリビニルアルコール）、ポリ（メタ）アクリル酸およびその塩、ポリビニルピロリドン、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどの水溶性高分子；リン酸カルシウム、珪酸マグネシウムなどの水不溶性無機化合物などが挙げられる。これらの分散剤は、単独で使用してもよいし、２種以上を組合せて使用してもよい。 An appropriate substance may be selected as the above-mentioned dispersant at the time of carrying out the polymerization, depending on the kind and amount of monomers to be used, but specifically, polyvinyl alcohol (partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol And water soluble polymers such as polyvinyl pyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; and water insoluble inorganic compounds such as calcium phosphate and magnesium silicate. These dispersants may be used alone or in combination of two or more.
　分散剤の使用量は、使用する単量体の種類などにもよるが、単量体の総質量に対して、０．０１～１０質量％が好ましく、０．０５～５質量％がより好ましい。 The amount of the dispersing agent used is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total mass of the monomers, although it depends on the kind of monomers to be used, etc. .
　さらに、前記分散剤の界面活性効果などを調整するため、アルカリ金属、アルカリ土類金属などの水溶性塩を添加することもできる。例えば塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化リチウム、無水硫酸ナトリウム、硫酸カリウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸三ナトリウム及びリン酸三カリウムなどが挙げられ、これらの水溶性塩は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Furthermore, water-soluble salts such as alkali metals and alkaline earth metals can also be added to adjust the surface active effect and the like of the dispersant. Examples thereof include sodium chloride, potassium chloride, calcium chloride, lithium chloride, anhydrous sodium sulfate, potassium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate and tripotassium phosphate, etc., and their water solubility The salts may be used alone or in combination of two or more.
　水溶性塩の使用量は、使用する分散剤の種類、量などにもよるが、分散剤水溶液の質量に対して通常０．０１～１０質量％である。 The amount of the water-soluble salt used is usually 0.01 to 10% by mass with respect to the mass of the aqueous dispersant solution, depending on the type, amount and the like of the dispersant used.
　単量体を重合させる温度は、重合触媒の１０時間半減期温度に対して－２０～２０℃が好ましく、－１０～１０℃がより好ましい。例えば、ラウリルパーオキシドの１０時間半減期温度は約６２℃である。 The temperature for polymerizing the monomer is preferably -20 to 20 ° C, more preferably -10 to 10 ° C, with respect to the 10 hour half-life temperature of the polymerization catalyst. For example, the 10 hour half-life temperature of lauryl peroxide is about 62 ° C.
　１０時間半減期温度に対して－２０℃未満では、重合反応が完結しない場合があり、２０℃を超えると、得られるビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の結着効果が十分でない場合がある。 When the temperature is less than -20 ° C with respect to the 10 hour half-life temperature, the polymerization reaction may not be completed, and when the temperature exceeds 20 ° C, a copolymer of vinyl alcohol obtained and alkali metal neutralized with ethylenically unsaturated carboxylic acid is obtained. The binding effect of may not be sufficient.
　単量体を重合させる時間は、使用する重合触媒の種類、量、重合温度などにもよるが、通常数時間～数十時間である。 The time for polymerizing the monomers depends on the type and amount of the polymerization catalyst used, the polymerization temperature and the like, but is usually several hours to several tens of hours.
　重合反応終了後、共重合体は遠心分離、濾過などの方法により分離され、含水ケーキ状で得られる。得られた含水ケーキ状の共重合体はそのまま、もしくは必要に応じて乾燥し、ケン化反応に使用することができる。 After completion of the polymerization reaction, the copolymer is separated by a method such as centrifugation, filtration and the like, and is obtained as a water-containing cake. The obtained water-containing cake-like copolymer can be used as it is or, if necessary, dried for saponification reaction.
　本明細書における重合体の数平均分子量は、溶媒としてＤＭＦを用いＧＦＣカラム（例えばＳｈｏｄｅｘ社製ＯＨｐａｋ）を備えた分子量測定装置にて求めた値である。このような分子量測定装置としては、例えばウォーターズ社製２６９５、ＲＩ検出器２４１４が挙げられる。 The number average molecular weight of the polymer in the present specification is a value determined by a molecular weight measurement apparatus equipped with a GFC column (for example, OHpak manufactured by Shodex Corp.) using DMF as a solvent. As such a molecular weight measuring device, for example, 2695 manufactured by Waters, RI detector 2414 can be mentioned.
　ケン化前の共重合体の数平均分子量は、１０，０００～１，０００，０００が好ましく、５０，０００～８００，０００がより好ましい。ケン化前の数平均分子量を１０，０００～１，０００，０００の範囲内にすることで、結着剤として結着力がより向上する傾向がある。従って、電極用合剤（特に負極合剤）が水系スラリーであっても、スラリーの厚塗りが容易になる。 The number average molecular weight of the copolymer before saponification is preferably 10,000 to 1,000,000, and more preferably 50,000 to 800,000. When the number average molecular weight before saponification is in the range of 10,000 to 1,000,000, the binding power tends to be further improved as a binder. Therefore, even if the electrode mixture (particularly, the negative electrode mixture) is an aqueous slurry, thick coating of the slurry is facilitated.
　ケン化反応は、例えば、アルカリ金属を含むアルカリの存在下、水性有機溶媒のみ、又は水性有機溶媒と水との混合溶媒中で実施することができる。前記ケン化反応に使用するアルカリ金属を含むアルカリとしては、従来公知のものを使用することができるが、アルカリ金属水酸化物が好ましく、反応性が高いという観点より、水酸化ナトリウム及び水酸化カリウムが特に好ましい。 The saponification reaction can be carried out, for example, in the presence of an alkali containing an alkali metal, in an aqueous organic solvent alone, or in a mixed solvent of an aqueous organic solvent and water. As the alkali containing an alkali metal used for the saponification reaction, conventionally known ones can be used, but alkali metal hydroxide is preferable, and sodium hydroxide and potassium hydroxide are preferable from the viewpoint of high reactivity. Is particularly preferred.
　前記アルカリの量は、単量体のモル数に対して６０～１４０モル％が好ましく、８０～１２０モル％がより好ましい。６０モル％より少ないアルカリ量ではケン化が不十分となる場合があり、１４０モル％を超えて使用してもそれ以上の効果が得られず経済的でない。 The amount of the alkali is preferably 60 to 140% by mole, and more preferably 80 to 120% by mole, relative to the number of moles of the monomer. If the alkali amount is less than 60 mol%, saponification may be insufficient, and even if it is used more than 140 mol%, no further effect is obtained and it is not economical.
　前記ケン化反応には、水性有機溶媒のみ、又は水性有機溶媒と水との混合溶媒を用いることが好ましい。当該水性有機溶媒としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、ｔ－ブタノールなどの低級アルコール類；アセトン、メチルエチルケトンなどのケトン類；およびこれらの混合物などが挙げられるが、なかでも低級アルコール類が好ましく、優れた結着効果と機械的せん断に対して優れた耐性を有するビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体が得られることから、特にメタノールおよびエタノールが好ましい。 In the saponification reaction, it is preferable to use only an aqueous organic solvent or a mixed solvent of an aqueous organic solvent and water. Examples of the aqueous organic solvent include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol; ketones such as acetone and methyl ethyl ketone; and mixtures thereof Lower alcohols are preferable, and in particular, a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid having excellent binding effect and excellent resistance to mechanical shear can be obtained, particularly methanol. And ethanol are preferred.
　前記水性有機溶媒と水の混合溶媒における水性有機溶媒／水の質量比は、３０／７０～８５／１５が好ましく、４０／６０～８５／１５がより好ましく、４０／６０～８０／２０がさらに好ましい。３０／７０～８５／１５の範囲を逸脱する場合、ケン化前の共重合体の溶媒親和性またはケン化後の共重合体の溶媒親和性が不足し、充分にケン化反応を進行させることができないおそれがある。水性有機溶媒が３０／７０の比率より少ない場合、結着剤としての結着力が低下するだけでなく、ケン化反応の際に著しく増粘するため工業的にビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物を得ることが難しく、水性有機溶媒が８５／１５の比率より多い場合、得られるビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物の水溶性が低下するので電極に使用すると、乾燥後の結着力が損なわれる場合がある。なお、含水ケーキ状の共重合体をそのままケン化反応に使用する場合、前記水性有機溶媒／水の質量比は、含水ケーキ状の共重合体中の水を含むものとする。 The mass ratio of the aqueous organic solvent / water in the mixed solvent of the aqueous organic solvent and water is preferably 30/70 to 85/15, more preferably 40/60 to 85/15, and further preferably 40/60 to 80/20. preferable. If it deviates from the range of 30/70 to 85/15, the solvent affinity of the copolymer before saponification or the solvent affinity of the copolymer after saponification is insufficient, and the saponification reaction is sufficiently advanced May not be When the ratio of the aqueous organic solvent is less than 30/70, not only the binding ability as a binder is lowered, but also the viscosity is significantly increased in the saponification reaction, so that vinyl ester / ethylenically unsaturated carboxylic acid is industrially It is difficult to obtain a saponified ester copolymer, and when the ratio of the aqueous organic solvent is more than 85/15, the water solubility of the resulting vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer decreases, so that the electrode If used, the binding after drying may be impaired. When the water-containing cake copolymer is used as it is for the saponification reaction, the mass ratio of the aqueous organic solvent / water includes water in the water-containing cake copolymer.
　ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体をケン化させる温度は、単量体のモル比にもよるが、例えば２０～６０℃が好ましく、２０～５０℃がより好ましい。２０℃より低い温度でケン化させた場合、ケン化反応が完結しないおそれがあり、６０℃を超える温度の場合、反応系内が増粘し撹拌不能となる場合がある。 The temperature at which the vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer is saponified is, for example, preferably 20 to 60 ° C., more preferably 20 to 50 ° C., although it depends on the molar ratio of the monomers. When saponification is performed at a temperature lower than 20 ° C., there is a possibility that the saponification reaction may not be completed, and in the case of a temperature higher than 60 ° C., the inside of the reaction system may be thickened and stirring becomes impossible.
　ケン化反応の時間は、使用するアルカリの種類、量などにより異なるが、通常数時間程度で反応は終了する。 The time for the saponification reaction varies depending on the type and amount of alkali used, but the reaction is usually completed in about several hours.
　ケン化反応が終了した時点で通常、ペーストないしスラリー状の共重合体ケン化物の分散体となる。遠心分離、濾過など従来公知の方法により固液分離し、メタノールなどの低級アルコールなどでよく洗浄して得られた含液共重合体ケン化物を乾燥することにより、球状単一粒子または球状粒子が凝集した凝集粒子として共重合体ケン化物、すなわちビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を得ることができる。 When the saponification reaction is completed, a paste or slurry-like copolymer saponified dispersion is usually obtained. Spherical single particles or spherical particles can be obtained by solid-liquid separation according to a conventionally known method such as centrifugation, filtration, and thoroughly washed with a lower alcohol such as methanol to obtain a saponified liquid-containing copolymer obtained. It is possible to obtain a saponified copolymer, that is, a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid as aggregated agglomerated particles.
　前記ケン化反応以降において、塩酸、硫酸、燐酸、硝酸などの無機酸；ギ酸、酢酸、シュウ酸、クエン酸などの有機酸等の酸を用いて共重合体ケン化物を酸処理した後に、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化フランシウムなど任意のアルカリ金属を用いて、異種の（つまり、アルカリ金属が異なる）、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物の共重合体を得ることもできる。 After the above saponification reaction, the acid saponification of the saponified copolymer with an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; an organic acid such as formic acid, acetic acid, oxalic acid or citric acid; Different alkali metals such as lithium oxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide and the like (that is, different alkali metals), vinyl alcohol and ethylenic unsaturated carbon Copolymers of acid alkali metal neutralized products can also be obtained.
　含液共重合体ケン化物を乾燥する条件は、特に限定されないが通常、常圧もしくは減圧下、３０～１２０℃の温度で乾燥することが好ましい。 The conditions for drying the liquid-containing copolymer saponified product are not particularly limited, but in general, it is preferable to dry at a temperature of 30 to 120 ° C. under normal pressure or reduced pressure.
　乾燥時間は、乾燥時の圧力、温度にもよるが通常数時間～数十時間である。 The drying time is usually from several hours to several tens of hours, depending on the pressure and temperature at the time of drying.
　ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の体積平均粒子径は、１～２００μｍであることが好ましく、１０～１００μｍであることがより好ましい。１μｍ以上でより好ましく結着効果が得られ、２００μｍ以下であることで水系増粘液がより均一になり好ましい結着効果が得られる。なお、共重合体の体積平均粒子径はレーザー回折式粒度分布測定装置（例えば島津製作所社製、ＳＡＬＤ－７１００）に回分セル（例えば、同社製、ＳＡＬＤ－ＢＣ）を設置し、分散溶媒に２－プロパノールまたはメタノールを用い測定した値である。 The volume average particle diameter of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid is preferably 1 to 200 μm, and more preferably 10 to 100 μm. A binding effect can be obtained more preferably at 1 μm or more, and by making it 200 μm or less, the water-based thickening liquid becomes more uniform and a preferable binding effect can be obtained. The volume average particle size of the copolymer is determined by installing a batch cell (for example, SALD-BC manufactured by Shimadzu Corporation, for example, SALD-BC manufactured by Shimadzu Corporation) and using 2 as the dispersion solvent. It is a value measured using propanol or methanol.
　含液共重合体ケン化物を乾燥し、得られた共重合体ケン化物の体積平均粒子径が１００μｍを超える場合は、メカニカルミリング処理などの従来公知の粉砕方法にて粉砕することにより体積平均粒子径を例えば１０～１００μｍに調整することができる。 The saponified liquid-containing copolymer is dried, and when the volume-average particle diameter of the obtained saponified copolymer exceeds 100 μm, the volume-average particle is obtained by grinding using a conventionally known grinding method such as mechanical milling. The diameter can be adjusted to, for example, 10 to 100 μm.
　メカニカルミリング処理とは、衝撃・引張り・摩擦・圧縮・せん断等の外力を得られた共重合体ケン化物に与える方法で、そのための装置としては、転動ミル、振動ミル、遊星ミル、揺動ミル、水平ミル、アトライターミル、ジェットミル、擂潰機、ホモジナイザー、フルイダイザー、ペイントシェイカー、ミキサー等などが挙げられる。例えば、遊星ミルは、共重合体ケン化物とボールとを共に容器に入れ、自転と公転をさせることによって生じる力学的エネルギーにより、共重合体ケン化物粉末を粉砕又は混合させるものである。この方法によれば、ナノオーダーまで粉砕されることが知られている。 Mechanical milling is a method of applying to the saponified copolymer obtained with external force such as impact, tension, friction, compression, shear, etc., and a device for that purpose is a rolling mill, a vibration mill, a planetary mill, a rocking motion. Mills, horizontal mills, attritor mills, jet mills, grinders, homogenizers, fluidizers, paint shakers, mixers and the like. For example, in a planetary mill, saponified copolymer and balls are put together in a container, and the kinetic energy generated by rotating and revolving is used to grind or mix the saponified copolymer powder. According to this method, it is known to be crushed to nano order.
　ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の結着剤における増粘効果としては、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を１質量％含む水溶液の粘度が３０ｍＰａ・ｓ～１００００ｍＰａ・ｓであることが好ましく、４０～５０００ｍＰａ・ｓであることがより好ましい。前記粘度が３０ｍＰａ・ｓ以上であれば、作製したスラリー状電極用合剤の粘度が好ましく得られ、集電体へ塗工する際に合剤が広がりすぎず塗工が容易となり得、また合剤中の活物質や導電助剤の分散性も良好となる。前記粘度が１００００ｍＰａ・ｓ以下であると、作製した合剤の粘度が高過ぎず、集電体に薄く均一に塗工することがより簡単となる。なお、前記１質量％水溶液の粘度は、ＢＲＯＯＫＦＩＥＬＤ製回転粘度計（型式ＤＶ－Ｉ＋）、スピンドルＮｏ．５、５０ｒｐｍ（液温２５℃）にて測定した値である。 As a thickening effect in the binder of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid, copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid is used. The viscosity of the aqueous solution containing 1% by mass is preferably 30 mPa · s to 10000 mPa · s, and more preferably 40 to 5000 mPa · s. If the viscosity is 30 mPa · s or more, the viscosity of the prepared slurry-like electrode mixture is preferably obtained, and when the composition is applied to a current collector, the mixture does not spread too much and coating may be facilitated, and The dispersibility of the active material and the conductive aid in the agent also becomes good. If the viscosity is 10000 mPa · s or less, the viscosity of the prepared mixture is not too high, and it becomes easier to thinly and uniformly coat the current collector. The viscosity of the 1% by mass aqueous solution was measured using a rotational viscometer (model DV-I +) manufactured by BROOK FIELD, spindle No. 5 and 50 rpm (liquid temperature 25 ° C.).
　ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体は、結着力と結着持続性に優れるリチウムイオン二次電池電極用結着剤として機能し得る。その理由としては、限定的な解釈を望むものではないが、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体は、集電体と活物質および活物質同士を強固に結着し、充放電の繰り返しに起因する活物質の体積変化によって集電体から電極用合剤が剥離したり、活物質が脱落したりすることがないような結着持続性を有することで、活物質の容量を低下させることがないためであると考えられる。 A copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid can function as a binder for a lithium ion secondary battery electrode which is excellent in binding ability and binding persistence. Although the reason is that it is not desired to be interpreted in a limited way, a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid strengthens the current collector and the active material and the active material to each other. By having binding durability such that the electrode mixture does not peel off from the current collector or the active material falls off due to the volume change of the active material caused by the repetition of charge and discharge. It is considered that this is because the capacity of the active material is not reduced.
　本実施形態リチウムイオン二次電池電極用合剤（好ましくは電極スラリー）には、本発明の効果を損なわない範囲で、結着剤として、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体にさらに他の水系結着剤を加えてもよい。この場合、他の水系結着剤の添加量は、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体と他の水系結着剤との合計質量に対して８０質量％未満であることが好ましい。より好ましくは、７０質量％未満である。すなわち、換言すれば、結着剤中におけるビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体の含有割合は、２０質量％以上１００質量％以下であることが好ましく、より好ましくは、３０質量％以上１００質量％以下である。さらに、当該下限は、例えば４０質量％以上、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、又は９５質量％以上であり得る。 In this embodiment, the mixture for a lithium ion secondary battery electrode (preferably, electrode slurry) contains vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid as a binder, as long as the effects of the present invention are not impaired. Other aqueous binders may be added to the copolymer of In this case, the addition amount of the other water-based binder is 80% by mass based on the total mass of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid and the other water-based binder. Preferably it is less than. More preferably, it is less than 70% by mass. That is, in other words, the content ratio of the copolymer of vinyl alcohol and the alkali metal neutralized product of ethylenic unsaturated carboxylic acid in the binder is preferably 20% by mass or more and 100% by mass or less. Preferably, it is 30% by mass or more and 100% by mass or less. Furthermore, the said minimum may be 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
　他の水系結着剤の材料としては、例えば、カルボキシメチルセルロース（ＣＭＣ）、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリル酸塩などのアクリル樹脂、アルギン酸ナトリウム、ポリイミド（ＰＩ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリアミド、ポリアミドイミド、スチレンブタジエンゴム（ＳＢＲ）、ポリビニルアルコール（ＰＶＡ）、エチレン酢酸共重合体（ＥＶＡ）等の材料が挙げられる。これらは、一種単独で用いてもよく、二種以上を併用してもよい。他の水系結着剤のうち、ポリアクリル酸ナトリウムに代表されるアクリル樹脂、アルギン酸ナトリウム、ポリイミド等が好適に用いられ、アクリル樹脂が特に好適に用いられる。 Other water-based binder materials include, for example, carboxymethylcellulose (CMC), polyacrylic acid, sodium polyacrylate, acrylic resin such as polyacrylate, sodium alginate, polyimide (PI), polytetrafluoroethylene ( Materials such as PTFE), polyamide, polyamide imide, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), ethylene acetic acid copolymer (EVA) and the like can be mentioned. These may be used singly or in combination of two or more. Among the other water-based binders, acrylic resins represented by sodium polyacrylate, sodium alginate, polyimide and the like are suitably used, and acrylic resins are particularly suitably used.
　（架橋剤）
　本発明に用いられる架橋剤は、架橋能を有する金属キレート錯体化合物である。当該金属キレート錯体化合物としては、例えばチタンキレート錯体化合物、ジルコニウムキレート錯体化合物、及びアルミニウムキレート錯体化合物等が挙げられ、中でもチタンキレート錯体化合物及びジルコニウムキレート錯体化合物が好ましく、チタンキレート錯体化合物がより好ましい。 (Crosslinking agent)
The crosslinking agent used in the present invention is a metal chelate complex compound having a crosslinking ability. Examples of the metal chelate complex compound include titanium chelate complex compounds, zirconium chelate complex compounds, and aluminum chelate complex compounds. Among them, titanium chelate complex compounds and zirconium chelate complex compounds are preferable, and titanium chelate complex compounds are more preferable.
　当該架橋剤（金属キレート錯体化合物）は、カルボキシル基および／または水酸基と反応可能な官能基を２個以上（好ましくは２、３、又は４個であり、より好ましくは２個）有する架橋剤が好ましい。また、架橋剤は、水系架橋剤（水溶性架橋剤）であることが好ましい。カルボキシル基および／または水酸基と反応可能な官能基とは、カルボキシル基および／または水酸基と反応して化学結合を形成する官能基をいう。アルコキシ基のように、自らは反応により脱離してしまっても、結果として結合が形成されていれば、これに含まれる。触媒の必要性、加熱の必要性は特に限定されない。このような官能基の具体例としては、アルコキシ基及びアシレート基等が好ましく挙げられる。アルコキシ基としては、例えば、炭素数１～１８（１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、又は１８）の、直鎖若しくは分岐鎖状のアルコキシ基が挙げられる。アシレート基としては、例えばラクテート基、ステアレート基、イソステアレート基等が挙げられる。 The said crosslinking agent (metal chelate complex compound) is a crosslinking agent which has 2 or more (preferably 2, 3 or 4, preferably 2) functional groups capable of reacting with a carboxyl group and / or a hydroxyl group. preferable. The crosslinking agent is preferably an aqueous crosslinking agent (water-soluble crosslinking agent). The functional group capable of reacting with the carboxyl group and / or the hydroxyl group means a functional group that reacts with the carboxyl group and / or the hydroxyl group to form a chemical bond. Like an alkoxy group, even if oneself is eliminated by a reaction, if a bond is formed as a result, it is included in this. The need for the catalyst and the need for heating are not particularly limited. As a specific example of such a functional group, an alkoxy group, an acylate group, etc. are mentioned preferably. Examples of the alkoxy group include, for example, 1 to 18 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18) And linear or branched alkoxy groups. As an acylate group, a lactate group, a stearate group, an isostearate group etc. are mentioned, for example.
　これら官能基がビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体分子鎖のカルボキシル基および／または水酸基と反応することによって、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体が架橋され、機械強度が向上する。架橋剤として作用するために、カルボキシル基および／または水酸基と反応可能な官能基は、架橋剤分子中に２個以上（好ましくは２、３、又は４個であり、より好ましくは２個）存在する必要がある。架橋剤一分子内に存在する当該官能基は同一であっても異なっていてもよい。官能基の数が多いほど架橋点が増えるため機械強度が向上し得るが、多すぎると電極塗工液の状態でゲル化が進むため塗工が困難になってしまう場合があり、この場合不便である。ゲル化が生じるかどうかはビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体分子鎖中のカルボキシル基および／または水酸基の個数の他、当該共重合体と架橋剤との混合比によっても左右されるため、これらを適宜調整することでゲル化を回避可能である。 By reacting these functional groups with the carboxyl group and / or hydroxyl group of the molecular chain of the copolymer of vinyl alcohol and alkali metal of ethylenically unsaturated carboxylic acid, in vinyl alcohol and alkali metal of ethylenically unsaturated carboxylic acid The copolymer with the hydrate is crosslinked to improve the mechanical strength. In order to act as a crosslinker, two or more (preferably two, three or four, and more preferably two) functional groups capable of reacting with the carboxyl group and / or the hydroxyl group are present in the crosslinker molecule. There is a need to. The functional groups present in one molecule of crosslinker may be the same or different. As the number of functional groups increases, the crosslinking point increases and mechanical strength may be improved. However, if the number is too large, gelation may progress in the state of the electrode coating liquid, which may make coating difficult, and in this case, it is inconvenient. It is. Whether or not gelation occurs depends on the number of carboxyl groups and / or hydroxyl groups in the molecular chain of the copolymer of vinyl alcohol and alkali metal neutralized with ethylenically unsaturated carboxylic acid, the copolymer and the crosslinking agent Since it also depends on the mixing ratio, gelation can be avoided by appropriately adjusting these.
　アルコキシ基及び／又はアシレート基を有する架橋剤（金属キレート錯体化合物）としてはマツモトファインケミカル（株）製　オルガチックスシリーズ等の金属キレート化合物が例示される。 As a crosslinking agent (metal chelate complex compound) which has an alkoxy group and / or an acylate group, metal chelate compounds, such as Matsumoto Fine Chemical Co., Ltd. product organics series, are illustrated.
　チタンキレート錯体化合物としては、具体的には、例えばチタンラクテートアンモニウム塩、チタンラクテート、チタントリエタノールアミネート、チタンジエタノールアミネート、チタンアミノエチルアミノエタノレート、チタンアセチルアセトネート、チタンテトラアセチルアセトネート、チタンエチルアセトアセテート、ドデシルベンゼンスルホン酸チタン化合物、リン酸チタン化合物、チタンオクチレングリコート、チタンエチルアセトアセテート等が好ましく挙げられ、中でもチタンラクテートアンモニウム塩、チタンラクテート、チタントリエタノールアミネート、チタンジエタノールアミネート、チタンアミノエチルアミノエタノレートがより好ましい。より具体的には、例えば（ｉ－Ｃ３Ｈ７Ｏ）２Ｔｉ（Ｃ６Ｈ１４ＮＯ３）２、（ＨＯ）２Ｔｉ［ＯＣＨ（ＣＨ３）ＣＯＯ－］２（ＮＨ４ ＋）２、（ＨＯ）２Ｔｉ［ＯＣＨ（ＣＨ３）ＣＯＯＨ］２、（ｉ－Ｃ３Ｈ７Ｏ）Ｔｉ（ＯＣ２Ｈ４ＮＨＣ２Ｈ４ＮＨ２）３、（ｉ－Ｃ３Ｈ７Ｏ）２Ｔｉ（Ｃ６Ｈ７Ｏ２）２、Ｔｉ（Ｃ５Ｈ７Ｏ２）４、（ｉ－Ｃ３Ｈ７Ｏ）２Ｔｉ（Ｃ６Ｈ９Ｏ３）２、Ｔｉ（Ｏ－ｉ－Ｃ３Ｈ７）４、（Ｃ８Ｈ１７Ｏ）２Ｔｉ（Ｏ２Ｃ８Ｈ１７）２、（ｉ－Ｃ３Ｈ７Ｏ）２Ｔｉ（Ｃ６Ｈ９Ｏ３）２、等が挙げられる。 Specific examples of the titanium chelate complex compound include titanium lactate ammonium salt, titanium lactate, titanium triethanol aminate, titanium diethanol aminate, titanium aminoethyl aminoethanolate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium Preferred are ethyl acetoacetate, titanium dodecylbenzene sulfonate, titanium phosphate, titanium octyrene glycolate, titanium ethyl acetoacetate, etc. Among them, titanium lactate ammonium salt, titanium lactate, titanium triethanol aminate, titanium diethanol aminate And titanium aminoethyl aminoethanolate are more preferred. More specifically, for example, (i-C 3 H 7 O) 2 Ti (C 6 H 14 NO 3 ) 2 , (HO) 2 Ti [OCH (CH 3 ) COO − ] 2 (NH 4 + ) 2 , (HO) 2 Ti [OCH (CH 3 ) COOH] 2 , (i-C 3 H 7 O) Ti (OC 2 H 4 NHC 2 H 4 NH 2 ) 3 , (i-C 3 H 7 O) 2 Ti (C 6 H 7 O 2 ) 2 , Ti (C 5 H 7 O 2 ) 4 , (i-C 3 H 7 O) 2 Ti (C 6 H 9 O 3 ) 2 , Ti (Oi-C 3 H 7 ) 4 , (C 8 H 17 O) 2 Ti (O 2 C 8 H 17 ) 2 , (i-C 3 H 7 O) 2 Ti (C 6 H 9 O 3 ) 2 , and the like.
　このようなチタンキレート錯体化合物の市販品としては、例えばマツモトファインケミカル（株）製　オルガチックスＴＣシリーズが挙げられ、より具体的には、例えばオルガチックスＴＣ－３００、ＴＣ－３１０、ＴＣ－４００、ＴＣ－３１５、ＴＣ－３３５、ＴＣ－５００、及びＴＣ－５１０等が挙げられる。 Commercially available products of such titanium chelate complex compounds include, for example, Organics TC series manufactured by Matsumoto Fine Chemical Co., Ltd., more specifically, for example, organics TC-300, TC-310, TC-400, TC -315, TC-335, TC-500, and TC-510.
　また、ジルコニウムキレート錯体化合物としては、例えば塩化ジルコニル化合物、ジルコニウムラクテートアンモニウム塩、炭酸ジルコニウムアンモニウム等が好ましく挙げられる。より具体的には、例えば（ＨＯ）Ｚｒ［ＯＣＨ（ＣＨ３）ＣＯＯ－］３（ＮＨ４ ＋）３等が挙げられる。 Moreover, as a zirconium chelate complex compound, a zirconyl chloride compound, a zirconium lactate ammonium salt, a zirconium ammonium carbonate etc. are mentioned preferably, for example. More specifically, for example, (HO) Zr [OCH (CH 3 ) COO − ] 3 (NH 4 + ) 3 and the like can be mentioned.
　このようなジルコニウムキレート錯体化合物の市販品としては、例えばマツモトファインケミカル（株）製　オルガチックスＺＡシリーズ、オルガチックスＺＣシリーズ（例えばオルガチックスＺＣ－１２６、ＺＣ－３００等）及びサンノプコ（株）製　ＡＺ　コート　５８００ＭＴ等が挙げられる。 Commercially available products of such zirconium chelate complex compounds include, for example, Orgatics ZA series manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics ZC series (for example Organics ZC-126, ZC-300, etc.) and Sannopco Co., Ltd. AZ coat 5800 MT etc. are mentioned.
　アルミニウムキレート錯体化合物としては、例えばアルミニウムトリスアセチルアセトネート、アルミニウムビスエチルアセトアセテートモノアセチルアセトネート、アルミニウムトリスエチルアセトアセテート等が挙げられ、より具体的には例えばＡｌ（Ｃ５Ｈ７Ｏ２）３、Ａｌ（Ｃ５Ｈ７Ｏ２）（Ｃ６Ｈ９Ｏ３）２、Ａｌ（Ｃ６Ｈ９Ｏ３）３が挙げられる。 Examples of aluminum chelate complex compounds include aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate and the like, and more specifically, for example, Al (C 5 H 7 O 2 ) 3 And Al (C 5 H 7 O 2 ) (C 6 H 9 O 3 ) 2 and Al (C 6 H 9 O 3 ) 3 .
　このような有機アルミニウム化合物の市販品としては、例えばマツモトファインケミカル（株）製　オルガチックスＡＬシリーズが挙げられる。 As a commercial item of such an organic aluminum compound, Matsumoto Fine Chemical Co., Ltd. product organics AL series are mentioned, for example.
　架橋剤は１種単独で又は２種以上を組み合わせて用いることができる。 A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
　架橋剤の含有量は、架橋剤及び結着剤の合計質量を１００質量部としたとき、０．２質量部以上１０質量部未満である。０．３、０．４、又は０．５質量部以上であることがより好ましく、０．６、０．７、０．８、０．９又は１質量部以上であることがさらに好ましい。また、９、８、又は７又は６質量部以下であることがより好ましく、５又は４質量部以下であることがさらに好ましく、３質量％以下であることがよりさらに好ましい。当該架橋剤の含有比率が１０質量部未満であることにより、電極塗工液の状態でゲル化が進みづらくなり塗工を簡便に行うことができる。またさらに、活物質の比率が相対的に高くなり得られる電極の電気抵抗値が特に好ましく低下し得る。また、当該架橋剤の含有比率が０．２質量部以上であることにより、架橋効果が十分に発現し、結着剤樹脂の機械強度が高く好ましい電池性能が好ましく得られる。 The content of the crosslinking agent is 0.2 parts by mass or more and less than 10 parts by mass, when the total mass of the crosslinking agent and the binder is 100 parts by mass. The content is more preferably 0.3, 0.4, or 0.5 parts by mass or more, and still more preferably 0.6, 0.7, 0.8, 0.9, or 1 parts by mass or more. Moreover, it is more preferable that it is 9, 8 or 7 or 6 mass parts or less, It is more preferable that it is 5 or 4 mass parts or less, It is still more preferable that it is 3 mass% or less. By the content rate of the said crosslinking agent being less than 10 mass parts, gelatinization can not advance easily in the state of an electrode coating liquid, and coating can be performed simply. Furthermore, the electrical resistance value of the electrode obtained in which the proportion of the active material is relatively high may be particularly preferably lowered. Moreover, when the content ratio of the said crosslinking agent is 0.2 mass part or more, the crosslinking effect fully expresses and the mechanical strength of binder resin is high and preferable battery performance is obtained preferably.
　（正極活物質）
　正極活物質としては、本技術分野で使用される正極活物質が使用できる。例えば、リン酸鉄リチウム（ＬｉＦｅＰＯ４）、リン酸マンガンリチウム（ＬｉＭｎＰＯ４）、リン酸コバルトリチウム（ＬｉＣｏＰＯ４）、ピロリン酸鉄（Ｌｉ２ＦｅＰ２Ｏ７）、コバルト酸リチウム複合酸化物（ＬｉＣｏＯ２）、スピネル型マンガン酸リチウム複合酸化物（ＬｉＭｎ２Ｏ４）、マンガン酸リチウム複合酸化物（ＬｉＭｎＯ２）、ニッケル酸リチウム複合酸化物（ＬｉＮｉＯ２）、ニオブ酸リチウム複合酸化物（ＬｉＮｂＯ２）、鉄酸リチウム複合酸化物（ＬｉＦｅＯ２）、マグネシウム酸リチウム複合酸化物（ＬｉＭｇＯ２）、カルシウム酸リチウム複合酸化物（ＬｉＣａＯ２）、銅酸リチウム複合酸化物（ＬｉＣｕＯ２）、亜鉛酸リチウム複合酸化物（ＬｉＺｎＯ２）、モリブデン酸リチウム複合酸化物（ＬｉＭｏＯ２）、タンタル酸リチウム複合酸化物（ＬｉＴａＯ２）、タングステン酸リチウム複合酸化物（ＬｉＷＯ２）、リチウム－ニッケル－コバルト－アルミニウム複合酸化物（ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２）、リチウム－ニッケル－コバルト－マンガン複合酸化物（ＬｉＮｉｘＣｏｙＭｎ１－ｘ－ｙＯ２　ここで０＜ｘ＜１，０＜ｙ＜１，ｘ＋ｙ＜１）、Ｌｉ過剰系ニッケル－コバルト－マンガン複合酸化物、酸化マンガンニッケル（ＬｉＮｉ０．５Ｍｎ１．５Ｏ４）、酸化マンガン（ＭｎＯ２）、バナジウム系酸化物、硫黄系酸化物、シリケート系酸化物、等が好適に使用される。これらは、１種を単独で又は２種以上を組み合わせて用いることができる。 (Positive electrode active material)
As a positive electrode active material, the positive electrode active material used in this technical field can be used. For example, lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium cobalt phosphate (LiCoPO 4 ), iron pyrophosphate (Li 2 FeP 2 O 7 ), lithium cobaltate complex oxide (LiCoO 2) ), Spinel type lithium manganate complex oxide (LiMn 2 O 4 ), lithium manganate complex oxide (LiMnO 2 ), lithium nickelate complex oxide (LiNiO 2 ), lithium niobate complex oxide (LiNbO 2 ), ferrate lithium composite oxide (LiFeO 2), magnesium lithium composite oxide (LiMgO 2), lithium composite oxide of calcium acid (LiCaO 2), cuprate lithium composite oxide (LiCuO 2), lithium zincate complex oxide (LiZnO 2 ), lithium molybdate Complex oxide (LiMoO 2 ), lithium tantalate complex oxide (LiTaO 2 ), lithium tungstate complex oxide (LiWO 2 ), lithium-nickel-cobalt-aluminum complex oxide (LiNi 0.8 Co 0.15 Al) 0.05 O 2), lithium - nickel - cobalt - manganese composite oxide (LiNi x Co y Mn 1- x-y O 2 where 0 <x <1,0 <y < 1, x + y <1), Li Excess system nickel-cobalt-manganese complex oxide, manganese nickel oxide (LiNi 0.5 Mn 1.5 O 4 ), manganese oxide (MnO 2 ), vanadium oxide, sulfur oxide, silicate oxide, etc. Is preferably used. These can be used singly or in combination of two or more.
　（負極活物質）
　負極活物質としては、特に限定はなく、例えばケイ素（Ｓｉ）やスズ（Ｓｎ）あるいはこれらを含む材料、炭素（特に炭素材料（例えばグラファイト、ハードカーボン、ソフトカーボン））、チタン酸リチウムなどのようにリチウムイオンを大量に吸蔵放出可能な材料、等を用いることができる。このような材料であれば、単体、合金、化合物、固溶体およびケイ素含有材料やスズ含有材料を含む複合活物質の何れであっても、本実施形態の効果を発揮させることは可能である。ケイ素含有材料としては、Ｓｉ（ケイ素）の他に、酸化ケイ素（好ましくはＳｉＯｘ（０．０５＜ｘ＜１．９５）、より具体的には例えばＳｉＯ）、またはこれらのいずれかにＢ、Ｍｇ、Ｎｉ、Ｔｉ、Ｍｏ、Ｃｏ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｎ、Ｎｂ、Ｔａ、Ｖ、Ｗ、Ｚｎ、Ｃ、Ｎ、Ｓｎからなる群から選択される少なくとも１つ以上の元素でＳｉの一部を置換した合金や化合物、もしくは固溶体などを用いることができる。これらはケイ素化合物ということができる。スズ含有材料としてはＮｉ２Ｓｎ４、Ｍｇ２Ｓｎ、ＳｎＯｘ（０＜ｘ＜２）、ＳｎＯ２、ＳｎＳｉＯ３、ＬｉＳｎＯなどを挙げることができる。炭素材料としては結晶質炭素、非晶質炭素またはこれらを共に使用しても良い。これらの材料は、それぞれ１種単独で、あるいは２種以上を組み合わせて用いることができる。特に、ケイ素、ケイ素化合物、および炭素材料からなる群から選ばれる少なくとも１種が好ましい。また、特に、ケイ素及び／又はケイ素化合物と炭素材料とを組み合わせて用いる場合、炭素材料とケイ素及び／又はケイ素化合物との比率（炭素材料／ケイ素又はケイ素化合物）が質量比で５／９５～５０／５０であることが好ましい。当該質量比の上限は、１０／９０又は１５／８５であってもよい。また、当該質量比の下限は、４０／６０、３５／６５、３０／７０、又は２５／７５であってもよい。 (Anode active material)
The negative electrode active material is not particularly limited, and examples thereof include silicon (Si) and tin (Sn) or materials containing these, carbon (especially carbon materials (eg, graphite, hard carbon, soft carbon)), lithium titanate and the like. For example, materials capable of absorbing and desorbing lithium ions in large quantities can be used. If it is such a material, it is possible to exhibit the effect of the present embodiment regardless of any one of a simple substance, an alloy, a compound, a solid solution, and a composite active material containing a silicon-containing material and a tin-containing material. As the silicon-containing material, in addition to Si (silicon), silicon oxide (preferably SiOx (0.05 <x <1.95), more specifically, for example, SiO), or B or Mg in any of these At least one element selected from the group consisting of Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, W, Zn, C, N, Sn, and Si An alloy, a compound, a solid solution or the like in which a part is substituted can be used. These can be referred to as silicon compounds. Examples of tin-containing materials include Ni 2 Sn 4 , Mg 2 Sn, SnO x (0 <x <2), SnO 2 , SnSiO 3 , LiSnO, and the like. As a carbon material, crystalline carbon, amorphous carbon, or these may be used together. These materials can be used singly or in combination of two or more. In particular, at least one selected from the group consisting of silicon, silicon compounds, and carbon materials is preferable. In particular, when using a combination of silicon and / or silicon compound and carbon material, the ratio of carbon material to silicon and / or silicon compound (carbon material / silicon or silicon compound) is 5/95 to 50 in mass ratio It is preferable that it is / 50. The upper limit of the mass ratio may be 10/90 or 15/85. Also, the lower limit of the mass ratio may be 40/60, 35/65, 30/70, or 25/75.
　（導電助剤）
　導電助剤を用いる場合、導電助剤は、導電性を有していれば、特に限定されることはない。例えば、金属、炭素、導電性高分子、導電性ガラスなどの粉末が例示でき、アセチレンブラック（ＡＢ）、ケッチェンブラック（ＫＢ）、カーボンブラック（例えばＳｕｐｅｒＰ（ＳＰ））、黒鉛、サーマルブラック、ファーネスブラック、ランプブラック、チャンネルブラック、ローラーブラック、ディスクブラック、ソフトカーボン、ハードカーボン、グラフェン、アモルファスカーボンカーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（例えば、登録商標であるＶＧＣＦという名称の気相成長炭素繊維）などが挙げられる。これらは一種単独で用いてもよいし、または二種以上を併用してもよい。特に制限されないが、伝導助剤は、電極合剤中例えば０．０１～５質量％程度含有させることが好ましく、０．０２～３質量％又は０．０５～２質量％程度含有させることがより好ましい。 (Conduction agent)
When using a conductive aid, the conductive aid is not particularly limited as long as it has conductivity. For example, powder of metal, carbon, conductive polymer, conductive glass and the like can be exemplified, and acetylene black (AB), ketjen black (KB), carbon black (for example, SuperP (SP)), graphite, thermal black, furnace Black, lamp black, channel black, roller black, disc black, soft carbon, hard carbon, graphene, amorphous carbon carbon nanotube (CNT), carbon nanofiber (for example, vapor grown carbon fiber named VGCF which is a registered trademark) Etc. These may be used alone or in combination of two or more. Although not particularly limited, it is preferable that the conduction aid be contained in the electrode mixture, for example, about 0.01 to 5% by mass, and it is more preferable to contain about 0.02 to 3% by mass or about 0.05 to 2% by mass. preferable.
　（分散助剤）
　分散助剤を用いる場合、分散助剤としては、例えば、グルクロン酸、フミン酸、グリシン、ポリグリシン、アスパラギン酸、グルタミン酸などが例示される。 (Dispersion aid)
When a dispersion aid is used, examples of the dispersion aid include glucuronic acid, humic acid, glycine, polyglycine, aspartic acid, glutamic acid and the like.
　（電極合剤）
　電極活物質（正極活物質又は負極活物質）に、架橋剤、結着剤、および必要に応じて液体媒体（好ましくは水）を加えてペースト状のスラリーとすることにより電極合剤（正極合剤又は負極合剤）が得られる。結着剤は、あらかじめ水に溶かして用いてもよいし、活物質、結着剤の粉末をあらかじめ混合し、その後に水を加え混合してもよい。また、その他の成分を加える場合にも当該スラリーへ混合することができる。 (Electrode mix)
By adding a crosslinking agent, a binder and, if necessary, a liquid medium (preferably water) to an electrode active material (positive electrode active material or negative electrode active material) to form a paste-like slurry, an electrode mixture (positive electrode combination) Agent or negative electrode mixture) is obtained. The binder may be dissolved in water in advance, and may be used, or the active material and the powder of the binder may be mixed in advance, and then water may be added and mixed. Moreover, also when adding other components, it can mix with the said slurry.
　液体媒体（好ましくは水）の使用量については、特に限定的ではないが、例えば、活物質、架橋剤、結着剤の合計を１００質量％とした場合、４０質量％以上２０００質量％以下が好ましく５０質量％以上１０００質量％以下がより好ましく、６０質量％以上５００質量％以下がさらに好ましい。
結着剤は、活物質同士、およびこれらと集電体との接着を目的として使用される。すなわち、両極の集電体上にスラリーを塗布し、乾燥させたときに良好な活物質層を形成するために使用される。 The use amount of the liquid medium (preferably water) is not particularly limited, but, for example, 40% by mass or more and 2000% by mass or less when the total of the active material, the crosslinking agent, and the binding agent is 100% by mass. Preferably, 50% by mass or more and 1000% by mass or less are more preferable, and 60% by mass or more and 500% by mass or less are more preferable.
The binder is used for the purpose of bonding the active materials to each other and the current collector. That is, it is used to form a good active material layer when the slurry is applied onto the current collectors of both electrodes and dried.
　結着剤の使用量についても、特に限定的ではないが、例えば、電極活物質、架橋剤、及び結着剤の合計質量に対して、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましく、２質量％以上であることがさらに好ましい。また、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましく、１０質量％以下であることがよりさらに好ましい。結着剤が当該上限以下であることで、活物質の割合が相対的に少なすぎず、電池の充放電時に高容量がより得られうる。また、当該下限以上であることで、より好ましく結着力が得られ、好ましいサイクル寿命特性を得られ、またスラリーの粘性不足による凝集が生じる傾向も減少する。 The amount of the binder used is also not particularly limited, but is preferably 0.5% by mass or more based on the total mass of the electrode active material, the crosslinking agent, and the binder, for example. % Or more is more preferable, and 2% by mass or more is more preferable. The content is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less. When the binder is at or below the upper limit, the proportion of the active material is not relatively too small, and a high capacity can be further obtained during charge and discharge of the battery. Moreover, by being more than the said lower limit, more preferable binding strength is obtained, preferable cycle life characteristics can be obtained, and the tendency of aggregation due to insufficient viscosity of the slurry also decreases.
　当該電極合剤は、正極用合剤又は負極用合剤で有り得、特に負極用合剤であることが好ましい。 The electrode mixture may be a positive electrode mixture or a negative electrode mixture, and is particularly preferably a negative electrode mixture.
　なお、特に制限はされないが、電極合剤においては、電極活物質の含有量が８０質量％以上であることが好ましく、８５質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。 There is no particular limitation, but in the electrode mixture, the content of the electrode active material is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more More preferable.
　また、特に制限はされないが、電極合剤における架橋剤及び結着剤の合計含有量は、２０質量％より小さいことが好ましく、１５質量％より小さいことがより好ましく、１０質量％より小さいことがさらに好ましい。 Further, although not particularly limited, the total content of the crosslinking agent and the binder in the electrode mixture is preferably less than 20% by mass, more preferably less than 15% by mass, and less than 10% by mass More preferable.
　（正極）
　正極は、本技術分野で使用される手法を用いて作製することができる。 (Positive electrode)
The positive electrode can be made using techniques used in the art.
　正極の集電体は、電子伝導性を有し、保持した正極材料に通電し得る材料であれば特に限定されない。例えば、Ｃ、Ｔｉ、Ｃｒ、Ｍｏ、Ｒｕ、Ｒｈ、Ｔａ、Ｗ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ａｌ等の導電性物質、これら導電性物質の二種類以上を含有する合金（例えば、ステンレス鋼）を使用し得る。電気伝導性が高く、電解液中の安定性と耐酸化性がよい観点から、集電体としてはＣ、Ａｌ、ステンレス鋼等が好ましく、さらに材料コストの観点からＡｌ等が好ましい。 The current collector of the positive electrode is not particularly limited as long as it is a material having electron conductivity and capable of supplying a current to the held positive electrode material. For example, conductive materials such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, etc., alloys containing two or more of these conductive materials (for example, stainless steel) ) Can be used. C, Al, stainless steel and the like are preferable as the current collector from the viewpoints of high electrical conductivity and stability in the electrolytic solution and oxidation resistance, and Al and the like are preferable from the viewpoint of material cost.
　集電体の形状には、特に制約はないが、箔状基材、三次元基材などを用いることができる。ただし、三次元基材（発泡メタル、メッシュ、織布、不織布、エキスパンド等）を用いると、集電体との密着性に欠けるような結着剤であっても高い容量密度の電極が得られる。加えて、高率充放電特性も良好になる。 The shape of the current collector is not particularly limited, and a foil-like substrate, a three-dimensional substrate or the like can be used. However, when a three-dimensional substrate (foam metal, mesh, woven fabric, non-woven fabric, expand, etc.) is used, an electrode of high capacity density can be obtained even with a binder that lacks adhesion to the current collector. . In addition, high rate charge and discharge characteristics are also improved.
　（負極）
　負極は、本技術分野で使用される手法を用いて作製することができる。 (Negative electrode)
The negative electrode can be made using techniques used in the art.
　負極の集電体は、電子伝導性を有し、保持した負極材料に通電し得る材料であれば特に限定されない。例えば、Ｃ、Ｃｕ、Ｎｉ、Ｆｅ、Ｖ、Ｎｂ、Ｔｉ、Ｃｒ、Ｍｏ、Ｒｕ、Ｒｈ、Ｔａ、Ｗ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ａｌ等の導電性物質、これら導電性物質の二種類以上を含有する合金（例えば、ステンレス鋼）を使用し得る。あるいは、ＦｅにＣｕをめっきしたものであってもよい。電気伝導性が高く、電解液中の安定性と耐酸化性がよい観点から、集電体としてはＣ、Ｎｉ、ステンレス鋼等が好ましく、さらに材料コストの観点からＣｕ、Ｎｉが好ましい。 The current collector of the negative electrode is not particularly limited as long as it is a material having electron conductivity and capable of supplying a current to the held negative electrode material. For example, conductive materials such as C, Cu, Ni, Fe, V, Nb, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, etc., and two kinds of these conductive materials Alloys containing the above, such as stainless steel, may be used. Alternatively, Fe may be plated with Cu. From the viewpoints of high electrical conductivity and good stability and oxidation resistance in the electrolyte, C, Ni, stainless steel and the like are preferable as the current collector, and Cu and Ni are more preferable from the viewpoint of material cost.
　集電体の形状には、特に制約はないが、箔状基材、三次元基材などを用いることができる。なかでも、三次元基材（発泡メタル、メッシュ、織布、不織布、エキスパンド基材等）を用いると、集電体との密着性に欠けるような結着剤であっても高い容量密度の電極が得られる。加えて、高率充放電特性も良好になる。 The shape of the current collector is not particularly limited, and a foil-like substrate, a three-dimensional substrate or the like can be used. Among them, when a three-dimensional substrate (foam metal, mesh, woven fabric, non-woven fabric, expanded substrate, etc.) is used, an electrode having a high capacity density even with a binder which lacks adhesion to the current collector. Is obtained. In addition, high rate charge and discharge characteristics are also improved.
　(電池）
　本実施形態の非水電解質二次電池用電極を用い、本実施形態の非水電解質二次電池とすることができる。非水電解質二次電池としては、例えばリチウムイオン二次電池が好ましい。 (battery)
The nonaqueous electrolyte secondary battery of the present embodiment can be obtained by using the electrode of the nonaqueous electrolyte secondary battery of the present embodiment. As a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery is preferable.
　本実施形態の非水電解質二次電池のなかでもリチウムイオン二次電池は、リチウムイオンを含有する必要があることから、電解質塩としてはリチウム塩が好ましい。このリチウム塩としては特に制限されないが、具体例としては、ヘキサフルオロリン酸リチウム、過塩素酸リチウム、テトラフルオロホウ酸リチウム、トリフルオロメタンスルホン酸リチウム、トリフルオロメタンスルホン酸イミドリチウムなどを挙げることができる。これらのリチウム塩は、１種単独又は２種以上混合して用いることができる。上記のリチウム塩は、電気的陰性度が高くイオン化しやすいことから、充放電サイクル特性に優れ、二次電池の充放電容量を向上させることができる。 Among the non-aqueous electrolyte secondary batteries of the present embodiment, a lithium ion secondary battery needs to contain lithium ions, and therefore, a lithium salt is preferable as the electrolyte salt. The lithium salt is not particularly limited, and specific examples thereof include lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, and the like. . These lithium salts can be used singly or in combination of two or more. The above-mentioned lithium salt has high electronegativity and is easy to ionize, so it is excellent in charge and discharge cycle characteristics, and can improve the charge and discharge capacity of the secondary battery.
　上記電解質の溶媒としては、例えば、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、γ－ブチロラクトン等を用いることができ、これらの溶媒を一種単独又は２種以上混合して用いることができる。特に、プロピレンカーボネート単体、エチレンカーボネートとジエチルカーボネートとの混合物又はγ－ブチロラクトン単体が好適である。なお、上記エチレンカーボネートとジエチルカーボネートとの混合物の混合比は、一方の成分が１０体積％以上９０体積％以下となる範囲で任意に調整することができる。 As a solvent for the electrolyte, for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone and the like can be used, and these solvents can be used singly or in combination of two or more. In particular, propylene carbonate alone, a mixture of ethylene carbonate and diethyl carbonate, or γ-butyrolactone alone is preferable. The mixing ratio of the mixture of ethylene carbonate and diethyl carbonate can be arbitrarily adjusted in the range in which one component is 10% by volume or more and 90% by volume or less.
　また、本実施形態のリチウム二次電池の電解質は、固体電解質やイオン性液体であっても構わない。 In addition, the electrolyte of the lithium secondary battery of the present embodiment may be a solid electrolyte or an ionic liquid.
　上述の構造のリチウム二次電池によれば、寿命特性に優れるリチウム二次電池として機能することができる。 According to the lithium secondary battery of the above-mentioned structure, it can function as a lithium secondary battery excellent in the life characteristic.
　リチウム二次電池の構造としては、特に限定されないが、積層式電池、捲回式電池などの既存の電池形態・構造に適用できる。 Although it does not specifically limit as a structure of a lithium secondary battery, It can apply to the existing battery forms and structures, such as a lamination type battery and a wound type battery.
　（電気機器）
　本実施形態の負極を具備した非水電解質二次電池は、寿命特性に優れており、様々な電気機器（電気を使用する乗り物を含む）の電源として利用することができる。 (Electric equipment)
The non-aqueous electrolyte secondary battery provided with the negative electrode of the present embodiment has excellent life characteristics, and can be used as a power source for various electric devices (including vehicles using electricity).
　電気機器としては、例えば、ポータブルテレビ、ノートパソコン、タブレット、スマートフォン、パソコンキーボード、パソコン用ディスプレイ、デスクトップ型パソコン、ＣＲＴモニター、パソコンラック、プリンター、一体型パソコン、ウェアラブルコンピュータ、ワープロ、マウス、ハードディスク、パソコン周辺機器、アイロン、冷房機器、冷蔵庫、温風ヒーター、ホットカーペット、衣類乾燥機、布団乾燥機、加湿器、除湿器、ウインドウファン、送風機、換気扇、洗浄機能付便座、カーナビ、懐中電灯、照明器具、携帯カラオケ機、マイク、空気清浄器、血圧計、コーヒーミル、コーヒーメーカー、こたつ、携帯電話、ゲーム機、音楽レコーダー、音楽プレーヤー、ディスクチェンジャー、ラジオ、シェーバー、ジューサー、シュレッダー、浄水器、食器乾燥機、カーコンポ、ステレオ、スピーカー、ヘッドホン、トランシーバー、ズボンプレッサー、掃除機、体脂肪計、体重計、ヘルスメーター、ムービープレーヤー、電気釜、電気かみそり、電気スタンド、電気ポット、電子ゲーム機、携帯ゲーム機、電子辞書、電子手帳、電磁調理器、電卓、電動カート、電動車椅子、電動工具、電動歯ブラシ、あんか、散髪器具、電話機、時計、インターホン、電撃殺虫器、ホットプレート、トースター、ドライヤー、電動ドリル、給湯器、パネルヒーター、粉砕機、はんだごて、ビデオカメラ、ファクシミリ、フードプロセッサー、マッサージ機、豆電球、ミキサー、ミシン、もちつき機、リモコン、冷水器、冷風器、泡だて器、電子楽器、オートバイ、おもちゃ類、芝刈り機、うき、自転車、自動車、ハイブリッド自動車、プラグインハイブリッド自動車、電気自動車、鉄道、船、飛行機、非常用蓄電池などが挙げられる。 Examples of the electric devices include portable TVs, laptops, tablets, smartphones, PC keyboards, displays for PCs, desktop PCs, CRT monitors, PC racks, printers, integrated PCs, wearable computers, word processors, word processors, mice, hard disks, PCs Peripheral equipment, Iron, Cooling equipment, Refrigerator, Hot air heater, Hot carpet, Clothes dryer, Futon dryer, Humidifier, Dehumidifier, Window fan, Blower, Ventilation fan, Toilet seat with cleaning function, Car navigation system, Flashlight, Lighting equipment , Mobile karaoke machine, microphone, air purifier, blood pressure monitor, coffee mill, coffee maker, Kotatsu, mobile phone, game machine, music recorder, music player, disc changer, radio, shaver, juicer, Guredder, water purifier, dish dryer, car component, stereo, speaker, headphone, transceiver, trouser press, vacuum cleaner, body fat scale, weight scale, health meter, movie player, electric kettle, electric razor, electric stand, electric pot, Electronic game machines, portable game machines, electronic dictionaries, electronic organizers, electromagnetic cookers, calculators, electric carts, electric wheelchairs, electric tools, electric toothbrushes, electric toothbrushes, electric toothbrushes, haircuts, telephones, watches, intercoms, electric shock insecticides, hot plates , Toaster, dryer, electric drill, water heater, panel heater, grinder, soldering iron, video camera, facsimile, food processor, massage machine, bean light bulb, mixer, sewing machine, sewing machine, rice cooker, remote control, water cooler, air cooler, Foamer, electronic musical instrument, motorcycle, toys, lawn mower Machine, float, bicycle, motor vehicles, hybrid vehicles, plug-in hybrid vehicles, electric vehicles, rail, ship, airplane, such as an emergency storage battery, and the like.
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes"consisting essentially of” and "consisting of."）。 In the present specification, "including" also includes "consisting essentially of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of.").
　また、上述した本発明の各実施形態について説明した各種特性（性質、構造、機能等）は、本発明に包含される主題を特定するにあたり、どのように組み合わせられてもよい。すなわち、本発明には、本明細書に記載される組み合わせ可能な各特性のあらゆる組み合わせからなる主題が全て包含される。 In addition, various characteristics (properties, structures, functions, etc.) described for each embodiment of the present invention described above may be combined in any way in specifying the subject matter included in the present invention. That is, the present invention includes all the subject matter consisting of all combinations of the combinable features described in the present specification.
　以下、実施例により本実施形態を更に具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、Ｇｒはグラファイトを示す。 Hereinafter, the present embodiment will be more specifically described by way of examples, but the present invention is not limited to these examples. Gr represents graphite.
　（結着剤の作製）
　（製造例１）ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体の合成
　撹拌機、温度計、Ｎ２ガス導入管、還流冷却機および滴下ロートを備えた容量２Ｌの反応槽に、水７６８ｇ、無水硫酸ナトリウム１２ｇを仕込み、Ｎ２ガスを吹き込んで系内を脱酸素した。続いて部分ケン化ポリビニルアルコール（ケン化度８８％）１ｇ、ラウリルパーオキシド１ｇを仕込み内温６０℃まで昇温した後、アクリル酸メチル１０４ｇ（１．２０９ｍｏｌ）および酢酸ビニル１５５ｇ（１．８０２ｍｏｌ）の単量体を滴下ロートにより４時間かけて適下した後、内温６５℃で２時間保持し反応を完結させた。その後、固形分を濾別することによりビニルエステル／エチレン性不飽和カルボン酸エステル共重合体２８８ｇ(１０．４質量％含水)を得た。得られた重合体をＤＭＦに溶解させた後フィルターにてろ過を実施、分子量測定装置（ウォーターズ社製２６９５、ＲＩ検出器２４１４）により求めた数平均分子量は１８．８万であった。 (Preparation of binding agent)
Production Example 1 Synthesis of vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer 768 g of water in a 2 L reactor equipped with a stirrer, thermometer, N 2 gas introduction pipe, reflux condenser and dropping funnel Then, 12 g of anhydrous sodium sulfate was charged, and N 2 gas was blown into the system to deoxygenate the system. Subsequently, 1 g of partially saponified polyvinyl alcohol (88% saponification degree) and 1 g of lauryl peroxide were charged and heated to an internal temperature of 60 ° C., then 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate The monomer of (1) was dropped over 4 hours by a dropping funnel, and then maintained at an internal temperature of 65 ° C. for 2 hours to complete the reaction. Thereafter, the solid content was separated by filtration to obtain 288 g (10.4 mass% water content) of a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer. The obtained polymer was dissolved in DMF and then filtered through a filter, and the number average molecular weight determined with a molecular weight measuring apparatus (2695 manufactured by Waters, RI detector 2414) was 188,000.
　（製造例２）ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物の調製
　　上記同様の反応槽に、メタノール４５０ｇ、水４２０ｇ、水酸化ナトリウム１３２ｇ（３．３ｍｏｌ）および製造例１で得られた含水共重合体２８８ｇ（１０．４質量％含水）を仕込み、撹拌下で３０℃、３時間ケン化反応を行った。ケン化反応終了後、得られた共重合体ケン化物をメタノールで洗浄、濾過し、７０℃で６時間乾燥させ、ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物（ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体、アルカリ金属はナトリウム）１９３ｇを得た。ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物の体積平均粒子径は１８０μｍであった。なお、体積平均粒子径は、レーザー回折式粒度分布測定装置（株式会社島津製作所社製ＳＡＬＤ－７１００）により測定した。 Production Example 2 Preparation of Saponified Vinyl Ester / Ethylene Unsaturated Carboxylic Acid Ester Copolymer In the same reaction vessel as described above, 450 g of methanol, 420 g of water, 132 g (3.3 mol) of sodium hydroxide and 288 g (10.4 mass% water content) of the obtained water-containing copolymer was charged, and a saponification reaction was carried out under stirring at 30 ° C. for 3 hours. After completion of the saponification reaction, the resulting saponified copolymer is washed with methanol, filtered, dried at 70 ° C. for 6 hours, and saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer (vinyl alcohol and ethylene As a result, 193 g of a copolymer with an alkali metal neutralized with an unsaturated unsaturated carboxylic acid (the alkali metal is sodium) was obtained. The volume average particle diameter of the saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer was 180 μm. The volume average particle size was measured by a laser diffraction type particle size distribution measuring apparatus (SALD-7100 manufactured by Shimadzu Corporation).
　（製造例３）ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物の粉砕
　上記ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物１９３ｇを、ジェットミル（日本ニューマチック工業社製ＬＪ）により粉砕し、微粉末状のビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物１７３ｇを得た。得られた共重合体ケン化物の粒子径をレーザー回折式粒度分布測定装置（島津製作所社製ＳＡＬＤ－７１００）により測定したところ、体積平均粒子径は３９μｍであった。以下、製造例３で得られたビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物を共重合体〔１〕として検討に用いた。 Production Example 3 Pulverization of Saponified Product of Vinyl Ester / Ethylene Unsaturated Carboxylic Acid Ester Copolymer 193 g of the above saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer is a jet mill (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) The resultant mixture was pulverized according to LJ to obtain 173 g of a finely powdered vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified product. The particle diameter of the obtained saponified copolymer was measured by a laser diffraction type particle size distribution analyzer (SALD-7100 manufactured by Shimadzu Corporation), and the volume average particle diameter was 39 μm. Hereinafter, the saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer obtained in Production Example 3 was used as a copolymer [1] in the examination.
　なお、共重合体〔１〕の１質量％水溶液の粘度は１，６３０ｍＰａ・ｓ、ビニルエステルとエチレン性不飽和カルボン酸エステルの共重合組成比はモル比で６／４であった。前記１質量％水溶液の粘度は、ＢＲＯＯＫＦＩＥＬＤ製回転粘度計（型式ＤＶ－Ｉ＋）を用いて、スピンドルＮｏ．５、５０ｒｐｍ（液温２５℃）の条件で測定した。 The viscosity of a 1% by mass aqueous solution of the copolymer [1] was 1,630 mPa · s, and the copolymerization composition ratio of vinyl ester to ethylenically unsaturated carboxylic acid ester was 6/4 in molar ratio. The viscosity of the 1% by mass aqueous solution was measured using a rotational viscometer (model DV-I +) manufactured by BROOK FIELD, and spindle No. 1 was used. It measured on the conditions of 5 and 50 rpm (liquid temperature 25 degreeC).
　（製造例４）
　製造例１において、アクリル酸メチル１０４ｇ（１．２０９ｍｏｌ）および酢酸ビニル１５５ｇ（１．８０２ｍｏｌ）に代えて、アクリル酸メチル２５．９ｇ（０．３０１ｍｏｌ）および酢酸ビニル２３２．８ｇ（２．７０４ｍｏｌ）を用いた以外は製造例１～３と同様の操作を行い、ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物を得た。当該ビニルエステル／エチレン性不飽和カルボン酸エステル共重合体ケン化物を共重合体〔２〕とした。 (Production Example 4)
In Production Example 1, 25.9 g (0.301 mol) of methyl acrylate and 232.8 g (2.704 mol) of vinyl acetate are used instead of 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate. The same procedures as in Production Examples 1 to 3 were carried out except using, to obtain a saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer. The said vinyl ester / ethylenic unsaturated carboxylic acid ester copolymer saponification thing was made into copolymer [2].
　なお、共重合体〔２〕の体積平均粒子径は３４μｍであった。また、共重合体〔２〕の１質量％水溶液の粘度は５０ｍＰａ・ｓ、ビニルエステルとエチレン性不飽和カルボン酸エステルの共重合組成比は９／１であった。当該体積平均粒子径及び１質量％水溶液の粘度は、共重合体〔１〕と同様にして測定した。 The volume average particle diameter of the copolymer [2] was 34 μm. Further, the viscosity of a 1% by mass aqueous solution of the copolymer [2] was 50 mPa · s, and the copolymer composition ratio of the vinyl ester and the ethylenically unsaturated carboxylic acid ester was 9/1. The volume average particle diameter and the viscosity of the 1% by mass aqueous solution were measured in the same manner as in the copolymer [1].
　（架橋剤量の検討）
　（実施例１）
　ＳｉＯ（平均粒子径５－１０μｍ：日立化成社製）１８．８質量部、Ｇｒ（Ｇ１：江西紫宸科技社製）７５．２質量部（ＳｉＯ／Ｇｒ＝２／８の質量比）、ＳＰ（ＳｕｐｅｒＰ：Ｔｉｍｃａｌ社製カーボンブラック）１．０質量部、製造例３で得られた共重合体〔１〕　４．９５質量部、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）０．０５質量部、及び水１００質量部を混合してスラリー状の負極合剤を調製した。 (Examination of the amount of crosslinking agent)
Example 1
18.8 parts by mass of SiO (average particle diameter: 5-10 μm: manufactured by Hitachi Chemical Co., Ltd.), 75.2 parts by mass of Gr (G1: manufactured by Kosai Shioshi Technology), (mass ratio of SiO / Gr = 2/8), SP (SuperP: carbon black manufactured by Timcal) 1.0 part by mass, 4.95 parts by mass of the copolymer [1] obtained in Production Example 3, organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400) 0 The slurry-like negative electrode mixture was prepared by mixing .05 parts by mass and 100 parts by mass of water.
　得られた合剤を厚さ１０μｍの電解銅箔上に塗布し乾燥させた後、ロールプレス（大野ロール社製）を用いて圧力を加えることで、電解銅箔と塗膜とを密着接合させ、次に、加熱処理（減圧中、１２０℃、１２時間）を行って負極を作製した。活物質層（塗膜）の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 The obtained mixture is applied on an electrolytic copper foil having a thickness of 10 μm and dried, and then pressure is applied using a roll press (manufactured by Ono Roll Co., Ltd.) to closely bond the electrolytic copper foil and the coating film. Then, heat treatment (under reduced pressure, 120 ° C., 12 hours) was performed to fabricate a negative electrode. The thickness of the active material layer (coated film) was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（実施例２）
　実施例１において、共重合体〔１〕　４．９５質量部に代えて、共重合体〔１〕　４．９質量部を用い、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．０５質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．１質量部を用いた以外は実施例１と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Example 2)
In Example 1, 4.9 parts by mass of the copolymer [1] is used in place of 4.95 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.1 part by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（実施例３）
　実施例１において、共重合体〔１〕　４．９５質量部に代えて、共重合体〔１〕　４．６５質量部を用い、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．０５質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．３５質量部を用いた以外は実施例１と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Example 3)
In Example 1, in place of 4.95 parts by mass of the copolymer [1], 4.65 parts by mass of the copolymer [1] is used, and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.35 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（比較例Ａ）
　実施例１において、共重合体〔１〕　４．９５質量部に代えて、架橋剤を加えず、共重合体〔１〕　５．０質量部のみを混合した以外は実施例１と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Comparative example A)
Example 1 is the same as Example 1 except that in place of 4.95 parts by mass of the copolymer [1], no crosslinking agent is added, and only 5.0 parts by mass of the copolymer [1] is mixed. A negative electrode was produced. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（比較例１）
　実施例１において、共重合体〔１〕　４．９５質量部に代えて、共重合体〔１〕　４．９９５質量部を用い、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．０５質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．００５質量部を用いた以外は実施例１と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Comparative example 1)
In Example 1, 4.95 parts by mass of the copolymer [1] is replaced with 4.995 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode was produced in the same manner as in Example 1 except that 0.005 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（参考例１）
　実施例２において、共重合体〔１〕　４．９５質量部に代えて、共重合体〔１〕　４．５質量部を用い、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．０５質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．５質量部を用いた以外は実施例１と同様にして負極スラリーを作製しようとしたところ、ゲル化をおこしスラリーが得られず、このため電解銅箔への塗工が困難であった。 (Reference Example 1)
In Example 2, 4.5 parts by mass of the copolymer [1] is used in place of 4.95 parts by mass of the copolymer [1], and an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) A negative electrode slurry was prepared in the same manner as in Example 1 except that 0.5 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of .05 parts by mass. And no slurry was obtained, which made it difficult to coat the electrodeposited copper foil.
　（架橋剤種の検討）
　（実施例４）
　実施例２において、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．１質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－３００）　０．１質量部を用いた以外は実施例２と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Study of crosslinker species)
(Example 4)
In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., TC-300) is used. A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（実施例５）
　実施例２において、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．１質量部に代えて、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－３１５）　０．１質量部を用いた以外は実施例２と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Example 5)
In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., TC-315) A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（実施例６）
　実施例２において、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．１質量部に代えて、有機ジルコニア化合物架橋剤（サンノプコ社製、ＡＺ－コート　５８００ＭＴ）０．１質量部を用いた以外は実施例２と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Example 6)
In Example 2, in place of 0.1 part by mass of the organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of the organic zirconia compound crosslinking agent (manufactured by Sannopco, AZ-coated 5800 MT) is used. A negative electrode was produced in the same manner as in Example 2 except that it was used. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　（比較例２）
　実施例２において、有機チタン化合物架橋剤（マツモトファインケミカル社製、ＴＣ－４００）　０．１質量部に代えて、エポキシ系架橋剤（ナガセケムテック社製、デナコール ＥＸ－８１０）０．１質量部を用いた以外は実施例２と同様にして負極を作製した。活物質層の厚みは５０μｍ、負極の目付重量は１０ｍｇ／ｃｍ２であった。 (Comparative example 2)
In Example 2, in place of 0.1 part by mass of an organic titanium compound crosslinking agent (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-400), 0.1 part by mass of an epoxy-based crosslinking agent (Nagase Chemtech Co., Ltd., Denacol EX-810) A negative electrode was produced in the same manner as in Example 2 except for using. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .
　なお、上記各実施例で用いた架橋剤について、表１にまとめて示す。 In addition, about the crosslinking agent used by said each Example, it collects in Table 1 and shows.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に、各負極の組成を示す。 Table 2 shows the composition of each negative electrode.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（正極）
　（実施例Ａ）
　活物質（Ｌｉ（Ｎｉ０．８Ｃｏ０．１Ｍｎ０．１）Ｏ２：北京当升科技社製）９５質量部、バインダーとして共重合体〔１〕３質量部、導電助剤としてアセチレンブラック（デンカブラック：デンカ製）２質量部、及び水１００質量部を混合してスラリー状の正極合剤を調製した。 (Positive electrode)
Example A
Active material (Li (Ni 0.8 Co 0.1 Mn 0.1) O 2: 95 parts by weight of Beijing Toshin Technology Co., Ltd.), 3 parts by weight of copolymer [1] as a binder, acetylene black (denka black: made by Denka as a conductive aid 2 parts by mass and 100 parts by mass of water were mixed to prepare a slurry-like positive electrode mixture.
　厚さ１０μｍのアルミニウム箔上に前記合剤を塗布・乾燥後、ロールプレス機（大野ロール社製）により、アルミニウム箔と塗膜とを密着接合させ、次に、加熱処理（減圧中、１２０℃、１２時間以上）して、正極を作製した。当該正極において、正極容量密度は１．６ｍＡｈ／ｃｍ２（活物質物質層の平均厚み：５０μｍ）であった。なお、以下に示すいずれの検討においても、正極電極として当該正極を用いた。 After applying and drying the above mixture on an aluminum foil with a thickness of 10 μm, the aluminum foil and the coating film are closely bonded with a roll press machine (made by Ono Roll Co., Ltd.), and then heat treatment (under reduced pressure, 120 ° C. , 12 hours or more) to prepare a positive electrode. In the positive electrode, the capacity density of the positive electrode was 1.6 mAh / cm 2 (average thickness of the active material layer: 50 μm). In addition, the said positive electrode was used as a positive electrode also in any examination shown below.
　（電池の組立）
　実施例１～７、比較例Ａおよび比較例１～２で得られた負極電極と、実施例Ａで得た正極を用い、セパレータとしてＰＰ（セルガード＃２５００：セルガード社製）、電解液として、ＬｉＰＦ６　１ｍｏｌ／Ｌの電解質入りのＥＣ／ＤＥＣ（１／１　ｖ／ｖ％）＋１質量％ＶＣ溶液（キシダ化学社製）を具備した２０ｍＡｈの小型パウチセルを作製した。 (Assembly of battery)
Using the negative electrodes obtained in Examples 1 to 7 and Comparative Examples A and 1 and 2 and the positive electrode obtained in Example A, PP (Celgard # 2500: made by Celgard) as a separator, and an electrolytic solution, LiPF 6 A small pouch cell of 20 mAh was prepared, which was provided with an EC / DEC (1/1 v / v%) + 1 mass% VC solution (manufactured by Kishida Chemical Co., Ltd.) containing 1 mol / L of electrolyte.
　なお、ＰＰはポリプロピレンを、ＬｉＰＦ６はヘキサフルオロリン酸リチウムを、ＥＣはエチレンカルボナートを、ＤＥＣは炭酸ジエチルを、ＶＣはビニレンカーボネートを、それぞれ示す。 PP indicates polypropylene, LiPF6 indicates lithium hexafluorophosphate, EC indicates ethylene carbonate, DEC indicates diethyl carbonate, and VC indicates vinylene carbonate.
　＜エージング後高率放電試験＞
　上記のようにして作製したパウチセルを用いて以下（１）～（１０）に示すような手順で、エージングから高率放電試験を行い、ＤＣ－ＩＲ抵抗値を算出した。
　　　　試験温度　　　：３０℃
　　　　カットオフ電位：２．５－４．３Ｖ（ｖｓ．Ｌｉ＋／Ｌｉ）
（１）ＣＣ（ＣＶ）充電／ＣＣ放電において、０．２Ｃ(０．０５Ｃ)／０．２Ｃの条件で１０サイクルエージングを実施した。この際、エージング最後の平均放電電圧値を記録した。
※充電／放電の順に記載。カッコ内はＣＶの終端電流である。
（２）０．２Ｃ（０．０５Ｃ）／０．５Ｃの条件で３サイクル実施し、３サイクル目の平均放電電圧値を記録した。
（３）０．２Ｃ（０．０５Ｃ）／０．２Ｃで２サイクル実施した。
（４）（２）の放電レートを０．７Ｃにして３サイクル実施し、３サイクル目の平均放電電圧値を記録した。
（５）０．２Ｃ（０．０５Ｃ）／０．２Ｃで２サイクル実施した。
（６）（２）の放電レートを１．０Ｃにして３サイクル実施し、３サイクル目の平均放電電圧値を記録した。
（７）０．２Ｃ（０．０５Ｃ）／０．２Ｃで２サイクル実施した。
（８）（２）の放電レートを２．０Ｃにして３サイクル実施し、３サイクル目の平均放電電圧値を記録した。
（９）横軸に放電電流（レート）、縦軸に平均放電電圧のグラフを作成した。その際、０．２、０．５、０．７、１．０、２．０Ｃ時の平均電圧値を入力した。
（１０）グラフの傾きをＤＣ－ＩＲの値（Ω）とした。
なお、作製した全てのパウチセルを用いて、本条件にて試験を行った。
試験により算出したＤＣ－ＩＲ値を、表３に示す。 <High rate discharge test after aging>
Using the pouch cell produced as described above, a high-rate discharge test was carried out from aging according to the following procedures (1) to (10) to calculate the DC-IR resistance value.
Test temperature: 30 ° C
Cut-off potential: 2.5-4.3 V (vs. Li + / Li)
(1) In CC (CV) charge / CC discharge, 10 cycle aging was implemented on the conditions of 0.2C (0.05C) /0.2C. At this time, the average discharge voltage value at the end of aging was recorded.
※ Described in order of charge / discharge. In parentheses are the termination currents of CV.
(2) Three cycles were carried out under the conditions of 0.2 C (0.05 C) /0.5 C, and the average discharge voltage value of the third cycle was recorded.
(3) Two cycles of 0.2 C (0.05 C) /0.2 C were performed.
(4) Three cycles were carried out with the discharge rate of (2) set to 0.7 C, and the average discharge voltage value of the third cycle was recorded.
(5) Two cycles of 0.2 C (0.05 C) /0.2 C were performed.
(6) Three cycles were carried out with the discharge rate of (2) set to 1.0 C, and the average discharge voltage value at the third cycle was recorded.
(7) Two cycles of 0.2 C (0.05 C) /0.2 C were performed.
(8) Three cycles were carried out with the discharge rate of (2) set to 2.0 C, and the average discharge voltage value at the third cycle was recorded.
(9) The horizontal axis is the discharge current (rate), and the vertical axis is the graph of the average discharge voltage. At that time, average voltage values at 0.2, 0.5, 0.7, 1.0, and 2.0 C were input.
(10) The slope of the graph was taken as the value (Ω) of DC-IR.
In addition, it tested on this condition using all the manufactured pouch cells.
The DC-IR values calculated by the test are shown in Table 3.
　＜サイクル試験＞
　上記のようにして高率放電試験を終えた各パウチセルを用いて、以下に示すような手順で、サイクル試験を行った。
　　　　試験温度　　　：３０℃
　　　　カットオフ電位：２．５－４．３Ｖ（ｖｓ．Ｌｉ＋／Ｌｉ）
　　　　サイクルレート：０．５Ｃ（０．０５Ｃ）／０．５Ｃ
　　　　サイクル数　　：１００
サイクル後、次の式を用いて容量維持率を算出した。結果を表３に示す。
※　容量維持率（％）＝［１００サイクル後の放電容量（ｍAh／ｇ）］／［エージング後の初期放電容量（ｍAh／ｇ）］×１００ <Cycle test>
The cycle test was conducted according to the following procedure using each pouch cell finished the high rate discharge test as described above.
Test temperature: 30 ° C
Cut-off potential: 2.5-4.3 V (vs. Li + / Li)
Cycle rate: 0.5C (0.05C) /0.5C
Number of cycles: 100
After the cycle, the capacity retention rate was calculated using the following equation. The results are shown in Table 3.
※ Capacity retention rate (%) = [Discharge capacity after 100 cycles (mAh / g)] / [Initial discharge capacity after aging (mAh / g)] x 100
　＜１００サイクル後高率放電試験＞
　上記のようにしてサイクル試験を終えた各パウチセルを用いて、高率放電試験を行った。なお、試験方法・条件はエージング後高率放電試験と同様とした。
試験により算出したＤＣ－ＩＲ値を、表３に示す。 <High-rate discharge test after 100 cycles>
The high rate discharge test was performed using each pouch cell which finished the cycle test as mentioned above. The test method and conditions were the same as in the high-rate discharge test after aging.
The DC-IR values calculated by the test are shown in Table 3.
　なお、ＤＣ－ＩＲ抵抗値（Ω）は、値が低いほど電池性能（放電特性）において良好と言え、容量維持率（％）は値が高いほど電池性能（サイクル特性）において良好と言える。 The lower the DC-IR resistance value (Ω), the better the battery performance (discharge characteristics), and the higher the capacity retention rate (%), the better the battery performance (cycle characteristics).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Claims (9)

  1. 　電極活物質と、架橋剤と、結着剤とを含有し、
    前記結着剤が、ビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体を含み、
    前記架橋剤が、金属キレート錯体化合物であり、
    前記結着剤及び前記架橋剤の合計量１００質量部に対して前記架橋剤が０．２質量部以上１０質量部未満含有される、
    非水電解質二次電池用電極合剤。     Containing an electrode active material, a crosslinking agent, and a binder,
    The binder includes a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid,
    The crosslinker is a metal chelate complex compound,
    The crosslinking agent is contained in an amount of 0.2 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the binding agent and the crosslinking agent.
    Electrode mixture for non-aqueous electrolyte secondary batteries.
  2. 金属キレート錯体化合物が、チタンキレート錯体化合物及びジルコニウムキレート錯体化合物からなる群より選択される少なくとも１種である、請求項１に記載の非水電解質二次電池用電極合剤。 The electrode mixture for a non-aqueous electrolyte secondary battery according to claim 1, wherein the metal chelate complex compound is at least one selected from the group consisting of a titanium chelate complex compound and a zirconium chelate complex compound.
  3. 　前記架橋剤は、カルボキシル基および／または水酸基と反応可能な官能基を２個以上有する架橋剤である、請求項１又は２に記載の非水電解質二次電池用電極合剤。 The electrode mixture for a non-aqueous electrolyte secondary battery according to claim 1, wherein the crosslinking agent is a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group and / or a hydroxyl group.
  4. 前記架橋剤は、アルコキシ基及びアシレート基からなる群より選択される官能基を、同一又は異なって２個以上有する架橋剤である、請求項１又は２に記載の非水電解質二次電池用電極合剤。 The electrode for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the crosslinking agent is a crosslinking agent having the same or different two or more functional groups selected from the group consisting of alkoxy groups and acylate groups. Combination drug.
  5. 　前記エチレン性不飽和カルボン酸アルカリ金属中和物が、アクリル酸アルカリ金属中和物および／またはメタクリル酸アルカリ金属中和物である、請求項１～４のいずれかに記載の非水電解質二次電池用電極合剤。 The non-aqueous electrolyte secondary according to any one of claims 1 to 4, wherein said ethylenically unsaturated carboxylic acid alkali metal neutralized product is alkali metal acrylate neutralized product and / or alkali metal methacrylate neutralized product. Electrode mixture for batteries.
  6. 　請求項１～５のいずれかに記載の非水電解質二次電池用電極合剤を用いた非水電解質二次電池用電極。 An electrode for a non-aqueous electrolyte secondary battery using the electrode mixture for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 5.
  7. 　請求項６に記載の非水電解質二次電池用電極を備えた非水電解質二次電池。 A non-aqueous electrolyte secondary battery comprising the electrode for a non-aqueous electrolyte secondary battery according to claim 6.
  8. 　請求項７に記載の非水電解質二次電池を備えた電気機器。 An electrical apparatus comprising the non-aqueous electrolyte secondary battery according to claim 7.
  9. 電極活物質、架橋剤、及び結着剤を混合する工程を含み、
    ここで、前記架橋剤は金属キレート錯体化合物であり、前記結着剤はビニルアルコールとエチレン性不飽和カルボン酸アルカリ金属中和物との共重合体であり、前記結着剤及び前記架橋剤の合計量１００質量部に対して前記架橋剤が０．２質量部以上１０質量部未満となるよう混合される、
    非水電解質二次電池用電極合剤の製造方法。     Mixing the electrode active material, the crosslinking agent, and the binding agent,
    Here, the crosslinking agent is a metal chelate complex compound, and the binding agent is a copolymer of vinyl alcohol and an alkali metal neutralized with an ethylenically unsaturated carboxylic acid, and the binding agent and the crosslinking agent may be used. The crosslinking agent is mixed so as to be 0.2 parts by mass or more and less than 10 parts by mass with respect to a total amount of 100 parts by mass.
    The manufacturing method of the electrode mixture for nonaqueous electrolyte secondary batteries.
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