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WO2019054350A1 - Mélange d'électrodes pour batterie secondaire à électrolyte non aqueux - Google Patents

Mélange d'électrodes pour batterie secondaire à électrolyte non aqueux 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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English (en)
Japanese (ja)
Inventor
靖仁 牛島
隼一 藤重
藤田　浩司
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to CN201880043053.8A priority Critical patent/CN110832679B/zh
Priority to KR1020197033363A priority patent/KR20200051521A/ko
Priority to JP2019542053A priority patent/JP7139342B2/ja
Publication of WO2019054350A1 publication Critical patent/WO2019054350A1/fr
Anticipated expiration legal-status Critical
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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

L'invention concerne un mélange d'électrodes ayant une faible résistance en dépit de l'agent de liaison qu'il contient. L'invention concerne plus précisément un mélange d'électrodes pour une batterie secondaire à électrolyte non aqueux, ledit mélange d'électrodes comprenant une substance active d'électrode, un agent de réticulation, et un agent de liaison, l'agent de liaison comprenant un copolymère d'un alcool vinylique et d'un produit de neutralisation de carboxylate de métal alcalin à insaturation éthylénique, l'agent de réticulation étant un composé complexe de chélate de métal, et l'agent de réticulation étant compris en une quantité supérieure ou égale à 0,2 partie en masse et inférieure à 10 parties en masse pour 100 parties en masse de la quantité totale de l'agent de liaison et de l'agent de réticulation.
PCT/JP2018/033553 2017-09-12 2018-09-11 Mélange d'électrodes pour batterie secondaire à électrolyte non aqueux Ceased WO2019054350A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220021771A (ko) * 2020-08-14 2022-02-22 주식회사 엘지에너지솔루션 전극 슬러리 조성물, 이의 제조방법 및 이의 용도
KR20220074868A (ko) 2019-09-30 2022-06-03 니폰 제온 가부시키가이샤 이차 전지용 바인더 조성물, 이차 전지 전극용 슬러리 조성물, 이차 전지용 전극 및 이차 전지
JP2023121481A (ja) * 2022-02-21 2023-08-31 Tdk株式会社 リチウムイオン二次電池用硬化物、リチウムイオン二次電池用負極及びリチウムイオン二次電池
WO2024241999A1 (fr) * 2023-05-24 2024-11-28 Tdk株式会社 Produit durci pour batteries secondaires au lithium-ion, électrode négative pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion
WO2025192512A1 (fr) * 2024-03-12 2025-09-18 Tdk株式会社 Produit durci pour batterie secondaire au lithium-ion, électrode négative pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion

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WO2019087258A1 (fr) * 2017-10-30 2019-05-09 日立化成株式会社 Composition de résine, objet durci, corps moulé ainsi que procédé de fabrication de celui-ci, et condensateur à film ainsi que procédé de fabrication de celui-ci
CN112164799A (zh) * 2020-09-29 2021-01-01 浙江大学 一种硼交联粘结剂、电极片及制备方法
CN112670506B (zh) * 2020-12-22 2022-04-19 北京理工大学重庆创新中心 快离子导体包覆的镍钴锰钽复合四元正极材料及其制备方法
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US20240409756A1 (en) 2021-10-28 2024-12-12 Toagosei Co., Ltd. Binder for secondary cell electrode, use thereof, and method for manufacturing binder for secondary cell electrode
CN114614017B (zh) * 2022-03-24 2024-09-03 深圳市皓飞实业有限公司 粘结剂、负极极片以及锂离子电池
US20250266459A1 (en) 2022-04-27 2025-08-21 Toagosei Co., Ltd. Secondary battery electrode binder and use of same
CN119400959B (zh) * 2024-11-01 2025-10-03 浙江极氪智能科技有限公司 电解液、电池二次注液方法和电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000021408A (ja) * 1998-06-30 2000-01-21 Shin Kobe Electric Mach Co Ltd 非水電解液二次電池
WO2014057627A1 (fr) * 2012-10-12 2014-04-17 独立行政法人産業技術総合研究所 Liant à utiliser dans une électrode positive pour batterie secondaire au lithium-ion, électrode positive pour batterie secondaire au lithium-ion contenant ledit liant, batterie secondaire au lithium-ion utilisant ladite électrode positive, machinerie et appareil électriques
JP2017152121A (ja) * 2016-02-23 2017-08-31 Tdk株式会社 リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3066682B2 (ja) * 1992-09-10 2000-07-17 富士写真フイルム株式会社 化学電池
JP2000348730A (ja) 2000-01-01 2000-12-15 Seiko Instruments Inc 非水電解質二次電池
JP2012069457A (ja) * 2010-09-27 2012-04-05 Konica Minolta Holdings Inc 多孔質層及びリチウムイオン二次電池
JP5684620B2 (ja) 2011-03-25 2015-03-18 三井化学株式会社 非水系二次電池用バインダー樹脂組成物、非水系二次電池用負極及び非水系二次電池
PL3016180T3 (pl) * 2013-06-28 2019-02-28 Sumitomo Seika Chemicals Co. Ltd. Mieszanina elektrody ujemnej dla ogniwa wtórnego z niewodnym elektrolitem, elektroda ujemna dla ogniwa wtórnego z niewodnym elektrolitem zawierająca wymienioną mieszaninę, ogniwo wtórne z niewodnym elektrolitem dostarczające wymienioną elektrodę ujemną i urządzenie elektryczne
WO2015098507A1 (fr) * 2013-12-25 2015-07-02 日本ゼオン株式会社 Composition de liant pour accumulateur lithium-ion, composition de pâte pour accumulateur lithium-ion, procédé de fabrication d'électrode pour accumulateur lithium-ion et accumulateur lithium-ion
US10068717B2 (en) * 2014-04-01 2018-09-04 Sumitomo Seika Chemicals Co., Ltd. Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus
JP6278804B2 (ja) * 2014-04-04 2018-02-14 住友精化株式会社 リチウムイオン二次電池電極用合剤、この合剤を含むリチウムイオン二次電池用電極およびこの電極を備えたリチウムイオン二次電池並びに電気機器
KR102475886B1 (ko) * 2015-06-25 2022-12-08 삼성전자주식회사 리튬금속전지용 음극 및 이를 포함하는 리튬금속전지
JP6844240B2 (ja) * 2015-12-16 2021-03-17 三菱ケミカル株式会社 二次電池負極用バインダー組成物、二次電池負極及び二次電池
JP6647624B2 (ja) * 2016-02-08 2020-02-14 住友精化株式会社 非水電解質二次電池電極用合剤、当該合剤を含む非水電解質二次電池用電極、並びに当該電極を備えた非水電解質二次電池及び電気機器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000021408A (ja) * 1998-06-30 2000-01-21 Shin Kobe Electric Mach Co Ltd 非水電解液二次電池
WO2014057627A1 (fr) * 2012-10-12 2014-04-17 独立行政法人産業技術総合研究所 Liant à utiliser dans une électrode positive pour batterie secondaire au lithium-ion, électrode positive pour batterie secondaire au lithium-ion contenant ledit liant, batterie secondaire au lithium-ion utilisant ladite électrode positive, machinerie et appareil électriques
JP2017152121A (ja) * 2016-02-23 2017-08-31 Tdk株式会社 リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220074868A (ko) 2019-09-30 2022-06-03 니폰 제온 가부시키가이샤 이차 전지용 바인더 조성물, 이차 전지 전극용 슬러리 조성물, 이차 전지용 전극 및 이차 전지
KR20220021771A (ko) * 2020-08-14 2022-02-22 주식회사 엘지에너지솔루션 전극 슬러리 조성물, 이의 제조방법 및 이의 용도
KR102880140B1 (ko) 2020-08-14 2025-11-04 주식회사 엘지에너지솔루션 전극 슬러리 조성물, 이의 제조방법 및 이의 용도
JP2023121481A (ja) * 2022-02-21 2023-08-31 Tdk株式会社 リチウムイオン二次電池用硬化物、リチウムイオン二次電池用負極及びリチウムイオン二次電池
WO2024241999A1 (fr) * 2023-05-24 2024-11-28 Tdk株式会社 Produit durci pour batteries secondaires au lithium-ion, électrode négative pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion
WO2025192512A1 (fr) * 2024-03-12 2025-09-18 Tdk株式会社 Produit durci pour batterie secondaire au lithium-ion, électrode négative pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion

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