WO2019132036A1 - Pâte de mélange d'électrode positive pour batterie au lithium-ion - Google Patents

Pâte de mélange d'électrode positive pour batterie au lithium-ion Download PDF

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Publication number
WO2019132036A1
WO2019132036A1 PCT/JP2018/048589 JP2018048589W WO2019132036A1 WO 2019132036 A1 WO2019132036 A1 WO 2019132036A1 JP 2018048589 W JP2018048589 W JP 2018048589W WO 2019132036 A1 WO2019132036 A1 WO 2019132036A1
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Prior art keywords
positive electrode
mixture paste
electrode mixture
organic polymer
mass
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PCT/JP2018/048589
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English (en)
Japanese (ja)
Inventor
森下正典
境哲男
隠岐一雄
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花王株式会社
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Priority claimed from JP2017254063A external-priority patent/JP7057665B2/ja
Priority claimed from JP2017254068A external-priority patent/JP7057666B2/ja
Application filed by 花王株式会社 filed Critical 花王株式会社
Publication of WO2019132036A1 publication Critical patent/WO2019132036A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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 a positive electrode mixture paste for lithium ion battery and a method for producing the same, a lithium ion battery electrode and a lithium ion battery including a positive electrode mixture layer manufactured using the positive electrode mixture paste for lithium ion battery, and The present invention relates to a method for improving the storage stability of a positive electrode material mixture paste for lithium ion batteries.
  • Lithium ion batteries have higher energy density per unit weight and volume than lead storage batteries and nickel hydrogen batteries, and so contribute to the downsizing and weight reduction of mounted electronic devices.
  • hybrid cars and electric cars have been widely used as an approach for zero emission of cars, and the performance improvement of lithium ion batteries is important for improving the fuel efficiency and extending the driving distance.
  • a lithium ion battery generally has a structure in which a non-aqueous electrolytic solution is filled in a three-layer structure of a positive electrode, a separator, and a negative electrode.
  • the positive electrode and the negative electrode are manufactured, for example, by coating a current collector with a mixture paste in which an active material, a conductive material, and a binder are mixed.
  • a mixture paste in which an active material, a conductive material, and a binder are mixed.
  • an aqueous process in which an aqueous slurry (mixture paste) is coated and dried on a copper foil serving as a current collector is mainly used as a method of manufacturing a negative electrode, and an organic method such as N-methylpyrrolidone is used as a method of manufacturing a positive electrode.
  • a non-aqueous process in which a positive electrode mixture paste is produced using a solvent and applied to an aluminum foil serving as a current collector is the mainstream.
  • the positive electrode mixture paste may gradually lose its fluidity, and may have problems such as thickening and gelation.
  • the positive electrode mixture paste loses its fluidity, it not only becomes difficult to obtain a uniform coating thickness, but in some cases, it can not be applied and leads to waste of material.
  • lithium-nickel transition metal complex oxides show this problem remarkably.
  • Patent Document 1 discloses a technology for suppressing the gelation of the positive electrode mixture paste by preparing the positive electrode mixture paste so as not to show strong alkalinity even when dispersed in water. Etc. are disclosed.
  • the present invention provides a positive electrode material mixture positive electrode material mixture paste for lithium ion batteries in which storage stability is improved by suppressing thickening and gelation by a simple method.
  • the present invention includes, in one aspect, a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent, wherein the organic polymer has a concentration of 0.001% by mass to 3% by mass.
  • the present invention relates to a positive electrode mixture paste for a lithium ion battery, which is an organic polymer exhibiting spinnability.
  • the present invention in another aspect, is a method for producing a positive electrode mixture paste for lithium ion batteries, comprising the steps of mixing a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent,
  • the polymer relates to a method for producing a positive electrode mixture paste for lithium ion batteries, which is an organic polymer exhibiting spinnability in the solvent having a concentration of 0.001% by mass to 3% by mass.
  • the present invention in still another aspect, is a method for improving the storage stability of a positive electrode material mixture paste for lithium ion batteries containing a positive electrode active material, a conductive material, a binder, and a solvent, wherein the positive electrode mixture paste for lithium ion batteries And a step of mixing the positive electrode active material, the conductive material, the binder, the organic polymer, and the solvent in the production process, wherein the concentration of the organic polymer is 0.001% by mass or more and 3% by mass or less
  • the present invention relates to a method for improving the storage stability of a positive electrode material mixture paste for a lithium ion battery, which is an organic polymer exhibiting spinnability in the solvent.
  • the present invention relates, in yet another aspect, to a lithium ion battery electrode including a positive electrode mixture layer formed using the positive electrode mixture paste for a lithium ion battery of the present invention.
  • the present invention relates to a lithium ion battery including a positive electrode mixture layer formed using the positive electrode mixture paste for a lithium ion battery of the present invention.
  • the positive electrode mixture paste for lithium ion batteries and the positive electrode mixture paste for lithium ion batteries in which storage stability is improved by suppressing thickening and gelation by a simple method
  • the electrode for lithium ion batteries and lithium ion batteries which were produced can be provided.
  • the storage stability improvement method of the positive electrode mixture paste for lithium ion batteries can be provided.
  • the present invention is based on the finding that when the positive electrode mixture paste for lithium ion batteries contains an organic polymer exhibiting spinnability under predetermined conditions, thickening and gelation are suppressed.
  • the present invention is a positive electrode mixture paste for a lithium ion battery, comprising a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent, wherein the organic polymer has a concentration of A positive electrode for a lithium ion battery, which is an organic polymer exhibiting spinnability in the above-mentioned solvent having a content of 0.001% by mass or more and 3% by mass or less (hereinafter sometimes abbreviated as “spinky organic polymer”)
  • the present invention relates to a mixture paste (hereinafter may be abbreviated as “positive electrode mixture paste”).
  • the organic polymer is spiny in a solvent having a concentration of 0.001% by mass to 3% by mass
  • concentration of the organic polymer in the solvent is 0.001 It means that the solution which is concentration of mass% or more and 3 mass% or less exhibits spinnability. More specifically, when the solvent is water, the organic polymer exhibits spinnability in an aqueous solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C.
  • the organic polymer is an organic polymer exhibiting spinnability in an aqueous solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C.” It means that an aqueous solution having a concentration of 0.001% by mass or more and 3% by mass or less and a liquid temperature of 25 ° C. exhibits spinnability.
  • the organic polymer is an organic polymer exhibiting spinnability in an N methyl pyrrolidone solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C.
  • the organic polymer is an organic polymer exhibiting spinnability in an N-methylpyrrolidone solution having a concentration of 0.001% to 3% by mass and a liquid temperature of 25 ° C.
  • N-methylpyrrolidone solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C. exhibits spinnability.
  • the spinnable organic polymer in the positive electrode mixture paste, the spinnable organic polymer forms a polymer network, for example, by interaction with water as a solvent (for example, hydrogen bond).
  • water for example, hydrogen bond.
  • the interaction between a trace amount of water contained in N methyl pyrrolidone and the spinnable organic polymer enables suppression of thickening and gelation, and storage stability Is considered to be an improvement.
  • the dispersibility of solid components such as the positive electrode active material and the conductive material in the positive electrode mixture paste is improved, so that uniform positive electrode synthesis is achieved. It becomes possible to form an agent layer. Therefore, in one embodiment, reduction in the initial capacity of the battery can also be suppressed. In one embodiment, it is also possible to improve the concentration of solid content in the positive electrode mixture paste.
  • the storage stability of the positive electrode mixture paste can be improved by a simple method of adding and mixing a spinnable organic polymer in the production process of the positive electrode mixture paste. Therefore, when the positive electrode material mixture paste of the present invention is used for producing a lithium ion battery electrode (positive electrode), it is considered that cost reduction can be achieved in the production of a lithium ion battery.
  • the solid content of the positive electrode mixture paste can be increased, so the amount of solvent such as N-methylpyrrolidone can be reduced, and the energy required for drying to remove it can be reduced. Cost reduction can be achieved.
  • these are only estimates, and the present invention is not interpreted as being limited to these mechanisms.
  • the positive electrode material mixture paste of the present invention contains a positive electrode active material, a conductive material, a binder, a spinnable organic polymer, a solvent, and other components added as necessary.
  • the mass ratio of the positive electrode active material, the conductive material, and the binder (binder) contained in the positive electrode mixture paste of the present invention may be the same as that of a conventionally known battery, and can be arbitrarily adjusted according to the use suitability of the battery.
  • the other components include thickeners, reinforcing materials, antioxidants, additives having a function of suppressing the decomposition of the electrolyte, and the like, and these other components may be known ones.
  • the thickener include polysaccharide thickeners, alginic acid, carboxymethylcellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone and the like.
  • lithium metal complex oxide LiNiO 2 system
  • LiNiO 2 lithium metal complex oxide mainly containing LiNiO 2 containing a large amount of alkali component
  • a lithium metal complex oxide mainly containing Li-rich type as a positive electrode active material, particularly lithium nickel containing in the case of using a composite oxide as a positive electrode active material
  • the present invention can be effectively utilized.
  • lithium metal complex mainly composed of LiNiO 2 type or Li-rich type as a positive electrode active material When a positive electrode mixture paste is prepared using an oxide and water as the solvent, the elution of LiOH is strong, and the positive electrode mixture paste exhibits strong alkalinity of about pH 12, so that the present invention can be effectively utilized.
  • the positive electrode active material is used as particulate matter, and the average particle diameter thereof can be, for example, 2 ⁇ m or more and 40 ⁇ m or less.
  • the content of the positive electrode active material in the positive electrode mixture paste of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of increasing the capacity with respect to the total solid content of the positive electrode mixture paste. And, from the viewpoint of improving the binding strength of the positive electrode mixture layer to the current collector, it is preferably 99% by mass or less, more preferably 98% by mass or less.
  • the conductive material is for efficiently performing charge / discharge reaction and enhancing the electrical conductivity, and examples thereof include carbon materials such as acetylene black, ketjen black, graphite, CNT (carbon nanotube), etc. It can be used alone or in combination of two or more.
  • the content of the conductive material in the positive electrode mixture paste of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving the conductivity relative to the total solid content of the positive electrode mixture paste. And from the viewpoint of improving the battery capacity, it is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the binder has an adhesive function between the positive electrode mixture layer and the current collector, and when the solvent is water, for example, sodium polyacrylate, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and styrene butadiene rubber (SBR), carboxyl cellulose etc. are mentioned, These can be used individually or in mixture of 2 or more types. Among them, sodium polyacrylate is preferable from the viewpoint of the improvement of the electrochemical stability and the improvement of the binding strength between the positive electrode mixture layer and the current collector.
  • the solvent is N methyl pyrrolidone
  • PVDF polyvinylidene fluoride
  • PVDF is prone to gelation due to the alkali component.
  • N-methylpyrrolidone contains a trace amount of water, the binder and the alkali component derived from the water and the positive electrode active material easily cause gelation of the binder. Therefore, the present invention is remarkably effective in a system using PVDF as a binder.
  • the content of the binder in the positive electrode mixture paste of the present invention is preferably 0.5% by mass or more from the viewpoint of improving the binding strength between the positive electrode mixture layer and the current collector with respect to the total solid content of the positive electrode mixture paste. More preferably, it is 1% by mass or more, and from the viewpoint of improving the battery capacity, it is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the positive electrode mixture paste of the present invention contains water as a dispersion medium capable of dispersing the positive electrode active material and the conductive material, and as a solvent capable of dissolving the binder and the spinnable organic polymer.
  • water is used as a solvent, a part of lithium (Li) ions contained in the positive electrode active material is eluted and the positive electrode mixture paste becomes alkaline, gradually losing its fluidity, thickening, and causing gelation. It occurs.
  • the water contained in the positive electrode mixture paste of the present invention is preferably pure water or purified water.
  • the content of water in the positive electrode mixture paste of the present invention is preferably 30 parts by mass or more, relative to 100 parts by mass of the total solid content of the positive electrode mixture paste, from the viewpoint of improving the coating properties of the positive electrode mixture paste. More preferably, it is 40 parts by mass or more, and from the same viewpoint, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.
  • the positive electrode material mixture paste of the present invention is N methyl as a dispersion medium capable of dispersing the positive electrode active material and the conductive material, and as a solvent capable of dissolving the binder and the spinnable organic polymer.
  • the content of N methyl pyrrolidone in the positive electrode mixture paste of the present invention is preferably 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of improving the coatability of the positive electrode mixture paste. Preferably, it is 50% by weight or less, more preferably 40% by weight or less.
  • the positive electrode mixture paste of the present invention contains a spinnable organic polymer from the viewpoint of improving storage stability or from the viewpoint of improving storage stability and increasing the solid content of the positive electrode mixture paste.
  • spinnability is a so-called “threading” property in which the stretching property of the object appears, and for example, “natto threading” etc. can be mentioned as a prominent example.
  • the spinnability is the property of exhibiting a continuous thread-like structure without breaking up and forming droplets when the liquid composition is dropped at a low speed or stretched while holding one end thereof, for example, “mucus of animals and plants "Yarning” etc. are mentioned as an example.
  • spinnability is one of the elastic relaxation phenomena of liquid compositions, and it is known that surface tension and viscosity are physical properties completely independent of each other.
  • the spinnability referred to in the present invention refers to spinnability in which aqueous liquid compositions of special organic polymers can be developed while maintaining high fluidity under extremely dilute concentrations.
  • the spinnable organic polymer referred to in the present invention is an organic polymer in which a solution obtained by dissolving a spinnable organic polymer in a solvent exhibits the above spinnability.
  • the spinnable organic polymer is generally different from a so-called “thickening organic polymer" in which a high molecular weight organic polymer is expressed.
  • the solvent is water
  • the solution is an aqueous solution
  • the solvent is N methyl pyrrolidone
  • the solution is an N methyl pyrrolidone solution.
  • a spinnable organic polymer is, for example, an organic polymer exhibiting spinnability in an aqueous solution or N methyl pyrrolidone solution having a concentration of 3% by mass or less, preferably an aqueous solution or its concentration at a concentration of 1% by mass or less. It is an organic polymer exhibiting spinnability in an N-methylpyrrolidone solution, more preferably an organic polymer exhibiting spinnability in an aqueous solution or N-methylpyrrolidone solution having a concentration of 0.5% by mass or less.
  • organic polymer which exhibits spinnability in an aqueous solution or N methyl pyrrolidone solution whose concentration is 0.001 mass% or more, preferably in an aqueous solution or N methyl pyrrolidone solution whose concentration is 0.01 mass% or more. It is an organic polymer exhibiting spinnability.
  • the spinnability of the organic polymer is determined by the following method. Using an organic polymer aqueous solution obtained by dissolving 0.5 parts by weight of an organic polymer in 99.5 parts by weight of purified water, it is judged by a method according to the following [Spinability evaluation method], and has spinnability And spinnable organic polymer.
  • the presence or absence of spinnability of the organic polymer is determined by the following method.
  • N-methylpyrrolidone solution of an organic polymer obtained by dissolving 1 part by weight of an organic polymer in 99 parts by weight of N-methylpyrrolidone it is determined by a method according to the following [Spinability evaluation method] and has spinnability In the case, a spinnable organic polymer is used.
  • the aqueous solution or N-methylpyrrolidone solution in which a thread is twisted exhibits spinnability in the present invention
  • aqueous solution or N methyl pyrrolidone solution makes an aqueous solution or N methyl pyrrolidone solution.
  • the long threading solution is made into an aqueous solution having strong (or high) spinnability or N-methylpyrrolidone solution.
  • the aqueous solution or N methyl pyrrolidone solution is well stirred at 25 ° C.
  • the tip of the Pasteur pipette is separated by 5 mm from the dropping point to perform the dropping operation.
  • the aqueous solution having a strong spinnability or the N-methylpyrrolidone solution it is easier to confirm if the dropping operation is performed from a higher position.
  • the dropping operation may be performed a plurality of times to confirm.
  • the "yarn" confirmed during the dropping operation is thinner than 1 mm.
  • the spinnable organic polymer includes cross-linked polymers and non-cross-linked polymers. Among them, non-cross-linked polymers have higher spinnability and are preferred in the present invention.
  • the spinnable organic polymer is, for example, sulfonic acid group (—SO 2 —OH), sulfuric acid group (—O—SO 2 —OH) and salts thereof
  • the polymer A containing the structural unit derived from the ethylenically unsaturated monomer a1 which has at least 1 sort (s) of groups chosen from group, or a polyethylene oxide (PEO) is mentioned. These can be used 1 type or in combination of 2 or more types.
  • the monomer a1 for example, 2- (meth) acryloyloxyethane sulfonic acid, 2- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamido-2-alkyl (1 to 4 carbon atoms) propane sulfone Monomers such as acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, vinyl sulfuric acid and the like can be mentioned.
  • 2- (meth) acryloyloxyethanesulfonic acid 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-alkyl (carbon) because of high polymerizability and easy to obtain high molecular weight.
  • the number 1 to 4) propane sulfonic acid and styrene sulfonic acid are preferable, 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and styrene sulfonic acid are more preferable, and from the viewpoint of improving the storage stability of the positive electrode mixture paste And AMPS are more preferred.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • These constituent monomers may be used in the acid form, or some or all of the sulfonic acid group and / or the sulfuric acid group may be neutralized with a base to be used as a salt group.
  • a counter ion which forms a salt type group of a sulfonic acid group or a sulfuric acid group for example, metal ion, ammonium ion, alkyl or alkenyl ammonium ion having 1 to 22 carbon atoms in total, alkyl or alkenyl substitution having 1 to 22 carbon atoms
  • metal ion, ammonium ion, alkyl or alkenyl ammonium ion having 1 to 22 carbon atoms in total alkyl or alkenyl substitution having 1 to 22 carbon atoms
  • pyridinium ion alkanol ammonium ion having 1 to 22 carbon atoms in total
  • alkali ion such as sodium ion, potassium ion or ammonium ion is preferable, and sodium ion and potassium ion are more preferable.
  • the monomer a1 may be used alone or in combination of two or more types, and when the monomer a1 is two or more types, as the arrangement of the structural units derived from these constituent monomers, in particular, There is no limitation, and random arrangement, alternating arrangement, or block arrangement may be used.
  • the polymer A is preferably a copolymer of the monomer a1 and another polymerizable monomer from the viewpoint of improving the storage stability of the positive electrode mixture paste, and as the polymerizable monomer, it is preferably It is at least one monomer a2 selected from unsaturated carboxylic acids and salts thereof, more preferably at least one monomer a2 selected from ethylenically unsaturated carboxylic acids and salts thereof.
  • (meth) acrylic acid is acrylic acid (AA), methacrylic acid or a mixture thereof.
  • salts thereof styrene carboxylic acid and salts thereof, maleic acid monomers [maleic anhydride, maleic acid, maleic acid monoester, and maleic acid monoamide or a mixture of two or more thereof] and salts thereof, and itacon It is an acid and its salt etc., and 1 or more types chosen from these can be used.
  • (meth) acrylic acid and a salt thereof styrenecarboxylic acid and a salt thereof are preferable, (meth) acrylic acid and a salt thereof are more preferable, and acrylic acid and a salt thereof are further preferable because copolymerization is easy. preferable.
  • a counter ion which forms a salt it is sufficient if it is the said counter ion.
  • the polymer A is a copolymer containing a structural unit derived from the monomer a1 and a structural unit derived from the monomer a2, the structural unit derived from the monomer a1 in all the structural units in the polymer A
  • the ratio of is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, from the viewpoint of improving the storage stability of the positive electrode mixture aqueous paste, and the spinnability is enhanced. From the viewpoint, it is preferably 99 mol% or less, more preferably 98 mol% or less, and still more preferably 96 mol% or less.
  • the polymer A is a copolymer containing a structural unit derived from the monomer a1 and a structural unit derived from the monomer a2, the structural unit derived from the monomer a1 in all the structural units in the polymer A
  • the molar ratio of the structural unit derived from the monomer a2 is preferably from the viewpoint of improving the storage stability of the positive electrode mixture paste Is 3 or more, more preferably 4 or more, further preferably 9 or more, and preferably 99 or less, more preferably 50 or less, and still more preferably 24 or less from the viewpoint of enhancing spinnability.
  • the arrangement of the structural unit derived from the monomer a1 and the structural unit derived from the monomer a2 is not particularly limited, and may be random arrangement, alternating arrangement, or block arrangement.
  • the polymer A is a copolymer containing a structural unit derived from the monomer a1 and a structural unit derived from the monomer a2, it further includes a structural unit derived from another polymerizable monomer a3 Although the ratio of the structural unit derived from the monomer a3 in all the structural units in the polymer A is preferably 2 mol% or less, more preferably 1 mol% or less, still more preferably 0.5 mol% or less Still more preferably, it is 0 mol%.
  • the spinnable organic polymer is preferably a homopolymer of PEO, a monomer a1, a salt thereof, a monomer a1 and a monomer, from the viewpoint of improving the storage stability of the positive electrode mixture paste.
  • the spinnable organic polymer is a copolymer of AMPS and AA or a salt thereof
  • the ratio of the structural unit derived from AMPS to the total structural units constituting the spinnable organic polymer is the same as that of the positive electrode mixture paste.
  • it is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and from the viewpoint of improving spinnability, preferably 99 mol% or less More preferably, it is 98 mol% or less, still more preferably 96 mol% or less.
  • the synthesis method of the polymer A is not particularly limited, and a known method can be selected.
  • hydrophilic polymers such as starch / cellulose, derivatives of starch / cellulose, polyvinyl alcohol, polyacrylic acid (salt), cross-linked polyacrylic acid (salt), hypophosphorous acid (salt), etc. Chain transfer agents may be added.
  • polymer A polymerizes a monomer unit mainly composed of at least one selected from AMPS and a salt thereof, bulk polymerization and precipitation polymerization can be performed, but it is possible to control performance and polymerization. From the viewpoint of easiness, it is preferable to carry out aqueous solution polymerization and reverse phase suspension polymerization by making the monomer unit water-soluble.
  • peroxide initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, hydrogen peroxide and the like may be used as a polymerization initiator, or 2, 2 Azo initiators such as' -azobis (2-amidinopropane) dihydrochloride may be used, or these may be used in combination with reducing agents such as sodium sulfite, sodium bisulfite, ferrous sulfate, L-ascorbic acid, etc. It may be used as a redox type initiator system.
  • the polymerization may be initiated by irradiation with ultraviolet light, electron beam, ⁇ -ray or the like.
  • Activation energy etc. can be used.
  • redox polymerization may be performed using a reducing agent such as sodium sulfite, sodium bisulfite, ferrous sulfate, L-ascorbic acid and the like in combination.
  • the spinnable organic polymer is obtained from the viewpoint of improving the storage stability of the positive electrode mixture paste and increasing the solid content of the positive electrode mixture paste,
  • the polymer is preferably a polymer containing a structural unit derived from ethylene oxide (EO), more preferably polyethylene oxide (PEO) exhibiting high spinnability.
  • the weight average molecular weight of the spinnable organic polymer is preferably 2.2 million or more, more preferably 2.5 million or more, still more preferably 3 million from the viewpoint of improving the storage stability of the positive electrode mixture paste and suppressing the decrease in initial capacity of the battery. From the above and from the same viewpoint, it is preferably 30 million or less, more preferably 20 million or less, and still more preferably 10 million or less.
  • the weight average molecular weight of a spinnable organic polymer can be measured by the method as described in the below-mentioned Example.
  • the content of the spinnable organic polymer in the positive electrode mixture paste of the present invention is the storage stability of the positive electrode mixture paste with respect to the total solid content of the positive electrode mixture paste. From the viewpoint of improving the properties, it is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and from the viewpoint of suppressing the initial capacity reduction of the battery, preferably 0.1% by mass or less, more preferably It is 0.03 mass% or less.
  • the content of the spinnable organic polymer in the positive electrode mixture paste of the present invention is the content of the positive electrode mixture paste relative to the total solid content of the positive electrode mixture paste.
  • the viewpoint of improving storage stability it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and from the viewpoint of suppressing the initial capacity decrease of the battery, preferably 0.1% by mass or less, more Preferably it is 0.03 mass% or less.
  • the pH at 25 ° C. of the positive electrode mixture paste of the present invention is preferably 7 or more, more preferably 10 or more, and further preferably from the viewpoint of suppressing the initial capacity decrease It is preferably 11 or more, and preferably 14 or less from the viewpoint of improving the storage stability of the positive electrode mixture paste.
  • the pH of the positive electrode mixture paste can be measured by the method described in the examples.
  • the concentration of total solids in the positive electrode material mixture paste of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, from the viewpoint of cost reduction in manufacturing lithium ion batteries.
  • the content is more preferably 70% by mass or more, and preferably 90% by mass or less, and more preferably 80% by mass or less from the viewpoint of securing a good coating property of the paste.
  • the present invention relates, in one embodiment, to a method for producing a positive electrode mixture paste of the present invention (hereinafter sometimes referred to as “the method for producing the present invention”).
  • the manufacturing method of the present invention includes, in one embodiment, a step of mixing a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent
  • the present invention relates to a method for producing a positive electrode material mixture paste for lithium ion battery, which is an organic polymer exhibiting spinnability in a solvent having a concentration of 0.001% by mass to 3% by mass.
  • the solvent is, for example, water
  • the organic polymer has spinelability in an aqueous solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C.
  • the solvent is, for example, N methyl pyrrolidone
  • the organic polymer has a concentration of 0.001 mass% or more and 3 mass% or less in an aqueous solution having a liquid temperature of 25 ° C. It is an organic polymer that exhibits threadability.
  • the production method of the present invention includes the step of mixing the positive electrode active material, the conductive material, the binder, the spinnable organic polymer, and the solvent, and preferably, a solid content other than the spinnable organic polymer
  • a step of adding a solution obtained by dissolving a spinnable organic polymer in a solvent is added to a mixture containing a solvent, for example, a mixture containing a positive electrode active material, a conductive material, a binder and a solvent.
  • a conductive material and a solution obtained by dissolving a binder in a solvent are mixed and stirred until they become homogeneous to prepare a slurry [1] to prepare the slurry [1].
  • a positive electrode active material and a solvent are added, and the mixture is stirred until it becomes homogeneous to obtain a slurry [2].
  • a solution obtained by dissolving a spinnable organic polymer in a solvent is added to the slurry [2] and stirred until homogeneous. It can be obtained by It is not limited to the mixing of the respective components, the means of stirring the slurry [1] and the slurry [2].
  • a self-revolving stirrer can be used.
  • the production method of the present invention includes, for example, a step of mixing a positive electrode active material, a conductive material, a binder, a spinnable organic polymer, and water, and from the viewpoint of increasing capacity, preferably other than spinnable organic polymer
  • the method includes the step of adding an aqueous solution of a spinnable organic polymer to a mixture containing solid content and water, for example, a mixture containing a positive electrode active material, a conductive material, a binder and water.
  • a conductive material and an aqueous solution of a binder are mixed and stirred until they become homogeneous to prepare a slurry [1], and a positive electrode active material and water are added to the slurry [1].
  • the mixture is stirred until it becomes homogeneous to obtain a slurry [2], and an aqueous solution of a spinnable organic polymer is added to the slurry [2], and the mixture can be obtained by stirring until it becomes homogeneous.
  • a self-revolving stirrer can be used.
  • the production method of the present invention includes, for example, a step of mixing a positive electrode active material, a conductive material, a binder, a spinnable organic polymer and N-methylpyrrolidone, and from the viewpoint of increasing the concentration, preferably a spinnable organic polymer
  • a spinnable organic polymer A mixture containing solid content other than N methyl pyrrolidone, for example, a mixture containing a positive electrode active material, a conductive material, a binder, and N methyl pyrrolidone, an N methyl pyrrolidone solution (additive composition) of a spinnable organic polymer Including the step of adding.
  • a conductive material and an N-methylpyrrolidone solution of a binder are mixed, and the mixture is stirred until it becomes homogeneous to prepare a slurry [1].
  • N-Methylpyrrolidone as necessary to the substance and stir until it becomes homogeneous to make a slurry [2]
  • N-methylpyrrolidone solution of spinnable organic polymer to the slurry [2] and stir until homogeneous It can be obtained by It is not limited to the mixing of the respective components, the means of stirring the slurry [1] and the slurry [2].
  • a self-revolving stirrer can be used.
  • the present invention in one embodiment, is an additive composition used for preparation of a positive electrode mixture paste.
  • the additive composition comprises an organic polymer and N methyl pyrrolidone, wherein the organic polymer is dissolved in N methyl pyrrolidone.
  • the content of the spinnable organic polymer in the additive composition is set so that, for example, the positive electrode material mixture paste of the present invention can be prepared by mixing with the above-mentioned slurry [2]. From the viewpoint of exhibiting high spinnability, the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and from the viewpoint of securing the solubility of the organic polymer, preferably 5% by mass or less More preferably, it is 3% by mass or less.
  • the additive composition of the present invention may contain, as optional components, for example, a thickener, a reinforcing material, an antioxidant, an additive having a function of suppressing the decomposition of the electrolytic solution, etc., and these components. Any known one can be used.
  • the amount of optional components in the additive composition is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, from the viewpoint of storage stability of the positive electrode mixture paste .
  • the present invention relates, in one embodiment, to the use of the additive composition of the present invention for the preparation of a positive electrode mixture paste for lithium ion batteries.
  • the present invention relates, in one embodiment, to a method for improving the storage stability of the positive electrode material mixture paste of the present invention (hereinafter sometimes referred to as “the method for improving the storage stability of the present invention”).
  • the storage stability improvement method of the present invention is, in one embodiment, a method for improving the storage stability of a positive electrode material mixture paste for lithium ion batteries, which contains a positive electrode active material, a conductive material, a binder and a solvent. Including a step of mixing a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent in the process of producing the positive electrode mixture paste, The organic polymer is The present invention relates to a method of improving the storage stability of a positive electrode material mixture paste for a lithium ion battery, which is an organic polymer exhibiting spinnability in a solvent having a concentration of 0.001% by mass to 3% by mass.
  • the solvent is, for example, water, and the organic polymer is in an aqueous solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C. It is an organic polymer exhibiting spinnability.
  • the solvent is, for example, N methyl pyrrolidone, and the organic polymer is N having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C. It is an organic polymer that exhibits spinnability in methyl pyrrolidone solution.
  • the present invention relates, in one embodiment, to a lithium ion battery electrode (hereinafter also referred to as “the electrode of the present invention”) including a positive electrode mixture layer formed using the positive electrode mixture paste of the present invention.
  • the electrode of the present invention can be produced by a known method for producing an electrode except that the positive electrode mixture paste of the present invention is used. For example, after the positive electrode mixture paste of the present invention is applied to a current collector and dried, It is obtained by processing according to a predetermined size by pressing accordingly.
  • a conventionally known current collector can be used for the current collector.
  • the present invention relates, in one embodiment, to a lithium ion battery (hereinafter also referred to as “the battery of the present invention”) including the electrode of the present invention.
  • the shape of the battery of the present invention may be any shape such as coin shape, cylindrical shape, square shape, and laminated shape.
  • the battery of the present invention can be manufactured by a known method for manufacturing a lithium ion battery except that the electrode of the present invention is used.
  • the electrode (positive electrode) of the present invention and a negative electrode are stacked via a separator, wound or stacked in a battery shape, and inserted into a battery container or a laminate container. And a method in which the container is filled with an electrolytic solution and sealed.
  • the separator is a member having a function such as insulation between the positive electrode and the negative electrode, and further holding an electrolytic solution.
  • a separator thin microporous membranes, such as polyethylene, a polypropylene, or those laminated products, can be used, for example.
  • the electrolytic solution usually, a solution in which an electrolyte is dissolved in an organic solvent can be used.
  • organic solvent include cyclic carbonates such as ethylene carbonate and propylene carbonate; linear carbonates such as diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate; and the like, and these may be used alone or in combination of two or more .
  • the electrolyte refers to an ionic compound having a function of dissolving in an organic solvent to conduct electricity.
  • lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiCF 3 CO 2 , LiCl, LiBr, LiSCN, etc. alone or in combination of two or more You may use together.
  • the present application further discloses the following invention.
  • [1] containing a positive electrode active material, a conductive material, a binder, an organic polymer, and a solvent,
  • the positive electrode material mixture paste for lithium ion batteries wherein the organic polymer is an organic polymer exhibiting spinnability in a solvent having a concentration of 0.001% by mass to 3% by mass.
  • the content of the organic polymer relative to the total solid content of the positive electrode mixture paste is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and preferably 0.1
  • the positive electrode mixture paste according to the above [1] which is not more than mass%, more preferably not more than 0.03 mass%.
  • the weight average molecular weight of the organic polymer is preferably 2.2 million or more, more preferably 2.5 million or more, still more preferably 3 million or more, and preferably 30 million or less, more preferably 20 million or less, furthermore
  • the pH of the positive electrode mixture paste at 25 ° C. is preferably 7 or more, more preferably 10 or more, still more preferably 11 or more, and preferably 14 or less. Positive electrode mixture paste.
  • the organic polymer preferably has at least one group selected from the group consisting of sulfonic acid group (-SO 2 -OH), sulfuric acid group (-O-SO 2 -OH) and salts thereof.
  • the monomer a1 is 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-alkyl (having 1 to 6 carbon atoms) 4) At least one selected from propanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, vinylsulfuric acid and salts thereof, more preferably 2- (meth) acryloyloxyethanesulfonic acid, 2- (Meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamido-2-alkyl (1 to 4 carbon atoms) propane sulfonic acid, styrene sulfonic acid, and one or more selected from salts thereof, more preferably 2-acrylamido-2-methylpropane sulfonic acid, styren
  • a copolymer wherein the polymer A contains a structural unit derived from at least one monomer a2 selected from unsaturated carboxylic acids and salts thereof, and a structural unit derived from the monomer a1
  • Monomer a2 is preferably one or more selected from (meth) acrylic acid, styrene carboxylic acid, maleic acid monomers, itaconic acid, and salts thereof, and more preferably (meth) acrylic acid.
  • the molar ratio of the structural unit derived from the monomer a1 in the polymer A is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably The positive electrode material mixture paste according to the above [8] or [9], which is 99 mol% or less, more preferably 98 mol% or less, still more preferably 96 mol% or less.
  • the molar ratio of the structural unit derived from the monomer a1 to the structural unit derived from the monomer a2 in all the structural units in the polymer A (structural unit derived from the monomer a1 / monomer a2
  • the constituent unit derived from “(3)” is preferably 3 or more, more preferably 4 or more, further preferably 9 or more, and preferably 99 or less, more preferably 50 or less, still more preferably 24 or less.
  • the positive electrode mixture paste according to any one of [10] to [10].
  • the organic polymer is preferably one or more selected from PEO, a homopolymer of monomer a1, a salt thereof, a copolymer of monomer a1 and monomer a2, and a salt thereof, Preferably, it is one or more selected from PEO, homopolymers of AMPS, salts thereof, copolymers of AMPS and AA, and salts thereof, more preferably PEO, copolymers of AMPS and AA, and salts thereof More preferably PEO, and more preferably The monomer a1 is ethylenically unsaturated having at least one group selected from a sulfonic acid group (—SO 2 —OH), a sulfuric acid group (—O—SO 2 —OH) and a group in the salt form thereof.
  • the solvent is preferably N methyl pyrrolidone.
  • the organic polymer is preferably a polymer containing a structural unit derived from ethylene oxide, more preferably polyethylene oxide.
  • the concentration of total solids in the positive electrode mixture paste is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and still more preferably 70% by mass or more.
  • the positive electrode material mixture paste in any one of said [1] to [15] which is preferably 90 mass% or less, more preferably 80 mass% or less.
  • a lithium ion battery including a positive electrode mixture layer formed using the positive electrode mixture paste according to any one of the above [1] to [16].
  • An organic polymer and N methyl pyrrolidone wherein the organic polymer is dissolved in N methyl pyrrolidone,
  • the additive composition wherein the organic polymer exhibits spinnability in an N-methylpyrrolidone solution having a concentration of 0.001% by mass to 3% by mass and a liquid temperature of 25 ° C.
  • [21] including the step of mixing the positive electrode active material, the conductive material, the binder, the organic polymer, and water,
  • a method for improving the storage stability of a positive electrode material mixture paste for a lithium ion battery comprising a positive electrode active material, a conductive material, a binder, and water, Including a step of mixing a positive electrode active material, a conductive material, a binder, an organic polymer, and water in the process of producing the positive electrode mixture paste,
  • a method for improving the storage stability of a positive electrode material mixture paste for a lithium ion battery comprising a positive electrode active material, a conductive material, a binder, and water, Including the step of mixing the positive electrode active material, the conductive material, the binder, the organic polymer, and N-methylpyrrolidone in the production process of the positive electrode mixture paste,
  • the organic polymer is Storage stability of positive electrode material mixture paste for lithium ion battery, which is an organic polymer exhibiting spinnability in N methyl pyrrolidone solution having a concentration of 0.001% by mass to 3% by mass and a solution temperature of 25 ° C. How to improve.
  • the weight average molecular weight of the organic polymer can be determined by gel permeation chromatography (GPC) measurement under the following measurement conditions. Polyethylene oxide (PEO) is used as a standard sample, and the weight average molecular weight in terms of PEO is used.
  • GPC gel permeation chromatography
  • the pH value of the positive electrode mixture paste at 25 ° C. is a value measured using a pH meter (D-54 manufactured by Horiba, Ltd.), and the value after 1 minute of immersing the electrode of the pH meter in the positive electrode mixture paste is there.
  • Solid content concentration of positive electrode mixture paste and each component The total solid content concentration of the positive electrode mixture paste and the solid content concentration of each component were calculated by drying at 150 ° C. for 24 hours and measuring the weight loss.
  • a solution B is prepared by dissolving 0.80 g of the stock (manufactured by K.K.) in 510 g of ion exchange water. With respect to the solution A, the solution B was dropped and dispersed over 1 hour while maintaining the reaction temperature at 10 ° C. or less, and the solution was further stirred for 30 minutes. After azeotropic dehydration and drying, 674 g of a colorless granular polymer (Na salt of AMPS-AA) was obtained. As a result of GPC measurement of the obtained polymer, the weight average molecular weight was 7,800,000. The average particle size of the polymer was 220 ⁇ m.
  • Positive electrode mixture paste of Example 1 A binder (sodium polyacrylate, manufactured by Wako Pure Chemical Industries, Ltd., "high viscosity”) was dissolved in water to obtain an 8% by mass aqueous binder solution. Next, 0.65 g of a conductive material (acetylene black, manufactured by Denka, "HS-100") and 8.13 g of a binder aqueous solution are mixed to prepare a slurry [1], and then, the slurry [1] is prepared. A slurry [2] was prepared by adding 15 g of a positive electrode active material (NCA, “NC-02” manufactured by Nippon Chemical Industrial Co., Ltd.) and 1.6 g of water and mixing them.
  • NCA positive electrode active material
  • the solid content concentration in the slurry [2] is 64.2% by mass, and the mass ratio of the positive electrode active material, the conductive material, and the binder is 92: 4: 4 (in terms of solid content).
  • 0.26 g of a 0.2 mass% aqueous solution of an organic polymer (polyethylene oxide, weight average molecular weight: 4,000,000, manufactured by Wako Pure Chemical Industries, Ltd.) is added to slurry [2] and mixed.
  • a positive electrode mixture paste was prepared.
  • the solid content in the positive electrode mixture paste is a positive electrode active material, a conductive material, a binder, and an organic polymer, and the total solid concentration in the positive electrode mixture paste is 63.6% by mass, and the positive electrode active material, conductive material
  • the mass ratio of the binder to the organic polymer is 92: 4: 4: 0.003 (in terms of solid content).
  • the contents of the organic polymers described in Tables 3 and 4 are values relative to the total solid content in the positive electrode mixture paste (the same applies to Examples 2 to 5 and Comparative Examples 1 to 5 below).
  • the content of water is 57 parts by mass with respect to 100 parts by mass of the total solid content in the positive electrode mixture paste.
  • Awatori Neritaro (ARV-310) was used to mix each component.
  • Example 2 Cathode mix paste of Example 2
  • a slurry [2] is prepared by the same method as in Example 1, and then, to a slurry [2], an organic polymer aqueous solution (polyethylene oxide, weight average molecular weight: 4,000,000, A positive electrode mixture paste of Example 2 was prepared by adding and mixing 0.26 g of a 0.5% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.).
  • the solid content in the positive electrode mixture paste is a positive electrode active material, a conductive material, a binder, and an organic polymer, and the total solid concentration in the positive electrode mixture paste is 63.6% by mass, and the positive electrode active material, conductive material
  • the mass ratio of the binder to the organic polymer is 92: 4: 4: 0.008 (in terms of solid content).
  • the pH (25 ° C.) immediately after preparation of the positive electrode mixture paste of Example 2 is 13.2, and the pH (25 ° C.) after storage for 1 week in a polyethylene container under an atmosphere of 25 ° C. is also 13.2 there were.
  • a slurry [2] is prepared by the same method as in Example 1, and then, the organic compound synthesized in the above-mentioned [Synthesis of spiny organic polymer] into a slurry [2]
  • a positive electrode material mixture paste of Example 3 was prepared by adding and mixing 0.26 g of a 1% by mass aqueous solution of a polymer (Na salt of AMPS-AA).
  • the solid content in the positive electrode mixture paste is a positive electrode active material, a conductive material, a binder, and an organic polymer, and the total solid concentration in the positive electrode mixture paste is 63.6% by mass, and the positive electrode active material, conductive material
  • the mass ratio of the binder to the organic polymer is 92: 4: 4: 0.016 (in terms of solid content).
  • the pH (25 ° C.) immediately after preparation of the positive electrode mixture paste of Example 3 is 13.2, and the pH (25 ° C.) after storage for 1 week in a polyethylene container under an atmosphere of 25 ° C. is also 13.2 there were.
  • Cathode mix paste of Comparative Example 2 A slurry [2] is prepared by the same method as in Example 1, and then, to a slurry [2], a 0.2 mass% sodium polyacrylate aqueous solution (manufactured by Aldrich Co.)
  • the positive electrode mixture paste of Comparative Example 2 was prepared by adding and mixing 0.26 g of polyacrylic acid (weight-average molecular weight: 4,000,000) neutralized and dissolved with an aqueous solution of sodium hydroxide).
  • the solid content in the positive electrode mixture paste is a positive electrode active material, a conductive material, a binder, and an organic polymer, and the total solid concentration in the positive electrode mixture paste is 63.6% by mass, and the positive electrode active material, conductive material
  • the mass ratio of the binder to the organic polymer is 92: 4: 4: 0.003 (in terms of solid content).
  • the solid content in the non-aqueous positive electrode mixture paste is a positive electrode active material, a conductive material, and a binder, and the total solid concentration in the non-aqueous positive electrode mixture paste is 64.2 mass%.
  • the mass ratio of the material to the binder is 92: 4: 4 (in terms of solid content).
  • the solid content in the slurry [2] is a positive electrode active material, a conductive material, and a binder, and the total solid concentration in the non-aqueous positive electrode mixture paste is 64.2% by mass, and the positive electrode active material, the conductive material, and the binder
  • the mass ratio of (F) is 92: 4: 4 (solid content conversion).
  • 0.26 g of a 1 wt% N methyl pyrrolidone solution of polyethylene oxide (weight average molecular weight: 4,000,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to slurry [2] and mixed, thereby the positive electrode of Example 4 A mixture paste was prepared.
  • the total solid concentration of the positive electrode mixture paste is 63.6% by mass, and the mass ratio of the positive electrode active material, the conductive material, the binder, and the polyethylene oxide is 92: 4: 4: 0.016 (in terms of solid content). is there.
  • Example 5 The positive electrode mixture paste of Example 5 (high concentration product of Example 4) A slurry [1] is prepared in the same manner as in Example 4, and then 15 g of a positive electrode active material (NCA, “NC-02” manufactured by Nippon Chemical Industrial Co., Ltd.) is added to the slurry [1], and polyethylene oxide (weight average) A positive electrode material mixture paste of Example 5 was prepared by adding and mixing 0.21 g of a 1% by weight N methyl pyrrolidone solution of molecular weight: 4,000,000, manufactured by Wako Pure Chemical Industries, Ltd.).
  • NCA negative electrode active material
  • the total solid concentration of the positive electrode mixture paste is 76.6% by mass, and the mass ratio of the positive electrode active material, the conductive material, the binder, and the polyethylene oxide is 92: 4: 4: 0.013 (in terms of solid content). is there.
  • a slurry [2] is prepared by the same method as in Example 4, and then a slurry [2] is polyacrylic acid (weight average molecular weight: 4,000,000, manufactured by Aldrich)
  • the positive electrode material mixture paste of Comparative Example 4 was prepared by adding and mixing 0.26 g of 1 wt% N methyl pyrrolidone solution.
  • the total solid concentration of the positive electrode mixture paste is 63.6% by mass, and the mass ratio of the positive electrode active material, the conductive material, the binder, and the polyacrylic acid is 92: 4: 4: 0.016 (in terms of solid content) It is.
  • Cathode mix paste of Comparative Example 5 A slurry [1] was prepared by the same method as in Example 4, and then, the slurry [1] was coated with a cathode active material (NCA, manufactured by Nippon Chemical Industrial Co., Ltd. "NC-02 And 0.21 g of 1% by weight N methyl pyrrolidone solution of polyacrylic acid (weight average molecular weight: 4,000,000, manufactured by Aldrich) were added and mixed, but the paste was still wet powdery. It did not become.
  • NCA cathode active material
  • Electrode (positive electrode) and battery [Use of positive electrode mixture paste of Examples 1 to 3 and Comparative Examples 1 to 3]
  • the positive electrode material mixture paste is coated on a 10 ⁇ m thick stainless steel foil so that the positive electrode capacity density is 1.0 to 1.2 mAh / cm 2, and dried at 100 ° C. for 12 hours using a vacuum dryer.
  • the electrode material in which the positive electrode mixture layer was formed on the current collector was produced.
  • the positive electrode material was punched and pressed to a diameter of 13 mm to obtain an electrode (positive electrode).
  • a separator of 19 mm in diameter and coin-like metal lithium of 15 mm in diameter and 0.5 in thickness were disposed to prepare a 2032 type coin cell.
  • the positive electrode material was punched and pressed to a diameter of 13 mm to obtain an electrode (positive electrode).
  • a separator of 19 mm in diameter and coin-like metal lithium of 15 mm in diameter and 0.5 in thickness were disposed to prepare a 2032 type coin cell.
  • 1 M LiPF 6 EC / DEC (volume ratio) 3/7 was used.
  • the positive electrode mixture paste immediately after preparation was used as each of the positive electrode mixture pastes of Examples 4 to 5 and Comparative Examples 3 to 5.
  • the storage stability of the positive electrode material mixture pastes of Examples 1 to 3 containing spinnable organic polymers was the same as the positive electrode material mixture pastes of Comparative Examples 1 to 2 which did not contain spinnable organic polymers. In comparison, it was good.
  • the positive electrode mixture pastes of Comparative Examples 1 and 2 which do not contain a spinnable organic polymer and the non-aqueous positive electrode mixture paste of Comparative Example 3 are gelled after storage for one week, and coating on the current collector itself was difficult.
  • the storage stability of the positive electrode mixture pastes of Examples 4 to 5 containing spiny organic polymers was higher than that of Comparative Examples 4 to 5 containing an organic polymer having no spinnability. It was good compared with.
  • the positive electrode mixture of Comparative Example 5 containing an organic polymer without spinnability has a high solid content concentration of 76.6% and does not become paste-like, and coating on the current collector itself is difficult. there were.
  • the positive electrode mixture containing the spinnable organic polymer of Example 5 was in the form of a paste and could be applied to the current collector. From this, it is understood that when using a spinnable organic polymer, it is possible to prepare a positive electrode mixture paste having a high concentration of solid content.
  • the present invention it is possible to provide a water-based positive electrode mixture paste in which thickening and gelation are suppressed and storage stability is improved by a simple method. Therefore, the present invention can contribute to the reduction of the initial capacity of the battery and the cost reduction in the manufacture of the battery. In addition, the present invention can increase the solid concentration in the non-aqueous positive electrode mixture paste by a simple method, and because the storage stability is good, it can contribute to cost reduction in the manufacture of lithium ion batteries. . According to the present invention, since thickening and gelation of the positive electrode mixture paste are suppressed, the dispersibility of solid components such as the positive electrode active material and the conductive material in the positive electrode mixture paste becomes good, and homogeneous positive electrode combination is achieved. Since the agent layer can be formed, quality improvement of the lithium ion battery electrode and the lithium ion battery can be expected.

Abstract

La présente invention concerne une pâte de mélange d'électrode positive pour une batterie au lithium-ion qui contient une substance active d'électrode positive, un matériau conducteur, un liant, un polymère organique et un solvant. Le polymère organique, lorsque sa concentration dans un solvant est de 0,001 à 3% en masse, présente un caractère filandreux dans le solvant. La teneur en polymère organique par rapport à la quantité totale en solides de la pâte de mélange d'électrode positive est de préférence de 0 ,001 à 0,1 % en masse. Le poids moléculaire moyen en poids du polymère organique est de préférence de 2,2 à 30 millions.
PCT/JP2018/048589 2017-12-28 2018-12-28 Pâte de mélange d'électrode positive pour batterie au lithium-ion WO2019132036A1 (fr)

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JP2017-254063 2017-12-28
JP2017-254068 2017-12-28
JP2017254063A JP7057665B2 (ja) 2017-12-28 2017-12-28 リチウムイオン電池用正極合剤ペースト及びその製造方法
JP2017254068A JP7057666B2 (ja) 2017-12-28 2017-12-28 リチウムイオン電池用正極合剤ペースト及びその製造方法

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2009004222A (ja) * 2007-06-21 2009-01-08 Jsr Corp 二次電池電極用バインダー組成物、二次電池電極用スラリー、及び二次電池電極
WO2011062232A1 (fr) * 2009-11-18 2011-05-26 三井化学株式会社 Pâte aqueuse pour cellule électrochimique, plaque d'électrode pour cellule électrochimique obtenue par application de la pâte aqueuse, et batterie comprenant la plaque d'électrode
WO2014192238A1 (fr) * 2013-05-29 2014-12-04 日本ゼオン株式会社 Composition de boue pour électrode positive de batterie secondaire lithium-ion, procédé de production pour électrode positive de batterie secondaire lithium-ion, électrode positive de batterie secondaire lithium-ion, et batterie secondaire lithium-ion
JP2016076493A (ja) * 2013-06-20 2016-05-12 Jsr株式会社 蓄電デバイス用組成物、蓄電デバイス用スラリー、蓄電デバイス電極およびその製造方法、保護膜およびその製造方法、ならびに蓄電デバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009004222A (ja) * 2007-06-21 2009-01-08 Jsr Corp 二次電池電極用バインダー組成物、二次電池電極用スラリー、及び二次電池電極
WO2011062232A1 (fr) * 2009-11-18 2011-05-26 三井化学株式会社 Pâte aqueuse pour cellule électrochimique, plaque d'électrode pour cellule électrochimique obtenue par application de la pâte aqueuse, et batterie comprenant la plaque d'électrode
WO2014192238A1 (fr) * 2013-05-29 2014-12-04 日本ゼオン株式会社 Composition de boue pour électrode positive de batterie secondaire lithium-ion, procédé de production pour électrode positive de batterie secondaire lithium-ion, électrode positive de batterie secondaire lithium-ion, et batterie secondaire lithium-ion
JP2016076493A (ja) * 2013-06-20 2016-05-12 Jsr株式会社 蓄電デバイス用組成物、蓄電デバイス用スラリー、蓄電デバイス電極およびその製造方法、保護膜およびその製造方法、ならびに蓄電デバイス

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