WO2023282248A1 - 電極形成用組成物 - Google Patents

電極形成用組成物 Download PDF

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Publication number
WO2023282248A1
WO2023282248A1 PCT/JP2022/026681 JP2022026681W WO2023282248A1 WO 2023282248 A1 WO2023282248 A1 WO 2023282248A1 JP 2022026681 W JP2022026681 W JP 2022026681W WO 2023282248 A1 WO2023282248 A1 WO 2023282248A1
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electrode
group
forming composition
composition according
organic compound
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English (en)
French (fr)
Japanese (ja)
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辰也 畑中
麻里 岡
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to KR1020247003551A priority Critical patent/KR20240027798A/ko
Priority to JP2023533135A priority patent/JPWO2023282248A1/ja
Priority to US18/574,122 priority patent/US20240322158A1/en
Priority to CN202280042534.3A priority patent/CN117501471A/zh
Priority to EP22837663.8A priority patent/EP4369436A4/en
Publication of WO2023282248A1 publication Critical patent/WO2023282248A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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-forming composition.
  • Lithium-ion secondary batteries have high energy density, high voltage, and no memory effect during charging and discharging. And with the expansion of the amount of use, there is a demand for further lower resistance, longer life, higher capacity, safety, and lower cost.
  • Lithium-ion secondary batteries have the problem of deterioration due to repeated charging and discharging.
  • Various factors have been reported as the mechanism of deterioration, but the main reasons are the deterioration of the active material due to the decomposition of the electrolyte solution and the trace amount of water remaining inside the battery, and the formation of decomposition products of the electrolyte solution. Examples include an increase in internal resistance and isolation of the active material caused by cracks generated in the electrode mixture layer (hereinafter sometimes referred to as "electrode layer").
  • Non-Patent Document 1 the surface of the positive electrode active material is coated with metal oxides such as Mg, Al, Ti, Sn, Si and Cu, phosphorus compounds, carbon, and the like.
  • Inorganic compounds such as transition metal oxides containing alkali metals and transition metal chalcogens are known as positive electrode active materials for lithium ion secondary batteries capable of obtaining a battery voltage of about 4V.
  • high nickel positive electrode active materials represented by Li x NiO 2 have high discharge capacity and are attractive positive electrode materials.
  • the high-nickel positive electrode active material has, on its surface, LiOH formed by a proton exchange reaction with the residue of the raw material and moisture, and Li 2 CO 3 etc. produced by reaction of this LiOH with carbon dioxide gas in the air.
  • LiOH is an alkaline component
  • a composition containing the positive electrode active material, polyvinylidene fluoride (PVdF) as a binder, and N-methyl-2-pyrrolidone (NMP) as a solvent is kneaded. Gelation of the slurry occurs when the composition is kneaded or when the composition is applied after kneading.
  • the alkaline component not only increases the resistance of the battery by corroding aluminum, which is generally used as the current collecting foil of the positive electrode, but also reacts with the electrolyte in the battery to increase the resistance of the battery. It becomes a factor that deteriorates life expectancy.
  • Li 2 CO 3 decomposes during charging and discharging to generate CO 2 gas and CO 3 gas, and these gas components increase the pressure inside the battery, causing swelling of the battery and deterioration of the cycle life. . Moreover, there is a possibility that the battery may be damaged due to an increase in internal pressure caused by the generated gas.
  • Patent Document 1 reports a method of treating a positive electrode active material with fluorine gas to fix residual LiOH as LiF, thereby preventing gelation and suppressing gas generation.
  • fluorine gas is highly toxic and difficult to handle
  • LiF produced as a by-product increases the internal resistance of the battery, and corrosion of the positive electrode active material by the fluorine gas also reduces the capacity.
  • residual fluorine reacts with a small amount of moisture present in the active material or the electrolyte to produce hydrogen fluoride, which tends to cause cycle deterioration.
  • Patent Document 2 reports a method of removing unreacted lithium hydroxide and impurities derived from raw materials by washing a positive electrode active material with an aqueous solution containing a lithium salt.
  • Patent Document 2 reports a method of removing unreacted lithium hydroxide and impurities derived from raw materials by washing a positive electrode active material with an aqueous solution containing a lithium salt.
  • the resistance of a battery has a plurality of resistance components, which are roughly divided into electronic resistance, ion diffusion resistance in solution, ion diffusion resistance in particles, and charge transfer resistance.
  • the electronic resistance can be relatively easily solved by adding a carbon material, and the intra-particle ion diffusion resistance can be solved by reducing the particle size and shortening the diffusion length.
  • the group -M - is a group having a lithium ion coordination energy of 100 to 1500 kJ / mol determined by density functional calculation (B3LYP/6-31G (d)), and has a lithium salt structure (- M ⁇ Li + ) and a compound having a polymerizable group is used in an electrode or an electrolyte solution, so that a lithium ion-coordinating polymer film is formed on the surface of the active material, and the main resistance component of the charge transfer resistance is It has been reported that the desolvation energy, which is However, since a large amount of polyvinylidene fluoride is used in the electrode and a large amount of the compound is added, the Li diffusion resistance increases, and the resistance cannot be sufficiently reduced.
  • Patent Document 4 in a non-aqueous electrolyte solution for a secondary battery containing a non-aqueous solvent and a lithium salt, ethylene carbonate in a mixed solvent containing ethylene carbonate and chain carbonates contained in the non-aqueous solvent
  • the low-temperature characteristics of the battery are improved by controlling the ratio and using an electrolytic solution to which a compound having an SF bond in the molecule, which is a sulfonyl fluoride or a fluorosulfonic acid ester, is added.
  • a compound having an SF bond in the molecule which is a sulfonyl fluoride or a fluorosulfonic acid ester
  • Non-Patent Document 2 Journal of The Electrochemical Society, 165 (5) A1027-A1037 (2016) reports that the use of methyl acetate improves ionic conduction and improves charge-discharge characteristics. However, the deterioration of the battery is accelerated, and complicated additive technology and the use of high-cost active materials are required, and the problem has not yet been solved.
  • the present invention has investigated the formulation of an electrode-forming composition for the purpose of reducing the above resistance, and has found that a specific organic compound having an acidic functional group has a weight average molecular weight within a specific range.
  • a fluorine-based binder By combining a fluorine-based binder, it is possible to improve the adhesion between the current collector and the electrode layer.
  • An object of the present invention is to provide an electrode-forming composition capable of improving battery characteristics even when the amount of a system binder used is small.
  • an electrode-forming composition containing an organic compound, a fluorine-based binder, a conductive carbon material and an active material includes four organic compounds as the above.
  • an organic compound having an acidic functional group and/or a salt thereof as described above and using a small amount of a fluorine-based binder having a weight average molecular weight within a specific range, the adhesion between the current collector and the electrode layer is improved. It was found that the diffusion resistance of metal ions such as Li can be reduced while the amount of the fluorine-based binder used is reduced, and the battery characteristics are maintained, and the present invention has been completed.
  • the present invention provides the following electrode-forming composition.
  • the fluorine-based binder has a weight average molecular weight of 600,000 to 3,000,000, and its content is 0.01 to 1.0% by mass in the total solid content
  • a composition for forming an electrode 2.
  • 3. The electrode-forming composition of 1 or 2 wherein the fluorine-based binder has a heat of fusion of 10 to 35.8 J/g as measured by a differential scanning calorimeter (DSC). 4.
  • DSC differential scanning calorimeter
  • 11. The organic compound is a repeating unit derived from a monomer having a group selected from the group consisting of an aromatic ring, an alkyl group, an amino group, an ether group, a nitrile group, a hydroxy group and a carbonyl group, and a carboxylic acid group and/or 10.
  • composition for forming an electrode according to 9 or 10 which is a copolymer comprising a repeating unit derived from a monomer having a salt.
  • 11 electrode-forming compositions 11.
  • Electrode-forming composition wherein said dispersant comprises a nonionic polymer. 15. 14.
  • Electrode-forming polymer wherein the nonionic polymer is polyvinylpyrrolidone or a polymer having at least one group selected from the group consisting of a nitrile group, a hydroxyl group, a carbonyl group, an amino group, a sulfonyl group and an ether group.
  • Composition 16. 16.
  • 17. 17 The electrode-forming composition according to any one of 1 to 16, wherein the active material contains an oxide containing Li and at least one selected from Ni and Fe, or S, and is a composition for a positive electrode. 18.
  • It has a collector substrate and an electrode mixture layer formed on at least one surface of the collector substrate, wherein the electrode mixture layer is formed of the electrode-forming composition according to any one of 1 to 17.
  • electrode 19.
  • An energy storage device comprising 18 electrodes.
  • the electrode-forming composition of the present invention can be suitably used to form an electrode for an energy storage device. Reduction of resistance by improving adhesion, reduction of diffusion resistance of metal ions such as Li (improvement of battery characteristics) and cost reduction by reducing the amount of fluorine-based binder used, extension of life by improvement of reaction uniformity, reduction of environmental load It is expected to reduce the amount of solvent used and shorten the drying time due to the high solidification of the slurry, and it is also expected to suppress deterioration due to the neutralization effect of the alkaline component by adding an organic compound having an acidic functional group.
  • alkaline impurities are neutralized and further neutralized.
  • Carboxylate and the like are thought to be immobilized on the surface of the active material because they are insoluble in the electrode slurry.
  • the amount of fluorine-based binders that are usually used is on the order of several mass % in the electrode, whereas the present invention uses a specific organic compound having an acidic functional group as an electrode additive.
  • the required amount in the electrode can be as low as 1% by mass or less, so that the organic component that inhibits the diffusion of metal ions such as Li in the electrode can be greatly reduced.
  • the ability to greatly reduce the amount of fluorine-based binder used means that the cost of manufacturing batteries can be reduced, and the environmental load for manufacturing batteries can also be reduced. It is expected that the recyclability of the electrode will be improved, and that it will also have a longer life and improve safety.
  • FIG. 2 is an enlarged view showing a part of the NMR spectrum of the fluorine-based binder Solef5140;
  • FIG. 2 is an enlarged view showing a part of the NMR spectrum of the fluorine-based binder Solef5130;
  • FIG. 2 is an enlarged view showing a part of the NMR spectrum of the fluorine-based binder KF1100;
  • FIG. 2 is an enlarged view showing a part of the NMR spectrum of the fluorine-based binder KF1700;
  • FIG. 2 is an enlarged view showing a part of the NMR spectrum of the fluorine-based binder KF9100;
  • the electrode-forming composition of the present invention comprises an organic compound, a fluorine-based binder, a conductive carbon material and an active material, the organic compound having four or more acidic functional groups and/or salts thereof, and the fluorine
  • the composition for electrode formation wherein the weight average molecular weight (Mw) of the system binder is 600,000 to 3,000,000, and the content thereof is 0.01 to 1.0% by mass based on the total solid content.
  • a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC).
  • the organic compound has 4 or more acidic functional groups and/or salts thereof, preferably 5 or more acidic functional groups and/or salts thereof.
  • the acidic functional group is preferably a carboxylic acid group, a phosphoric acid group, or a sulfonic acid group, and more preferably a carboxylic acid group.
  • Salts of carboxylic acid group, phosphoric acid group and sulfonic acid group include alkali metal salts such as sodium and potassium; group 2 metal salts such as magnesium and calcium; ammonium salts; fats such as propylamine, dimethylamine, triethylamine and ethylenediamine.
  • amine salts alicyclic amine salts such as imidazoline, piperazine, and morpholine; aromatic amine salts such as aniline and diphenylamine; more preferred.
  • acidic functional groups and salts thereof may be contained alone, or two or more thereof may be contained.
  • the organic compound is preferably a polymer, and specific examples include polyacrylic acid, polyitaconic acid, polymaleic acid, polyfumaric acid, polymethacrylic acid, poly(vinylsulfonic acid), poly(4-styrenesulfonic acid), and salts thereof, etc., and polyacrylic acid, polyitaconic acid, polymaleic acid, and salts thereof are preferred.
  • the polymer may be a copolymer, and specific examples include monomers having a group selected from the group consisting of an aromatic ring, an alkyl group, an amino group, an ether group, a nitrile group, a hydroxy group and a carbonyl group.
  • Examples include copolymers containing repeating units derived from and repeating units derived from monomers having a carboxylic acid group and / or a salt thereof, and derived from a monomer having a group selected from the group consisting of a nitrile group, a hydroxy group and a carbonyl group and repeating units derived from monomers having carboxylic acid groups and/or salts thereof are preferred.
  • the aromatic ring examples include benzene ring, biphenyl ring, naphthalene ring, anthracene ring, and phenanthrene ring.
  • the above alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. , isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.
  • the organic compound is a polymer
  • its average molecular weight is not particularly limited, but the weight average molecular weight (Mw) is preferably 250 to 2,000,000, more preferably 1,000 to 1,000. ,000 is more preferred, and between 1,000 and 250,000 is even more preferred.
  • the content of the organic compound is preferably 0.001 to 0.5% by mass, more preferably 0.001 to 0.3% by mass, and still more preferably 0.001 to 0.2% by mass of the total solid content. is. Moreover, the more preferable lower limit of the content of the organic compound is 0.01% by mass or more based on the total solid content.
  • solid content means components other than the solvent which comprise a composition (the same applies hereafter).
  • the fluorine-based binder can be appropriately selected from known materials and used, and is not particularly limited. Specific examples thereof include polyvinylidene fluoride (PVdF), polytetrafluoroethylene; vinylidene fluoride , copolymers containing at least one monomer selected from the group consisting of tetrafluoroethylene and hexafluoropropylene. Moreover, the fluorine-based binder is preferably modified with a polar functional group such as a carboxy group or a hydroxyl group. The polar functional group can be confirmed by the presence or absence of a clear peak detected in the range of 10 to 15 ppm in measurement by a nuclear magnetic resonance apparatus (NMR apparatus).
  • NMR apparatus nuclear magnetic resonance apparatus
  • Mw of the fluorine-based binder is 600,000 to 3,000,000, preferably 700,000 to 2,000,000, more preferably from the viewpoint of improving the adhesion between the current collector and the electrode layer. 700,000 to 1,500,000, more preferably 700,000 to 900,000.
  • the heat of fusion of the fluorine-based binder obtained by a differential scanning calorimeter (DSC) is preferably 10 to 35.8 J / g, more preferably 15, from the viewpoint of improving the adhesion between the current collector and the electrode layer. ⁇ 35.5 J/g, more preferably 20 to 35.5 J/g, even more preferably 25 to 35.5 J/g. Adhesion between the current collector and the electrode layer can be improved by using a fluorine-based binder having a heat of fusion within the above range.
  • the content of the fluorine-based binder is 0.01 to 1.0% by mass, preferably 0.05 to 0.6% by mass, more preferably 0.07 to 0.5% by mass, based on the total solid content. , more preferably 0.1 to 0.4% by mass. If the content of the fluorine-based binder is too large, the composition may gel and become unusable.
  • the conductive carbon material is not particularly limited, and known conductive materials such as carbon black, ketjen black, acetylene black (AB), carbon whisker, carbon nanotube (CNT), carbon fiber, natural graphite, artificial graphite, etc. Although it can be used by appropriately selecting it from carbon materials having a high conductivity, AB and CNT are particularly preferable from the viewpoint of conductivity, dispersibility, availability, and the like.
  • CNTs are generally produced by an arc discharge method, a chemical vapor deposition method (CVD method), a laser ablation method, or the like, and the CNTs used in the present invention may be obtained by any method.
  • the CNT has a single-layer CNT (hereinafter also abbreviated as SWCNT) in which one sheet of carbon film (graphene sheet) is cylindrically wound, and a two-layer structure in which two graphene sheets are concentrically wound.
  • SWCNT single-layer CNT
  • DWCNTs multilayer CNTs
  • MWCNTs multilayer CNTs
  • Baytubes [manufactured by Bayer: trade name], GRAPHISTRENGTH [manufactured by Arkema: trade name], MWNT7 [manufactured by Hodogaya Chemical Co., Ltd.: trade name], Hyperion CNT [manufactured by Hyperion Catalysis International] : product name], TC series [manufactured by Toda Kogyo Co., Ltd.: product name], FloTube series [manufactured by Jiangsu Cnano Technology: product name], LUCAN BT1003M [LG Chem. Ltd. Product: trade name] and the like.
  • the content of the conductive carbon material is not particularly limited, it is preferably 0.1 to 4.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total solid content. Good electrical conductivity can be obtained by setting the content of the conductive carbon material within the above range.
  • active material various active materials conventionally used in electrodes for energy storage devices such as secondary batteries can be used.
  • active materials for positive electrodes can be preferably used.
  • the positive electrode active material for example, in the case of a lithium secondary battery or a lithium ion secondary battery, a chalcogen compound capable of adsorbing and desorbing lithium ions, a chalcogen compound containing lithium ions, a polyanion compound, elemental sulfur and its compounds, etc. are used. be able to.
  • Examples of such chalcogen compounds capable of adsorbing and desorbing lithium ions include FeS 2 , TiS 2 , MoS 2 , V 2 O 6 , V 6 O 13 and MnO 2 .
  • Examples of lithium ion - containing chalcogen compounds include LiCoO2 , LiMnO2 , LiMn2O4 , LiMo2O4 , LiV3O8 , LiNiO2 , LixNiyM1 - yO2 ( M is Co , represents at least one metal element selected from Mn, Ti, Cr, V, Al, Sn, Pb, and Zn, 0.05 ⁇ x ⁇ 1.10, 0.3 ⁇ y ⁇ 1.0), LiaNi ( 1 - xy) CoxM1yM2zXwO2 ( M1 is at least one selected from the group consisting of Mn and Al; M2 is Zr, Ti, Mg, W and represents at least one selected from the group consisting of V, 1.00 ⁇ a ⁇ 1.
  • oxides containing Li and at least one selected from Ni and Fe, or materials containing S that is, FeS 2 , TiS 2 , MoS 2 , LiNiO 2 , Li x Ni y M 1-y O 2
  • M represents at least one metal element selected from Co, Mn, Ti, Cr, V, Al, Sn, Pb, and Zn, and 0.05 ⁇ x ⁇ 1 .10 , 0.3 ⁇ y ⁇ 1.0
  • LiaNi ( 1 - xy) CoxM1yM2zXwO2 M1 is at least one selected from the group consisting of Mn and Al
  • M2 represents at least one selected from the group consisting of Zr, Ti, Mg, W and V, and 1.00 ⁇ a ⁇ 1.50 , 0.00 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 0.50, 0.000 ⁇ z ⁇ 0.020, 0.000 ⁇ w ⁇ 0.020), LiFePO4 , Li2S , rubeanic acid are preferred.
  • the content of the active material is preferably 94.5-99.88% by mass, more preferably 95.0-99.0% by mass, based on the total solid content.
  • the electrode-forming composition of the present invention may contain binders other than the fluorine-based binder as long as the effects of the present invention are not impaired.
  • binders can be appropriately selected from known materials and used, and are not particularly limited, but non-aqueous binders can be preferably used in the present invention. Specific examples include polyimide, ethylene-propylene-diene terpolymer, styrene-butadiene rubber, polyethylene and polypropylene. These can be used individually by 1 type or in combination of 2 or more types.
  • the content is not particularly limited, but is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and 3.0% by mass of the total solid content The following are even more preferred, and most preferably not included.
  • the electrode-forming composition of the present invention may further contain a dispersant in order to improve the dispersibility of the conductive carbon material and active material.
  • the dispersing agent can be appropriately selected from those conventionally used as dispersing agents for conductive carbon materials such as CNTs. preferable.
  • the nonionic polymer include polyvinylpyrrolidone (PVP), and polymers having at least one group selected from the group consisting of nitrile groups, hydroxy groups, carbonyl groups, amino groups, sulfonyl groups and ether groups. be done.
  • polymer examples include polyvinyl alcohol, polyacrylonitrile, polylactic acid, polyester, polyimide, polyphenylether, polyphenylsulfone, polyethyleneimine, and polyaniline.
  • the above dispersants may be used singly or in combination of two or more.
  • the dispersant When the dispersant is included, its content is not particularly limited, but is preferably 0.001 to 0.5% by mass, more preferably 0.001 to 0.3% by mass, based on the total solid content, 0.001 to 0.2% by mass is even more preferable. Moreover, a more preferable lower limit of the content of the dispersant is 0.01% by mass or more based on the total solid content. Further, considering the adhesion between the resulting electrode layer and the current collector, the total amount of the organic compound and the dispersant is preferably 0.001 to 1% by mass, more preferably 0.001 to 1% by mass of the total solid content. It is 0.01 to 1% by mass.
  • a solvent can also be used in the preparation of the electrode-forming composition.
  • the solvent is not particularly limited as long as it is conventionally used for the preparation of electrode-forming compositions. Examples include water; ethers such as tetrahydrofuran (THF), diethyl ether, and 1,2-dimethoxyethane (DME). Halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc.
  • ethers such as tetrahydrofuran (THF), diethyl ether, and 1,2-dimethoxyethane (DME).
  • Halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane
  • amides amides; acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol; n-heptane, n-hexane, cyclohexane, etc.
  • Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; Ethylene glycol, propylene glycol, etc. glycols; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; organic solvents such as ⁇ -butyrolactone, dimethylsulfoxide (DMSO), dioxolane, sulfolane, and the like. These solvents can be used singly or in combination of two or more.
  • Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether
  • Suitable solvents in this case include water, NMP, DMSO, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ -butyrolactone, THF, dioxolane, sulfolane, DMF, DMAc and the like.
  • NMP is suitable for water-insoluble binders such as PVdF, and water is suitable for water-soluble binders.
  • the solid content concentration of the electrode-forming composition of the present invention is appropriately set in consideration of the coatability of the composition, the thickness of the thin film to be formed, etc., but is usually about 50 to 90% by mass. Yes, preferably about 55 to 85% by mass, more preferably about 60 to 80% by mass.
  • the electrode-forming composition of the present invention can be obtained by mixing the components described above at a predetermined temperature.
  • the additive and active material may be mixed together with the optional component, or both components may be mixed in advance and then mixed with the optional component. good.
  • the surface of the active material can be coated with the additive, and the effects of the present invention can be fully exhibited.
  • the electrode of the present invention comprises an electrode layer made of the electrode-forming composition described above on at least one surface of a substrate which is a current collector.
  • a method for forming the electrode layer on the substrate an electrode-forming composition prepared without using a solvent is pressure-molded onto the substrate (dry method), or an electrode-forming composition is formed using a solvent.
  • dry method a method of preparing a substance, coating it on a substrate, and drying it (wet method) can be mentioned. These methods are not particularly limited, and conventionally known various methods can be used.
  • wet methods include various printing methods such as offset printing and screen printing, blade coating method, dip coating method, spin coating method, bar coating method, slit coating method, inkjet method, die coating method and the like.
  • the temperature is preferably about 50 to 400°C, more preferably about 70 to 150°C.
  • the substrate used for the electrode examples include metal substrates such as platinum, gold, iron, stainless steel, copper, aluminum, and lithium, alloy substrates made of any combination of these metals, indium tin oxide (ITO), Examples include oxide substrates such as indium zinc oxide (IZO) and antimony tin oxide (ATO), and carbon substrates such as glassy carbon, pyrolytic graphite, and carbon felt.
  • ITO indium tin oxide
  • oxide substrates such as indium zinc oxide (IZO) and antimony tin oxide (ATO)
  • carbon substrates such as glassy carbon, pyrolytic graphite, and carbon felt.
  • the thickness of the substrate is not particularly limited, but is preferably 1 to 100 ⁇ m in the present invention.
  • the film thickness of the electrode layer is not particularly limited, it is preferably about 0.01 to 1,000 ⁇ m, more preferably about 5 to 300 ⁇ m. In addition, when using an electrode layer as an electrode independently, it is preferable that the film thickness shall be 10 micrometers or more.
  • the electrodes may be pressed if necessary.
  • a generally employed method can be used as the pressing method, but a die pressing method and a roll pressing method are particularly preferred.
  • the press pressure is not particularly limited, but is preferably 1 kN/cm or more, preferably 2 kN/cm or more, and more preferably 5 kN/cm or more.
  • the upper limit of the press pressure is not particularly limited, but is preferably 50 kN/cm or less.
  • the secondary battery of the present invention includes the electrodes described above, and more specifically, includes at least a pair of positive and negative electrodes, a separator interposed between the electrodes, and an electrolyte. At least one of the negative electrodes is composed of the electrodes described above. Other constituent members of the battery element may be appropriately selected from conventionally known ones and used.
  • Examples of materials used for the separator include glass fiber, cellulose, porous polyolefin, polyamide, and polyester.
  • the electrolyte may be either a liquid or a solid, and may be either aqueous or non-aqueous. From the viewpoint of easily exhibiting practically sufficient performance, an electrolytic solution composed of an electrolyte salt, a solvent, etc. can be preferably used.
  • electrolyte salt examples include LiPF6 , LiBF4 , LiN( SO2F ) 2 , LiN ( C2F5SO2 ) 2 , LiAsF6 , LiSbF6 , LiAlF4 , LiGaF4 , LiInF4 , LiClO4 . , LiN ( CF3SO2)2 , LiCF3SO3 , LiSiF6 , LiN ( CF3SO2 ), Lithium salts such as ( C4F9SO2 ), LiI, NaI, KI, CsI , CaI2 , etc.
  • electrolyte salts of quaternary imidazolium compounds, iodides and perchlorates of tetraalkylammonium compounds, and metal bromides such as LiBr, NaBr, KBr, CsBr and CaBr2 .
  • electrolyte salts can be used singly or in combination of two or more.
  • the solvent is not particularly limited as long as it does not corrode or decompose the substances constituting the battery to deteriorate the performance, and dissolves the electrolyte salt.
  • non-aqueous solvents include cyclic esters such as ethylene carbonate, propylene carbonate, butylene carbonate and ⁇ -butyrolactone; ethers such as tetrahydrofuran and dimethoxyethane; esters, nitriles such as acetonitrile, and the like are used. These solvents can be used singly or in combination of two or more.
  • solid electrolyte inorganic solid electrolytes such as sulfide solid electrolytes and oxide solid electrolytes, and organic solid electrolytes such as polymer electrolytes can be suitably used. By using these solid electrolytes, it is possible to obtain an all-solid battery that does not use an electrolytic solution.
  • the sulfide-based solid electrolyte examples include Li 2 S—SiS 2 -lithium compounds (here, the lithium compound is at least one selected from the group consisting of Li 3 PO 4 , LiI and Li 4 SiO 4 ) , Li 2 SP 2 O 5 , Li 2 SB 2 S 5 , Li 2 SP 2 S 5 --GeS 2 and other thiolysicone-based materials.
  • Oxygenate compounds based on the 3 PO 4 structure, perovskite type, Li 3.3 PO 3.8 N 0.22 generically called LIPON, sodium/alumina, and the like can be mentioned.
  • polymer solid electrolyte examples include polyethylene oxide materials, hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, and methyl methacrylate. , polymer compounds obtained by polymerizing or copolymerizing monomers such as styrene and vinylidene fluoride.
  • the polymer-based solid electrolyte may contain a supporting salt and a plasticizer.
  • Examples of supporting salts contained in the polymer solid electrolyte include lithium (fluorosulfonylimide), and examples of plasticizers include succinonitrile.
  • a battery manufactured using the electrode-forming composition of the present invention has high battery characteristics even if the amount of fluorine binder is less than that of a general secondary battery.
  • the form of the secondary battery and the type of electrolyte are not particularly limited, and any form such as a lithium ion battery, a nickel hydrogen battery, a manganese battery, an air battery, etc. may be used, but a lithium ion battery is preferable. .
  • the lamination method and production method are also not particularly limited.
  • the electrode of the present invention described above When applied to a coin shape, the electrode of the present invention described above may be punched into a predetermined disk shape and used. For example, in a lithium-ion secondary battery, one of the electrodes is placed on the lid to which the washer and spacer of the coin cell are welded. It can be made by stacking the electrodes of the present invention layer down, placing a case and gasket on top, and sealing with a coin cell crimping machine.
  • GPC Gel permeation chromatography
  • Fluorine-based binder Apparatus manufactured by Shimadzu Corporation, high performance liquid chromatograph
  • Prominence Eluent 10 mM LiBr in NMP
  • Column temperature: 40°C Detector Differential refractometer
  • a diluted solution was prepared by dissolving 1 mg of the fluoropolymer in 1 mL of N-methyl-2-pyrrolidone (NMP) in which 10 mM of LiBr was dissolved.
  • NMP N-methyl-2-pyrrolidone
  • the resulting diluted solution was filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.45 ⁇ m) to obtain a measurement sample.
  • This measurement sample was supplied to a gel permeation chromatograph, GPC measurement was performed under the above conditions, the polystyrene equivalent molecular weight of the fluoropolymer was measured, and the weight average molecular weight (Mw) was determined.
  • the resulting diluted solution was filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.45 ⁇ m) to obtain a measurement sample.
  • This measurement sample was supplied to a gel permeation chromatograph, GPC measurement was performed under the above conditions, the polystyrene equivalent molecular weight of the synthetic polymer was measured, and the weight average molecular weight (Mw) was obtained.
  • DSC Differential scanning calorimeter
  • NCM811 Ningbo Ronbay New Energy Technology Co. , Ltd. manufactured by Lithium Nickel Manganese Cobaltate (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ), “S-800” Solef5140: manufactured by SOLVAY, modified PVdF, Mw 1,033,408 (measured value), heat of fusion 32.94 J / g (measured value), with polar functional group Solef5130: manufactured by SOLVAY, modified PVdF, Mw729, 202 (measured value ), heat of fusion 32.77 J / g (actual value), with polar functional group KF1100: Kureha Co., Ltd., PVdF, Mw 356,917 (actual value), heat of fusion 50.88 J / g (actual value), polar functional group No group, purified NMP solution grade (KF1120) of KF1100 KF1700: Kureha Co., Ltd., PVdF
  • CNT2 LUCAN BT1003, manufactured by LG Chemical PAA1: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., polyacrylic acid, Mw 5,000 PAA2: Fujifilm Wako Pure Chemical Co., Ltd., polyacrylic acid, Mw 1,800 PAA3: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyacrylic acid, Mw 25,000 PAA4: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyacrylic acid, Mw 250,000 AC-10P: manufactured by Toagosei Co., Ltd., polyacrylic acid, Mw 5,000 PAA-Li: Polyacrylic acid (50% Li neutralized product of PAA1), synthetic product PVPA: Made by Aldrich, poly (vinylphosphonic acid), Mw 24,817 (manufacturer's measurement value) PSSA: Aldrich, poly(4-styrenesulfonic acid) solution (18 wt% in H 2 O), Mw ⁇ 75,000 AA/AN-8: acrylic
  • PIA polyitaconic acid, Mw 2,387 (actual value), synthetic citric acid: Fuji Film Wako Pure Chemical Industries, Ltd.
  • PVP1 Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone, Mw 1,200,000
  • PVP2 Polyvinylpyrrolidone, Mw 10,000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • PVA Sigma-Aldrich, polyvinyl alcohol, Mw 61,000
  • PAN Sigma-Aldrich, polyacrylonitrile, Mw 150,000 H-PAN: from Dolan GmbH, polyacrylonitrile, Mw 200,000 Phosphorous acid: manufactured by Junsei Chemical Co., Ltd.
  • NMP manufactured by Junsei Chemical Co., Ltd.
  • N-methyl-2-pyrrolidone NMP (for GPC) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
  • N-methyl-2-pyrrolidone dehydration NMP manufactured by Kanto Chemical Co., Ltd., N-methyl-2-pyrrolidone, water content of 50 ppm or less
  • KF1100 KF1120 manufactured by Kureha Co., Ltd., PVdF, NMP solution grade of KF1100 was added to acetone for reprecipitation, and the resulting precipitate was vacuum-heated and dried to obtain powdery KF1100.
  • Electrode composition (electrode slurry) [Examples 1-1 to 1-35, Comparative Examples 1-1 to 1-19] Based on the compositions shown in Tables 2 to 4, the active material, fluorine-based binder, conductive carbon material, organic compound, dispersant, and solvent were mixed in a dry base. This was mixed with a homodisper at 8,000 rpm for 1 minute, and then mixed twice at a peripheral speed of 20 m/sec for 30 seconds using a thin-film rotating high-speed mixer to prepare an electrode slurry. The properties and coatability of the obtained electrode slurry were evaluated by the following methods. Each table also summarizes these evaluations.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene copolymer
  • Four disc-shaped electrodes of 13 mm were punched out.
  • the mass of the negative electrode layer (the mass of the punched electrode minus the mass of the uncoated portion punched out to a diameter of 13 mm) and the thickness of the electrode layer (the thickness of the punched electrode minus the thickness of the base material) ) was measured, vacuum-dried at 120°C for 15 hours, and then transferred to a dry booth.
  • a sheet of separator glass fiber circular filter paper GF/F, manufactured by WATT MANN CO., LTD.
  • a positive electrode was stacked from above with the surface coated with the active material facing down. After dropping one drop of the electrolytic solution, the case and the gasket to which the washer and spacer were welded were placed and sealed with a coin cell caulking machine. After that, they were allowed to stand still for 24 hours, and four secondary batteries for testing were produced.
  • the secondary battery using the positive electrode produced using the electrode-forming composition according to the present invention has high battery characteristics even with a small amount of fluorine binder. .

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