WO2015098116A1 - Pâte de matériau conducteur pour électrode de batterie rechargeable, procédé de production de suspension épaisse pour cathode de batterie rechargeable, procédé de production de cathode de batterie rechargeable, et batterie rechargeable - Google Patents

Pâte de matériau conducteur pour électrode de batterie rechargeable, procédé de production de suspension épaisse pour cathode de batterie rechargeable, procédé de production de cathode de batterie rechargeable, et batterie rechargeable Download PDF

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Publication number
WO2015098116A1
WO2015098116A1 PCT/JP2014/006464 JP2014006464W WO2015098116A1 WO 2015098116 A1 WO2015098116 A1 WO 2015098116A1 JP 2014006464 W JP2014006464 W JP 2014006464W WO 2015098116 A1 WO2015098116 A1 WO 2015098116A1
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Prior art keywords
conductive material
binder
secondary battery
positive electrode
material paste
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PCT/JP2014/006464
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English (en)
Japanese (ja)
Inventor
真弓 福峯
高橋　直樹
麻貴 片桐
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日本ゼオン株式会社
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Priority claimed from JP2013273124A external-priority patent/JP6398191B2/ja
Priority claimed from JP2014005329A external-priority patent/JP6413242B2/ja
Priority claimed from JP2014066739A external-priority patent/JP6394027B2/ja
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to KR1020167015523A priority Critical patent/KR102393257B1/ko
Priority to CN201480067820.0A priority patent/CN105814718B/zh
Publication of WO2015098116A1 publication Critical patent/WO2015098116A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a conductive paste for a secondary battery electrode, a method for producing a slurry for a secondary battery positive electrode, a method for producing a positive electrode for a secondary battery, and a secondary battery.
  • Secondary batteries especially lithium ion secondary batteries, are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications.
  • lithium ion secondary batteries have attracted attention as an energy source for electric vehicles (EV) and hybrid electric vehicles (HEV), and higher performance is required. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of secondary batteries such as lithium ion secondary batteries.
  • EV electric vehicles
  • HEV hybrid electric vehicles
  • improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of secondary batteries such as lithium ion secondary batteries.
  • it has been studied to improve the electrical characteristics by improving battery members such as electrodes.
  • an electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer for example, the positive electrode mixture layer is usually formed by dispersing a positive electrode slurry as an electrode slurry on a current collector, in which a positive electrode active material, a conductive material, a binder, and the like are dispersed or dissolved in a dispersion medium. It is formed by applying and drying and binding a positive electrode active material, a conductive material, and the like with a binder.
  • the composition of the electrode slurry and the manufacturing process thereof affect the properties of the obtained electrode slurry.
  • Patent Document 1 a mixture of a fluorine-based polymer and nitrile rubber or hydrogenated nitrile rubber is used as a binder to be blended in an electrode slurry for forming an electrode mixture layer, and nitrile rubber or hydrogenated nitrile rubber is used. It has been proposed to improve the performance of the electrode and improve the energy density and cycle characteristics of the secondary battery by a synergistic effect of having high adhesiveness and bonding of the fluoropolymer in the fiber state. Yes.
  • Patent Document 2 when preparing a slurry for a positive electrode containing a mixture of a fluorinated polymer and a hydrogenated nitrile rubber as a binder, an organic solvent solution of the fluorinated polymer, a hydrogenated nitrile rubber, and a conductive material are previously added. After mixing to obtain a conductive material paste, the conductive material paste and the positive electrode active material are mixed to prepare a positive electrode slurry, thereby improving the performance of the positive electrode and reducing the battery capacity in large current discharge. It has been proposed to provide fewer secondary batteries.
  • Patent Document 3 a lithium-containing transition metal oxide as a positive electrode active material, a first binder A such as a fluorine-based polymer and a paste A containing a dispersion medium, carbon black as a conductive material, hydrogenated nitrile rubber, and the like
  • the second binder B and the paste B (conductive material paste) containing the dispersion medium are prepared, and the positive electrode slurry obtained by mixing the paste A and the paste B is used for forming the positive electrode.
  • a hydrogenated nitrile rubber having a low affinity with a fluorine-based polymer is disposed on the surface to suppress aggregation of the conductive material due to the fluorine-based polymer.
  • Patent Document 4 a conductive material paste containing a conductive material and a binder is prepared, and the obtained conductive material paste is diluted with a solvent, and then a lithium-transition metal composite oxide as a positive electrode active material is added and stirred.
  • a lithium-transition metal composite oxide as a positive electrode active material is added and stirred.
  • the secondary battery is not only required to improve the low temperature characteristics by further reducing the internal resistance and ensure high output, but also, for example, the above-described electric vehicle (EV) or hybrid electric vehicle (HEV). It is required to ensure high-temperature storage characteristics and high-temperature cycle characteristics in order to fully exhibit its performance even in a high-temperature environment such as In order to improve the electrical characteristics of such a secondary battery, it is necessary to ensure durability (potential stability) with respect to voltage application of the electrode while ensuring conductivity in the electrode. Furthermore, when manufacturing a battery industrially, the dispersion stability of the electrode slurry and the conductive material paste used for preparing the electrode slurry is also very important.
  • an object of this invention is to provide the electrically conductive material paste for secondary battery electrodes which can form the electrode which is excellent in dispersion stability and excellent in electric potential stability. Moreover, an object of this invention is to provide the manufacturing method of the slurry for secondary battery positive electrodes which can improve the electrical property and can improve the performance of a secondary battery. Furthermore, an object of this invention is to provide the manufacturing method of the positive electrode for secondary batteries which can improve the electrical property and can improve the performance of a secondary battery. In addition, an object of the present invention is to provide a secondary battery having excellent electrical characteristics.
  • the present inventors have intensively studied for the purpose of solving the above-mentioned problems and found the following points.
  • the present inventors have excellent dispersion stability when a conductive material paste containing a binder having a specific repeating unit and the amount of the binder adsorbed on the conductive material is controlled within a predetermined range. I found out.
  • the conductive material paste for the preparation of secondary battery electrode slurry especially positive electrode slurry
  • the oxidation of the binder is suppressed and the potential stability is improved. It has been found that electrical characteristics such as high temperature storage characteristics can be enhanced.
  • the present inventors have formed the above conventional electrode slurry from an electrode slurry because the binder and the conductive material are sufficiently kneaded with a relatively high solid content. There is a possibility that a good conductive network may not be formed between the conductive materials due to excessive dispersion of the conductive material in the electrode mixture layer, and a secondary where the conductive network between the conductive materials is insufficient. It was further found that the battery may not be able to suppress capacity deterioration due to internal resistance, particularly capacity deterioration at low temperatures. Accordingly, the present inventors have repeatedly studied and have come up with the idea of forming a good conductive network between conductive materials by adjusting the manufacturing conditions and the like of electrode slurry (especially positive electrode slurry).
  • the inventors further studied and prepared a slurry for an electrode by mixing the solid content concentration of the conductive material paste containing the binder containing the specific repeating unit and the conductive material within a predetermined range. And / or by producing a slurry for a secondary battery electrode by a specific manufacturing process using a binder containing the specific repeating unit described above, it is possible to form a good conductive network between conductive materials, It has been found that the internal resistance of the secondary battery manufactured using the obtained secondary battery electrode slurry is reduced, and the high-temperature cycle characteristics and low-temperature characteristics are improved.
  • the conductive material paste for a secondary battery electrode of the present invention contains a conductive material and a binder A, and the binder A is an alkylene. It includes at least one of a structural unit and a (meth) acrylic acid ester monomer unit, and the binder adsorption amount of the conductive material is 100 mg / g or more and 600 mg / g or less.
  • the secondary battery containing the binder A containing the alkylene structural unit and / or the (meth) acrylic acid ester monomer unit, and the binder adsorption amount of the conductive material is 100 mg / g or more and 600 mg / g or less.
  • the electrode conductive material paste has excellent dispersion stability, and an electrode having excellent potential stability can be produced by using the conductive material paste.
  • the electrode obtained using the conductive material paste can exhibit excellent electrical characteristics for the secondary battery.
  • the “binder adsorption amount of the conductive material” can be measured by the method described in this specification.
  • the binder A preferably includes an alkylene structural unit.
  • the binder A contains an alkylene structural unit, the dispersion stability of the conductive material paste and the potential stability of the electrode can be further improved, and the electrical characteristics of the secondary battery can be further enhanced. Because.
  • the binder A includes both an alkylene structural unit and a (meth) acrylate monomer unit. If the binder A includes both an alkylene structural unit and a (meth) acrylic acid ester monomer unit, the dispersion stability of the conductive material paste and the potential stability of the electrode can be further improved. This is because the electrical characteristics of the battery can be further enhanced.
  • the binder A further contains 2% by mass to 50% by mass of a nitrile group-containing monomer unit. If the binder A contains a nitrile group-containing monomer unit in the range of 2% by mass to 50% by mass, the dispersion stability of the conductive material paste and the potential stability of the electrode can be further improved. Moreover, it is because the electrical property of a secondary battery can be improved further while improving the stability with respect to the electrolyte solution of the positive electrode for secondary batteries manufactured using the electrically conductive material paste.
  • the conductive material paste for a secondary battery electrode of the present invention preferably has a viscosity of 1000 mPa ⁇ s or more and 10,000 mPa ⁇ s or less.
  • the dispersion stability of the conductive material paste can be made excellent by setting the viscosity of the conductive material paste to 1000 mPa ⁇ s or more and 10,000 mPa ⁇ s or less.
  • the conductive material paste for a secondary battery electrode of the present invention preferably has a solid content concentration of 5% by mass or more and 15% by mass or less.
  • the conductive material is well dispersed in the obtained electrode mixture layer, and the electrical characteristics of the secondary battery are further enhanced. Because it can.
  • the conductive material is “dispersed well” means that the conductive material is appropriately dispersed without excessively dispersing or aggregating in the electrode mixture layer. It refers to a state where each other can form a conductive network.
  • the manufacturing method of the slurry for secondary battery positive electrodes of this invention uses the electrically conductive paste for any of the above-mentioned secondary battery electrodes. It includes a step (X) of preparing, and a step (Y) of mixing the conductive material paste for a secondary battery electrode and a positive electrode active material.
  • the secondary battery positive electrode slurry obtained by using any one of the above-described conductive pastes for secondary battery electrodes is excellent in dispersion stability, and if the positive electrode slurry is used, a positive electrode excellent in potential stability is produced. Thus, the secondary battery can exhibit excellent electrical characteristics.
  • the step (X) mixes and premixes the conductive material and the first binder component containing the binder A as a main component.
  • the positive electrode slurry is prepared using the conductive material paste through the first step and the second step, the electrical characteristics of the secondary battery can be further enhanced.
  • "it contains as a main component” shows containing in the ratio of 50 mass% or more in conversion of solid content.
  • the manufacturing method of the positive electrode for secondary batteries of this invention was obtained by the manufacturing method of the slurry for secondary battery positive electrodes mentioned above.
  • the method includes a step of applying a slurry for a secondary battery positive electrode to at least one surface of a current collector and drying to form a positive electrode mixture layer. If the positive electrode mixture layer is formed from the above-described slurry for the secondary battery positive electrode, a positive electrode having excellent potential stability can be produced, and the positive electrode can exhibit excellent electrical characteristics in the secondary battery. .
  • the secondary battery of this invention is a secondary battery which has a positive electrode, a negative electrode, a separator, and electrolyte solution, Comprising:
  • the said positive electrode is A secondary battery positive electrode manufactured by the above-described method for manufacturing a secondary battery positive electrode.
  • a secondary battery provided with the positive electrode for secondary batteries manufactured by the manufacturing method of the positive electrode for secondary batteries mentioned above is excellent in an electrical property.
  • the electrically conductive material paste for secondary battery electrodes which can form the electrode which is excellent in dispersion stability and is excellent in electric potential stability can be provided.
  • the manufacturing method of the slurry for secondary battery positive electrodes which can improve an electrical characteristic and can improve the performance of a secondary battery can be provided.
  • the manufacturing method of the positive electrode for secondary batteries which can improve an electrical characteristic and can improve the performance of a secondary battery can be provided.
  • a secondary battery having excellent electrical characteristics can be provided.
  • the conductive material paste for a secondary battery electrode of the present invention is used as a material for producing a slurry for a secondary battery electrode, preferably a slurry for a secondary battery positive electrode.
  • the manufacturing method of the slurry for secondary battery positive electrodes of this invention manufactures the slurry for secondary battery positive electrodes used for formation of the positive electrode of a secondary battery using the electrically conductive material paste for secondary battery electrodes of this invention.
  • the method for producing a positive electrode for a secondary battery according to the present invention is characterized in that a positive electrode mixture layer is formed from the slurry for a secondary battery positive electrode produced by using the method for producing a slurry for a secondary battery positive electrode according to the present invention.
  • the secondary battery of the present invention is characterized by using a positive electrode manufactured by the method for manufacturing a positive electrode for a secondary battery of the present invention.
  • the conductive material paste of the present invention comprises at least a conductive material and a binder A, and the binder A includes at least one of an alkylene structural unit and a (meth) acrylic acid ester monomer unit.
  • the binder adsorption amount of the conductive material is 100 mg / g or more and 600 mg / g or less.
  • the conductive material paste containing at least the binder A containing an alkylene structural unit and / or a (meth) acrylic acid ester monomer unit as a binder, and the binder adsorption amount of the conductive material is within a specific range, If the conductive material paste is excellent in dispersion stability, an electrode having excellent potential stability can be produced, and the secondary battery can exhibit excellent electrical characteristics.
  • “including an alkylene structural unit” means “a repeating structure composed only of an alkylene structure represented by the general formula —C n H 2n — [where n is an integer of 2 or more] in a polymer. It means "unit is included”.
  • including a monomer unit means “a repeating unit derived from a monomer is contained in a polymer obtained using the monomer”.
  • (meth) acryl means acryl and / or methacryl.
  • the conductive material is, for example, for ensuring electrical contact between the positive electrode active materials in the positive electrode mixture layer.
  • a well-known electrically conductive material can be used, without being specifically limited.
  • the conductive material acetylene black, ketjen black (registered trademark), furnace black, graphite, carbon fiber, carbon flake, carbon ultrashort fiber (for example, carbon nanotube, vapor grown carbon fiber, etc.), etc.
  • Conductive carbon materials various metal fibers, foils and the like can be used. Among these, from the viewpoint of sufficiently improving the rate characteristics while maintaining the battery capacity of the secondary battery, it is preferable to use acetylene black, ketjen black, or furnace black as the conductive material.
  • the specific surface area of the conductive material is preferably 10 m 2 / g or more, more preferably 50 m 2 / g or more, further preferably 65 m 2 / g or more, preferably 1500 m 2 / g or less, more preferably 1000 m 2 / g Hereinafter, it is more preferably 500 m 2 / g or less. If the specific surface area of the conductive material is 10 m 2 / g or more, the amount of binder adsorbed on the conductive material is easy to adjust, and if it is 1500 m 2 / g or less, the conductive due to excessive adsorption of the binder as an insulator. Sexual deterioration can be suppressed.
  • the “specific surface area of the conductive material” is a BET specific surface area by a nitrogen adsorption method, and can be measured in accordance with ASTM D3037-81.
  • Binder A is an electrode manufactured by forming an electrode mixture layer on a current collector with an electrode slurry containing the conductive material paste of the present invention, and the components contained in the electrode mixture layer are detached from the electrode mixture layer. It is a component that can be retained so as not to be present.
  • the binder in the electrode mixture layer for example, the positive electrode mixture layer, when immersed in the electrolytic solution absorbs the electrolytic solution and swells, while the positive electrode active materials are in contact with each other, the positive electrode active material and the conductive material, or The conductive materials are bound to each other to prevent the positive electrode active material and the like from dropping from the current collector.
  • the binder A used for the electrically conductive material paste of this invention needs to contain at least one of an alkylene structural unit and a (meth) acrylic acid ester monomer unit.
  • the binder A may optionally contain other monomer units other than the alkylene structural unit and the (meth) acrylate monomer unit.
  • the binder A contains an alkylene structural unit and / or a (meth) acrylic acid ester monomer unit, so that the adsorbing ability of the binder A to the conductive material is ensured, and the aggregation of the conductive material is suppressed and the conductive material is suppressed.
  • the dispersion stability of the paste can be improved.
  • the electrode slurry containing such a conductive material paste is also excellent in dispersion stability, the conductive material is well dispersed in the electrode mixture layer formed from the electrode slurry.
  • the binder A containing an alkylene structural unit and a (meth) acrylic acid ester monomer unit has excellent oxidation resistance, and ensures the potential stability of an electrode prepared using an electrode slurry containing a conductive material paste. Can do.
  • the internal resistance of the secondary battery including the electrode formed using the conductive material paste of the present invention is reduced.
  • the secondary battery can be improved in low temperature characteristics, high temperature cycle characteristics and high temperature storage characteristics, and excellent in electrical characteristics.
  • the binder A used in the conductive material paste of the present invention preferably includes at least an alkylene structural unit, and more preferably includes both an alkylene structural unit and a (meth) acrylic acid ester monomer unit.
  • the alkylene structural unit is included and when both the alkylene structural unit and the (meth) acrylate monomer unit are included, the dispersion stability of the conductive material paste and the potential stability of the electrode are further improved. This is because the electrical characteristics of a secondary battery including an electrode manufactured using a conductive material paste can be improved.
  • the alkylene structural unit may be linear or branched, but from the viewpoint of improving the dispersion stability of the conductive material paste and the potential stability of the electrode, the alkylene structural unit is linear. It is preferably a linear alkylene structural unit.
  • the method for introducing the alkylene structural unit into the binder A is not particularly limited.
  • the following methods (1) and (2) (1) A method of preparing a polymer from a monomer composition containing a conjugated diene monomer and converting the conjugated diene monomer unit to an alkylene structural unit by hydrogenating the polymer (2) Examples thereof include a method for preparing a polymer from a monomer composition containing a 1-olefin monomer.
  • the method (1) is preferable because the production of the binder A is easy.
  • examples of the conjugated diene monomer include conjugated diene compounds having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. It is done. Of these, 1,3-butadiene is preferred. That is, the alkylene structural unit is preferably a structural unit (conjugated diene hydride unit) obtained by hydrogenating a conjugated diene monomer unit, and a structure obtained by hydrogenating a 1,3-butadiene monomer unit. More preferred are units (1,3-butadiene hydride units).
  • Examples of the 1-olefin monomer include ethylene, propylene, 1-butene and the like. These conjugated diene monomers and 1-olefin monomers can be used singly or in combination of two or more.
  • the content ratio of the alkylene structural unit in the binder A is preferably 30% by mass or more when all repeating units (total of monomer units and structural units) in the binder A are 100% by mass. 50 mass% or more is more preferable, 98 mass% or less is preferable, and 80 mass% or less is more preferable.
  • the dispersion stability of the conductive material paste is improved by suppressing the sedimentation of the conductive material in the conductive material paste, and in addition, the electrode Is ensured.
  • the conductive material is well dispersed and the conductive network is well formed. The electrical characteristics of the secondary battery having the layer are improved.
  • the solubility of the binder A in a solvent such as N-methylpyrrolidone (NMP) becomes excessively high.
  • NMP N-methylpyrrolidone
  • the binder A becomes conductive.
  • Dispersion stability declines by not being able to adsorb
  • the adsorption amount to the conductive material is reduced, the internal resistance of the secondary battery manufactured using them is increased, and the low temperature characteristics, the high temperature storage characteristics, and the high temperature cycle characteristics may be decreased.
  • Examples of the (meth) acrylate monomer that can form a (meth) acrylate monomer unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, Alkyl acrylates such as isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate
  • the (meth) acrylic acid ester monomer is a non-carbonyl oxygen.
  • Acrylic acid alkyl ester having 4 to 10 carbon atoms in the alkyl group bonded to the atom is preferable, and specifically, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are preferable, and n-butyl acrylate is more preferable. preferable. These can be used alone or in combination of two or more.
  • the content rate of the (meth) acrylic acid ester monomer unit in the said binder A shall be 10 mass% or more and 40 mass% or less, when all the repeating units in the binder A are 100 mass%. Is preferred.
  • the content ratio of the (meth) acrylic acid ester monomer unit in the binder A 40% by mass or less, particularly the solubility of the binder A in a solvent such as NMP is improved, and the conductive material paste is dispersed. Stability can be further improved.
  • the content ratio of the (meth) acrylic acid ester monomer unit in the binder A is 10% by mass or more, thereby improving the stability of the electrode mixture layer formed using the conductive material paste with respect to the electrolytic solution.
  • the high temperature storage characteristic and high temperature cycling characteristic of the secondary battery manufactured using the electrically conductive material paste can be improved.
  • the content rate of the (meth) acrylic acid ester monomer unit in the binder A is less than 10% by mass, the strength of the electrode mixture layer formed using the conductive material paste is lowered, and the degree of swelling with respect to the electrolytic solution Increases and peel strength decreases. Therefore, there is a possibility that the high-temperature storage characteristics and high-temperature cycle characteristics of a secondary battery provided with such electrodes will deteriorate.
  • the content ratio of the (meth) acrylic acid ester monomer unit in the binder A exceeds 40% by mass, the solubility of the binder A particularly in a solvent such as NMP is lowered.
  • the conductive material paste and In the slurry for secondary battery electrodes the dispersion of the conductive material may be biased, and the dispersion stability thereof may be impaired. Therefore, the electrodes formed using them are inferior in uniformity, the internal resistance of the secondary battery including the electrodes is increased, and the low temperature characteristics, the high temperature storage characteristics, and the high temperature cycle characteristics may be decreased.
  • the binder A may contain other monomer units in addition to the above-described alkylene structural unit and (meth) acrylic acid ester monomer unit.
  • Such other monomer units include nitrile group-containing monomer units, hydrophilic group-containing monomer units, crosslinkable monomer units, aromatic vinyl monomer units, ethylenically unsaturated carboxylic acids. Examples thereof include an amide monomer unit and a fluorine-containing monomer unit.
  • the binder A contains a nitrile group containing monomer unit.
  • the binder A does not substantially contain a hydrophilic group-containing monomer unit.
  • Examples of the nitrile group-containing monomer that can form a nitrile group-containing monomer unit include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
  • the nitrile group-containing monomer is preferably acrylonitrile and methacrylonitrile, and more preferably acrylonitrile. These can be used alone or in combination of two or more.
  • the content ratio of the nitrile group-containing monomer unit in the binder A is preferably 2% by mass or more and more preferably 10% by mass or more when the total repeating unit in the binder A is 100% by mass. 12 mass% or more is particularly preferable, 50 mass% or less is preferable, 40 mass% or less is more preferable, 35 mass% or less is even more preferable, 30 mass% or less is particularly preferable, and 25 mass% or less is most preferable.
  • the stability of the electrode with respect to the electrolytic solution is improved, and the low-temperature characteristics, high-temperature storage characteristics, and high-temperature cycle characteristics of the secondary battery can be improved.
  • the nitrile group-containing monomer by setting the nitrile group-containing monomer to 35% by mass or less, the content ratio of the alkylene structural unit and / or the (meth) acrylic acid ester monomer unit can be sufficiently ensured. Can be improved.
  • the binder A when the content ratio of the nitrile group-containing monomer unit in the binder A exceeds 40% by mass, the binder A is easily dissolved in the electrolytic solution and cannot be stably adsorbed to the conductive material and dissociates in the solvent. As a result, the dispersion stability decreases. As a result, the high-temperature storage characteristics and high-temperature cycle characteristics of the secondary battery may be degraded. Moreover, the adsorption capacity of the binder A with respect to the conductive material is lowered, and it becomes difficult to adjust the binder adsorption amount of the conductive material.
  • the ratio of the nitrile group-containing monomer unit in the binder A is less than 2% by mass, the solubility of the binder A in a solvent such as NMP is particularly reduced, and the conductive material paste and the secondary battery electrode are used. There is a possibility that the dispersibility of the conductive material in the slurry may be lowered. Therefore, the internal resistance of the secondary battery including the electrode manufactured using them is increased, and the low temperature characteristics, the high temperature storage characteristics, and the high temperature cycle characteristics may be deteriorated.
  • hydrophilic group-containing monomer examples include a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphate group, and a hydroxyl group A monomer having can be used.
  • Examples of the monomer having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids and acid anhydrides, and derivatives thereof.
  • Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, ⁇ -diaminoacrylic acid, and the like.
  • Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, methylallyl maleate, diphenyl maleate, nonyl maleate, decyl maleate, dodecyl maleate And maleate esters such as octadecyl maleate and fluoroalkyl maleate.
  • the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • generates a carboxyl group by hydrolysis can also be used.
  • monoesters and diesters of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acids such as monobutyl itaconate and dibutyl itaconate.
  • Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid. In the present specification, “(meth) allyl” means allyl and / or methallyl.
  • Examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl phosphate- (meth) acryloyloxyethyl, and the like.
  • (meth) acryloyl means acryloyl and / or methacryloyl.
  • Examples of the monomer having a hydroxyl group include those described in International Publication No. 2013/088099.
  • (meth) acrylic acid ester monomer and nitrile group-containing monomer which can constitute binder A, crosslinkable monomer, aromatic vinyl monomer, and ethylenic unsaturation described later
  • the carboxylic acid amide monomer and the fluorine-containing monomer do not contain a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a hydroxyl group.
  • a hydrophilic group-containing monomer such as a monomer having a carboxylic acid group can contribute to an improvement in the production stability of the binder A, while a hydrophilic group-containing monomer unit is included in the binder A.
  • the dispersibility of the conductive material included in the binder A may be impaired. Therefore, from the viewpoint of ensuring the dispersion stability of the conductive material paste, the content ratio of the hydrophilic group-containing monomer unit in the binder A is 0 when the total repeating unit in the binder A is 100% by mass. Less than 0.05 mass% (substantially free) is preferable, and 0 mass% is more preferable.
  • the crosslinkable monomer that can form a crosslinkable monomer unit includes an epoxy group-containing monomer, a carbon-carbon double bond and an epoxy group-containing monomer, a halogen atom and an epoxy group.
  • aromatic vinyl monomer units examples include styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, and chlorostyrene.
  • Examples of the ethylenically unsaturated carboxylic acid amide monomer that can form an ethylenically unsaturated carboxylic acid amide monomer unit include acrylamide, methacrylamide, N, N-dimethylacrylamide, and the like.
  • fluorine-containing monomer unit As the fluorine-containing monomer that can form a fluorine-containing monomer unit, the same monomer as the fluorine-containing monomer that can form a fluorine-based polymer described later can be used. In addition, when the binder A contains a fluorine-containing unit, the ratio of the fluorine-containing unit is less than 70% when the total repeating unit of the binder A is 100% by weight.
  • the method for producing the binder A is not particularly limited.
  • a polymer is obtained by polymerizing a monomer composition containing the above-mentioned monomers, and optionally prepared by hydrogenating the obtained polymer. can do.
  • the content ratio of each monomer in the monomer composition in the present specification can be determined according to the content ratio of each monomer unit and structural unit (repeating unit) in the binder A.
  • the polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
  • the hydrogenation method is not particularly limited, and a general method using a catalyst (for example, see International Publication No. 2012/165120, International Publication No. 2013/088099 and Japanese Patent Application Laid-Open No. 2013-8485) may be used. it can.
  • the iodine value of the hydrogenated polymer is preferably 60 mg / 100 mg or less, more preferably 30 mg / 100 mg or less, and particularly preferably 20 mg / 100 mg or less. Further, the lower limit is preferably 3 mg / 100 mg or more, and more preferably 8 mg / 100 mg or more.
  • the iodine value is obtained by measuring the iodine value of a dried polymer obtained by coagulating 100 g of an aqueous dispersion of a polymer with 1 liter of methanol and then vacuum drying at 60 ° C. for 12 hours according to JIS K6235 (2006). Can be obtained.
  • the binder A is used in the state of a dispersion liquid or a dissolved solution dispersed in a dispersion medium.
  • the dispersion medium of the binder A is not particularly limited as long as the binder A can be uniformly dispersed or dissolved, and water or an organic solvent can be used, and an organic solvent is preferably used.
  • an organic solvent it does not specifically limit, The organic solvent used as a solvent of the electrically conductive material paste mentioned later can be used.
  • the blending amount of the binder A in the conductive material paste is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, per 100 parts by mass of the conductive material. It is. When the blending amount of the binder A in the conductive material paste is within the above range, the dispersion stability of the conductive material paste becomes good.
  • the conductive material paste of the present invention may contain another binder different from the binder A (hereinafter referred to as the binder B).
  • the binder B for example, is held in a positive electrode produced by forming a positive electrode mixture layer on a current collector so that components contained in the positive electrode mixture layer are not detached from the positive electrode mixture layer.
  • the binder B it is preferable to use a fluoropolymer. This is because, as will be described later, by using a fluorine-based polymer, the temporal stability of the secondary battery positive electrode slurry can be further improved.
  • the fluorine polymer is a polymer containing a fluorine-containing monomer unit.
  • a fluorine-based polymer a homopolymer or copolymer of one or more kinds of fluorine-containing monomers, one or more kinds of fluorine-containing monomers and a monomer not containing fluorine (hereinafter referred to as “fluorine-containing monomers”) And a copolymer with “fluorine-free monomer”).
  • the ratio of the fluorine-containing monomer unit in a fluorine-type polymer is 70 mass% or more normally, Preferably it is 80 mass% or more.
  • the ratio of the fluorine-free monomer unit in the fluoropolymer is usually 30% by mass or less, preferably 20% by mass or less.
  • examples of the fluorine-containing monomer that can form a fluorine-containing monomer unit include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, vinyl fluoride, and perfluoroalkyl vinyl ether. It is done. Among these, as the fluorine-containing monomer, vinylidene fluoride is preferable.
  • fluorine-free monomer that can form a fluorine-free monomer unit
  • fluorine-free monomer examples include a fluorine-free monomer copolymerizable with the fluorine-containing monomer, such as ethylene, propylene, and 1-butene.
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene; unsaturated nitrile compounds such as (meth) acrylonitrile; methyl (meth) acrylate, ( (Meth) acrylic acid ester compounds such as (meth) butyl acrylate and (meth) acrylic acid 2-ethylhexyl; (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide Acrylamide compounds; (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid Vinyl compounds containing carboxyl groups such as maleic acid; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; amino such as dimethylaminoethy
  • the fluorine-based polymer is preferably a polymer using vinylidene fluoride as the fluorine-containing monomer and a polymer using vinyl fluoride as the fluorine-containing monomer, and vinylidene fluoride as the fluorine-containing monomer.
  • a polymer using is more preferable.
  • the fluoropolymer a homopolymer of vinylidene fluoride (polyvinylidene fluoride), a copolymer of vinylidene fluoride and hexafluoropropylene, and polyvinyl fluoride are preferable, and polyvinylidene fluoride is more preferable.
  • the fluoropolymer mentioned above may be used individually by 1 type, and may use 2 or more types together.
  • the weight average molecular weight in terms of polystyrene by gel permeation chromatography of the fluoropolymer is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000, and particularly Preferably, it is 400,000 to 1,000,000.
  • the glass transition temperature (Tg) of the fluoropolymer is preferably 0 ° C. or lower, more preferably ⁇ 20 ° C. or lower, and particularly preferably ⁇ 30 ° C. or lower.
  • the lower limit of the Tg of the fluoropolymer is not particularly limited, but is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 40 ° C. or higher.
  • Tg of a fluorine-type polymer can be adjusted by changing the kind of monomer used for superposition
  • the melting point (Tm) of the fluoropolymer is preferably 190 ° C. or lower, more preferably 150 to 180 ° C., and further preferably 160 to 170 ° C.
  • Tm of a fluoropolymer can be adjusted by changing the kind of monomer used for superposition
  • Tm can be measured based on JIS K7121; 1987 using a differential scanning calorimeter.
  • the method for producing the above-described fluoropolymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
  • a solution polymerization method emulsion polymerization method
  • addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization and the like can be used.
  • a polymerization initiator a known polymerization initiator can be used as a known polymerization initiator.
  • the fluoropolymer is used in a state of a dispersion liquid or a dissolved solution dispersed in a dispersion medium.
  • the dispersion medium of the fluorine-based polymer is not particularly limited as long as the fluorine-based polymer can be uniformly dispersed or dissolved, and water or an organic solvent can be used, and an organic solvent is preferably used.
  • an organic solvent it does not specifically limit, The organic solvent used as a solvent of the electrically conductive material paste mentioned later can be used.
  • the blending amount of the binder B such as a fluoropolymer is preferably 10% by mass or less based on the blending amount of the binder A so that the binder A is suitably attached to the conductive material and the dispersion stability of the conductive material paste is improved. , More preferably 5% by mass or less, particularly preferably 0% by mass. That is, the conductive material paste preferably does not contain a binder B other than the binder A, such as a fluoropolymer, from the viewpoint of ensuring the dispersion stability of the conductive material paste.
  • the fluorine-based polymer has an advantage while there is a possibility that the dispersion stability of the conductive material paste may be lowered as described above.
  • the fluorine-based polymer can suppress the precipitation of the positive electrode active material having a relatively heavy specific gravity in the slurry for the positive electrode of the secondary battery, in the slurry for the positive electrode. Stability over time can be improved.
  • the conductive material paste may contain a fluorine-based polymer.
  • the blending amount of the fluoropolymer in the conductive material paste is preferably 50% by weight or more, based on 100% by weight of the total solid content of the binder (binder resin) in the conductive material paste, and 80% by weight. % Or more is more preferable.
  • the blending amount of the fluoropolymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more per 100 parts by mass of the positive electrode active material. It is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less. If the blending amount of the fluoropolymer is within such a range, it is possible to suppress the precipitation of the positive active material having a relatively high specific gravity in the secondary battery positive electrode slurry, and the secondary battery positive electrode slurry is stable over time. This is because the performance can be improved.
  • the blending amount of the binder A in the conductive material paste is the solid content of all the binders (binder resin) in the conductive material paste.
  • 100 mass% it is preferable that it is 10 mass% or more, It is more preferable that it is 15 mass% or more, It is preferable that it is 70 mass% or less, It is more preferable that it is 50 mass% or less.
  • Which of the conductive material paste and the positive electrode slurry is selected as the addition destination of the fluoropolymer may be appropriately determined according to the mode of implementation.
  • the conductive material paste preferably contains a solvent.
  • blended with an electrically conductive material paste the organic solvent which has the polarity which can melt
  • the organic solvent acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methylformamide, methyl ethyl ketone, furfural, ethylenediamine, or the like may be used. it can.
  • N-methylpyrrolidone (NMP) is most preferable as the organic solvent from the viewpoints of ease of handling, safety, and ease of synthesis.
  • these organic solvents may be used independently and may mix and use 2 or more types.
  • components such as a viscosity modifier, a reinforcing material, an antioxidant, and an electrolytic solution additive having a function of suppressing the decomposition of the electrolytic solution may be mixed in the conductive material paste.
  • a viscosity modifier for example, a viscosity modifier, a reinforcing material, an antioxidant, and an electrolytic solution additive having a function of suppressing the decomposition of the electrolytic solution may be mixed in the conductive material paste.
  • the binder adsorption amount of the conductive material needs to be 100 mg / g or more and 600 mg / g or less, preferably 150 mg / g or more, more preferably 170 mg / g or more, It is still more preferably 200 mg / g or more, particularly preferably 250 mg / g or more, preferably 400 mg / g or less, and more preferably 390 mg / g or less.
  • the binder adsorption amount of the conductive material is less than 100 mg / g, the conductive material aggregates and the dispersion stability of the conductive material paste cannot be ensured, and the interior of the secondary battery including the electrode obtained using the conductive material paste Resistance increases, and low temperature characteristics, high temperature storage characteristics, and high temperature cycle characteristics decrease.
  • the binder adsorption amount of the conductive material is more than 600 mg / g, the conductive material becomes excessively adsorbed with the binder as an insulator, and the inside of the secondary battery including the electrode obtained using the conductive material paste Resistance increases, and low temperature characteristics, high temperature storage characteristics, and high temperature cycle characteristics decrease.
  • the binder adsorption amount of the conductive material can be calculated by the following method. First, if necessary, a solvent is further added to the conductive material paste to adjust the solid content concentration (for example, 1% by mass) that can be easily centrifuged. In addition, since the binder once adsorbed to the conductive material is difficult to desorb from the conductive material, the influence on the measured value of the binder adsorption amount due to the adjustment of the solid content concentration can be ignored. Next, the conductive material paste or the diluted solution thereof is subjected to a centrifugal separation process until the supernatant and the precipitate are separated using a centrifuge, and the precipitate is collected.
  • the solid content concentration for example, 1% by mass
  • the precipitate is dried under conditions where the solvent is vaporized but the binder is not thermally decomposed until there is no change in weight, and the solvent remaining in the precipitate is removed to obtain a dried product (mainly composed of a binder and a conductive material). obtain.
  • the drying may be performed under reduced pressure.
  • the obtained dried product is gradually heated to a temperature at which the binder is sufficiently decomposed and vaporized using a thermobalance (for example, heated to 500 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere) in the dried product. Remove the binder.
  • the binder adsorption amount of the conductive material measured as described above is a value correlated with the amount of the total binder adsorbed per 1 g of the conductive material.
  • the binder adsorption amount of the conductive material is the composition of the binder A, the composition of the binder B other than the binder A, the specific surface area of the conductive material, the blending amount of the binder with respect to the conductive material, the viscosity of the conductive material paste, the solid content concentration, and It can be controlled by the preparation method. Specifically, for example, by increasing the ratio of the nitrile group-containing monomer in the binder A, the binder adsorption amount of the conductive material can be reduced.
  • the binder adsorption amount of the conductive material can be reduced by using a polymer having a low adsorption capacity for the conductive material, for example, the binder B made of polyvinylidene fluoride. Furthermore, the binder adsorption amount of the conductive material can be increased by increasing the specific surface area of the conductive material and the blending amount of the binder with respect to the conductive material.
  • the conductive material paste preferably has a viscosity of 1000 mPa ⁇ s or more, more preferably 3000 mPa ⁇ s or more, particularly preferably 4000 mPa ⁇ s or more, and preferably 10,000 mPa ⁇ s or less, and 8000 mPa ⁇ s. It is more preferably s or less, and particularly preferably 6000 mPa ⁇ s or less. When the viscosity of the conductive material paste is within the above range, the dispersion stability of the conductive material paste is good.
  • the viscosity of the conductive material paste can be adjusted by the amount of the solvent added during mixing, the solid content concentration of the conductive material paste, the type and molecular weight of the binder, and the like.
  • the upper limit of the viscosity of the conductive material paste exceeds 10,000 mPa ⁇ s, it can be dispersed only by using only a part of the mixing device, the dispersibility of the conductive material is inferior, and further, the conductive material paste is used. There is a possibility that the electric resistance of the formed electrode mixture layer is increased.
  • the lower limit value of the conductive material paste is less than 1000 mPa ⁇ s, the dispersion stability of the conductive material paste may be impaired.
  • the conductive material paste preferably has a solid content concentration of 5% by mass or more, more preferably 8% by mass or more, preferably 15% by mass or less, and more preferably 12% by mass or less.
  • the solid content concentration of the conductive material paste is preferably within the above range from the start of mixing to the end of mixing when preparing the conductive material paste.
  • the dispersion stability of the conductive material paste may be impaired, and the electric resistance of the obtained electrode may be increased.
  • the solid content concentration of the conductive material paste is less than 5% by mass, the conductive material is precipitated in the conductive material paste, and the dispersion stability of the conductive material paste may be impaired.
  • the concentration of the positive electrode slurry becomes too low, and sedimentation may occur.
  • ⁇ Method for preparing conductive paste> There are no particular restrictions on the mixing method for obtaining the conductive material paste by mixing the above-mentioned conductive material and binder A and, if necessary, binder B, solvent and other components. For example, disper, mill, kneader, etc.
  • the following general mixing apparatus can be used. For example, when using a disper, it is preferable to stir at 2000 rpm or more and 5000 rpm or less, preferably 5 minutes or more, more preferably 10 minutes or more, and preferably 60 minutes or less.
  • the conductive material paste may be prepared by employing the steps (X-1) and (X-2) described later in the section “Method for producing slurry for secondary battery positive electrode”.
  • the slurry for the secondary battery positive electrode includes the above-described conductive material paste for the secondary battery electrode and the positive electrode active material, and more specifically includes at least the conductive material, the binder A, and the positive electrode active material.
  • the secondary battery positive electrode slurry containing the conductive material paste described above is excellent in stability over time, and a positive electrode excellent in potential stability can be produced by using the positive electrode slurry.
  • the positive electrode formed from the positive electrode slurry can reduce the internal resistance of the secondary battery, and can improve the low temperature characteristics, high temperature cycle characteristics, and high temperature storage characteristics. The characteristics can be exhibited.
  • blended with the slurry for secondary battery positive electrodes it is not specifically limited, A known positive electrode active material can be used.
  • a positive electrode active material used for a lithium ion secondary battery is not particularly limited, and lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2).
  • Lithium-containing composite oxide of Co—Ni—Mn Lithium-containing composite oxide of Co—Ni—Mn, lithium-containing composite oxide of Ni—Mn—Al, lithium-containing composite oxide of Ni—Co—Al, olivine type lithium iron phosphate (LiFePO 4 ), olivine Type lithium manganese phosphate (LiMnPO 4 ), Li 1 + x Mn 2 ⁇ x O 4 (0 ⁇ X ⁇ 2), an excess lithium spinel compound, Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 , LiNi 0.5 Mn 1.5 O 4 and the like.
  • lithium-containing cobalt oxide LiCoO 2
  • lithium-containing nickel oxide LiNiO 2
  • Co—Ni—Mn lithium-containing cobalt oxide
  • the compounding quantity and particle size of a positive electrode active material are not specifically limited, It can be made to be the same as that of the positive electrode active material used conventionally.
  • the blending ratio of the positive electrode active material and the conductive material is not particularly limited, but the blending amount of the conductive material is preferably 1 part by mass or more per 100 parts by mass of the positive electrode active material, and is 2 parts by mass or more. Is more preferably 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • the amount of the conductive material is too small, sufficient electrical contact between the positive electrode active materials cannot be ensured, the internal resistance of the secondary battery increases, and the low temperature characteristics cannot be sufficiently improved. There is.
  • the slurry for secondary battery positive electrode may contain the components mentioned in the section of “conductive material paste for secondary battery electrode” in addition to the conductive material, binder A, and positive electrode active material.
  • a positive electrode is produced using the positive electrode slurry, a good conductive network can be formed between the conductive materials, and capacity deterioration due to internal resistance can be suppressed. As a result, the electrical characteristics of the secondary battery produced using the secondary battery positive electrode slurry can be improved.
  • step (X) a conductive material paste is prepared.
  • a method for preparing the conductive material paste the method described above in “Preparation Method of Conductive Material Paste” can be used.
  • (X) is a first step (X-1) in which a conductive material and a first binder component containing binder A as a main component are mixed to obtain a premixed paste; It is preferable to include a second step (X-2) of adding a second binder component containing a polymer as a main component to obtain the conductive material paste for a secondary battery electrode.
  • the material is properly dispersed. Therefore, if a positive electrode is manufactured using the slurry for a secondary battery positive electrode, a better conductive network can be formed between the conductive materials, and in particular, capacity deterioration at a low temperature can be suppressed. And the electrical characteristic of the secondary battery manufactured using the slurry for secondary battery positive electrodes can further be improved.
  • First step (X-1) In the first step (X-1) of the step (X), the conductive material and the first binder component containing the binder A as a main component are mixed in a solvent as necessary, and a premixed paste Get. In addition, as long as the 1st binder component contains the binder A as a main component, binders (binder resin) other than the binder A may be included.
  • the ratio of the binder A in the first binder component blended in the first step (X-1) is the solid content of the binder (binder resin) constituting the first binder component contained in the premixed paste.
  • the amount is 100% by mass, it is necessary to be 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more.
  • the ratio of binder A in the first binder component is 100% by mass.
  • the secondary battery manufactured using this pre-mixing paste and conductive material paste is excellent in electrical characteristics (low temperature characteristics, cycle characteristics, etc.).
  • binders other than the binder A which can be used as a binder which comprises a 1st binder component A well-known binder, the fluorine-type polymer mentioned above, etc. are mentioned.
  • the blending amount of the binder A in the premixed paste is preferably 5% by mass or more, and more preferably 15% by mass or more. 100 wt% or less, and more preferably 50 wt% or less, the binder A content within the above range, the binder A is sufficiently adsorbed to the conductive material, the premixed paste Dispersion stability is improved. And the secondary battery manufactured using this pre-mixed paste is excellent in electrical characteristics (low temperature characteristics, high temperature cycle characteristics, etc.).
  • the first binder component and the second binder component are added in the first step (X-1) and the second step (X-2), respectively.
  • the total amount of the first binder component and the second binder component is 1 part by mass or more and 5 parts by mass when the amount of the positive electrode active material added in the step (Y) described later is 100 parts by mass. Part or less, preferably 2 parts by mass or more and 4 parts by mass or less. This is because if the amount of the binder is too small, the strength of the positive electrode is impaired, and if it is too large, the resistance of the positive electrode becomes too high.
  • the compounding ratio of the 1st binder component with respect to the total compounding quantity of a 1st binder component and a 2nd binder component is 10 mass parts or more by making the total compounding quantity of these binder components into 100 mass parts. 90 parts by mass or less is preferable.
  • solvent that can be used in the first step (X-1) for example, an organic solvent having a polarity capable of dissolving the binder A described above in the section of “conductive material paste for secondary battery electrode” can be used.
  • a component such as a viscosity modifier, a reinforcing material, an antioxidant, an electrolytic solution additive having a function of suppressing decomposition of the electrolytic solution, and the like. You may mix.
  • known ones can be used.
  • the conductive material and the first binder component described above, and optionally the solvent and other components are mixed in the first step (X-1) to obtain a premixed paste.
  • a general mixing device such as a disper, a mill, or a kneader can be used.
  • binder A and binders other than binder A may mix with a electrically conductive material after premixing.
  • the conductive material may be mixed without premixing.
  • the solvent in which the binder A is dispersed may be used as it is, or a solvent may be added separately.
  • the viscosity of the premixed paste obtained in the first step (X-1) is a viscosity that can be mixed by the general mixing method as described above, and the viscosity range of the conductive material paste is within the above range.
  • the viscosity is not particularly limited as long as the viscosity can be set as follows.
  • a conductive material paste is prepared by adding a second binder component containing a fluoropolymer as a main component to the premixed paste prepared in the first step.
  • the second binder component may contain a binder (binder resin) other than the fluoropolymer as long as it contains the fluoropolymer as a main component.
  • the proportion of the fluoropolymer in the second binder component to be blended in the second step is 50% by mass or more, where the solid content of the binder (binder resin) constituting the second binder is 100% by mass. It is necessary to be 80% by mass or more. Most preferably, the ratio of the fluoropolymer in the second binder component is 100% by mass.
  • the blending amount of the fluoropolymer in the second binder component is within the above range, and the first binder component is adsorbed on the conductive material by adding the fluoropolymer in such a ratio in the second step. It is possible to improve the stability of the conductive material paste without hindering the operation.
  • the binder other than the fluoropolymer that can be used as the binder constituting the second binder component is not particularly limited, and examples thereof include a known binder and the above-described binder A.
  • the blending ratio of the second binder component to the total blending amount of the first binder component and the second binder component is the total blending amount of the binder (binder resin) from the viewpoint of the stability of the positive electrode slurry.
  • binder binder resin
  • 100 mass parts 50 mass parts or more and 90 mass parts or less are preferable.
  • a solvent may be added.
  • Usable solvents include the same solvents as those described above with respect to the first step (X-1).
  • a solvent may be, for example, an organic solvent having a polarity capable of dissolving the above-described second binder component.
  • the conductive material paste is added with, for example, a viscosity modifier, a reinforcing material, an antioxidant, and an electrolytic solution having a function of suppressing decomposition of the electrolytic solution. You may mix components, such as an agent. As these other components, known ones can be used.
  • the second binder component is added to the premixed paste to obtain a conductive material paste, and there is no particular limitation on the mixing method.
  • disper mill, kneader
  • a general mixing apparatus such as can be used.
  • a disper it is preferable to stir at 2000 rpm to 5000 rpm for 20 minutes to 120 minutes.
  • the second step (X-2) by adding and mixing the second binder component to the premixed paste obtained by mixing the conductive material and the first binder component in advance, A plurality of types of binders (binder resins) having different properties can be mixed, and the positive electrode active material added in the step (Y) described later can be favorably dispersed in the positive electrode slurry. Thereby, the battery capacity of the secondary battery can be increased.
  • step (Y) the conductive material paste prepared in step (X), the positive electrode active material described above, and, in some cases, a solvent and other components are mixed.
  • the solvent the same solvents as those described above with respect to the first step (X-1) and the second step (X-2) in the step (X) can be used.
  • the slurry for the secondary battery positive electrode includes, for example, a viscosity modifier, a reinforcing material, an antioxidant, and an electrolytic solution additive having a function of suppressing decomposition of the electrolytic solution in addition to the above components.
  • the components may be mixed. As these other components, known ones can be used.
  • the mixing method is not particularly limited, and for example, a general mixing device such as a disper, mill, kneader or the like is used. be able to. For example, when a disper is used, it is preferable to stir at 2000 rpm to 5000 rpm for 20 minutes to 120 minutes.
  • step (X) by mixing the positive electrode active material not in the step (X) but in the step (Y), in the step (X), a good network between the conductive materials is formed, and in the secondary battery positive electrode slurry. Dispersibility of the positive electrode active material can be improved. Note that the step (Y) does not affect the network between the conductive materials formed as a result of the step (X). Further, by mixing the positive electrode active material in the step (Y) instead of the step (X), it is possible to prevent the decrease in the binder adsorption amount of the conductive material due to the binder A preferentially adsorbing to the positive electrode active material, The deterioration of the stability with time of the battery positive electrode slurry can be suppressed.
  • the conductive material is coordinated via the binder in the vicinity of the positive electrode active material during the dispersion process.
  • electrical characteristics such as low temperature characteristics of the obtained secondary battery are improved.
  • the viscosity of the secondary battery positive electrode slurry is preferably 1500 mPa ⁇ s or more and 10,000 mPa ⁇ s or less, and the solid content concentration is 50% by mass or more and 90% or less. It is preferable that it is below mass%.
  • the viscosity of the secondary battery positive electrode slurry can be measured by the same method as that of the conductive material paste. The ratio between the amount of conductive material paste (corresponding to solid content) and the amount of positive electrode active material can be adjusted as appropriate.
  • the secondary battery positive electrode manufacturing method of the present invention is obtained by applying the secondary battery positive electrode slurry obtained by the secondary battery positive electrode slurry manufacturing method of the present invention to at least one surface of the current collector and drying. And forming a positive electrode mixture layer. More specifically, the manufacturing method includes a step of applying the slurry for a secondary battery positive electrode to at least one surface of the current collector (application step), and a secondary battery applied to at least one surface of the current collector. A step of drying the positive electrode slurry to form a positive electrode mixture layer on the current collector (drying step).
  • the positive electrode for secondary battery manufactured in this way since the positive electrode mixture layer is formed using the slurry for secondary battery positive electrode described above, if the positive electrode for secondary battery is used, the secondary battery The internal resistance of the battery can be reduced, and the low temperature characteristics, high temperature storage characteristics, and high temperature cycle characteristics can be improved, and excellent electrical characteristics can be exhibited in the secondary battery.
  • a method for applying the slurry for a secondary battery positive electrode on the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the secondary battery positive electrode slurry may be applied to only one side of the current collector, or may be applied to both sides. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the positive electrode mixture layer obtained by drying.
  • an electrically conductive and electrochemically durable material is used as the current collector to which the slurry for the secondary battery positive electrode is applied.
  • a current collector made of aluminum or an aluminum alloy can be used as the current collector.
  • aluminum and an aluminum alloy may be used in combination, or different types of aluminum alloys may be used in combination.
  • Aluminum and aluminum alloys are excellent current collector materials because they have heat resistance and are electrochemically stable.
  • a method for drying the slurry for the secondary battery positive electrode on the current collector is not particularly limited, and a known method can be used. For example, drying with hot air, hot air, low-humidity air, vacuum drying, infrared rays, electron beam, etc. And a drying method by irradiation.
  • a positive electrode mixture layer is formed on the current collector, and a positive electrode for a secondary battery comprising the current collector and the positive electrode mixture layer is provided. Obtainable.
  • the positive electrode mixture layer may be subjected to pressure treatment using a die press or a roll press. By the pressure treatment, the adhesion between the positive electrode mixture layer and the current collector can be improved. Furthermore, when the positive electrode mixture layer contains a curable polymer, the polymer is preferably cured after the positive electrode mixture layer is formed.
  • the secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and the positive electrode for a secondary battery obtained by the method for producing a positive electrode for a secondary battery of the present invention is used as the positive electrode. It is. Since the secondary battery of the present invention uses the positive electrode manufactured by the method for manufacturing the positive electrode for secondary battery of the present invention, the internal resistance is reduced, and the low temperature characteristics, high temperature storage characteristics, and high temperature cycle characteristics are reduced. Excellent and high performance.
  • a lithium ion secondary battery will be described in detail as an example of the secondary battery of the present invention.
  • a known negative electrode used as a negative electrode for a secondary battery can be used.
  • the negative electrode for example, a negative electrode made of a thin plate of metallic lithium or a negative electrode formed by forming a negative electrode mixture layer on a current collector can be used.
  • a collector what consists of metal materials, such as iron, copper, aluminum, nickel, stainless steel, titanium, a tantalum, gold
  • the negative electrode mixture layer a layer containing a negative electrode active material and a binder can be used.
  • the binder is not particularly limited, and any known material can be used.
  • an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used as the supporting electrolyte.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable because it is easily dissolved in a solvent and exhibits a high degree of dissociation.
  • electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
  • carbonates because they have a high dielectric constant and a wide stable potential region, and it is more preferable to use a mixture of ethylene carbonate and ethyl methyl carbonate.
  • concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate. For example, it is preferably 0.5 to 15% by mass, more preferably 2 to 13% by mass, and 5 to 10% by mass. Is more preferable.
  • known additives such as fluoroethylene carbonate and ethyl methyl sulfone may be added to the electrolytic solution.
  • the separator is not particularly limited, and for example, those described in JP 2012-204303 A can be used. Among these, since the film thickness of the entire separator can be reduced, and the ratio of the electrode active material in the secondary battery can be increased, and the capacity per volume can be increased.
  • a microporous film made of a resin such as polyethylene, polypropylene, polybutene, or polyvinyl chloride is preferable.
  • the secondary battery of the present invention includes, for example, a positive electrode and a negative electrode that are overlapped with a separator, wound in accordance with the battery shape as necessary, folded into a battery container, and electrolyzed in the battery container. It can be manufactured by injecting and sealing the liquid. In order to prevent an increase in pressure inside the secondary battery, overcharge / discharge, and the like, a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, and the like may be provided as necessary.
  • the shape of the secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape.
  • This diluted solution was centrifuged for 10 minutes at a rotational speed of 1000 rpm using a centrifuge.
  • the obtained precipitate was dried in a vacuum dryer at 150 ° C. for 3 hours to obtain a dried product. At this time, it was confirmed that there was no weight change due to drying.
  • This dried product was heated to 500 ° C. in a nitrogen atmosphere at a heating rate of 10 ° C./min using a thermobalance, and the weight W1 (g) before the heat treatment (dry product) by the thermobalance was measured.
  • volume average particle diameter D50 (that is, the closer to the average particle diameter of the conductive material in the state where the binder is not adsorbed), the smaller the cohesiveness and the better the dispersion stability of the conductive material paste.
  • Volume average particle diameter D50 is from 10 ⁇ m to less than 15 ⁇ m
  • E Volume average Particle diameter D50 is 15 ⁇ m or more ⁇ Dispersion stability of conductive material paste [Evaluation method 2]>
  • the conductive material paste was put to a height of 5 cm in a glass test tube having an inner diameter of 8 mm, and allowed to stand for one week.
  • ⁇ Potential stability of conductive paste The conductive material paste is applied on an aluminum foil (thickness 20 ⁇ m) as a current collector with a comma coater so that the weight per unit area after drying is 10 mg / cm 2 , 20 minutes at 90 ° C., 20 minutes at 120 ° C. After drying, heat treatment was further performed at 60 ° C.
  • This laminate A has a conductive material coating film on the current collector.
  • This laminate A is cut into a circle having a diameter of 12 mm, and a circular polypropylene porous film (diameter 18 mm, thickness 25 ⁇ m), metallic lithium (diameter 14 mm), and expanded are formed on the cut-out laminate A on the conductive material coating film side.
  • Metals were laminated in this order to obtain a laminate B.
  • This laminate B was accommodated in a stainless steel coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm) provided with polypropylene packing.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a 0.2 mm thick stainless steel cap is placed on the outer container via a polypropylene packing, and the battery can is sealed to produce a coin cell having a diameter of 20 mm and a thickness of about 2 mm. did.
  • a voltage of 4.4 V was applied to the obtained coin cell for 10 hours in an atmosphere at 25 ° C.
  • the current density per unit mass (mA / g) of the conductive material flowing after 10 hours was determined and used as the oxidation current density. As the oxidation current density is smaller, the oxidation reaction of the binder when a voltage is applied is suppressed, that is, the potential stability of the electrode using the conductive material paste is excellent.
  • Viscosity change rate (%) ⁇ (BA) / A ⁇ ⁇ 100
  • the IV resistance was measured as follows. After charging to 50% of SOC (State Of Charge: Depth of Charge) at 1C (C is a numerical value expressed by rated capacity (mA) / 1h (hour)) in a 25 ° C atmosphere, focusing on 50% of SOC Charging for 20 seconds and discharging for 20 seconds at 0.5C, 1.0C, 1.5C, and 2.0C, respectively, and the battery voltage after 20 seconds in each case (charging side and discharging side) with respect to the current value The slope was obtained as IV resistance ( ⁇ ) (IV resistance during charging and IV resistance during discharging). The obtained IV resistance value ( ⁇ ) was evaluated according to the following criteria.
  • IV resistance is 2 ⁇ or less
  • B IV resistance is more than 2 ⁇ , 2.3 ⁇ or less
  • C IV resistance is more than 2.3 ⁇ , 2.5 ⁇ or less
  • D IV resistance is more than 2.5 ⁇ , 3.0 ⁇ or less
  • E IV resistance is 3 More than 0 ⁇ ⁇ Low-temperature characteristics of secondary battery>
  • the IV resistance was measured as follows.
  • IV resistance is 10 ⁇ or less
  • E: IV resistance is more than 20 ⁇ ⁇ high temperature cycle characteristics of secondary battery [ Evaluation method 1] >> The secondary battery was charged to 4.2 V by a constant current method of 0.5 C in an atmosphere of 45 ° C., and charging / discharging to discharge to 3.0 V was repeated 200 cycles. Charge / discharge capacity retention represented by the ratio of the electric capacity at the end of 200 cycles to the electric capacity at the end of 5 cycles ( (electric capacity at the end of 200 cycles / electric capacity at the end of 5 cycles) ⁇ 100) (%) The rate was determined.
  • the rate was determined. It shows that it is excellent in high temperature cycling characteristics, so that this value is large.
  • the obtained value (%) was evaluated according to the following criteria.
  • the secondary battery was charged to a cell voltage of 4.2 V by a constant current method of 0.5 C in an atmosphere of 25 ° C., then discharged to 3.0 V, and an initial discharge capacity C 0 was measured. Thereafter, the battery was charged to a cell voltage of 4.2 V by a constant current method of 0.5 C in a 25 ° C.
  • Example 1-1 Preparation of binder A1>
  • 240 parts of ion-exchanged water, 2.5 parts of sodium alkylbenzenesulfonate as an emulsifier, 35 parts of n-butyl acrylate (BA) as a (meth) acrylate monomer, a nitrile group-containing monomer 20 parts of acrylonitrile (AN) are added in this order, and the inside of the bottle is replaced with nitrogen.
  • BD 1,3-butadiene
  • ammonium persulfate as a polymerization initiator and polymerization reaction at a reaction temperature of 40 ° C.
  • the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate was dissolved in 60 ml of ion-exchanged water added with 4-fold mol of nitric acid with respect to Pd as a hydrogenation reaction catalyst. After the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. under pressure with hydrogen gas up to 3 MPa and subjected to hydrogenation reaction (second stage hydrogenation reaction) for 6 hours. .
  • binder aqueous dispersion 320 parts of NMP is added to 100 parts of this binder aqueous dispersion, water is evaporated under reduced pressure, and a polymer containing an alkylene structural unit, a (meth) acrylate monomer unit and a nitrile group-containing monomer unit An NMP solution of binder A1 was obtained.
  • ⁇ Manufacture of conductive material paste > 3.0 parts of acetylene black (Denka black powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm) as a conductive material, and an NMP solution of binder A1 obtained as described above corresponding to solid content Then, 3.0 parts (100 parts per 100 parts of the conductive material) and an appropriate amount of NMP are stirred with a disper (3000 rpm, 10 minutes), and then the solid content concentration of the conductive material paste is 10% by mass. An appropriate amount of NMP was added and stirred with a disper (3000 rpm, 10 minutes) to prepare a conductive material paste.
  • acetylene black Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm
  • the binder adsorption amount of the conductive material was 375 mg / g, and the viscosity was 5500 mPa ⁇ s.
  • Dispersion stability [Evaluation Method 1] and potential stability of the conductive material paste were evaluated using the produced conductive material paste. The results are shown in Table 1.
  • Example 1-2 Binder A2 was produced in the same manner as in Example 1-1 except that 49 parts of BD, 27 parts of BA, and 24 parts of AN were used as the monomer composition during the production of the binder. Then, a conductive material paste having a solid content concentration of 10% was produced in the same manner as in Example 1-1 except that binder A2 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 390 mg / g and a viscosity of 4000 mPa ⁇ s. Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • Binder A3 was produced in the same manner as in Example 1-1 except that 30 parts of BD, 30 parts of BA, and 40 parts of AN were used as the monomer composition during the production of the binder.
  • a conductive material paste having a solid content concentration of 10% was produced in the same manner as in Example 1-1, except that binder A3 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 250 mg / g and a viscosity of 7000 mPa ⁇ s.
  • Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • Example 1-4 At the time of manufacturing the binder, except that 30 parts of BD, 25 parts of BA, 40 parts of AN, and 5 parts of monobutyl maleate (MBM) as a hydrophilic group-containing monomer were used as the monomer composition.
  • Binder A4 was produced in the same manner as Example 1-1. Then, a conductive material paste having a solid content concentration of 10% was produced in the same manner as in Example 1-1 except that binder A4 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 170 mg / g and a viscosity of 6000 mPa ⁇ s. Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • Binder A5 was produced in the same manner as in Example 1-1, except that 56 parts of BD and 44 parts of AN were used as the monomer composition during the production of the binder, and that BA was not used.
  • a conductive material paste having a solid content concentration of 10% was produced in the same manner as in Example 1-1, except that binder A5 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 150 mg / g and a viscosity of 3000 mPa ⁇ s.
  • Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • Example 1-6 In a reactor equipped with a stirrer, 70 parts of ion exchange water, 0.2 part of sodium dodecylbenzenesulfonate and 0.3 part of potassium persulfate were respectively supplied, the gas phase part was replaced with nitrogen gas, and the temperature was changed to 60 ° C. The temperature rose. Meanwhile, in a separate container, 50 parts of ion-exchanged water, 0.5 part of sodium dodecylbenzenesulfonate, 82 parts of BA, 15 parts of AN, 3 parts of methacrylic acid (MAA) (above, monomer composition with BA, AN, MAA) To obtain a mixture. This mixture was continuously added to the reactor over 4 hours for polymerization.
  • MAA methacrylic acid
  • An NMP solution of binder A6 made of a polymer containing was obtained.
  • a conductive material paste having a solid content concentration of 10% was produced in the same manner as in Example 1-1, except that binder A6 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 115 mg / g and a viscosity of 7500 mPa ⁇ s.
  • Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • Binder A7 was produced in the same manner as in Example 1-6, except that 2-ethylhexyl acrylate (2-HEA) was used instead of BA during the production of the binder. Then, a conductive material paste having a solid content concentration of 10% was manufactured in the same manner as in Example 1-1 except that binder A7 was used instead of binder A1.
  • the obtained conductive material paste had a binder adsorption amount of 80 mg / g and a viscosity of 8500 mPa ⁇ s.
  • Dispersion stability [Evaluation Method 1] and potential stability of the obtained conductive material paste were evaluated. The results are shown in Table 1.
  • the binder adsorption amount of the conductive material can be controlled by changing the composition of the binder, which improves the dispersion stability and potential stability of the conductive material paste.
  • a binder containing both an alkylene structural unit and a (meth) acrylate monomer unit is used.
  • the dispersion stability and potential stability of the conductive material paste were further improved as compared with the case where a binder containing only one of them was used.
  • Example 1-4 From the comparison of Example 1-4, by using a binder that does not contain a hydrophilic group-containing monomer unit, compared with the case where a binder that contains a hydrophilic group-containing monomer unit is used, the conductive material paste is dispersed. It can be seen that the stability is further improved.
  • Example 2-1 Provide of secondary battery positive electrode slurry and positive electrode> 100 parts of a ternary active material (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) (average particle size: 10 ⁇ m) having a layered structure as a positive electrode active material in the conductive material paste (including binder A6) of Example 1-6 Then, an appropriate amount of NMP was added as a solvent and stirred with a disper (3000 rpm, 20 minutes) to prepare a positive electrode slurry. The amount of NMP added was adjusted so that the solid content concentration of the positive electrode slurry was 65% by mass.
  • a ternary active material LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • NMP disper
  • An aluminum foil with a thickness of 20 ⁇ m was prepared as a current collector.
  • the positive electrode slurry obtained as described above was applied onto an aluminum foil with a comma coater so that the basis weight after drying was 20 mg / cm 2 , dried at 90 ° C. for 20 minutes, and 120 ° C. for 20 minutes, A positive electrode raw material was obtained by heat treatment at 10 ° C. for 10 hours.
  • This positive electrode original fabric was rolled by a roll press to produce a positive electrode comprising a positive electrode mixture layer having a density of 3.2 g / cm 3 and an aluminum foil.
  • the positive electrode had a thickness of 70 ⁇ m.
  • the slurry for the negative electrode was applied on a copper foil having a thickness of 20 ⁇ m as a current collector by a comma coater so that the film thickness after drying was about 150 ⁇ m and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Then, the negative electrode original fabric was obtained by heat-processing at 120 degreeC for 2 minute (s). This negative electrode original fabric was rolled with a roll press to obtain a negative electrode having a negative electrode mixture layer with a thickness of 80 ⁇ m.
  • An aluminum packaging exterior was prepared as the battery exterior.
  • the positive electrode obtained above was cut into a 4 cm ⁇ 4 cm square and arranged so that the current collector-side surface was in contact with the aluminum packaging exterior.
  • the square separator obtained above was disposed on the surface of the positive electrode mixture layer of the positive electrode.
  • the negative electrode obtained above was cut into a square of 4.2 cm ⁇ 4.2 cm, and this was arranged on the separator so that the surface on the negative electrode mixture layer side faces the separator.
  • vinylene carbonate (VC) containing 1.5% was charged with LiPF 6 solution having a concentration of 1.0 M.
  • the amount of NMP added was adjusted so that the solid content concentration of the positive electrode slurry was 65% by mass.
  • a positive electrode and a secondary battery were produced in the same manner as in Example 2-1, except that this positive electrode slurry was used, and the high-temperature storage characteristics of the secondary battery were evaluated. The results are shown in Table 2.
  • Table 2 shows that the secondary battery of Example 2-1 including the positive electrode formed using the conductive material paste of the present invention is obtained by mixing the conductive material, the binder, and the positive electrode active material all together without passing through the conductive material paste. It can be seen that it has excellent high-temperature storage characteristics as compared with the secondary battery of Comparative Example 2-1, which comprises a positive electrode formed from the prepared positive electrode slurry.
  • Example 3-1 Manufacture of binder A8> Except that the amount of AN used as a nitrile group-containing monomer was changed to 18.6 parts and the amount of BD used as a conjugated diene monomer was changed to 46.4 parts, the same as in Example 1-1, A polymer comprising a conjugated diene monomer unit, a (meth) acrylate monomer unit, and a nitrile group-containing monomer unit was obtained. The polymerization conversion was 85%, and the iodine value was 280 mg / 100 mg. In addition, the measurement procedure of iodine value is as follows.
  • the resulting polymer was subjected to a first stage hydrogenation reaction in the same manner as in Example 1-1. At this time, the iodine value of the polymer was 35 mg / 100 mg.
  • binder aqueous dispersion 320 parts of NMP is added to 100 parts of this binder aqueous dispersion, water is evaporated under reduced pressure, and a polymer containing an alkylene structural unit, a (meth) acrylate monomer unit and a nitrile group-containing monomer unit An NMP solution of binder A8 was obtained.
  • ⁇ Manufacture of conductive material paste > 3.0 parts of acetylene black (Denka black powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm) as a conductive material, and an NMP solution of binder A8 obtained as described above corresponding to solid content Then, 0.6 part and an appropriate amount of NMP are stirred with a disper (3000 rpm, 10 minutes), and then PVdF (KF polymer # 7200, manufactured by Kureha Co., Ltd.) is used as binder B in a solid equivalent amount).
  • acetylene black Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm
  • a positive electrode composed of a positive electrode mixture layer having a density of 3.2 g / cm 3 and an aluminum foil was produced in the same manner as in Example 2-1, except that the positive electrode slurry obtained above was used.
  • the positive electrode had a thickness of 70 ⁇ m.
  • Example 2-1 ⁇ Manufacture of slurry for negative electrode and negative electrode>
  • a negative electrode slurry was prepared, and a negative electrode having a negative electrode mixture layer having a thickness of 80 ⁇ m was obtained.
  • a lithium ion secondary battery was produced in the same manner as in Example 2-1, except that the positive electrode obtained above was used.
  • the obtained lithium ion secondary battery was evaluated for internal resistance and high-temperature cycle characteristics [Evaluation Method 1]. The results are shown in Table 3.
  • Example 3-2 A conductive material paste was manufactured in the same manner as in Example 3-1, except that the blending ratio of the binder A8 and the binder B was changed as shown in Table 3 when the conductive material paste was manufactured.
  • the binder amount of the conductive material of the obtained conductive material paste was 190 mg / g, and the viscosity was 7000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 3-1, and evaluation was performed on each evaluation item. The results are shown in Table 3.
  • Example 3-3 A conductive material paste was manufactured in the same manner as in Example 3-1, except that the blending ratio of the binder A8 and the binder B was changed as shown in Table 3 when the conductive material paste was manufactured.
  • the binder amount of the conductive material of the obtained conductive material paste was 250 mg / g, and the viscosity was 3000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 3-1, and evaluation was performed on each evaluation item. The results are shown in Table 3.
  • Example 3-4 A conductive material paste was manufactured in the same manner as in Example 3-1, except that the solid content concentration was 13% and the blending ratio of binder A8 and binder B was changed as shown in Table 3 when the conductive material paste was manufactured.
  • the binder amount of the conductive material of the obtained conductive material paste was 270 mg / g, and the viscosity was 7500 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 3-1, and evaluation was performed on each evaluation item. The results are shown in Table 3.
  • Example 3-5 At the time of production of the conductive material paste, first, acetylene black (DENKA BLACK powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm) 3.0 parts as a conductive material, and PVdF (KF polymer) as a binder B # 7200 (manufactured by Kureha Co., Ltd.) was 2.4 parts by solid equivalent, and an appropriate amount of NMP solution was stirred with a disper (3000 rpm, 10 minutes).
  • acetylene black DENKA BLACK powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm
  • PVdF KF polymer
  • an NMP solution of binder A8 is added in an amount of NMP corresponding to the solid content (solid content concentration 8.0% by mass) and the solid content concentration is 7% by mass, and stirred with a disper. (3000 rpm, 10 minutes) to prepare a conductive material paste.
  • the binder amount of the conductive material of the obtained conductive material paste was 170 mg / g, and the viscosity was 2000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were prepared in the same manner as in Example 3-1, except that the conductive material paste thus obtained was used, and each evaluation item was evaluated. The results are shown in Table 3.
  • binder A9 produced as follows was used. In the production of binder A9, n-butyl acrylate (BA) as a (meth) acrylic acid ester monomer is not blended, 37 parts of acrylonitrile (AN) as a nitrile group-containing monomer, and as a conjugated diene monomer A binder A9 was obtained in the same manner as in Example 3-1, except that 63 parts of 1,3-butadiene (BD) was used. The density
  • BA n-butyl acrylate
  • AN acrylonitrile
  • BD 1,3-butadiene
  • a conductive material paste was prepared in the same manner as in Example 3-1, except that the solid content concentration was 13% by mass during the production of the conductive material paste and the obtained binder A9 was used.
  • the amount of binder adsorbed on the conductive material of the obtained conductive material paste was 130 mg / g, and the viscosity was 5000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were prepared in the same manner as in Example 3-1, except that the conductive material paste obtained as described above was used, and each evaluation item was evaluated. The results are shown in Table 3.
  • a conductive material paste was prepared in the same manner as in Example 3-1, except that the binder A10 obtained as described above was used.
  • the conductive material of the obtained conductive material paste had a binder adsorption amount of 105 mg / g and a viscosity of 9300 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were prepared in the same manner as in Example 3-1, except that the conductive material paste obtained as described above was used, and each evaluation item was evaluated. The results are shown in Table 3.
  • the polymerization conversion rate determined from the solid content concentration was approximately 99%. 320 parts of NMP was added to 100 parts of this latex, and water was evaporated under reduced pressure to obtain a binder A11. The density
  • a conductive material paste was prepared in the same manner as in Example 3-1, except that the binder A11 obtained as described above was used.
  • the binder amount of the conductive material of the obtained conductive material paste was 103 mg / g, and the viscosity was 9150 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were prepared in the same manner as in Example 3-1, except that the conductive material paste obtained as described above was used, and each evaluation item was evaluated. The results are shown in Table 3.
  • Example 3-9 Example 3 except that the amount of the binder A8 was changed to 0.8 part, the binder B, PVdF, 3.2 parts, and the conductive material, acetylene black, 2.0 parts at the time of producing the conductive material paste.
  • a conductive material paste, a positive electrode slurry, a positive electrode, and a secondary battery were prepared, and evaluation was performed on each evaluation item.
  • the binder amount of the conductive material of the obtained conductive material paste was 240 mg / g, and the viscosity was 5000 mPa ⁇ s.
  • Example 3-1 A conductive material paste was produced in the same manner as in Example 3-1, except that the binder A9 produced in the same manner as in Example 3-6 was used and the solid content concentration was changed to 3% during the production of the conductive material paste.
  • the binder adsorption amount of the conductive material of the obtained conductive material paste was 50 mg / g, and the viscosity was lower than the detection lower limit of the apparatus. Evaluation was made for each evaluation item in the same manner as in Example 3-1, except that the conductive material paste thus obtained was used. The conductive material paste settled in 3 days, and the internal resistance of the secondary battery was reduced. Further, the high-temperature cycle characteristics [Evaluation Method 1] could not be evaluated. The results are shown in Table 3.
  • Binder A9 produced in the same manner as in Example 3-6, 0.6 part, PVdF (KF Polymer # 7200, manufactured by Kureha Co., Ltd.) as binder B, 2.4 parts corresponding to the solid content, and conductive material Of acetylene black (Denka black powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle size 35 nm) and ternary active material (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) (average particle size: 10 parts) and an appropriate amount of NMP as a solvent were stirred with a planetary mixer (3000 rpm, 40 minutes) to prepare a positive electrode slurry. The solid content concentration of the obtained slurry was the same as in Example 3-1.
  • a positive electrode and a secondary battery were produced in the same manner as in Example 3-1, except that the positive electrode slurry obtained as described above was used, and each evaluation item was evaluated. The results are shown in Table 3.
  • Example 3-3 Conductive material paste was prepared in the same manner as in Example 3-1, except that binder A was not used at the time of production of the conductive material paste, 3 parts by mass of PVdF was used as binder B, and the solid concentration was 7%. Manufactured. The binder amount of the conductive material of the obtained conductive material paste was 37 mg / g, and the viscosity was 8000 mPa ⁇ s. Except for using such a conductive material paste, a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 3-1, and evaluation was performed on each evaluation item. The results are shown in Table 3.
  • the conductive material paste of Examples 3-1 to 3-9, the slurry for secondary battery positive electrode, and the secondary battery are the conductive material paste of Comparative Examples 3-1 to 3-3, slurry for secondary battery positive electrode It can be seen that the internal resistance is low and the high-temperature cycle characteristics are good as compared with the secondary battery.
  • the aging stability of the secondary battery positive electrode slurry is improved, and the interior of the secondary battery is increased. It can be seen that the resistance can be reduced and the high-temperature cycle characteristics can be improved.
  • Example 3 by adjusting the blending ratio of the three types of monomer units blended in the binder A, the dispersion stability of the conductive material paste and the secondary It can be seen that the time stability of the battery positive electrode slurry can be increased, the internal resistance of the secondary battery can be decreased, and the high-temperature cycle characteristics can be improved.
  • Example 3-6 since acrylonitrile was not blended in binder A, the cycle characteristics of the secondary battery positive electrode were relatively low, and the viscosity of the conductive paste was relatively high. It can be seen that the internal resistance of the secondary battery positive electrode is relatively high.
  • Example 3-1 and Comparative Example 3-2 in Table 3 the conductive material, the binder, and the positive electrode active material are mixed together, resulting in insufficient dispersion of the conductive material in the slurry. It can be seen that not only the cycle characteristics but also the time stability of the slurry was deteriorated.
  • Example 4-1 Manufacture of binder A8> In the same manner as in Example 3-1, an NMP solution of binder A8 was obtained.
  • Premix paste production 3.0 parts of acetylene black (Denka black powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle diameter 35 nm) as a conductive material, and NMP solution of the binder A8 as a first binder component corresponding to a solid content 0.6 parts (solid content concentration 8.0% by mass) and an appropriate amount of NMP such that the solid content concentration of the premixed paste becomes 10% by mass is stirred with a disper (3000 rpm, 10 minutes) and premixed. A paste was obtained.
  • acetylene black Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle diameter 35 nm
  • NMP solution of the binder A8 as a first binder component corresponding to a solid content 0.6 parts (solid content concentration 8.0% by mass) and an appropriate amount of NMP such that the solid content concentration of the premixed paste becomes 10% by mass is stirred with a disper
  • the blending ratio of binder A8 to acetylene black, which is a conductive material, in the premixed paste was 20% when the blending amount of the conductive material was 100%. Further, the blending ratio of the binder A8 was 100% when the solid content of the total binder resin of the first binder component contained in the premix paste was 100%.
  • the binder amount of the conductive material of the obtained conductive material paste was 200 mg / g, and the viscosity was 5000 mPa ⁇ s.
  • the dispersion stability [Evaluation Method 1] of the conductive material paste was evaluated using the produced conductive material paste. The results are shown in Table 4.
  • a positive electrode composed of a positive electrode mixture layer having a density of 3.2 g / cm 3 and an aluminum foil was produced in the same manner as in Example 2-1, except that the positive electrode slurry obtained above was used.
  • the positive electrode had a thickness of 70 ⁇ m.
  • Example 2-1 ⁇ Manufacture of slurry for negative electrode and negative electrode>
  • a negative electrode slurry was prepared, and a negative electrode having a negative electrode mixture layer having a thickness of 80 ⁇ m was obtained.
  • a lithium ion secondary battery was produced in the same manner as in Example 2-1, except that the positive electrode obtained above was used.
  • the obtained lithium ion secondary battery was evaluated for high-temperature cycle characteristics [Evaluation Method 2] and low-temperature characteristics. The results are shown in Table 4.
  • Binder A8 blending ratio when binder A8 and fluoropolymer (PVdF) are used as the first binder component at the time of manufacturing the premixed paste, and the solid content of the first binder component is 100% was prepared in the same manner as in Example 4-1, except that the blending ratio of the fluoropolymer was changed to 70% (0.42 parts) and the blending ratio of the fluoropolymer was changed to 30% (0.18 parts).
  • the blending ratio of the binder A8 to the acetylene black as the conductive material in the premixed paste at this time was 14% when the blending amount of the conductive material was 100%.
  • a conductive material paste was prepared in the same manner as in Example 4-1, except for the above.
  • the binder amount of the conductive material of the obtained conductive material paste was 192 mg / g, and the viscosity was 6000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Binder A8 blending ratio when binder A8 and fluoropolymer (PVdF) are used as the first binder component at the time of manufacturing the premixed paste, and the solid content of the first binder component is 100% was mixed in the same manner as in Example 4-1, except that the blending ratio of the fluoropolymer was changed to 50% (0.3 part). Note that the blending ratio of the binder A8 to the acetylene black as the conductive material in the premixed paste at this time was 10% when the blending amount of the conductive material was 100%.
  • the first binder resin A1 is 0.3 parts corresponding to the solid content
  • the second binder resin (PVdF) is equivalent to the solid content 2.
  • a conductive material paste was prepared in the same manner as in Example 4-1, except that 1 part was added.
  • the binder amount of the conductive material of the obtained conductive material paste was 185 mg / g, and the viscosity was 7000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Example 4-4 In preparing a conductive material paste using a pre-mixed paste manufactured in the same manner as in Example 4-1, NMP was added so that the solid content concentration of the conductive material paste was 14% by mass, and a planetary mixer was used. Stirred (60 rpm, 60 minutes). The binder amount of the conductive material of the obtained conductive material paste was 190 mg / g, and the viscosity was 9000 mPa ⁇ s. Then, a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Example 4-5 In preparing a conductive material paste using a premixed paste produced in the same manner as in Example 4-1, NMP was added so that the solid content concentration of the conductive material paste was 7% by mass, and Example 4-1. And stirred under the same conditions.
  • the binder amount of the conductive material of the obtained conductive material paste was 175 mg / g, and the viscosity was 2500 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Example 4-6 At the time of manufacturing the premixed paste, the blending ratio of the binder A8 to the acetylene black as the conductive material in the premixed paste is 5% (0.15 when 3 parts as the blended amount of the conductive material is 100%) Part). Further, an appropriate amount of NMP was added so that the solid content concentration of the premixed paste was 12% by mass. A premixed paste was obtained in the same manner as in Example 4-1. Example 4-1 except that 0.45 part of binder A8 and 2.4 parts of a fluoropolymer (PVdF) were added as a second binder component to the premixed paste obtained. Thus, a conductive material paste was obtained.
  • PVdF fluoropolymer
  • the binder amount of the conductive material of the obtained conductive material paste was 102 mg / g, and the viscosity was 8000 mPa ⁇ s. Then, a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Example 4-7 At the time of manufacturing the premixed paste, the blending ratio of the binder A8 to the acetylene black that is the conductive material in the premixed paste is 50% (1.5% when 3 parts that is the blended amount of the conductive material is 100%). Part). Further, an appropriate amount of NMP was added so that the solid content concentration of the premixed paste was 8% by mass. Others were the same as in Example 1, and a premixed paste was obtained. A conductive material paste was obtained in the same manner as in Example 4-1, except that 1.5 parts of a fluoropolymer (PVdF) was added as a second binder component to the obtained premixed paste.
  • PVdF fluoropolymer
  • the conductive material of the obtained conductive material paste had a binder adsorption amount of 290 mg / g and a viscosity of 3500 mPa ⁇ s. Then, a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • a premixed paste 1 and a conductive material paste were produced in the same manner as in Example 4-1, except that the binder A9 obtained as described above was used.
  • the binder amount of the conductive material of the obtained conductive material paste was 130 mg / g, and the viscosity was 4000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • a premixed paste and 2 were produced in the same manner as in Example 4-1, except that the binder A10 obtained as described above was used.
  • the binder amount of the conductive material of the obtained conductive material paste was 105 mg / g, and the viscosity was 8000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Comparative Example 4-1 A conductive material paste was produced in the same manner as in Comparative Example 3-3.
  • the binder amount of the conductive material of the obtained conductive material paste was 37 mg / g, and the viscosity was 8000 mPa ⁇ s.
  • a positive electrode slurry, a positive electrode, and a secondary battery were produced in the same manner as in Example 4-1, except that such a conductive material paste was used, and each evaluation item was evaluated. The results are shown in Table 4.
  • Comparative Example 4-2 0.6 parts of the above-mentioned binder A9, acetylene black (DENKA BLACK powder: Denki Kagaku Kogyo, specific surface area 68 m 2 / g, average particle diameter 35 nm) as a conductive material, 3.0 parts, and solid content concentration of the premix paste was stirred with a disper (3000 rpm, 10 minutes) to obtain a premixed paste.
  • the binder adsorption amount of the conductive material in this premixed paste was less than 100 mg / g.
  • 100 parts of active material (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) (average particle size: 10 ⁇ m) and an appropriate amount of NMP were stirred to obtain a positive electrode active material paste.
  • active material LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • NMP average particle size: 10 ⁇ m
  • These premixed paste and positive electrode active material paste were mixed to obtain a positive electrode slurry.
  • a positive electrode and a secondary battery were prepared, and each evaluation item was evaluated. The results are shown in Table 4.
  • the conductive material paste of Examples 4-1 to 4-9, the slurry for secondary battery positive electrode, and the secondary battery are the conductive material paste of Comparative Examples 4-1 to 4-2, slurry for secondary battery positive electrode It can be seen that the dispersion stability of the conductive material paste is excellent as compared with the secondary battery, and the high-temperature cycle characteristics and low-temperature characteristics of the secondary battery are good.
  • the conductive material paste was dispersed by adjusting the blending ratio of binder A in the first binder component of the premixed paste and the viscosity of the conductive material paste. It can be seen that the stability and low temperature characteristics of the secondary battery can be improved.
  • Examples 4-1 and 4-4 to 4-5 in Table 4 by adjusting the viscosity and solid content concentration of the conductive material paste, the dispersion stability of the conductive material paste and the low-temperature characteristics of the secondary battery and It can be seen that the high-temperature cycle characteristics can be improved. Further, from Examples 4-1 and 4-6 to 4-7 in Table 4, the binder A having a specific property is blended mainly in the first step (X-1) of the step (X), and the blending thereof. It can be seen that by adjusting the amount, the dispersion stability of the conductive material paste and the low-temperature characteristics and high-temperature cycle characteristics of the secondary battery can be improved.
  • Example 4-1 and 4-8 to 4-9 in Table 4 the dispersion stability of the conductive material paste is improved by adjusting the composition of the binder A, and the high-temperature cycle characteristics of the secondary battery and It can be seen that the low temperature characteristics can be improved. Further, from Example 4-1 in Table 4 and Comparative Example 4-1 using only PVdF as the first binder component, the content of binder A in the first binder component is If it is insufficient, it can be seen that the low temperature characteristics and the high temperature cycle characteristics deteriorate. Further, from Example 4-1 and Comparative Example 4-2 in Table 4, the process (X) (first process (X-1) and second process (X-2)) and process (Y) were performed.
  • the slurry for the positive electrode is manufactured without the conductive material paste being sufficiently dispersible in the conductive material paste, the dispersion stability of the conductive material paste and the low-temperature characteristics and high-temperature cycle characteristics of the secondary battery may be deteriorated. I understand that.
  • the electrically conductive material paste for secondary battery electrodes which can form the electrode which is excellent in dispersion stability and is excellent in electric potential stability can be provided.
  • the manufacturing method of the slurry for secondary battery positive electrodes which can improve an electrical characteristic and can improve the performance of a secondary battery can be provided.
  • the manufacturing method of the positive electrode for secondary batteries which can improve an electrical characteristic and can improve the performance of a secondary battery can be provided.
  • a secondary battery having excellent electrical characteristics can be provided.

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Abstract

L'objet de la présente invention est de pourvoir à une pâte de matériau conducteur destinée à une électrode de batterie rechargeable et permettant d'obtenir une électrode présentant une excellente stabilité de potentiel électrique et une excellente stabilité de dispersion. La pâte de matériau conducteur destinée à une électrode de batterie rechargeable contient un matériau conducteur et un liant (A), le liant (A) contenant un motif structural alkylène et/ou un motif monomère d'ester (méth)acrylate, et la quantité d'adsorption de liant du matériau conducteur étant située dans la plage allant de 100 à 600 mg/g inclus.
PCT/JP2014/006464 2013-12-27 2014-12-25 Pâte de matériau conducteur pour électrode de batterie rechargeable, procédé de production de suspension épaisse pour cathode de batterie rechargeable, procédé de production de cathode de batterie rechargeable, et batterie rechargeable WO2015098116A1 (fr)

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CN201480067820.0A CN105814718B (zh) 2013-12-27 2014-12-25 电极用导电材料糊、正极用浆料的制造方法、正极的制造方法以及二次电池

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JP2014005329A JP6413242B2 (ja) 2014-01-15 2014-01-15 二次電池正極用スラリーの製造方法、二次電池用正極の製造方法、及び二次電池の製造方法
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CN110431697B (zh) * 2017-03-22 2022-07-19 株式会社Lg化学 制备二次电池正极用浆料组合物的方法、用该方法制备的正极和包含该正极的锂二次电池
JP2022041227A (ja) * 2020-08-31 2022-03-11 日本ゼオン株式会社 電気化学素子用導電材分散液、電気化学素子電極用スラリー組成物及びその製造方法、電気化学素子用電極、並びに電気化学素子
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CN115485886B (zh) * 2020-08-31 2024-09-24 日本瑞翁株式会社 电化学元件用分散剂组合物、电化学元件用导电材料分散液、电化学元件电极用浆料组合物及其制造方法、电化学元件用电极以及电化学元件
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US11658303B2 (en) 2020-09-03 2023-05-23 Toyo Ink Sc Holdings Co., Ltd. Conductive material dispersion, binder resin-containing conductive material dispersion, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery

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