WO2013054743A1 - Electrode de batterie rechargeable au lithium-ions et procédé de production de celle-ci - Google Patents

Electrode de batterie rechargeable au lithium-ions et procédé de production de celle-ci Download PDF

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Publication number
WO2013054743A1
WO2013054743A1 PCT/JP2012/075858 JP2012075858W WO2013054743A1 WO 2013054743 A1 WO2013054743 A1 WO 2013054743A1 JP 2012075858 W JP2012075858 W JP 2012075858W WO 2013054743 A1 WO2013054743 A1 WO 2013054743A1
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positive electrode
repeating unit
unit based
active material
lithium
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PCT/JP2012/075858
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English (en)
Japanese (ja)
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角崎　健太郎
丈裕 巨勢
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旭硝子株式会社
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Publication of WO2013054743A1 publication Critical patent/WO2013054743A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode for a lithium ion secondary battery, a method for producing a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • a lithium ion secondary battery has a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode includes a positive electrode active material, a binder, and a conductive material.
  • a composite oxide of lithium and a transition metal hereinafter also referred to as a lithium-containing composite oxide
  • Li-rich positive electrode material As a method for improving the discharge capacity, there is a case where the positive electrode active material is a composite oxide in which the ratio of Li element to the transition metal element such as Ni, Co, and Mn is increased (hereinafter referred to as “Li-rich positive electrode material”). .) Is proposed. As an example of the Li-rich positive electrode material, a solid solution of LiMO 2 (M is at least one transition metal element selected from Ni, Co, and Mn) and Li 2 MnO 3 has been proposed.
  • Patent Document 1 in a lithium ion secondary battery using a Li-rich positive electrode material as a positive electrode active material, 800,000 atomic mass is used as a positive electrode binder so that the positive electrode active material can be filled more highly. It has been proposed to use polyvinylidene fluoride (PVDF) having an average molecular weight greater than the unit. Further, Patent Document 2 comprises a fluorine-containing copolymer having a repeating unit based on ethylene tetrafluoride having a weight average molecular weight of 10,000 to 300,000 and a repeating unit based on propylene in order to improve cycle characteristics. Binders have been proposed.
  • PVDF polyvinylidene fluoride
  • the present invention provides a positive electrode for a lithium ion secondary battery having a high discharge capacity, excellent adhesion between a positive electrode active material and a conductive material and a positive electrode current collector, and excellent cycle characteristics that do not easily deteriorate even after repeated charge / discharge cycles.
  • An object of the present invention is to provide a method for producing a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery including the lithium ion secondary battery positive electrode.
  • the positive electrode for a lithium ion secondary battery of the present invention is a positive electrode for a lithium ion secondary battery in which a positive electrode active material layer containing a positive electrode active material, a binder, and a conductive material is formed on the surface of the positive electrode current collector,
  • the positive electrode active material contains Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is the total molar amount of the transition metal element)
  • the lithium-containing composite oxide is included, and the binder is at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride.
  • a fluorine-containing rubber having a fluorine content of 50 to 76% by mass.
  • the binder preferably contains a fluorinated rubber composed of a copolymer having a repeating unit based on ethylene tetrafluoride and a repeating unit based on propylene.
  • the copolymer having a repeating unit based on tetrafluoroethylene and a repeating unit based on propylene has a ratio of 40 to 70/60 to 30 (mol%) of the repeating unit based on ethylene tetrafluoride / the repeating unit based on propylene. It is preferable to have. It is preferable that the binder includes a fluorinated rubber made of a copolymer having a repeating unit based on ethylene tetrafluoride, a repeating unit based on propylene, and a repeating unit based on vinylidene fluoride.
  • the copolymer having a repeating unit based on ethylene tetrafluoride, a repeating unit based on propylene, and a repeating unit based on vinylidene fluoride is a repeating unit based on ethylene tetrafluoride / a repeating unit based on propylene / vinylidene fluoride. It is preferable to have a ratio of repeating units based on 30 to 70/20 to 60/1 to 40 (mol%).
  • the present invention is a method for producing a positive electrode for a lithium ion secondary battery of the present invention, comprising a mixing step of mixing the positive electrode active material and the binder to obtain a mixture, and a step of heat-treating the mixture.
  • a method for producing a positive electrode for a lithium ion secondary battery comprising a mixing step of mixing the positive electrode active material and the binder to obtain a mixture, and a step of heat-treating the mixture.
  • the positive electrode active material and the binder are preferably mixed in an organic solvent.
  • the present invention provides a lithium ion secondary battery comprising the positive electrode for a lithium ion secondary battery of the present invention, a negative electrode, and a nonaqueous electrolyte.
  • a lithium ion secondary battery having a high discharge capacity, excellent adhesion between a positive electrode active material and a conductive material and a positive electrode current collector, and excellent cycle characteristics that hardly deteriorate even after repeated charge and discharge cycles.
  • a positive electrode for use is obtained.
  • the lithium ion secondary battery of the present invention includes the positive electrode of the lithium ion secondary battery of the present invention, has a high discharge capacity, and excellent cycle characteristics.
  • the present invention is described in detail below.
  • the positive electrode active material in the present invention contains Li element and at least one transition metal element selected from Ni, Co, and Mn (provided that the molar amount of Li element is relative to the total molar amount of the transition metal element).
  • Including lithium-containing composite oxide hereinafter referred to as lithium-containing composite oxide (I)
  • a known positive electrode active material may be included in the lithium ion secondary battery.
  • 50 to 100% by mass of the positive electrode active material is preferably lithium-containing composite oxide (I), more preferably 75 to 100% by mass, and particularly preferably 100% by mass.
  • the shape of the positive electrode active material in the present invention is particulate.
  • the average particle size (D50) of the positive electrode active material is preferably 3 to 25 ⁇ m, more preferably 4 to 20 ⁇ m, and particularly preferably 5 to 15 ⁇ m.
  • the definition of the average particle diameter (D50) is as described later.
  • the composition ratio (molar ratio) of the Li element to the total molar amount of the transition metal element is preferably 1.25 to 1.70, and is 1.35 to 1.60. More preferably, it is particularly preferably 1.40 to 1.55.
  • the discharge capacity per unit mass of the lithium ion secondary battery can be further increased.
  • the lithium-containing composite oxide (I) contains at least one transition metal element selected from Ni, Co, and Mn. More preferably, Mn is included as an essential component, and it is particularly preferable that all elements of Ni, Co, and Mn are included.
  • the lithium-containing composite oxide (I) may contain a metal element other than Ni, Co, Mn, and Li (hereinafter referred to as other metal element). Examples of the other metal elements include at least one selected from Cr, Fe, Al, Ti, Zr, Mo, Nb, V, and Mg.
  • the proportion of the other metal elements is 0.001 to 0.1 mol in total when the total amount of metal elements other than Li in the lithium-containing composite oxide (I) is 1 mol. It is preferably 0.005 to 0.05 mol.
  • the lithium-containing composite oxide (I) is preferably a compound represented by the following formula (1).
  • the compound represented by Formula (1) in this invention is a composition before passing through the process of charging / discharging or activation.
  • activation means removing lithium oxide (Li 2 O) or lithium and lithium oxide from the lithium-containing composite oxide (I).
  • As a normal activation method there is an electrochemical activation method in which a voltage higher than 4.4 V or 4.6 V (expressed as a potential difference from the oxidation-reduction potential of Li + / Li) is applied.
  • the chemical activation method by performing chemical reaction using acids, such as a sulfuric acid, hydrochloric acid, or nitric acid, is mentioned.
  • Me is at least one element selected from Co, Ni, Cr, Fe, Al, Ti, Zr, Mo, Nb, V, and Mg.
  • Me is preferably one or more selected from Co, Ni, and Cr, and more preferably one or more selected from Co and Ni.
  • 0.09 ⁇ x ⁇ 0.3, y> 0, z> 0, 1.9 ⁇ p ⁇ 2.1, 0 ⁇ q ⁇ 0.1, and 0.4 ⁇ y / (y + z) ⁇ 0.8, x + y + z 1, 1.2 ⁇ (1 + x) / (y + z).
  • the ratio of Li exceeds 1.2 times mol with respect to the total of Mn and Me.
  • the formula (1) is also characterized in that it is a compound containing a specific amount of Mn, and the ratio of Mn to the total molar amount of Mn and Me is preferably 0.5 ⁇ y / (y + z) ⁇ 0.8, 0.55 ⁇ y / (y + z) ⁇ 0.75 is more preferable. If Mn is the said range, discharge capacity will become high capacity
  • the composition ratio of Li element with respect to the total molar amount of Mn and Me is preferably 1.25 ⁇ (1 + x) / (y + z) ⁇ 1.70, and 1.35 ⁇ (1 + x) / (y + z) ⁇ 1.60 is more preferable, and 1.40 ⁇ (1 + x) / (y + z) ⁇ 1.55 is particularly preferable.
  • the discharge capacity becomes high.
  • lithium-containing composite oxide (I) Li (Li 0.16 Ni 0.17 Co 0.08 Mn 0.59 ) O 2 , Li (Li 0.17 Ni 0.17 Co 0.17 Mn 0.49 ) O 2 , Li (Li 0.17 Ni 0.21 Co 0.08 Mn 0.54) O 2, Li (Li 0.17 Ni 0.14 Co 0.14 Mn 0.55 ) O 2 , Li (Li 0.18 Ni 0.12 Co 0.12 Mn 0.58 ) O 2 , Li (Li 0.18 Ni 0.16 Co 0.12 Mn 0.54 ) O 2 , Li (Li 0.20 Ni 0.12 Co 0.08 Mn 0.60 ) O 2 , Li (Li 0.20 Ni 0.16 Co 0.08 Mn 0.56 ) O 2 , Li (Li 0.20 Ni 0.13 Co 0.13 Mn 0.54 ) O 2 .
  • the shape of the lithium-containing composite oxide (I) is preferably particulate.
  • the average particle size (D50) of the lithium-containing composite oxide (I) is preferably 3 to 25 ⁇ m, more preferably 4 to 20 ⁇ m, and particularly preferably 5 to 15 ⁇ m.
  • the average particle size (D50) is a particle size distribution at a point where the cumulative curve is 50% in a cumulative curve where the particle size distribution is obtained on a volume basis and the total volume is 100%. It means% diameter.
  • the particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser scattering particle size distribution measuring apparatus.
  • the particle size is measured by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like and measuring the particle size distribution (for example, a laser diffraction / scattering particle size distribution measuring device Partica LA-950VII manufactured by HORIBA, etc.). Used).
  • the specific surface area of the lithium-containing composite oxide (I) is preferably 0.3 ⁇ 10m 2 / g, particularly preferably 0.5 ⁇ 5m 2 / g.
  • the specific surface area is measured by a nitrogen gas adsorption BET (Brunauer, Emmett, Teller) method (for example, using a high precision gas / vapor adsorption amount measuring device BELSORP-max manufactured by Bell Japan).
  • the method for producing the lithium-containing composite oxide (I) includes a method in which a precursor of the lithium-containing composite oxide obtained by the coprecipitation method and a lithium compound are mixed and fired, a hydrothermal synthesis method, a sol-gel method, and a dry mixing method.
  • a method (solid phase method), an ion exchange method, or a glass crystallization method can be appropriately used.
  • the precursor of the lithium-containing composite oxide obtained by the coprecipitation method (coprecipitation composition) It is preferable to use a method of mixing and baking a lithium compound.
  • the lithium-containing composite oxide (I) used as the positive electrode active material has Mg, Ca, Sr, Ba, Ti, Zr, Hf, Nb, Ta, Al, Ga, Y, La, Ce, Nd, Gd, on the surface. It is preferable that a coating layer (hereinafter referred to as coating layer (II)) made of an oxide containing at least one metal element selected from the group consisting of Er and Er is formed.
  • coating layer (II) made of an oxide containing at least one metal element selected from the group consisting of Er and Er is formed.
  • Al 2 O 3 , Ga 2 O 3 , Y 2 O 3 , La 2 O 3 , Ce 2 O 3 , Nd 2 O 3 , Gd 2 O 3 , or Er 2 O 3 is the cycle retention rate. Is particularly preferable because it can be greatly improved.
  • the coating layer (II) one or more of the above compounds may be used.
  • the coating layer (II) can be evaluated by transmission electron microscope-energy dispersive X-ray spectroscopy analysis (TEM-EDX) and X-ray electron spectroscopy (XPS).
  • TEM-EDX transmission electron microscope-energy dispersive X-ray spectroscopy analysis
  • XPS X-ray electron spectroscopy
  • the surface of the lithium-containing composite oxide (I) has Mg, Ca, Sr, Ba, Ti, Zr, Hf, Nb, Ta, Al, Ga, It can be confirmed that there is an oxide of at least one metal element selected from the group consisting of Y, La, Ce, Nd, Gd, and Er.
  • the coating layer (II) may be crystalline or amorphous, and is preferably amorphous.
  • amorphous means that no peak attributed to the coating layer (II) is observed in the X-ray diffraction measurement (hereinafter also referred to as XRD). Although the reason is not clear, it is considered that when the coating layer (II) is amorphous, the coating layer (II) can more uniformly cover the surface of the lithium-containing composite oxide (I).
  • the total total molar amount of Mg, Ca, Sr, Ba, Ti, Zr, Hf, Nb, Ta, Al, Ga, Y, La, Ce, Nd, Gd, and Er contained in the positive electrode active material is the positive electrode active material
  • the total molar amount of Ni, Co, and Mn in the total is 1 mol, it is preferably 0.0005 to 0.05 mol, more preferably 0.001 to 0.03 mol, Particularly preferred is 0.003 to 0.02 mol.
  • Mg, Ca, Sr, Ba, Ti, Zr, Hf, Nb, Ta, Al, Ga, Y, La contained in the positive electrode active material with respect to the total molar amount of Ni, Co, and Mn in the positive electrode active material , Ce, Nd, Gd, and Er can be measured by dissolving the positive electrode active material in an acid and performing ICP (high frequency inductively coupled plasma) measurement. If it is difficult to obtain by ICP measurement, it may be calculated based on the amount of preparation.
  • ICP high frequency inductively coupled plasma
  • the lithium-containing composite oxide (I) is subjected to heat treatment after contacting with the compound containing the metal element. Is mentioned.
  • the spray method is particularly preferable because of its excellent productivity.
  • the temperature for the heat treatment is preferably 200 to 650 ° C, more preferably 300 to 550 ° C. When the heat treatment temperature is in the above range, an oxide can be efficiently generated, and an amorphous oxide is easily obtained.
  • At least one lithium compound selected from the group consisting of a lithium phosphate compound, a lithium sulfate compound, and a lithium fluoride may be attached to the surface of the lithium-containing composite oxide (I).
  • the lithium compound include LiF, Li 3 PO 4 , Li 2 SO 4 , and Li 2 SO 4 .H 2 O.
  • the binder in the present invention is at least one selected from the group consisting of ethylene tetrafluoride (hereinafter also referred to as TFE), hexafluoropropylene (hereinafter also referred to as HFP), and vinylidene fluoride (hereinafter also referred to as VdF).
  • TFE ethylene tetrafluoride
  • HFP hexafluoropropylene
  • VdF vinylidene fluoride
  • Fluorine-containing rubber hereinafter referred to as fluorine-containing rubber (III)
  • fluorine-containing rubber (III) comprising a copolymer having a repeating unit based on a monomer and having a fluorine content of 50 to 76% by mass is included.
  • the fluorine-containing rubber (III) is a copolymer composed of two or more kinds of repeating units, and is a copolymer consisting of repeating units based on two or three monomers selected from the group consisting of TFE, HFP, and VdF. It may be a coalescence, one or more repeating units based on one or more monomers selected from the group consisting of TFE, HFP, and VdF, and one or more other monomers copolymerizable with the monomers It may be a copolymer comprising repeating units based on.
  • the fluorine content of the fluorine-containing rubber (III) is preferably 50 to 74% by mass, more preferably 53 to 70% by mass.
  • the fluorine content of the fluorine-containing rubber is obtained by fluorine content analysis, and indicates the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluorine-containing rubber.
  • the fluorine-containing rubber (III) has a repeating unit based on another monomer in addition to a repeating unit based on TFE, a repeating unit based on HFP, and a repeating unit based on VdF
  • P Propylene
  • E ethylene
  • PAVE perfluoro (alkyl vinyl ether)
  • PAVE perfluoro (methyl vinyl ether)
  • PMVE perfluoro (propyl vinyl ether)
  • PPVE perfluoro (propyl vinyl ether)
  • fluorine-containing rubber (III) examples include a TFE / P copolymer (meaning a copolymer comprising a repeating unit based on TFE and a repeating unit based on P. The same shall apply hereinafter), TFE / P / VdF copolymer.
  • TFE / P copolymer The ratio of the repeating unit based on TFE / the repeating unit based on P is 30 to 80/70 to 20 (mol%) (however, the repeating unit based on TFE and the repeating unit based on P are 100 mol% in total). The same shall apply hereinafter)), more preferably from 40 to 70/60 to 30 (mol%), and most preferably from 60 to 50/40 to 50 (mol%).
  • TFE / P / VdF copolymer The ratio of the repeating unit based on TFE / the repeating unit based on P / the repeating unit based on VdF is preferably in the range of 30 to 85/15 to 70 / 0.01 to 50 (mol%), more preferably 30 70/20 to 60/1 to 40 (mol%).
  • VdF / HFP copolymer The ratio of the repeating unit based on VdF / the repeating unit based on HFP is preferably 45 to 90/55 to 10 (mol%), and more preferably 50 to 80/50 to 20 (mol%).
  • VdF / TFE copolymer The ratio of the repeating unit based on VdF / the repeating unit based on HFP is preferably 50 to 90/50 to 10 (mol%).
  • TFE / VdF / HFP copolymer The ratio of the repeating unit based on TFE / the repeating unit based on VdF / the repeating unit based on HFP is preferably 2 to 50/30 to 90/1 to 35 (mol%).
  • TFE / PAVE copolymer The ratio of the repeating unit based on TFE / the repeating unit based on PAVE is preferably 50 to 90/50 to 10 (mol%), and more preferably 50 to 80/50 to 20 (mol%).
  • TFE / P / PAVE copolymer The ratio of the repeating unit based on TFE / the repeating unit based on P / the repeating unit based on PAVE is preferably 30 to 80/15 to 70 / 0.1 to 40 (mol%), and preferably 39 to 70/20 to More preferably 60/1 to 30 (mol%)
  • the weight average molecular weight of the fluorinated rubber (III) is preferably 10,000 to 300,000, more preferably 20,000 to 250,000, and even more preferably 30,000 to 190,000.
  • the weight average molecular weight (Mw) in the present specification is a molecular weight in terms of polystyrene obtained by measuring with gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample having a known molecular weight.
  • the tensile elongation at break is preferably 500% or more, more preferably 800% or more, and particularly preferably 1000% or more. When the tensile elongation at break is less than 500%, the adhesion with the positive electrode current collector tends to be lowered.
  • the tensile strength of the fluorine-containing rubber (III) is preferably 1 to 50 MPa, more preferably 5 to 20 MPa. When the tensile strength is within the above range, the adhesion is excellent.
  • the values of the tensile elongation at break and the tensile strength of the fluorinated rubber (III) are values obtained by a method according to JISK6251.
  • the fluorine-containing rubber (III) contained in the positive electrode binder may be one type or two or more types.
  • the binder may contain other fluororesins such as polytetrafluoroethylene and other polymer compounds as necessary.
  • 60% by mass or more of the binder is preferably fluorine-containing rubber (III), more preferably 80% by mass or more, and particularly preferably 100% by mass.
  • the fluorine-containing rubber (III) can be produced by a known polymerization method, and among them, the radical copolymerization method is preferable.
  • the radical polymerization method is not particularly limited, and various radical polymerization methods are used, but those initiated by an organic or inorganic radical polymerization initiator, light, heat, ionizing radiation, or the like are preferable.
  • the form of polymerization can be produced by a conventionally known polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization or the like, and emulsion polymerization is preferred. For example, a method of copolymerizing propylene and tetrafluoroethylene in an aqueous medium in the presence of a redox catalyst can be used.
  • a method for producing a fluorine-containing rubber (III) having a repeating unit based on TFE and a repeating unit based on P such as a TFE / P copolymer, an aqueous medium, an anionic emulsifier, and thermal decomposition type radical polymerization It has an emulsion polymerization step in which a monomer mixture containing tetrafluoroethylene and propylene is emulsion-polymerized at a polymerization temperature in the range of 50 ° C. to 100 ° C. to produce a fluorinated rubber (III) in the presence of an initiator.
  • a production method (hereinafter referred to as production method (IV)) can be preferably used.
  • the aqueous medium is composed of water alone or water and a water-soluble organic solvent, and the content of the water-soluble organic solvent is less than 1 part by mass with respect to 100 parts by mass of water.
  • the amount of the anionic emulsifier used is 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the fluorine-containing rubber (III) to be produced.
  • the emulsion polymerization step can be performed by a known emulsion polymerization method. For example, it can be performed by the following procedure. According to this production method (IV), since the fluorinated rubber (III) can be produced without using a redox catalyst, a latex of the fluorinated rubber (III) having a low metal content can be obtained. Moreover, although the content of the organic solvent is small, good stability in the latex of the fluorine-containing rubber (III) can be obtained.
  • water-soluble organic solvents meaning organic solvents that can be dissolved in water
  • Alcohols are preferable, and tert-butanol is particularly preferable.
  • the content of the water-soluble organic solvent in the aqueous medium is preferably small.
  • the water-soluble organic solvent is less than 1 part by mass with respect to 100 parts by mass of water, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and particularly preferably zero. That is, it is particularly preferable to use water that does not contain a water-soluble organic solvent alone as the aqueous medium.
  • anionic emulsifier those known in the emulsion polymerization method can be used.
  • hydrocarbon emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium succinate dialkyl ester sulfonate, sodium alkyl diphenyl ether disulfonate; perfluoro Fluorine-containing alkyl carboxylates such as ammonium octanoate and ammonium perfluorohexanoate; compounds represented by the following formula (2), and the like.
  • X represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms
  • A represents a hydrogen atom, an alkali metal atom, or —NH 4
  • p represents an integer of 1 to 10
  • Q represents 0 or an integer of 1 to 3.
  • anionic emulsifier sodium lauryl sulfate is particularly preferable.
  • the amount of the anionic emulsifier used is 1.5 to 5.0 parts by mass, and 1.5 to 3.8 parts by mass with respect to 100 parts by mass of the fluorinated rubber (III) produced in the emulsion polymerization step.
  • the content of the emulsifier in the fluorine-containing rubber (III) latex is within this range, the stability of the latex is excellent, and excellent charge / discharge characteristics can be obtained when the latex is used as a binder composition. When there is too much content of this emulsifier, this charge / discharge characteristic will deteriorate easily.
  • the thermal decomposition type radical polymerization initiator is water-soluble and has a one-hour half-life temperature of 50 to 100 ° C. It can be appropriately selected from water-soluble polymerization initiators used in ordinary emulsion polymerization. Specific examples include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; disuccinic acid peroxide; organic initiators such as azobisisobutylamidine dihydrochloride, and the like. Of these, persulfates are preferred, and ammonium persulfate is particularly preferred.
  • the amount of the thermal decomposition type radical polymerization initiator used is preferably 0.0001 to 3 parts by mass, and 0.001 to 1 part by mass with respect to 100 parts by mass of the fluorinated rubber (III) produced in the emulsion polymerization step. Is more preferable.
  • a pH adjuster may be added in the emulsion polymerization step of production method (IV).
  • Known inorganic salts can be used as the pH adjuster.
  • Specific examples include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; carbonates such as sodium hydrogen carbonate and sodium carbonate; and the like. More preferable specific examples of the phosphate include disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate.
  • the polymerization rate and the stability of the resulting latex can be improved.
  • the amount of the pH adjuster used is preferably as small as possible. Therefore, the emulsion polymerization process is preferably performed in the absence of a pH adjuster.
  • the positive electrode for a lithium ion secondary battery according to the present invention has a positive electrode active material layer containing the positive electrode active material, the binder, and a conductive material formed on the surface of a positive electrode current collector.
  • the conductive material include carbon black such as acetylene black, graphite, and ketjen black.
  • Examples of the positive electrode current collector include aluminum or an aluminum alloy.
  • the positive electrode for a lithium ion secondary battery of the present invention can be highly filled with the lithium-containing composite oxide (I) as a positive electrode active material, and can have a high capacity. Moreover, since the binder does not deteriorate even when charged at a high voltage, the cycle retention rate is excellent. That is, the discharge capacity can be improved by using the lithium-containing composite oxide (I) in which the molar amount of Li element is more than 1.2 times the total molar amount of the transition metal element as the positive electrode active material. .
  • the positive electrode for a lithium ion secondary battery using such a lithium-containing composite oxide (I) as the positive electrode active material it is preferable to activate the positive electrode active material at a high voltage, and for that purpose, the withstand voltage of the binder Is desired to be high. Furthermore, since lithium containing complex oxide (I) has comparatively low electroconductivity, it is desired to reduce the binder content in the positive electrode active material layer and increase the positive electrode active material content (high filling).
  • the positive electrode is interposed via the binder.
  • Good adhesion between the active material and conductive material layer and the positive electrode current collector can be obtained.
  • the content of the positive electrode active material in the positive electrode active material layer can be preferably 80 to 97% by mass. 85 to 95% by mass is more preferable.
  • the binder content in the positive electrode active material layer is preferably 1.5 to 10% by mass, more preferably 2.5 to 5% by mass.
  • the content of the conductive material in the positive electrode active material layer is preferably 1.5 to 10% by mass, and more preferably 2.5 to 5% by mass.
  • the content of the positive electrode active material, the binder, and the conductive material is within the above ranges, good conductivity can be obtained, and since the content of the positive electrode active material is large, the positive electrode has a high discharge capacity and is collected from the positive electrode active material. The adhesion of the electric body is improved.
  • the fluorine content of the fluorine-containing rubber (III) used as the binder is high, good voltage resistance is obtained, and the binder is hardly deteriorated even when charged at a high voltage. Further, the fluororubber (III) has good alkali resistance when it contains a repeating unit based on TFE and a repeating unit based on P. Therefore, even when the lithium-containing composite oxide (I) having a high Li element content is used as the positive electrode active material, the binder is hardly deteriorated, and a good cycle maintenance rate is obtained. Furthermore, since the fluorine-containing rubber (III) is excellent in flexibility, it has excellent followability to expansion and contraction of the positive electrode active material when charging and discharging are repeated, and contributes to improvement of cycle characteristics.
  • the positive electrode for a lithium ion secondary battery of the present invention can be manufactured by a method including a mixing step of mixing the positive electrode active material and the binder to obtain a mixture, and a step of heat-treating the mixture.
  • the mixture is preferably a slurry or a kneaded product further containing an organic solvent or an aqueous dispersion medium. That is, in the mixing step, it is preferable to mix the positive electrode active material and the binder in an organic solvent. Alternatively, in the mixing step, it is preferable to mix the positive electrode active material and the binder in an aqueous dispersion medium.
  • the conductive material is preferably contained in the mixture.
  • a conductive material When mixing the positive electrode active material and the binder, a conductive material may be added and mixed. Alternatively, the conductive material and the positive electrode active material may be mixed in advance and then mixed with the binder. The mixture is supported on the surface of the positive electrode current collector plate by coating or the like, and heat treated to remove the organic solvent and / or aqueous dispersion medium to form a positive electrode active material layer and the like, thereby forming a positive electrode for a lithium ion secondary battery Is obtained. The positive electrode active material layer may be further pressed.
  • the binder In the production of a positive electrode for a lithium ion secondary battery, the binder is preferably used as a binder composition containing a binder and an organic solvent or an aqueous dispersion medium.
  • the binder composition is preferably a binder composition containing a binder and an aqueous dispersion medium.
  • organic solvents examples include ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, hexane, octane, toluene, xylene, naphtha, acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, dimethylformamide, dimethyl sulfoxide , Methylformamide, methanol, ethanol and the like.
  • N-methylpyrrolidone or butyl acetate is preferable, and N-methylpyrrolidone is more preferable.
  • the organic solvent may be a single solvent or a mixed solvent of two or more solvents.
  • aqueous dispersion medium water alone or a mixture of water and a water-soluble organic solvent can be used.
  • water-soluble organic solvents include ketones such as acetone and methyl ethyl ketone; amines such as triethylamine and aniline; amides such as N-methylpyrrolidone and dimethylformamide; methanol, ethanol, propanol, isopropanol, n-butanol, and t-butanol.
  • alcohols Among these, alcohols or amides are preferable, and alcohols are more preferable.
  • methanol, isopropanol, or t-butanol is preferable, and t-butanol is more preferable.
  • Only one water-soluble organic solvent may be used in the aqueous dispersion medium, or two or more water-soluble organic solvents may be used in combination.
  • the ratio of the binder contained in the binder composition is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, based on the entire binder composition.
  • the fluorinated rubber (III) is preferably emulsified or dispersed in the aqueous dispersion medium, particularly in a latex state. preferable.
  • the production method of the binder composition is not particularly limited, but the fluorine-containing rubber (III) is produced by suspension polymerization, emulsion polymerization, solution polymerization, etc., and the fluorine-containing rubber (III) after polymerization is dissolved in an organic solvent.
  • the composition dispersed in an aqueous dispersion medium can be used as it is.
  • the solvent or dispersion medium used in the polymerization is preferably the same as the organic solvent or aqueous dispersion medium constituting the binder composition to be obtained.
  • the binder composition contains an organic solvent, the solution of fluorine-containing rubber (III) produced by solution polymerization can be used as it is.
  • the binder composition contains an aqueous dispersion medium
  • a composition produced by emulsion polymerization in which the fluorinated rubber (III) is dispersed in the aqueous dispersion medium can be used as it is.
  • the binder composition may be a composition obtained by purifying the fluorine-containing rubber obtained by polymerization to a solid state and dissolving the solid again in an organic solvent or dispersing in an aqueous dispersion medium.
  • the organic solvent or aqueous dispersion medium used in this case is preferably the aforementioned organic solvent or aqueous dispersion medium.
  • the lithium ion secondary battery in this invention contains the positive electrode for lithium ion secondary batteries of this invention, a negative electrode, and a nonaqueous electrolyte.
  • the negative electrode is formed by forming a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector.
  • a slurry can be prepared by kneading a negative electrode active material with an organic solvent, and the prepared slurry can be applied to a negative electrode current collector, dried, and pressed.
  • the negative electrode current collector for example, a metal foil such as a nickel foil or a copper foil can be used.
  • the negative electrode active material may be any material that can occlude and release lithium ions at a relatively low potential.
  • Carbon compounds, silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds, and the like can be used.
  • Examples of the carbon material of the negative electrode active material include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbon, coke such as pitch coke, needle coke, petroleum coke, graphite, glassy carbon, phenol Organic polymer compound fired bodies, carbon fibers, activated carbon, carbon blacks, etc., obtained by firing and carbonizing a resin, furan resin or the like at an appropriate temperature can be used.
  • the metal of the periodic table group 14 is, for example, silicon or tin, and most preferably silicon.
  • Non-silicon materials that can be used as the negative electrode active material include oxides such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and nitrides such as Li 2.6 Co 0.4 N. It is done.
  • non-aqueous electrolyte examples include a non-aqueous electrolyte obtained by dissolving an electrolyte salt in an organic solvent, a solid electrolyte containing an electrolyte salt, a solid electrolyte obtained by mixing or dissolving an electrolyte salt in a polymer electrolyte, a polymer compound, and the like. Or a gel electrolyte etc. are mentioned.
  • organic solvent those known as organic solvents for electrolytic solutions can be used.
  • propylene carbonate ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, Diglyme, triglyme, ⁇ -butyrolactone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, acetic acid ester, butyric acid ester, propionic acid ester and the like
  • cyclic carbonates such as propylene carbonate or chain carbonates such as dimethyl carbonate and diethyl carbonate.
  • such an organic solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • any material having lithium ion conductivity may be used.
  • an inorganic solid electrolyte or a polymer solid electrolyte can be used.
  • lithium nitride lithium iodide, or the like
  • polymer solid electrolyte an electrolyte salt and a polymer compound that dissolves the electrolyte salt can be used.
  • the polymer compound include polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, and polyhexafluoropropylene, or derivatives, mixtures, and composites thereof. Can be used.
  • any gel electrolyte may be used as long as it absorbs the non-aqueous electrolyte and gels, and various polymers can be used.
  • the polymer material used for the gel electrolyte for example, fluorine-based polymers such as poly (vinylidene fluoride) and poly (vinylidene fluoride-co-hexafluoropropylene) can be used.
  • the polymer material used for the gel electrolyte for example, polyacrylonitrile and a copolymer of polyacrylonitrile, as well as an ether polymer such as polyethylene oxide, a copolymer of polyethylene oxide, and a crosslinked product thereof can be used. .
  • the copolymerization monomer examples include polypropylene oxide, methyl methacrylate, butyl methacrylate, methyl acrylate, and butyl acrylate.
  • the matrix of the gel electrolyte is particularly preferably a fluoropolymer from the viewpoint of stability against redox reaction.
  • any electrolyte salt can be used as long as it is used for this type of battery.
  • LiClO 4 , LiPF 6 , LiBF 4 , CH 3 SO 3 Li, LiCl, LiBr, or the like can be used.
  • the shape of the lithium ion secondary battery of the present invention can be appropriately selected from coin shapes, sheet shapes (film shapes), folded shapes, wound bottomed cylindrical shapes, button shapes, and the like depending on the application.
  • the mother liquor was placed in a 2 L baffled glass reaction vessel, heated to 50 ° C. with a mantle heater, and a pH adjusting solution was added so that the pH was 11.0.
  • the raw material solution was added at a rate of 5.0 g / min and the ammonia source solution was added at a rate of 1.0 g / min, and a composite hydroxide of nickel, cobalt, and manganese was added.
  • the pH adjusting solution was added so as to keep the pH in the reaction vessel at 11.0.
  • nitrogen gas was flowed at a flow rate of 0.5 L / min in the reaction tank so that the precipitated hydroxide was not oxidized. Further, the liquid was continuously extracted so that the amount of the liquid in the reaction tank did not exceed 2 L.
  • This precursor (20 g) and lithium carbonate (12.8 g) having a lithium content of 26.9 mol / kg were mixed and calcined at 900 ° C. for 12 hours in an oxygen-containing atmosphere to obtain a lithium-containing composite oxide of the example. It was.
  • the composition of the lithium-containing composite oxide of the obtained example is Li (Li 0.2 Ni 0.128 Co 0.134 Mn 0.538 ) O 2 .
  • the average particle diameter D50 of the lithium-containing composite oxide of the example was 8.4 ⁇ m, and the specific surface area measured using the nitrogen gas adsorption BET method was 1.4 m 2 / g. When the tap density of the lithium-containing composite oxide was measured, it was 1.8 g / cm 3 .
  • Al aqueous solution an aqueous solution in which the aluminum compound was dissolved (hereinafter also referred to as an Al aqueous solution).
  • Al aqueous solution aqueous solution in which the aluminum compound was dissolved
  • 1 g of the prepared Al aqueous solution was spray-sprayed and added to 10 g of the lithium-containing composite oxide of the example under stirring, and the lithium-containing composite oxide of the example and the Al aqueous solution were brought into contact with mixing.
  • the obtained mixture was dried at 90 ° C. for 2 hours, and then heated at 400 ° C. for 8 hours in an oxygen-containing atmosphere to form a coating layer (II) on the surface of the lithium-containing composite oxide to form a positive electrode active material (1 )
  • the coating layer (II) formed using the Al aqueous solution contains an oxide of Al.
  • the aluminum of the coating layer is in a molar ratio (coating amount) with respect to the total of nickel, cobalt, and manganese, which are transition metal elements of the lithium-containing composite oxide.
  • Binder composition As a binder composition, a solution was prepared in which a fluoropolymer as a binder was dissolved or dispersed in an organic solvent or water.
  • Reference Example 1 Preparation of binder composition containing fluorine-containing rubber A
  • ion exchange water After degassing the inside of a 3200 mL stainless steel pressure-resistant reactor equipped with an anchor blade for stirring, 1700 g of ion exchange water, 5 g of disodium hydrogen phosphate 12 hydrate, 2 0.0 g sodium hydroxide, 13.3 g sodium lauryl sulfate, and 4.4 g ammonium persulfate were added.
  • the anchor blade was rotated at 300 rpm to initiate the polymerization reaction.
  • the pressure in the reactor decreases.
  • the internal pressure of the reactor was increased to 2.51 MPaG. This was repeated, and the internal pressure of the reactor was maintained at 2.49 to 2.51 MPaG, and the polymerization reaction was continued.
  • the total amount of the TFE / P monomer mixed gas injected reaches 900 g
  • the internal temperature of the reactor is cooled to 10 ° C.
  • the polymerization reaction is stopped, and the latex containing the fine fluorine-containing rubber A This was used as a binder composition.
  • the polymerization time was 8 hours.
  • the solid content in the binder composition was 34% by mass.
  • the fluorine content of the obtained fluorinated rubber is shown in Table 1 (hereinafter the same).
  • EDTA ethylenediaminetetraacetic acid disodium salt dihydrate
  • ferrous sulfate heptahydrate ferrous sulfate heptahydrate
  • a 1.5% by mass aqueous solution of calcium chloride was added to the latex to agglomerate the fluorinated rubber B, which was filtered and recovered.
  • the fluorinated rubber B was washed with ion-exchanged water and dried in an oven at 100 ° C. for 15 hours to obtain a white fluorinated rubber B.
  • This fluorinated rubber B was dissolved in an N-methylpyrrolidone solution to prepare a binder composition having a fluorinated rubber B concentration of 10% by mass.
  • the fluorine-containing rubber A which is a binder of Reference Example 1 was added to the binder composition obtained in Reference Example 1 by adding a 1.5% by mass aqueous solution of calcium chloride to aggregate the fluorine-containing rubber A, and filtered. The recovered and dried product was used.
  • the fluorine-containing rubbers B and C which are binders of Reference Examples 2 and 3 the dried fluorine-containing rubbers B and C used for preparing the binder composition were used, respectively.
  • the binder of Reference Example 4 a dried product of the above polytetrafluoroethylene aqueous dispersion was used.
  • the binder of Reference Example 5 the above powdery polyvinylidene fluoride was used.
  • the binder of Reference Example 6 the above styrene-butadiene rubber was used.
  • Example 1 10 parts by weight of a 2% by weight aqueous solution of sodium carboxymethylcellulose as a viscosity modifier, the positive electrode active material (1) prepared above and acetylene black are mixed, and water is added so that the solid content concentration becomes 70% by weight. After that, the binder composition containing the fluorinated rubber A obtained in Reference Example 1 was added and stirred to prepare a uniform slurry (mixture). This slurry was applied on one side to a 20 ⁇ m thick aluminum foil (positive electrode current collector) using a doctor blade. And it heat-processed at 120 degreeC, it was made to dry, and the positive electrode sheet
  • the mass ratio of positive electrode active material / acetylene black / binder (fluorinated rubber A) was 85/15/5.
  • the positive electrode material sheet had good adhesion between the positive electrode active material layer and the positive electrode current collector.
  • a stainless steel simple sealed cell type lithium ion secondary battery was assembled in an argon glove box.
  • a metal lithium foil having a thickness of 500 ⁇ m is used for the negative electrode
  • a stainless steel plate having a thickness of 1 mm is used for the negative electrode current collector
  • a porous polypropylene having a thickness of 25 ⁇ m is used for the separator
  • a concentration is used for the electrolyte.
  • the following evaluation was performed using the lithium ion secondary battery manufactured above. That is, it charged to 4.6V with a load current of 20 mA per 1 g of the positive electrode active material, and discharged to 2.5 V with a load current of 20 mA per 1 g of the positive electrode active material.
  • the discharge capacity at this time is defined as the initial discharge capacity.
  • the initial discharge capacity was 270 mAh / g.
  • charging to 4.6 V with a load current of 60 mA per 1 g of the charge / discharge positive electrode active material and discharging to 2.5 V with a load current of 60 mA per 1 g of the positive electrode active material were further repeated 99 times.
  • the 99th discharge capacity / initial discharge capacity is defined as a cycle maintenance ratio.
  • the cycle maintenance rate was 96%.
  • Example 2 The positive electrode active material (1) produced above and acetylene black are mixed, the binder composition containing the fluorinated rubber B obtained in Reference Example 2 and N-methylpyrrolidone are added and stirred, and the solid content concentration is 65 A uniform slurry having a mass% was prepared. The mass ratio of positive electrode active material / acetylene black / binder (fluorinated rubber B) was 85/15/5. Thereafter, the same procedure as in Example 1 was performed.
  • Example 3 The same procedure as in Example 2 was performed except that the binder composition shown in Reference Example 3 was used as the binder composition.
  • Comparative Example 1 The same procedure as in Example 1 was performed except that the binder composition shown in Reference Example 4 was used as the binder composition.
  • the obtained positive electrode body sheet peels off due to insufficient adhesion between the positive electrode active material layer and the current collector.
  • the battery evaluation is performed on the positive electrode sheet that was not peeled off.
  • Comparative Example 2 It carries out similarly to Example 2 except having used the binder composition shown in the reference example 5 as a binder composition. Part of the obtained positive electrode sheet is peeled off due to insufficient adhesion between the positive electrode active material layer and the current collector.
  • the battery evaluation is performed on the positive electrode sheet that was not peeled off.
  • Comparative Example 3 The same procedure as in Example 2 was performed except that the binder composition shown in Reference Example 6 was used as the binder composition.
  • Comparative Example 4 The same procedure as in Example 1 was performed except that the positive electrode active material (1) was changed to the positive electrode active material (2).
  • Example 1 to 3 and Comparative Examples 1 to 4 are shown in Table 2.
  • the adhesion was evaluated by a cross-cut peel test of JISK5400. That is, a grid-like cut with a 1 mm interval was made with a cutter knife in the produced positive electrode sheet coating film, cellophane tape (trade name, manufactured by Nichiban Co., Ltd.) was applied, and the number of peeled and remaining eyes was measured. evaluate.
  • the number of remaining eyes is 70% or more, ⁇ , more than 40% to less than 70% is represented by ⁇ , and less than 40% is represented by ⁇ .
  • the initial discharge capacity is over 250 mAh / g, ⁇ , 200 to 250 mAh / g is ⁇ , and less than 200 mAh / g is x.
  • the cycle maintenance rate is over 90% as ⁇ , 80 to 90% as ⁇ , and less than 80% as x.
  • Comparative Example 4 is inferior in the initial discharge capacity because the molar amount of Li element in the lithium-containing composite oxide used as the positive electrode active material is as small as 1.0 times the total molar amount of transition metal elements.
  • a positive electrode for a lithium-in secondary battery having a high discharge capacity per unit mass and excellent cycle characteristics can be obtained.
  • the positive electrode can be used for electronic devices such as mobile phones and lithium ion secondary batteries for vehicles.

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Abstract

La présente invention porte sur une électrode de batterie rechargeable au lithium-ions qui a une capacité de déchargement élevée, une excellente adhérence entre une matière active d'électrode positive et une matière conductrice et un collecteur de courant d'électrode positive et d'excellentes caractéristiques de cycle qui ne sont pas sujettes à une dégradation même lorsqu'un cycle de chargement-déchargement est répété. L'électrode de batterie rechargeable au lithium-ions a une couche de matière active d'électrode positive contenant une matière active d'électrode positive, un liant et une matière conductrice formée sur une surface du collecteur de courant d'électrode positive. La matière active d'électrode positive contient un oxyde complexe à teneur en lithium qui contient un élément Li, et au moins un type d'élément de métal de transition choisi dans un groupe comprenant Ni, Co et Mn (la quantité molaire de l'élément Li étant 1,2 fois la quantité totale molaire dudit ou desdits éléments de métal de transition). Le liant contient un caoutchouc à teneur en fluor, qui comprend un copolymère ayant des unités répétitives sur la base d'au moins un type de monomère choisi dans un groupe comprenant le tétrafluoroéthylène, l'hexafluoropropylène et le fluorure de vinylidène, et une teneur en fluor de 50-76 % en masse.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132641A1 (fr) * 2014-03-03 2015-09-11 Toyota Jidosha Kabushiki Kaisha Électrode positive de batterie rechargeable au lithium-ion, et procédé de fabrication de batterie rechargeable au lithium-ion
JP2015227263A (ja) * 2014-05-30 2015-12-17 住友金属鉱山株式会社 ニッケルコバルトマンガン複合水酸化物とその製造方法
JP2015232998A (ja) * 2014-05-12 2015-12-24 株式会社豊田自動織機 蓄電装置
JP2016042417A (ja) * 2014-08-15 2016-03-31 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． リチウムイオン（ｌｉｔｈｉｕｍｉｏｎ）二次電池
JP2019513285A (ja) * 2016-03-14 2019-05-23 スリーエム イノベイティブ プロパティズ カンパニー 高含有量の無機材料を含むフルオロポリマー組成物
JPWO2021015230A1 (ja) * 2019-07-25 2021-12-09 ダイキン工業株式会社 結着剤、固体電池用スラリー、固体電池用電極及び二次固体電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09306474A (ja) * 1996-05-14 1997-11-28 Kazuo Tagawa 電極用塗布ペースト及び非水系二次電池電極
JPH10233217A (ja) * 1996-12-16 1998-09-02 Daikin Ind Ltd 非水電解液二次電池用結着剤およびそれを用いた電池電極合剤
JP2009146871A (ja) * 2007-11-20 2009-07-02 Asahi Glass Co Ltd 環境負荷の小さな蓄電素子電極形成用水性ペースト
WO2010039732A2 (fr) * 2008-09-30 2010-04-08 Envia Systems, Inc. Matériaux de batterie pour électrode positive en oxyde métallique riche en lithium dopé au fluor de capacité spécifique élevée et batterie correspondante
WO2011055760A1 (fr) * 2009-11-06 2011-05-12 旭硝子株式会社 Composition de liant pour accumulateur secondaire, mélange pour électrode d'accumulateur secondaire comprenant ledit liant, et accumulateur secondaire
JP2011519126A (ja) * 2008-04-16 2011-06-30 エンビア・システムズ・インコーポレイテッド 高エネルギーリチウムイオン二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09306474A (ja) * 1996-05-14 1997-11-28 Kazuo Tagawa 電極用塗布ペースト及び非水系二次電池電極
JPH10233217A (ja) * 1996-12-16 1998-09-02 Daikin Ind Ltd 非水電解液二次電池用結着剤およびそれを用いた電池電極合剤
JP2009146871A (ja) * 2007-11-20 2009-07-02 Asahi Glass Co Ltd 環境負荷の小さな蓄電素子電極形成用水性ペースト
JP2011519126A (ja) * 2008-04-16 2011-06-30 エンビア・システムズ・インコーポレイテッド 高エネルギーリチウムイオン二次電池
WO2010039732A2 (fr) * 2008-09-30 2010-04-08 Envia Systems, Inc. Matériaux de batterie pour électrode positive en oxyde métallique riche en lithium dopé au fluor de capacité spécifique élevée et batterie correspondante
WO2011055760A1 (fr) * 2009-11-06 2011-05-12 旭硝子株式会社 Composition de liant pour accumulateur secondaire, mélange pour électrode d'accumulateur secondaire comprenant ledit liant, et accumulateur secondaire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Y. WU ET AL.: "High Capacity, Surface- Modified Layered Li[Li(1-x)/3Mn(2-x)/3Nix/3Cox/ 3]02 Cathodes with Low Irreversible Capacity Loss", ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 9, no. 5, 2006, pages A221 - A224, XP002460582, DOI: doi:10.1149/1.2180528 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132641A1 (fr) * 2014-03-03 2015-09-11 Toyota Jidosha Kabushiki Kaisha Électrode positive de batterie rechargeable au lithium-ion, et procédé de fabrication de batterie rechargeable au lithium-ion
CN106068573A (zh) * 2014-03-03 2016-11-02 丰田自动车株式会社 锂离子二次电池的正极和制造锂离子二次电池的方法
US9941513B2 (en) 2014-03-03 2018-04-10 Toyota Jidosha Kabushiki Kaisha Positive electrode of lithium ion secondary battery, and method of manufacturing lithium ion secondary battery
JP2015232998A (ja) * 2014-05-12 2015-12-24 株式会社豊田自動織機 蓄電装置
JP2015227263A (ja) * 2014-05-30 2015-12-17 住友金属鉱山株式会社 ニッケルコバルトマンガン複合水酸化物とその製造方法
JP2016042417A (ja) * 2014-08-15 2016-03-31 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． リチウムイオン（ｌｉｔｈｉｕｍｉｏｎ）二次電池
JP2019513285A (ja) * 2016-03-14 2019-05-23 スリーエム イノベイティブ プロパティズ カンパニー 高含有量の無機材料を含むフルオロポリマー組成物
US10947378B2 (en) 2016-03-14 2021-03-16 3M Innovative Properties Company Fluoropolymer compositions with high content of inorganic material
JPWO2021015230A1 (ja) * 2019-07-25 2021-12-09 ダイキン工業株式会社 結着剤、固体電池用スラリー、固体電池用電極及び二次固体電池
JP7260819B2 (ja) 2019-07-25 2023-04-19 ダイキン工業株式会社 結着剤、固体電池用スラリー、固体電池用電極及び二次固体電池

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