WO2024106074A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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Publication number
WO2024106074A1
WO2024106074A1 PCT/JP2023/036946 JP2023036946W WO2024106074A1 WO 2024106074 A1 WO2024106074 A1 WO 2024106074A1 JP 2023036946 W JP2023036946 W JP 2023036946W WO 2024106074 A1 WO2024106074 A1 WO 2024106074A1
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Prior art keywords
negative electrode
mixture layer
electrode mixture
lithium
secondary battery
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English (en)
French (fr)
Japanese (ja)
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真仁 大塚
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP23891232.3A priority Critical patent/EP4621901A4/en
Priority to JP2024558693A priority patent/JPWO2024106074A1/ja
Priority to CN202380077487.0A priority patent/CN120188295A/zh
Publication of WO2024106074A1 publication Critical patent/WO2024106074A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

  • This disclosure relates to a non-aqueous electrolyte secondary battery.
  • Patent Document 1 proposes an active material in which a surface layer containing a lithium sulfonate compound is formed on the particle surface of lithium titanate mainly composed of Li 4 Ti 5 O 12. Patent Document 1 describes that the use of this active material as a negative electrode active material can suppress the resistance change of a battery before and after storage under charge.
  • the nonaqueous electrolyte secondary battery according to the present disclosure includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode includes a lithium-containing composite oxide and a sulfonic acid compound present on the particle surface of the lithium-containing composite oxide, the sulfonic acid compound being a compound represented by formula (I).
  • the negative electrode includes a negative electrode core, a first negative electrode mixture layer disposed on the surface of the negative electrode, and a second negative electrode mixture layer disposed between the first negative electrode mixture layer and the negative electrode core.
  • the first negative electrode mixture layer and the second negative electrode mixture layer contain a negative electrode active material and a conductive agent, and a content C1 of the conductive agent in the first negative electrode mixture layer and a content C2 of the conductive agent in the second negative electrode mixture layer satisfy C1>C2.
  • A is a Group 1 or Group 2 element
  • R is a hydrocarbon group
  • n is 1 or 2.
  • the nonaqueous electrolyte secondary battery disclosed herein has high capacity and excellent charge/discharge cycle characteristics.
  • FIG. 1 is a cross-sectional view of a nonaqueous electrolyte secondary battery according to an embodiment
  • FIG. 2 is a cross-sectional view of a negative electrode according to an example of an embodiment.
  • the inventors therefore conducted further studies and succeeded in improving the charge-discharge cycle characteristics while ensuring high capacity by using a lithium-containing composite oxide with a specific sulfonic acid compound attached to the particle surface as the positive electrode active material, and by forming the negative electrode mixture layer into a two-layer structure and making the content of conductive agent in the first negative electrode mixture layer on the surface side higher than the content of conductive agent in the second negative electrode mixture layer on the core side. It is believed that the nonaqueous electrolyte secondary battery according to the present disclosure maintains the conductive path in the negative electrode mixture layer even under conditions of deep charge-discharge depth, improving the charge-discharge cycle characteristics.
  • a cylindrical battery in which a wound electrode body 14 is housed in a cylindrical exterior can 16 with a bottom is exemplified as a nonaqueous electrolyte secondary battery, but the exterior body of the battery is not limited to a cylindrical exterior can.
  • the nonaqueous electrolyte secondary battery according to the present disclosure may be, for example, a prismatic battery with a prismatic exterior can, a coin battery with a coin-shaped exterior can, or a pouch-type battery with an exterior body composed of a laminate sheet including a metal layer and a resin layer.
  • the electrode body is not limited to a wound type, and may be a laminated type electrode body in which multiple positive electrodes and multiple negative electrodes are alternately stacked with separators between them.
  • the nonaqueous electrolyte secondary battery 10 includes a wound electrode assembly 14, a nonaqueous electrolyte, and an exterior can 16 that contains the electrode assembly 14 and the nonaqueous electrolyte.
  • the electrode assembly 14 includes a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are wound in a spiral shape with the separator 13 interposed therebetween.
  • the exterior can 16 is a cylindrical metal container with a bottom that is open at one axial end, and the opening of the exterior can 16 is closed by a sealing body 17.
  • the sealing body 17 side of the battery is referred to as the top
  • the bottom side of the exterior can 16 is referred to as the bottom.
  • the non-aqueous electrolyte has lithium ion conductivity.
  • the non-aqueous electrolyte may be a liquid electrolyte (electrolytic solution) or a solid electrolyte.
  • the liquid electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • a non-aqueous solvent for example, esters, ethers, nitriles, amides, and mixed solvents of two or more of these are used as the non-aqueous solvent.
  • the non-aqueous solvent include ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and mixed solvents of these.
  • the non-aqueous solvent may contain a halogen-substituted product (e.g., fluoroethylene carbonate, etc.) in which at least a part of the hydrogen of these solvents is replaced with a halogen atom such as fluorine.
  • a halogen-substituted product e.g., fluoroethylene carbonate, etc.
  • a lithium salt such as LiPF6 is used as the electrolyte salt.
  • the solid electrolyte for example, a solid or gel-like polymer electrolyte, an inorganic solid electrolyte, etc. can be used.
  • the inorganic solid electrolyte a material known in all-solid-state lithium ion secondary batteries, etc. (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halogen-based solid electrolyte, etc.) can be used.
  • the polymer electrolyte includes, for example, a lithium salt and a matrix polymer, or a non-aqueous solvent, a lithium salt, and a matrix polymer.
  • the matrix polymer for example, a polymer material that absorbs a non-aqueous solvent and gels is used.
  • the polymer material for example, a fluororesin, an acrylic resin, a polyether resin, etc. can be used.
  • the positive electrode 11, negative electrode 12, and separator 13 that make up the electrode body 14 are all long, strip-shaped bodies that are wound in a spiral shape and stacked alternately in the radial direction of the electrode body 14.
  • the negative electrode 12 is formed to be slightly larger than the positive electrode 11 in order to prevent lithium precipitation. That is, the negative electrode 12 is formed to be longer in the length direction and width direction than the positive electrode 11.
  • the separator 13 is formed to be at least slightly larger than the positive electrode 11, and for example, two separators 13 are arranged to sandwich the positive electrode 11.
  • the electrode body 14 has a positive electrode lead 20 connected to the positive electrode 11 by welding or the like, and a negative electrode lead 21 connected to the negative electrode 12 by welding or the like.
  • Insulating plates 18, 19 are arranged above and below the electrode body 14.
  • the positive electrode lead 20 passes through a through hole in the insulating plate 18 and extends toward the sealing body 17, and the negative electrode lead 21 passes outside the insulating plate 19 and extends toward the bottom side of the outer can 16.
  • the positive electrode lead 20 is connected to the underside of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 and is electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner bottom inner surface of the outer can 16 by welding or the like, and the outer can 16 serves as the negative electrode terminal.
  • a gasket 28 is provided between the exterior can 16 and the sealing body 17 to ensure airtightness inside the battery.
  • the exterior can 16 has a grooved portion 22 formed with a portion of the side surface that protrudes inward to support the sealing body 17.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the exterior can 16, and supports the sealing body 17 on its upper surface.
  • the sealing body 17 is fixed to the top of the exterior can 16 by the grooved portion 22 and the open end of the exterior can 16 that is crimped against the sealing body 17.
  • the sealing body 17 has a structure in which, in order from the electrode body 14 side, an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are stacked.
  • Each member constituting the sealing body 17 has, for example, a disk or ring shape, and each member except for the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at their respective centers, and the insulating member 25 is interposed between their respective peripheral edges.
  • the positive electrode 11, negative electrode 12, and separator 13 that make up the electrode body 14 are described in detail below.
  • the positive electrode 11 has, for example, a positive electrode core and a positive electrode mixture layer disposed on the surface of the positive electrode core.
  • a foil of a metal such as aluminum that is stable in the potential range of the positive electrode 11, a film having the metal disposed on the surface, or the like can be used.
  • the positive electrode mixture layer contains a positive electrode active material, a conductive agent, and a binder, and is preferably provided on both sides of the positive electrode core except for the part to which the positive electrode lead 20 is connected.
  • the positive electrode 11 can be produced, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, and a binder to the surface of the positive electrode core, drying the coating, and then compressing it to form a positive electrode mixture layer on both sides of the positive electrode core.
  • Examples of the conductive agent contained in the positive electrode mixture layer include carbon black such as acetylene black and ketjen black, graphite, carbon nanotubes (CNT), carbon nanofibers, graphene, and other carbon materials.
  • Examples of the binder contained in the positive electrode mixture layer include fluorine-containing resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide, acrylic resin, polyolefin, and the like. These resins may also be used in combination with carboxymethylcellulose (CMC) or a salt thereof, polyethylene oxide, and the like.
  • the content of the conductive agent and the binder is, for example, 0.1% by mass or more and 5% by mass or less, respectively, relative to the mass of the positive electrode mixture layer.
  • the positive electrode 11 contains a lithium-containing composite oxide and a sulfonic acid compound present on the particle surface of the composite oxide.
  • the lithium-containing composite oxide having the sulfonic acid compound attached to the particle surface functions as a positive electrode active material.
  • the sulfonic acid compound is a compound represented by formula (I). In the formula, A is a Group 1 or Group 2 element, R is a hydrocarbon group, and n is 1 or 2.
  • the sulfonic acid compound represented by formula (I) reduces the reaction resistance in the positive electrode 11 and improves the output characteristics of the battery.
  • the lower resistance makes it possible to deepen the charge/discharge depth, thereby achieving a higher capacity.
  • the amount of sulfonic acid compound present on the surface of the lithium-containing composite oxide is preferably 0.1% by mass or more and 1% by mass or less relative to the mass of the lithium-containing composite oxide, from the viewpoint of increasing capacity.
  • the positive electrode active material may be composed mainly of composite particles that are lithium-containing composite oxides with sulfonic acid compounds attached to the particle surfaces, and may be substantially composed of the composite particles alone.
  • the positive electrode active material may also contain composite oxides or other compounds other than the composite particles, as long as the purpose of the present disclosure is not impaired.
  • the lithium-containing composite oxide preferably has a layered rock salt structure.
  • the layered rock salt structure of the lithium-containing composite oxide include a layered rock salt structure belonging to the space group R-3m and a layered rock salt structure belonging to the space group C2/m. Among these, from the viewpoints of high capacity and stability of the crystal structure, a layered rock salt structure belonging to the space group R-3m is preferred.
  • the layered rock salt structure of the lithium-containing composite oxide includes a transition metal layer, a Li layer, and an oxygen layer.
  • the lithium-containing complex oxide is a complex oxide that contains metal elements such as Ni, Co, Al, and Mn in addition to Li.
  • the metal elements that constitute the lithium-containing complex oxide are, for example, Ni, Co, and M (M is at least one element selected from the group consisting of Al, Mn, Fe, Ti, Si, Nb, Mo, W, and Zn). Among these, it is preferable to contain at least one element selected from Ni, Co, Al, and Mn.
  • suitable complex oxides include complex oxides containing Ni, Co, and Al, and complex oxides containing Ni, Co, and Mn.
  • the lithium-containing composite oxide contains 80 mol% or more of Ni based on the total number of moles of metal elements excluding Li. Furthermore, the effect of adding a sulfonic acid compound is more pronounced when a lithium-containing composite oxide with a high Ni content is used.
  • the Ni content may be 87 mol% or more, or may be 90 mol% or more, based on the total number of moles of metal elements excluding Li.
  • the upper limit of the Ni content is, for example, 95 mol%.
  • An example of a suitable lithium-containing composite oxide is a composite oxide containing Ni, Co, and M, as described above.
  • the Co content is, for example, 0 mol % or more and 20 mol % or less with respect to the total number of moles of metal elements excluding Li.
  • the M content is, for example, 0 mol % or more and 20 mol % or less with respect to the total number of moles of metal elements excluding Li.
  • Co does not have to be substantially added, but adding a small amount of Co improves battery performance.
  • M preferably contains at least one of Mn and Al.
  • x is preferably 0.87 ⁇ x ⁇ 0.95.
  • the content of the elements that make up the lithium-containing composite oxide can be measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES), an electron probe microanalyzer (EPMA), or an energy dispersive X-ray analyzer (EDX), etc.
  • ICP-AES inductively coupled plasma atomic emission spectrometer
  • EPMA electron probe microanalyzer
  • EDX energy dispersive X-ray analyzer
  • the lithium-containing composite oxide is, for example, a secondary particle formed by the aggregation of multiple primary particles.
  • the volume-based median diameter (D50) of the composite oxide is not particularly limited, but is, for example, 3 ⁇ m to 30 ⁇ m, and preferably 5 ⁇ m to 25 ⁇ m.
  • the D50 of the composite oxide means the D50 of the secondary particle.
  • D50 means the particle size at which the cumulative frequency is 50% from the smallest particle size in the volume-based particle size distribution, and is also called the median diameter.
  • the particle size distribution of the composite oxide (as well as that of the negative electrode active material) can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrack Bell Co., Ltd.) with water as the dispersion medium.
  • a laser diffraction type particle size distribution measuring device for example, MT3000II manufactured by Microtrack Bell Co., Ltd.
  • the average particle size of the primary particles constituting the lithium-containing composite oxide is, for example, 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the average particle size of the primary particles is calculated by averaging the diameters of the circumscribed circles of the primary particles extracted by analyzing scanning electron microscope (SEM) images of the cross sections of the secondary particles.
  • the sulfonic acid compound present on the particle surface of the lithium-containing composite oxide is the compound represented by formula (I) as described above.
  • A is a Group 1 or Group 2 element
  • R is a hydrocarbon group
  • n is 1 or 2.
  • A is preferably a Group 1 element. Among them, Li or Na is more preferable, and Li is particularly preferable.
  • R is preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 5 or less, and more preferably 3 or less. From the viewpoint of reducing reaction resistance, a suitable example of R is an alkyl group having 3 or less carbon atoms, and among these, a methyl group is preferable. Note that in R, some of the hydrogens bonded to the carbons may be substituted with fluorine. Also, n in formula (I) is preferably 1.
  • sulfonic acid compounds include lithium methanesulfonate, lithium ethanesulfonate, lithium propanesulfonate, sodium methanesulfonate, sodium ethanesulfonate, magnesium methanesulfonate, and lithium fluoromethanesulfonate.
  • at least one selected from the group consisting of lithium methanesulfonate, lithium ethanesulfonate, and sodium methanesulfonate is preferred, with lithium methanesulfonate being particularly preferred.
  • the sulfonic acid compound is present, for example, homogeneously on the entire particle surface of the lithium-containing composite oxide.
  • the presence of the sulfonic acid compound on the particle surface of the lithium-containing composite oxide can be confirmed by Fourier transform infrared spectroscopy (FT-IR).
  • FT-IR Fourier transform infrared spectroscopy
  • the positive electrode active material containing lithium methanesulfonate has absorption peaks, for example, near 1238 cm -1 , 1175 cm -1 , 1065 cm -1 , and 785 cm -1 .
  • the peaks near 1238 cm -1 , 1175 cm -1 , and 1065 cm -1 are peaks due to SO stretching vibration derived from lithium methanesulfonate.
  • the peak near 785 cm -1 is a peak due to CS stretching vibration derived from lithium methanesulfonate.
  • positive electrode active materials containing sulfonic acid compounds other than lithium methanesulfonate can also be confirmed from the absorption peaks due to sulfonic acid compounds in the infrared absorption spectrum.
  • the presence of sulfonic acid compounds on the particle surface of lithium-containing composite oxides can also be confirmed by ICP, atomic absorption spectrometry, X-ray photoelectron spectroscopy (XPS), synchrotron radiation XRD measurement, TOF-SIMS, etc.
  • the positive electrode active material which is an example of an embodiment, can be manufactured by the following method. Note that the manufacturing method described here is only one example, and the manufacturing method of the positive electrode active material is not limited to this method.
  • a metal oxide containing metal elements such as Ni, Co, Al, and Mn is synthesized.
  • the metal oxide is mixed with a lithium compound and baked to obtain a lithium-containing composite oxide.
  • the metal oxide can be synthesized, for example, by dropping an alkaline solution such as sodium hydroxide into a stirred solution of a metal salt containing Ni, Co, Al, Mn, etc., to adjust the pH to the alkaline side (e.g., 8.5 to 12.5) to precipitate (co-precipitate) a composite hydroxide containing metal elements such as Ni, Co, Al, and Mn, and then heat-treating the composite hydroxide.
  • the heat treatment temperature is not particularly limited, but an example is 300°C to 600°C.
  • lithium compounds include Li2CO3 , LiOH , Li2O2 , Li2O , LiNO3 , LiNO2 , Li2SO4 , LiOH.H2O , LiH, and LiF.
  • the metal oxide and the lithium compound are mixed so that the molar ratio of the metal element in the metal oxide to Li in the lithium compound is 1:0.98 to 1: 1.1 .
  • other metal raw materials may be added as necessary.
  • the mixture of metal oxide and lithium compound is fired, for example, under an oxygen atmosphere.
  • the mixture may be fired through multiple heating processes.
  • the firing process includes, for example, a first heating process in which the temperature is raised to 450°C to 680°C at a heating rate of 1.0°C/min to 5.5°C/min, and a second heating process in which the temperature is raised to a temperature exceeding 680°C at a heating rate of 0.1°C/min to 3.5°C/min.
  • the maximum temperature reached in the firing process may be set to 700°C to 850°C, and this temperature may be maintained for 1 hour to 10 hours.
  • the fired product (lithium-containing composite oxide) is washed with water and dehydrated to obtain a cake-like composition.
  • This washing step removes any remaining alkaline components.
  • the washing and dehydration can be carried out by a conventionally known method.
  • the cake-like composition is then dried to obtain a powder-like composition.
  • the drying step may be carried out in a vacuum atmosphere.
  • An example of the drying conditions is a temperature of 150°C to 400°C for 0.5 to 15 hours.
  • the sulfonic acid compound is added, for example, to the cake-like composition obtained in the washing step, or to the powder-like composition obtained in the drying step.
  • a sulfonic acid solution may be added in place of or together with the sulfonic acid compound. This results in a positive electrode active material in which the sulfonic acid compound is attached to the particle surface of the lithium-containing composite oxide.
  • the sulfonic acid compound may be added as an aqueous dispersion.
  • the sulfonic acid solution is preferably an aqueous solution of sulfonic acid.
  • the concentration of sulfonic acid in the sulfonic acid solution is, for example, 0.5% by mass or more and 40% by mass or less.
  • adding a sulfonic acid solution to the cake-like composition causes the Li dissolved in the water in the cake to react with the sulfonic acid, producing lithium sulfonate.
  • FIG. 2 is a cross-sectional view of the negative electrode 12 in one example of the embodiment.
  • the negative electrode 12 includes a negative electrode core 30, a first negative electrode mixture layer 31 arranged on the surface of the negative electrode 12, and a second negative electrode mixture layer 32 arranged between the first negative electrode mixture layer 31 and the negative electrode core.
  • a foil of a metal such as copper that is stable in the potential range of the negative electrode 12, a film having the metal arranged on the surface, or the like can be used.
  • the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 are preferably provided on both sides of the negative electrode core 30 except for the portion to which the negative electrode lead 21 is connected.
  • the aspect of the negative electrode 12 is not limited to the example of FIG. 2, and for example, a functional layer may be arranged between the second negative electrode mixture layer 32 and the negative electrode core 30.
  • the thickness T1 of the first negative electrode mixture layer 31 and the thickness T2 of the second negative electrode mixture layer 32 satisfy, for example, T1/(T1+T2) ⁇ 0.5. This allows the amount of conductive agent used when producing the negative electrode 12 to be reduced.
  • the lower limit of T1/(T1+T2) is, for example, 0.1.
  • the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 (hereinafter, the first negative electrode mixture layer and the second negative electrode mixture layer may be collectively referred to as the negative electrode mixture layer) contain a negative electrode active material and a conductive agent.
  • the negative electrode active material contained in the negative electrode mixture layer is not particularly limited as long as it can reversibly absorb and release lithium ions.
  • the negative electrode active materials contained in the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 may be different from each other, but are preferably the same.
  • a carbon material is used as the negative electrode active material.
  • the carbon material is, for example, at least one selected from the group consisting of natural graphite, artificial graphite, soft carbon, and hard carbon.
  • artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB), natural graphite such as flake graphite, massive graphite, and earthy graphite, or a mixture thereof.
  • the volume-based D50 of the carbon material is, for example, 1 ⁇ m or more and 30 ⁇ m or less, and preferably 5 ⁇ m or more and 25 ⁇ m or less.
  • Soft carbon and hard carbon are classified as amorphous carbons that do not have a developed graphite crystal structure. More specifically, they refer to carbon components with a d(002) interplanar spacing of 0.342 nm or more as determined by X-ray diffraction. Soft carbon is also called graphitizable carbon, and is carbon that is more easily graphitized by high-temperature treatment than hard carbon. Hard carbon is also called non-graphitizable carbon. In the configuration of the present invention, it is not necessary to clearly distinguish between soft carbon and hard carbon. Graphite and at least one of the amorphous carbons, soft carbon and hard carbon, may be used in combination as the negative electrode active material.
  • the negative electrode active material contained in the negative electrode mixture layer preferably contains a silicon-containing material from the viewpoint of high capacity. Since the volume change of the silicon-containing material during charging and discharging is larger than that of the carbon material, when the negative electrode mixture layer contains a silicon-containing material, the conductive path is likely to be disconnected between the negative electrode mixture layers. However, as described later, by making the content of the conductive agent in the first negative electrode mixture layer 31 larger than the content of the conductive agent in the second negative electrode mixture layer 32, the disconnection of the conductive path can be suppressed and the charge and discharge cycle characteristics can be improved.
  • the silicon-containing material may be any material containing Si, and examples include silicon alloys, silicon compounds, and composite materials containing Si. Among them, composite materials containing Si are preferable.
  • the D50 of the composite material is generally smaller than the D50 of graphite.
  • the volume-based D50 of the composite material is, for example, 1 ⁇ m or more and 15 ⁇ m or less. Note that one type of silicon-containing material may be used alone, or two or more types may be used in combination.
  • a suitable silicon-containing material is a composite particle containing an ion-conducting phase and a Si phase dispersed in the ion-conducting phase.
  • the ion-conducting phase is, for example, at least one selected from the group consisting of a silicate phase, a carbon phase, a silicide phase, and a silicon oxide phase.
  • the silicide phase is a phase of a compound consisting of Si and an element more electrically positive than Si, and examples thereof include NiSi, Mg 2 Si, and TiSi 2.
  • the Si phase is formed by dispersing Si in the form of fine particles.
  • the ion-conducting phase is a continuous phase constituted by a collection of particles finer than the Si phase.
  • the average size of the Si phase is preferably 1 nm or more and 200 nm or less, and more preferably 1 nm or more and 100 nm or less.
  • the average size of the Si phase is calculated by taking an SEM image of the particle cross section of the silicon-containing material and averaging the diameters of the circumscribed circles of the Si phase extracted by image analysis.
  • the average size of the Si phase may be, for example, 1 nm or more and 10 nm or less.
  • the composite material may have a conductive layer covering the surface of the ion conductive phase.
  • the conductive layer is made of a material with higher conductivity than the ion conductive layer, and forms a good conductive path in the negative electrode mixture layer.
  • the conductive layer is, for example, a carbon coating made of a conductive carbon material.
  • the conductive carbon material may be carbon black such as acetylene black or ketjen black, graphite, or amorphous carbon (amorphous carbon) with low crystallinity.
  • the thickness of the conductive layer is preferably 1 nm or more and 200 nm or less, more preferably 5 nm or more and 100 nm or less, taking into consideration the need to ensure conductivity and the diffusibility of Li ions into the particles. The thickness of the conductive layer can be measured by observing the cross section of the composite material using a SEM or a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • An example of a suitable composite material containing Si is a composite particle having a sea-island structure in which fine Si particles are substantially uniformly dispersed in an amorphous silicon oxide phase, and which is generally represented by the general formula SiO x (0.5 ⁇ x ⁇ 1.5).
  • the main component of the silicon oxide may be silicon dioxide.
  • the silicon oxide phase may be doped with Li.
  • a suitable composite material containing Si is a composite particle having a sea-island structure in which fine Si particles are dispersed approximately uniformly in an amorphous silicate phase.
  • the silicate phase contains, for example, at least one element selected from the group consisting of elements of Groups 1 and 2 of the periodic table.
  • the silicate phase may further contain at least one element selected from the group consisting of B, Al, Zr, Nb, Ta, V, La, Y, Ti, P, Bi, Zn, Sn, Pb, Sb, Co, Er, F, and W.
  • a suitable silicate phase is a lithium silicate phase containing Li.
  • the lithium silicate phase is, for example, a composite oxide phase represented by the general formula Li 2z SiO (2+z) (0 ⁇ z ⁇ 2).
  • Li 4 SiO 4 is an unstable compound that reacts with water to exhibit alkalinity, and may alter Si and cause a decrease in charge/discharge capacity.
  • a suitable composite material containing Si is a composite particle having an island structure in which fine Si particles are dispersed uniformly in a carbon phase.
  • the ion-conducting phase is preferably a carbon phase.
  • the carbon phase is preferably an amorphous carbon phase.
  • the carbon phase may contain a crystalline phase component, but it is preferable that the amorphous phase component is more prevalent.
  • the amorphous carbon phase is composed of a carbon material having an average interplanar spacing of (002) planes of more than 0.34 nm as measured by X-ray diffraction, for example.
  • the composite material containing a carbon phase may have a conductive layer separate from the carbon phase, or may not have the conductive layer.
  • the proportion of silicon-containing material contained in the negative electrode active material in the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 is, for example, 1 mass% or more and 20 mass% or less.
  • the proportion of silicon-containing material in the first negative electrode mixture layer 31 and the proportion of silicon-containing material in the second negative electrode mixture layer 32 may be different from each other, but are preferably the same.
  • the conductive agent content C1 in the first negative electrode mixture layer 31 and the conductive agent content C2 in the second negative electrode mixture layer 32 satisfy C1>C2. This makes it possible to improve the charge/discharge cycle characteristics while ensuring high capacity.
  • the first negative electrode mixture layer 31 disposed on the surface of the negative electrode 12 undergoes a greater volume change than the second negative electrode mixture layer 32 disposed inside the negative electrode 12, so the conductive path is more likely to be cut, and it is presumed that satisfying C1>C2 makes it easier to maintain the conductive path.
  • C1 and C2 preferably satisfy 1 ⁇ C1/C2 ⁇ 10.
  • the lower limit of C1/C2 is, for example, 1.1.
  • C1 is 0.01% by mass to 10% by mass with respect to the mass of the negative electrode active material contained in the first negative electrode mixture layer 31
  • C2 is 0.005% by mass to 5% by mass with respect to the mass of the negative electrode active material contained in the second negative electrode mixture layer 32.
  • the conductive agent may be particulate carbon such as carbon black, acetylene black, ketjen black, graphite, etc., but is preferably fibrous carbon. Fibrous carbon is more effective at preventing the conductive path from being broken than particulate carbon, and therefore can more significantly improve the charge-discharge cycle characteristics. Particulate carbon and fibrous carbon may be used in combination as the conductive agent.
  • fibrous carbon examples include carbon nanotubes (CNT), carbon nanohorns (CNH), carbon nanofibers (CNF), vapor-grown carbon fibers (VGCF), electrospun carbon fibers, polyacrylonitrile (PAN)-based carbon fibers, and pitch-based carbon fibers. These may be used alone or in combination of two or more. Of these, it is preferable to use CNT. There are no particular limitations on the layer structure of CNT, and it may be either single-walled carbon nanotubes (single-walled CNT) or multi-walled carbon nanotubes (multi-walled CNT).
  • the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 may further contain a binder.
  • binders include fluorine-containing resins such as styrene butadiene rubber (SBR), nitrile-butadiene rubber (NBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide, acrylic resin, and polyolefin.
  • SBR and NBR are preferred, and SBR is particularly preferred. These may be used alone or in combination of two or more types.
  • the binder contained in the first negative electrode mixture layer 31 and the binder contained in the second negative electrode mixture layer 32 may be different from each other, but are preferably the same.
  • the content of the conductive agent in the first negative electrode mixture layer 31 is, for example, 0% by mass to 10% by mass with respect to the mass of the negative electrode active material contained in the first negative electrode mixture layer 31.
  • the conductive agent content in the second negative electrode mixture layer 32 may be different from each other, but it is preferable that they are the same.
  • first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 a method for forming the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32 will be described.
  • a negative electrode active material, a conductive agent, and a solvent such as water are mixed to prepare a first negative electrode mixture slurry.
  • a negative electrode active material, a conductive agent, and a solvent such as water are mixed to prepare a second negative electrode mixture slurry.
  • the content of the conductive agent in the first negative electrode mixture slurry is made larger than the content of the conductive agent in the second negative electrode mixture slurry.
  • the second negative electrode mixture slurry is applied to both sides of the negative electrode core and dried, and then the first negative electrode mixture slurry is applied on the coating of the second negative electrode mixture slurry and dried. Furthermore, the coating film is rolled with a rolling roller to form the first negative electrode mixture layer 31 and the second negative electrode mixture layer 32.
  • the second negative electrode mixture slurry is applied and dried, and then the first negative electrode mixture slurry is applied.
  • the first negative electrode mixture slurry may be applied after the second negative electrode mixture slurry is applied and before drying.
  • the first negative electrode mixture slurry may be applied onto the second negative electrode mixture layer 32 after the second negative electrode mixture slurry is applied, dried, and rolled.
  • a porous sheet having ion permeability and insulating properties is used for the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • the material of the separator 13 is preferably a polyolefin such as polyethylene or polypropylene, or cellulose.
  • the separator 13 may have a single layer structure or a multi-layer structure.
  • a highly heat-resistant resin layer such as an aramid resin may be formed on the surface of the separator 13.
  • a filler layer containing an inorganic filler may be formed at the interface between the separator 13 and at least one of the positive electrode 11 and the negative electrode 12.
  • inorganic fillers include oxides and phosphate compounds containing metal elements such as Ti, Al, Si, and Mg.
  • the filler layer can be formed by applying a slurry containing the filler to the surface of the positive electrode 11, the negative electrode 12, or the separator 13.
  • Example 1 [Preparation of positive electrode active material]
  • the composite hydroxide represented by [Ni 0.90 Al 0.05 Mn 0.05 ] (OH) 2 obtained by the coprecipitation method was calcined at 500 ° C. for 8 hours to obtain an oxide (Ni 0.90 Al 0.05 Mn 0.05 O 2 ).
  • LiOH and the composite oxide were mixed so that the molar ratio of Li to the total amount of Ni, Al, and Mn was 1.03:1 to obtain a mixture.
  • This mixture was calcined from room temperature to 650 ° C. at a heating rate of 2.0 ° C.
  • the positive electrode active material, acetylene black, and polyvinylidene fluoride were mixed in a mass ratio of 98:1:1, and N-methyl-2-pyrrolidone (NMP) was used as a dispersion medium to prepare a positive electrode mixture slurry.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating was dried and compressed, and then the positive electrode core was cut into a predetermined electrode size to obtain a positive electrode in which a positive electrode mixture layer was disposed on both sides of the positive electrode core.
  • an exposed portion in which the surface of the positive electrode core was exposed was provided in a part of the positive electrode.
  • the second negative electrode mixture slurry was applied to both sides of a negative electrode core made of copper foil by the doctor blade method and dried to form a second negative electrode mixture layer. Furthermore, the above-mentioned first negative electrode mixture slurry was applied onto the second negative electrode mixture layer and dried to form a first negative electrode mixture layer. At this time, the application mass ratio per unit area of the first negative electrode mixture slurry and the second negative electrode mixture slurry was 50:50.
  • the first negative electrode mixture layer and the second negative electrode mixture layer were rolled with a rolling roller to prepare a negative electrode.
  • the value of T1/(T1+T2) calculated from the thickness T1 of the first negative electrode mixture layer and the thickness T2 of the second negative electrode mixture layer of the prepared negative electrode was 0.5. An exposed portion was provided in which the surface of the negative electrode core was exposed in a part of the negative electrode.
  • a non-aqueous electrolyte was prepared by dissolving LiPF6 at a concentration of 1.2 mol/L in a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 3:3:4 (25° C.).
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • test cell (secondary battery)
  • An aluminum lead was attached to the exposed part of the positive electrode, and a nickel lead was attached to the exposed part of the negative electrode, and the positive and negative electrodes were spirally wound through a polyolefin separator to prepare a wound electrode body.
  • Insulating plates were placed on the top and bottom of the electrode body, and the electrode body was housed in an outer can.
  • the negative electrode lead was welded to the bottom of a cylindrical outer can with a bottom, and the positive electrode lead was welded to a sealing body.
  • An electrolyte was poured into the outer can, and the opening of the outer can was sealed with a sealing body via a gasket to prepare a secondary battery as a test cell.
  • Example 2 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, lithium ethanesulfonate was used instead of lithium methanesulfonate, and the amount of lithium ethanesulfonate added was 0.5 mass% relative to the total mass of the lithium-containing composite oxide.
  • Example 3 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, sodium methanesulfonate was used instead of lithium methanesulfonate, and the amount of sodium methanesulfonate added was 0.5 mass% relative to the total mass of the lithium-containing composite oxide.
  • Example 1 A test cell was prepared and evaluated in the same manner as in Example 1, except that lithium methanesulfonate was not added in the preparation of the positive electrode active material.
  • Example 2 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, lithium succinate was used instead of methanesulfonic acid, and the amount of lithium succinate added was 0.5 mass% relative to the total mass of the lithium-containing composite oxide.
  • Example 3 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, lithium oxalate was used instead of methanesulfonic acid, and the amount of lithium oxalate added was 0.5 mass% relative to the total mass of the lithium-containing composite oxide.
  • the evaluation results of the test cells of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.
  • Table 1 the initial discharge capacity of the test cells of Examples 1 to 3 and Comparative Examples 2 and 3 is a relative value when the initial discharge capacity of the test cell of Comparative Example 1 is set to 100.
  • test cells of Examples 1 to 3 all have improved initial discharge capacity compared to the test cell of Comparative Example 1, and it can be seen that by including a methanesulfonic acid compound in the positive electrode, it is possible to achieve both battery capacity and charge/discharge characteristics.
  • the test cell of Example 1 which includes lithium methanesulfonate in the positive electrode, has a significantly improved initial discharge capacity.
  • the test cells of Comparative Examples 2 and 3 have the same initial discharge capacity as the test cell of Comparative Example 1, but have a lower capacity retention rate. This shows that sulfonic acid compounds have a more significant effect than succinic acid compounds and oxalic acid compounds.
  • Example 4 A test cell was produced and evaluated in the same manner as in Example 1, except that in the production of the negative electrode, the amount of single-walled CNTs added when preparing the first negative electrode mixture slurry was changed to 0.1 parts by mass.
  • Example 4 A test cell was produced and evaluated in the same manner as in Example 1, except that in the production of the negative electrode, the amount of single-walled CNTs added when preparing the first negative electrode mixture slurry was changed to 0.5 parts by mass.
  • Example 6 A test cell was prepared and evaluated in the same manner as in Example 4, except that lithium methanesulfonate was not added in the preparation of the positive electrode active material.
  • Example 5 A test cell was produced and evaluated in the same manner as in Example 1, except that in the production of the negative electrode, the amount of single-walled CNTs added when preparing the first negative electrode mixture slurry was changed to 1.0 part by mass.
  • Example 7 A test cell was prepared and evaluated in the same manner as in Example 5, except that lithium methanesulfonate was not added in the preparation of the positive electrode active material.
  • the evaluation results of the test cells of Examples 1, 4, and 5, and Comparative Examples 1 and 4 to 7 are shown in Table 2.
  • Table 2 the initial discharge capacity of the test cells of Examples 1, 4, and 5, and Comparative Examples 4 to 7 is a relative value when the initial discharge capacity of the test cell of Comparative Example 1 is set to 100.
  • Example 6 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the negative electrode, the coating mass ratio per unit area of the first negative electrode mixture slurry and the second negative electrode mixture slurry was set to 20:80. The value of T1/(T1+T2) was 0.2.
  • Example 8 A test cell was prepared and evaluated in the same manner as in Example 6, except that lithium methanesulfonate was not added in the preparation of the positive electrode active material.
  • the evaluation results of the test cells of Examples 1 and 6, and Comparative Examples 1 and 8 are shown in Table 3.
  • the initial discharge capacity of the test cells of Examples 1 and 6, and Comparative Example 8 is a relative value when the initial discharge capacity of the test cell of Comparative Example 1 is set to 100.
  • Configuration 1 A positive electrode, a negative electrode, and a non-aqueous electrolyte
  • the positive electrode includes a lithium-containing composite oxide and a sulfonic acid compound present on a particle surface of the lithium-containing composite oxide
  • the sulfonic acid compound is a compound represented by formula (I)
  • the negative electrode includes a negative electrode core, a first negative electrode mixture layer disposed on a surface of the negative electrode, and a second negative electrode mixture layer disposed between the first negative electrode mixture layer and the negative electrode core
  • the first negative electrode mixture layer and the second negative electrode mixture layer contain a negative electrode active material and a conductive agent, a content C1 of the conductive agent in the first negative electrode mixture layer and a content C2 of the conductive agent in the second negative electrode mixture layer satisfy C1>C2.
  • Configuration 2 2. The nonaqueous electrolyte secondary battery according to claim 1, wherein A is a Group 1 element.
  • Configuration 3 2. The nonaqueous electrolyte secondary battery according to claim 1, wherein A is Li.
  • Configuration 4 4. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein R is an alkyl group.
  • Configuration 5 4. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein R is a methyl group.
  • Configuration 6 The amount of the sulfonic acid compound present on the surface of the lithium-containing composite oxide is 0.1 mass% or more and 1 mass% or less with respect to the mass of the lithium-containing composite oxide.
  • Configuration 7 7. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 6, wherein the lithium-containing composite oxide has a layered rock salt structure.
  • Configuration 8 8. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 7, wherein C1 and C2 satisfy 1 ⁇ C1/C2 ⁇ 10.
  • Configuration 9 9. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 8, wherein the conductive agent is fibrous carbon.
  • Configuration 10 10.
  • non-aqueous electrolyte secondary battery 11 positive electrode, 12 negative electrode, 13 separator, 14 electrode body, 16 outer can, 17 sealing body, 18, 19 insulating plate, 20 positive electrode lead, 21 negative electrode lead, 22 grooved portion, 23 internal terminal plate, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cap, 28 gasket, 30 negative electrode core body, 31 first negative electrode mixture layer, 32 second negative electrode mixture layer

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JP2018006164A (ja) 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
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WO2021059706A1 (ja) * 2019-09-27 2021-04-01 パナソニックＩｐマネジメント株式会社 リチウムイオン二次電池用負極及びリチウムイオン二次電池
WO2021059705A1 (ja) * 2019-09-27 2021-04-01 パナソニックＩｐマネジメント株式会社 リチウムイオン二次電池用負極およびリチウムイオン二次電池

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JP2018006164A (ja) 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
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