WO2021166812A1 - 球状化黒鉛、被覆球状化黒鉛、リチウムイオン二次電池用負極およびリチウム二次電池 - Google Patents

球状化黒鉛、被覆球状化黒鉛、リチウムイオン二次電池用負極およびリチウム二次電池 Download PDF

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WO2021166812A1
WO2021166812A1 PCT/JP2021/005348 JP2021005348W WO2021166812A1 WO 2021166812 A1 WO2021166812 A1 WO 2021166812A1 JP 2021005348 W JP2021005348 W JP 2021005348W WO 2021166812 A1 WO2021166812 A1 WO 2021166812A1
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spheroidized graphite
negative electrode
graphite
secondary battery
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English (en)
French (fr)
Japanese (ja)
Inventor
遼太 山地
間所　靖
小比賀　基治
松崎　晃
弘之 増岡
幹人 須藤
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JFE Steel Corp
JFE Chemical Corp
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JFE Steel Corp
JFE Chemical Corp
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Priority to JP2021552677A priority Critical patent/JP7144625B2/ja
Priority to CN202180003562.XA priority patent/CN114080702B/zh
Priority to KR1020217037648A priority patent/KR102642860B1/ko
Publication of WO2021166812A1 publication Critical patent/WO2021166812A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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
    • 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 spheroidized graphite, coated spheroidized graphite, a negative electrode for a lithium ion secondary battery, and a lithium secondary battery.
  • Lithium-ion secondary batteries have a negative electrode, a positive electrode and a non-aqueous electrolyte as main components. Lithium ions act as a secondary battery by moving between the negative electrode and the positive electrode during the discharging and charging processes.
  • spheroidized graphite spheroidized graphite
  • Patent Document 1 Lithium-ion secondary batteries have a negative electrode, a positive electrode and a non-aqueous electrolyte as main components. Lithium ions act as a secondary battery by moving between the negative electrode and the positive electrode during the discharging and charging processes.
  • spheroidized graphite spheroidized graphite
  • Patent Document 1 spheroidized graphite
  • the negative electrode material of the lithium ion secondary battery may be required to have excellent output characteristics (small output resistance).
  • lithium-ion secondary batteries are expected to be widely installed in automobiles (hybrid vehicles, electric vehicles, etc.) in the future. For example, when a car suddenly starts, better output characteristics are required.
  • an object of the present invention is to provide spheroidized graphite having excellent output characteristics when used as a negative electrode material for a lithium ion secondary battery.
  • the present invention provides the following [1] to [9].
  • [1] In the particle size distribution of the primary particles obtained by using X-ray CT, the volume ratio of the primary particles having a sphere-equivalent diameter of 0.8 ⁇ m or less is 40.0% or less, and the sphere-equivalent diameter is 1.
  • the volume ratio of spherical secondary particles is 14.0% or more, and the volume ratio of rod-shaped secondary particles is The spheroidized graphite according to the above [1], which is 34.0% or less.
  • Spheroidized graphite is a geometrical shape distribution of secondary particles obtained by using X-ray CT.
  • [4] The spheroidized graphite according to any one of the above [1] to [3], which is obtained by spheroidizing natural graphite.
  • [5] A coated spheroidized graphite containing the spheroidized graphite according to any one of the above [1] to [4] and the carbonaceous material that coats the spheroidized graphite.
  • [6] The coating spheroidization according to the above [5], wherein the average secondary particle size is 5.0 ⁇ m or more and 50.0 ⁇ m or less, and the specific surface area is 0.5 m 2 / g or more and 10.0 m 2 / g or less. graphite.
  • the pore volume, pore size corresponding to 36.0nm following pores than 7.8nm is less than or equal 0.015 cm 3 / g or more 0.028 cm 3 / g, the [5] or [6]
  • the coated spheroidized graphite according to. [8] A negative electrode for a lithium ion secondary battery containing the coated spheroidized graphite according to any one of the above [5] to [7].
  • [9] A lithium ion secondary battery having the negative electrode according to the above [8].
  • 2A to 2C It is a three-dimensional image of other secondary particles. It is a three-dimensional image of other secondary particles observed from a different angle from FIG. 3A. 3A is a three-dimensional image of other secondary particles observed from different angles from FIGS. 3A to 3B. 3A is a three-dimensional image of other secondary particles observed from different angles from FIGS. 3A to 3C. It is sectional drawing of the evaluation battery produced for evaluating the battery characteristic in an Example and a comparative example.
  • the spheroidized graphite of the present invention has a volume ratio of primary particles (hereinafter, also referred to as “fine particles”) having a sphere-equivalent diameter of 0.8 ⁇ m or less in the particle size distribution of the primary particles obtained by using X-ray CT.
  • the volume ratio of primary particles (hereinafter, also referred to as “coarse particles”) having a sphere equivalent diameter of 1.5 ⁇ m or more and 3.0 ⁇ m or less is 13.0% or more.
  • the spheroidized graphite of the present invention has a fine grain volume ratio of 40.0% or less and a coarse grain volume ratio of 13.0% or more.
  • the volume ratio of the fine particles is preferably 39.0% or less, more preferably 34.0% or less, further preferably 28.0% or less, and particularly preferably 23.0% or less because the output characteristics are more excellent.
  • the lower limit of the volume ratio of the fine particles is not particularly limited, and is, for example, 5.0% or more, preferably 10.0% or more, more preferably 13.0% or more, still more preferably 15.0% or more. ..
  • the volume ratio of coarse grains is preferably 14.0% or more, more preferably 18.0% or more, further preferably 21.0% or more, and particularly preferably 25.0% or more, because the output characteristics are more excellent. ..
  • the upper limit of the volume ratio of the coarse grains is not particularly limited, and is, for example, 60.0% or less, preferably 50.0% or less, more preferably 40.0% or less, and further preferably 35.0% or less. It is preferable, and 32.0% or less is particularly preferable.
  • ⁇ Particle size distribution of primary particles A method for obtaining the particle size distribution of the primary particles constituting the spheroidized graphite will be described.
  • X-ray CT Computed Tomography
  • imaging type X-ray CT is performed at the beamline (BL24XU) of SPring-8 under the following conditions.
  • X-ray energy 8 keV -Image resolution: 1248 (H) x 2048 (W) pixels-Execution pixel size: 68 nm / pixel-Exposure time: 0.5 seconds-Number of projected images: 1200 images-Deforcus: 0.3 mm
  • the spheroidized graphite as a sample is filled in a quartz glass capillary (inner diameter: about 0.1 mm) and subjected to X-ray CT. After taking a projection image of spheroidized graphite, it is reconstructed into a cross-sectional slice image.
  • the spheroidized graphite of the present invention has a spherical secondary particle (hereinafter, also referred to as “spherical particle”) in the particle shape distribution of the secondary particle obtained by using X-ray CT because the output characteristic is more excellent. It is preferable that the volume ratio of the particles is 14.0% or more and the volume ratio of the rod-shaped secondary particles (hereinafter, also referred to as “rod-shaped particles”) is 34.0% or less.
  • the volume ratio of the spherical particles is preferably 16.0% or more, more preferably 18.0% or more, still more preferably 20.0% or more, because the output characteristics are further excellent.
  • the upper limit of the volume ratio of the spherical particles is not particularly limited, and is, for example, 50.0% or less, preferably 40.0% or less, more preferably 30.0% or less, and further preferably 25.0% or less. It is preferable, and 23.0% or less is particularly preferable.
  • the volume ratio of the rod-shaped particles is preferably 30.0% or less, more preferably 28.0% or less, still more preferably 25.0% or less, because the output characteristics are further excellent.
  • the lower limit of the volume ratio of the rod-shaped particles is not particularly limited, and is, for example, 5.0% or more, preferably 10.0% or more, more preferably 15.0% or more, and further 20.0% or more. preferable.
  • X-ray energy 20 keV -Image resolution: 2048 (H) x 2048 (W) pixels-Execution pixel size: 325 nm / pixel-Exposure time: 0.1 seconds-Number of projected images taken: 1800-Distance between sample and detector: 10mm
  • the spheroidized graphite as a sample is filled in a borosilicate glass capillary (inner diameter: about 0.6 mm) and subjected to X-ray CT. After taking a projection image of spheroidized graphite, it is reconstructed into a cross-sectional slice image.
  • Spherical S / L ⁇ 0.5 and M / L ⁇ 0.5
  • Rod S / L ⁇ 0.5 and M / L ⁇ 0.5
  • the volume ratio of the secondary particles (spherical particles) classified into spheres and the volume ratio of the secondary particles (rod-shaped particles) classified into rods are obtained with respect to the total volume of each secondary particle. In this way, the shape distribution of the secondary particles is obtained.
  • FIGS. 1A to 1D the same one secondary particle is observed, and the observation angles are different from each other. This also applies to FIGS. 2A to 3D and FIGS. 3A to
  • the average secondary particle size (also simply referred to as “average particle size”) of the spheroidized graphite of the present invention is preferably 5.0 ⁇ m or more, more preferably 6.5 ⁇ m or more, still more preferably 7.0 ⁇ m or more.
  • the average particle size of the spheroidized graphite of the present invention is preferably 15.0 ⁇ m or less, more preferably 14.0 ⁇ m or less, further preferably 12.0 ⁇ m or less, particularly preferably 10.0 ⁇ m or less, and 9.8 ⁇ m or less. Most preferred.
  • the average particle size is a particle size at which the cumulative frequency of the particle size distribution obtained by using a laser diffraction type particle size distribution meter (manufactured by Seishin Enterprise Co., Ltd., LMS2000e) is 50% by volume.
  • the specific surface area of the spheroidized graphite of the present invention is preferably 5.0 m 2 / g or more, more preferably 7.0 m 2 / g or more, and even more preferably 9.5 m 2 / g or more.
  • the specific surface area of the spherical graphite of the present invention is preferably 15.0 m 2 / g or less, more preferably 13.0m 2 / g or less, still more preferably 11.0 m 2 / g or less, 10.0 m 2 / G or less is particularly preferable.
  • the specific surface area is the BET specific surface area measured in accordance with JIS Z 8830: 2013 “Method for measuring the specific surface area of powder (solid) by gas adsorption”. Specifically, the sample is pre-dried at 50 ° C., then nitrogen gas is allowed to flow for 30 minutes, and then MONOSORB (manufactured by Kantachrome Instruments Japan GK) is used to obtain the sample by the BET 1-point method by nitrogen gas adsorption. ..
  • the method for producing the spheroidized graphite of the present invention is not particularly limited, and examples thereof include a method for processing a raw material into a spherical shape.
  • the raw material is graphite having a shape other than spherical (including ellipsoidal), for example, scaly graphite.
  • the graphite may be either natural graphite or artificial graphite, but natural graphite is preferable because of its high crystallinity and the like.
  • a method of mixing raw materials in the coexistence of a granulation aid such as an adhesive or a resin; a method of applying a mechanical external force to the raw material without using a granulation aid; a method of using both in combination. ; Etc. can be mentioned.
  • a method of applying a mechanical external force to the raw material without using a granulation aid is preferable.
  • this method will be described in more detail.
  • a raw material eg, scaly graphite
  • a pulverizer e.g., a mechanical external force using a pulverizer.
  • the raw material is spheroidized to obtain spheroidized graphite.
  • the crushing device include a rotary ball mill, a counter jet mill (manufactured by Hosokawa Micron), a current jet (manufactured by Nisshin Engineering Co., Ltd.), a hybridization system (manufactured by Nara Machinery Co., Ltd.), a CF mill (manufactured by Ube Kosan Co., Ltd.), and a mechano.
  • Examples thereof include a fusion system (manufactured by Hosokawa Micron Co., Ltd.) and a theta composer (manufactured by Tokuju Kosakusho Co., Ltd.), and among them, a hybridization system (manufactured by Nara Machinery Co., Ltd.) is preferable.
  • a plurality of crushing devices are arranged in series and then the raw material continuously passes through the plurality of crushing devices. That is, it is preferable to arrange a plurality of crushing devices in series so that crushing and granulation are performed in the next crushing device immediately after the raw material has passed through one crushing device.
  • the number of crushing devices is, for example, two or more, preferably three or more, more preferably four or more, further preferably five or more, and particularly preferably six or more.
  • the number of crushers is preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less.
  • the time for crushing and granulating the raw material (hereinafter, also referred to as “crushing time”) in one crushing device is preferably 8 minutes or more, more preferably 13 minutes or more, still more preferably 18 minutes or more.
  • the crushing time in one crushing device is preferably 60 minutes or less, more preferably 50 minutes or less, still more preferably 40 minutes or less.
  • total crushing time The product of the number of crushing devices and the crushing time in one crushing device (hereinafter, also referred to as “total crushing time”) is preferably 30 minutes or more, more preferably 50 minutes or more, still more preferably 90 minutes or more. On the other hand, the total crushing time is preferably 180 minutes or less, more preferably 160 minutes or less.
  • the crusher usually has a built-in rotor.
  • the peripheral speed of the rotor in each pulverizer is preferably 30 m / sec or more, more preferably 40 m / sec or more, still more preferably 60 m / sec or more.
  • the peripheral speed of the rotor in each pulverizer is preferably 100 m / sec or less, more preferably 80 m / sec or less.
  • the amount of the raw material to be filled in each crushing device is small in order to easily apply the shearing force and the compressive force to the raw material.
  • the coated spheroidized graphite of the present invention contains spheroidized graphite and a carbonaceous material that coats the spheroidized graphite.
  • the spheroidized graphite is the spheroidized graphite of the present invention described above.
  • the carbonaceous content in the coated spheroidized graphite of the present invention is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, further preferably 8.0% by mass or more, and 10.0% by mass or more. Is particularly preferable. When the carbonaceous content is in this range, the active edge surface of the spheroidized graphite is easily covered, and the initial charge / discharge efficiency is excellent.
  • the carbonaceous content in the coated spheroidized graphite of the present invention is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, further preferably 20.0% by mass or less, and 15.0% by mass. % Or less is particularly preferable.
  • the carbon content is in this range, the amount of carbon having a relatively low discharge capacity is reduced, and the discharge capacity is excellent.
  • the carbon content is in this range, the amount of the carbonaceous precursor described later is reduced, so that fusion is less likely to occur during mixing and firing described later, and the finally obtained carbon is obtained. Quality cracking and peeling are suppressed, and the initial charge / discharge efficiency is excellent.
  • the carbonaceous content may be such that the average value of the entire coated spheroidized graphite is within the above range. It is not necessary that all of the individual coated spheroidized graphites are within the above range, and coated spheroidized graphites other than the above range may be partially contained.
  • the carbonaceous content is determined from the amount of residual carbonaceous carbonaceous precursor by firing only the carbonaceous precursor under the same conditions as when firing the mixture of spheroidized graphite and the carbonaceous precursor.
  • the average secondary particle size (average particle size) of the coated spheroidized graphite of the present invention is preferably 5.0 ⁇ m or more, more preferably 7.0 ⁇ m or more.
  • the average particle size of the coated spheroidized graphite of the present invention is preferably 50.0 ⁇ m or less, more preferably 30.0 ⁇ m or less, and even more preferably 20.0 ⁇ m or less.
  • the specific surface area of the coated spherical graphite of the present invention is preferably at least 0.5 m 2 / g, more preferably at least 1.5 m 2 / g, more preferably not less than 3.0m 2 / g, 4.0m 2 / g The above is particularly preferable.
  • the specific surface area of the coated spherical graphite of the present invention is preferably 10.0 m 2 / g or less, more preferably 8.0 m 2 / g, still more preferably 7.0 m 2 / g or less, 5.5 m 2 / G or less is particularly preferable.
  • ⁇ Pore volume> The present inventors have focused on the pore volume calculated by the DFT (Density Functional Theory) method from the nitrogen adsorption isotherm as an index that correlates with the resistance associated with the occlusion and release of lithium in the coated spheroidized graphite.
  • the present inventors have found that the pore volume corresponding to pores having a pore diameter of less than 7.8 nm is derived from amorphous carbon and is unlikely to contribute to the resistance associated with occlusion and release of lithium. ..
  • the present inventors have clarified that the pore volume corresponding to pores having a pore diameter of 7.8 nm or more and 36.0 nm or less is a good index that correlates with resistance.
  • the pore volume corresponding to the pores having a pore diameter of 7.8 nm or more and 36.0 nm or less (hereinafter, for convenience, “also referred to as pore volume V ”) is preferably 0.015 cm 3 / g or more, 0.016 cm 3 / g or more is more preferable.
  • the pore volume V of the coated spherical graphite of the present invention is preferably not more than 0.028 cm 3 / g, more preferably 0.026cm 3 / g or less, more preferably 0.023 3 / g or less ..
  • the measurement of pore volume by the DFT method is based on JIS Z 8831-2 (measurement method of mesopores and macropores by gas adsorption) and JIS Z 8831-3 (measurement method of micropores by gas adsorption). Ask. At this time, the measurement of the pore volume is started from the relative pressure of 5 ⁇ 10 ⁇ 2 Pa.
  • the method for producing the coated spheroidized graphite of the present invention is not particularly limited, but for example, a method in which a carbonaceous precursor is added to the spheroidized graphite of the present invention as a core material, mixed, and then calcined is preferable. Listed in. According to this method, the carbonaceous precursor becomes a carbonaceous material that coats the core material (spheroidized graphite) through mixing and firing. That is, coated spheroidized graphite is obtained.
  • this method will be described in detail.
  • tar pitches and / or resins which are carbon materials having lower crystallinity than graphite and cannot be graphitized even by high-temperature treatment required for graphitization.
  • tar pitches include coal tar, tar light oil, tar medium oil, tar heavy oil, naphthaline oil, anthracene oil, coal tar pitch, pitch oil, mesophase pitch, oxygen-bridged oil pitch, and heavy oil.
  • the resins include thermoplastic resins such as polyvinyl alcohol and polyacrylic acid; thermosetting resins such as phenol resins and furan resins; and the like.
  • the carbonaceous precursor does not contain resins and consists only of tar pitches.
  • a carbonaceous precursor having a coal tar pitch of 80% by mass or more is preferably mentioned.
  • the core material (spheroidized graphite) and the carbonaceous precursor are mixed.
  • the mixing ratio is preferably a mixing ratio in which the carbonaceous content is the above-mentioned content in the finally obtained coated spheroidized graphite.
  • the mixing method is not particularly limited as long as it can be mixed homogeneously, and a known mixing method is used. For example, a method of heating and mixing using a biaxial kneader or the like having a heating mechanism such as a heater or a heat medium can be mentioned.
  • the atmosphere at the time of mixing is not particularly limited, and is, for example, an air atmosphere.
  • the temperature at the time of mixing (mixing temperature) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and even more preferably 25 ° C. or higher.
  • the mixing temperature is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 60 ° C. or lower.
  • the mixture obtained by the above-mentioned mixing is calcined.
  • the firing method is not particularly limited, but it is preferable to fire in an inert atmosphere in order to prevent oxidation during firing. At this time, it is preferable to use a tube furnace.
  • the atmosphere at the time of firing include an argon atmosphere, a helium atmosphere, and a nitrogen atmosphere as the non-oxidizing atmosphere.
  • the temperature at the time of firing (firing temperature) is preferably 700 ° C. or higher, more preferably 900 ° C. or higher.
  • the firing temperature is preferably 2000 ° C. or lower, more preferably 1300 ° C. or lower, and even more preferably 1200 ° C. or lower.
  • the firing time is preferably 5 minutes or more.
  • the firing time is preferably 30 hours or less.
  • various forms such as a linear temperature rise and a stepwise temperature rise in which the temperature is held at regular intervals can be adopted.
  • graphite materials may be attached to, embedded or composited with the core material (spheroidized graphite).
  • core material spheroidized graphite
  • different types of graphite materials include carbonic or graphitic fibers; carbonaceous precursor materials such as amorphous hard carbon; organic materials; inorganic materials; and the like.
  • spheroidized graphite of the present invention and “coated spheroidized graphite of the present invention” may be collectively referred to as “negative electrode material of the present invention” below.
  • the negative electrode for a lithium ion secondary battery of the present invention is a negative electrode for a lithium ion secondary battery containing the negative electrode material of the present invention.
  • the negative electrode for a lithium ion secondary battery is also simply referred to as a "negative electrode”.
  • the negative electrode of the present invention is manufactured according to a normal negative electrode.
  • a negative electrode mixture prepared in advance by adding a binder to the negative electrode material of the present invention.
  • the negative electrode mixture may contain an active material or a conductive material other than the negative electrode material of the present invention.
  • the binder is preferably one that is chemically and electrochemically stable with respect to the electrolyte, and is, for example, a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride; polyethylene, polyvinyl alcohol, styrene butadiene rubber, or the like. Resin; carboxymethyl cellulose; etc. are used, and two or more of these can be used in combination.
  • the binder is usually used in a proportion of about 1 to 20% by mass in the total amount of the negative electrode mixture.
  • the negative electrode material of the present invention is optionally adjusted to a desired particle size by classification or the like. Then, the negative electrode material of the present invention is mixed with a binder, and the obtained mixture is dispersed in a solvent to prepare a paste-like negative electrode mixture.
  • the solvent include water, isopyrpillar alcohol, N-methylpyrrolidone, dimethylformamide and the like.
  • a known stirrer, mixer, kneader, kneader or the like is used for mixing and dispersion.
  • the prepared paste is applied to one or both sides of the current collector and dried. In this way, a negative electrode mixture layer (negative electrode) that is uniformly and firmly adhered to the current collector can be obtained.
  • the thickness of the negative electrode mixture layer is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m. After forming the negative electrode mixture layer, crimping such as press pressure can further increase the adhesion strength between the negative electrode mixture layer (negative electrode) and the current collector.
  • the shape of the current collector is not particularly limited, but is, for example, a foil shape, a mesh shape, a mesh shape such as an expanded metal, or the like. As the material of the current collector, copper, stainless steel, nickel and the like are preferable.
  • the thickness of the current collector is preferably about 5 to 20 ⁇ m in the case of a foil shape.
  • the orientation of graphite is suppressed even if the density is high.
  • the degree of orientation of the negative electrode can be quantitatively evaluated by X-ray diffraction. The method will be described below. First, a 2 cm 2 disk-shaped negative electrode (density: 1.20 g / cm 3 ) is attached onto a glass plate so that the negative electrode faces upward. When the sample thus prepared is irradiated with X-rays and diffracted, a plurality of diffraction peaks corresponding to the crystal planes of graphite appear.
  • the degree of orientation (I 004 / I 110 ) is preferably 5.0 or less, and more preferably 4.0 or less. , 3.5 or less is more preferable.
  • the lithium ion secondary battery of the present invention is a lithium ion secondary battery having the negative electrode of the present invention.
  • the lithium ion secondary battery of the present invention further includes a positive electrode, a non-aqueous electrolyte, and the like, in addition to the negative electrode of the present invention.
  • the lithium ion secondary battery of the present invention is configured by, for example, laminating a negative electrode, a non-aqueous electrolyte, and a positive electrode in this order and accommodating them in the exterior material of the battery.
  • the lithium ion secondary battery of the present invention can be arbitrarily selected from a cylindrical type, a square type, a coin type, a button type, and the like according to an application, an on-board device, a required charge / discharge capacity, and the like.
  • ⁇ Positive electrode> It is preferable to select a material for the positive electrode (positive electrode active material) that can occlude / release a sufficient amount of lithium.
  • the positive electrode active material in addition to lithium, for example, lithium-containing transition metal oxides, transition metal chalcogenides, lithium-containing compounds such as vanadium oxides and lithium compounds thereof; formula M X Mo 6 S 8-Y (wherein M is at least one kind of transition metal element, X is a numerical value in the range of 0 ⁇ X ⁇ 4, Y is a numerical value in the range of 0 ⁇ Y ⁇ 1). Be done.
  • Vanadium oxides are represented by V 2 O 5 , V 6 O 13 , V 2 O 4 , and V 3 O 8 .
  • the lithium-containing transition metal oxide is a composite oxide of lithium and a transition metal, and may be a solid solution of lithium and two or more kinds of transition metals.
  • the composite oxide may be used alone or in combination of two or more.
  • Lithium-containing transition metal oxide specifically, LiM 1 1-X M 2 X O 2 (wherein M 1, M 2 is a transition metal element of at least one, X is the range of 0 ⁇ X ⁇ 1 is a numerical value), or, LiM 1 1-Y M 2 Y O 4 (wherein M 1, M 2 is a transition metal element of at least one, Y is a number in the range 0 ⁇ Y ⁇ 1) Indicated by.
  • the transition metal elements represented by M 1 and M 2 are Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn and the like, and preferably Co, Fe, Mn, Ti and Cr. , V, Al, etc.
  • Preferred specific examples are LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi 0.9 Co 0.1 O 2 , LiNi 0.5 Co 0.5 O 2 , and the like.
  • the lithium-containing transition metal oxide uses, for example, lithium, transition metal oxides, hydroxides, salts, etc. as starting materials, and these starting materials are mixed according to the desired composition of the metal oxide, and 600 in an oxygen atmosphere. It can be obtained by firing at a temperature of about 1000 ° C.
  • the above-mentioned compounds may be used alone or in combination of two or more.
  • a carbon salt such as lithium carbonate can be added to the positive electrode.
  • various additives such as conventionally known conductive agents and binders can be appropriately used.
  • a positive electrode mixture composed of a positive electrode active material, a binder, and a conductive agent for imparting conductivity to the positive electrode is applied to both sides of a current collector to form a positive electrode mixture layer.
  • a binder a binder used for producing a negative electrode can be used.
  • a conductive agent a known conductive agent such as graphitized product or carbon black is used.
  • the shape of the current collector is not particularly limited, and examples thereof include a foil shape and a net shape.
  • the material of the current collector is aluminum, stainless steel, nickel, or the like.
  • the thickness of the current collector is preferably 10 to 40 ⁇ m.
  • a paste-like positive electrode mixture may be applied to the current collector, dried, and then crimped by press pressure or the like.
  • the non-aqueous electrolyte may be a liquid non-aqueous electrolyte (non-aqueous electrolyte liquid), or may be a polymer electrolyte such as a solid electrolyte or a gel electrolyte.
  • the non-aqueous electrolyte battery is configured as a so-called lithium ion secondary battery.
  • the non-aqueous electrolyte battery is configured as a polymer electrolyte battery such as a polymer solid electrolyte battery or a polymer gel electrolyte battery.
  • an electrolyte salt used in the conventional non-aqueous electrolyte solution LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiB (C 6 H 5), LiCl, LiBr, LiCF 3 SO 3, LiCH 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 OSO 2 ) 2 , LiN (HCF 2 CF) 2 CH 2 OSO 2 ) 2 , LiN ((CF 3 ) 2 CHOSO 2 ) 2 , LiB [ ⁇ C 6 H 3 (CF 3 ) 2 ⁇ ] 4 , LiAlCl 4 , LiSiF 6 and other lithium salts are used.
  • the concentration of the electrolyte salt in the non-aqueous electrolyte liquid is preferably 0.1 to 5.0 mol / L, more preferably 0.5 to 3.0 mol / L.
  • Solvents for preparing the non-aqueous electrolyte solution include, for example, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate; 1,1- or 1,2-dimethoxyethane, 1,2-diethoxyethane, Ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran, ⁇ -butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, anisole, diethyl ether; thioethers such as sulfolane, methyl sulfolane; acetonitrile, chloronitrile, propio Nitriles such as nitriles; trimethyl borate, tetramethyl silicate, nitromethane, dimethyl formamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzoyl chloride, benzoyl bro
  • the non-aqueous electrolyte is a polymer electrolyte such as a solid electrolyte or a gel electrolyte
  • a polymer gelled with a plasticizer non-aqueous electrolyte solution
  • the polymer constituting the matrix include polyethylene oxide, an ether-based polymer compound such as a crosslinked product thereof; a poly (meth) acrylate-based polymer compound; polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and the like. Fluoropolymer compounds; etc. are preferably used.
  • the concentration of the electrolyte salt in the non-aqueous electrolyte liquid, which is a plasticizer, is preferably 0.1 to 5.0 mol / L, more preferably 0.5 to 2.0 mol / L.
  • the proportion of the plasticizer is preferably 10 to 90% by mass, more preferably 30 to 80% by mass.
  • a separator can also be used.
  • the material of the separator is not particularly limited, but for example, a woven fabric, a non-woven fabric, a microporous membrane made of synthetic resin, or the like is used.
  • a microporous membrane made of synthetic resin is preferable, and among them, a polyolefin-based microporous membrane is more preferable in terms of thickness, membrane strength, and membrane resistance.
  • the polyolefin-based microporous membrane include a polyethylene microporous membrane, a polypropylene microporous membrane, and a composite microporous membrane thereof.
  • Coal tar pitch which is a carbonaceous precursor
  • Coal tar pitch which is a carbonaceous precursor
  • the carbonaceous precursor was added in an amount such that the finally obtained carbonaceous material had the content shown in Table 1 below.
  • firing was performed at 1100 ° C. for 10 hours under a flow of 5 L / min of nitrogen (in a non-oxidizing atmosphere).
  • coated spheroidized graphite in which spheroidized graphite was coated with carbonaceous material was obtained.
  • the physical characteristics (average secondary particle size, etc.) of the obtained coated spheroidized graphite were determined by the above-mentioned method. The results are shown in Table 1 below.
  • a negative electrode mixture paste was prepared by adding 98 parts by mass of coated spheroidized graphite (negative electrode material), 1 part by mass of carboxymethyl cellulose (binder) and 1 part by mass of styrene butadiene rubber (binder) to water and stirring. ..
  • the prepared negative electrode mixture paste was applied onto a copper foil (thickness: 16 ⁇ m) to a uniform thickness, and further dried in vacuum at 90 ° C. to form a negative electrode mixture layer.
  • the negative electrode mixture layer was pressed by a hand press at a pressure of 120 MPa. Then, the copper foil and the negative electrode mixture layer were punched into a circular shape having a diameter of 15.5 mm.
  • FIG. 4 is a cross-sectional view showing a button type secondary battery.
  • the button-type secondary battery shown in FIG. 4 has a hermetically sealed structure in which the peripheral edges of the outer cup 1 and the outer can 3 are crimped via an insulating gasket 6. Inside the sealed structure, a current collector 7a, a positive electrode 4, a separator 5, a negative electrode 2, and a current collector 7b are laminated in this order from the inner surface of the outer can 3 toward the inner surface of the outer cup 1.
  • the button-type secondary battery shown in FIG. 4 was manufactured as follows. First, a non-aqueous electrolyte solution was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent of ethylene carbonate (33% by volume) and methyl ethyl carbonate (67% by volume). A polypropylene porous body (thickness: 20 ⁇ m) was impregnated with the obtained non-aqueous electrolyte solution to prepare a separator 5 impregnated with the non-aqueous electrolyte solution. Next, the produced separator 5 was sandwiched between the negative electrode 2 in close contact with the current collector 7b made of copper foil and the positive electrode 4 in close contact with the current collector 7a made of nickel net, and laminated.
  • the current collector 7b and the negative electrode 2 were housed inside the outer cup 1
  • the current collector 7a and the positive electrode 4 were housed inside the outer can 3
  • the outer cup 1 and the outer can 3 were combined. Further, the peripheral edge portion between the outer cup 1 and the outer can 3 is caulked and sealed with an insulating gasket 6 interposed therebetween. In this way, a button-type secondary battery was manufactured.
  • Example 2 The number of crushing devices for passing the raw material was set to 7, and the crushing time was set to 15 minutes and the peripheral speed of the rotor was set to 80 m / sec in each crushing device. Other than that, it was the same as in Example 1. The results are shown in Table 1 below.
  • Example 3 The number of crushing devices for passing the raw material was set to 4, and the crushing time was set to 10 minutes and the peripheral speed of the rotor was set to 60 m / sec in each crushing device. Other than that, it was the same as in Example 1. The results are shown in Table 1 below.
  • Example 4 The number of crushing devices for passing the raw material was set to 4, and the crushing time was set to 20 minutes and the peripheral speed of the rotor was set to 60 m / sec in each crushing device. Other than that, it was the same as in Example 1. The results are shown in Table 1 below.
  • Example 5 The number of crushing devices for passing the raw material was set to 4, and the crushing time was set to 25 minutes and the peripheral speed of the rotor was set to 60 m / sec in each crushing device. Other than that, it was the same as in Example 1. The results are shown in Table 1 below.
  • Example 6 The number of crushing devices for passing the raw material was set to 6, and the crushing time was set to 20 minutes and the peripheral speed of the rotor was set to 60 m / sec in each crushing device. Other than that, it was the same as in Example 1. The results are shown in Table 1 below.

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