WO2019151201A1 - 黒鉛材料、その製造方法及びその用途 - Google Patents

黒鉛材料、その製造方法及びその用途 Download PDF

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WO2019151201A1
WO2019151201A1 PCT/JP2019/002854 JP2019002854W WO2019151201A1 WO 2019151201 A1 WO2019151201 A1 WO 2019151201A1 JP 2019002854 W JP2019002854 W JP 2019002854W WO 2019151201 A1 WO2019151201 A1 WO 2019151201A1
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carbon material
mass
graphitic carbon
area
total
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PCT/JP2019/002854
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English (en)
French (fr)
Japanese (ja)
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崇 寺島
俊介 吉岡
安顕 脇坂
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昭和電工株式会社
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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
    • C01B32/205—Preparation
    • 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
    • H01M4/58—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a graphitic carbon material, a production method thereof, and an application thereof.
  • Graphite includes natural graphite and artificial graphite. Natural graphite is available at low cost. However, since natural graphite is scaly, when it is made into a paste together with a binder and applied to a current collector, the natural graphite is oriented in one direction. When charging with such an electrode, the electrode expands in only one direction, and the performance as an electrode is reduced. Although natural graphite granulated has been proposed, spherical natural graphite is crushed and oriented by pressing during electrode production. Moreover, since the surface of natural graphite was active, a large amount of gas was generated during the initial charge, the initial efficiency was low, and the cycle characteristics were not good. against this background, various graphitic carbon materials have been proposed.
  • Patent Document 1 discloses that the (002) plane spacing (d 002 ) is less than 0.337 nm, the crystallite size (Lc) is 90 nm or more, and 1580 cm ⁇ 1 in an argon ion laser Raman spectrum by wide-angle X-ray diffraction.
  • An electrode carbon material is disclosed in which an R value, which is a peak intensity ratio of 1360 cm ⁇ 1 to a peak intensity, is 0.20 or more and a tap density is 0.75 g / cm 3 or more.
  • Patent Document 2 discloses a graphite particle used for manufacturing a negative electrode for a lithium secondary battery, wherein the graphite particle is formed by integrating a mixture of a graphite particle and an organic binder and a current collector. Used for manufacturing a negative electrode for a lithium secondary battery having a density of 1.5 to 1.9 g / cm 3 , and for a negative electrode of a lithium secondary battery having an aspect ratio of 1.2 to 5 Graphite particles are disclosed.
  • Patent Document 3 discloses a graphite material comprising graphite particles composed of an optically anisotropic structure, an optically isotropic structure, and voids, and satisfying the following conditions (1) and (2): doing.
  • (1) In a cross section of a molded body made of a graphite material, when 10 square areas each having a side of 100 ⁇ m are arbitrarily selected, the total area of optically anisotropic structures in the cross section of the graphite particles appearing in the area (x)
  • (2) Among the optically anisotropic tissue domains in the cross section of arbitrary 100 particles, the maximum value of the length of the long side portion is L max , and the volume-based average particle diameter (D50) measured by the laser diffraction method is L
  • Patent Document 4 is composed of graphite particles composed of an optically anisotropic structure, an optically isotropic structure, and voids, and arbitrarily select 10 square regions each having a side of 100 ⁇ m in a cross section of a molded body made of a graphite material.
  • a sensitive color test plate in a crossed Nicol state
  • an interference color indicating the orientation of the graphite network surface of the optically anisotropic texture domain A graphite material is disclosed in which the total area C min of the smallest one of the total areas of the respective colors of magenta, blue and yellow is 12 to 32% with respect to the total cross-sectional area of the graphite particles.
  • Patent Document 5 is a non-flaky graphite powder produced by graphitizing mesophase pitch as a raw material at a temperature of 2000 ° C. or higher, the optical structure is a mosaic structure, and the C-axis direction in X-ray diffraction is The crystallite spacing d 002 is 0.3358 nm or more, the crystallite size Lc 002 is 100 nm or less, and the intensity ratio (I 1360 / I 1580 ) of two Raman bands of 1360 and 1580 cm ⁇ 1 in the Raman scattering spectrum is 0.
  • Non-aqueous solvent secondary battery using a negative electrode using graphite powder of 1 or more as a carbon material and an electrolytic solution in which a lithium salt is dissolved in a non-aqueous solvent containing propylene carbonate.
  • Patent Document 6 is a non-flaky graphite powder produced using mesophase pitch as a raw material at a temperature of 2000 ° C. or more, wherein the optical structure of the graphite powder is a mosaic structure, and in the C-axis direction in X-ray diffraction. non the size of the crystallite is not more 100nm or less, the intensity ratio of the two Raman bands of 1360 cm -1 and 1580 cm -1 in the Raman scattering spectrum (I 1360 / I 1580) is equal to or less than 0.1
  • a carbon material for a negative electrode of an aqueous solvent secondary battery is disclosed.
  • Patent Document 7 discloses a step of pulverizing and classifying a raw coal composition obtained by coking a heavy oil composition by a delayed coking process, and applying compressive stress and shear stress to the pulverized and classified raw coal composition.
  • a method of producing a graphite material for a negative electrode of a lithium ion secondary battery comprising at least a step of obtaining a material, wherein the raw carbon composition to be pulverized and classified has a ratio of hydrogen atoms H to carbon atoms C, H / C
  • a method for producing a graphite material for a negative electrode of a lithium ion secondary battery having an atomic ratio of 0.30 to 0.50 and a micro strength of 7 to 17% by mass is disclosed.
  • Patent Document 8 is a raw coal composition obtained by coking a heavy oil composition by a delayed coking process, wherein the ratio of hydrogen atom H to carbon atom C, H / C atomic ratio is 0.30 to 0.50,
  • the raw carbon composition of the negative electrode carbon material for a lithium ion secondary battery having a micro strength of 7 to 17% by mass is pulverized to an average particle size of 30 ⁇ m or less, and then carbonized and / or graphitized.
  • the manufacturing method of the negative electrode carbon material for lithium ion secondary batteries characterized by doing is disclosed.
  • JP 2000-340232 A (US 6632569 B1) Japanese Patent Laid-Open No. 10-188959 WO2011 / 049199A JP 2011-184293 A JP 2002-124255 A JP 2000-149946 A WO2012 / 020816A WO2011 / 152426A
  • Carbon materials according to the prior art have sufficiently good cycle capacity maintenance characteristics at high temperatures, input / output characteristics at low temperatures, and resistance to PC (propylene carbonate) electrolyte, which is effective for operation at low temperatures, as required for large batteries. Has not yet reached a balance at a certain level.
  • An object of the present invention is to provide a novel graphitic carbon material.
  • Another object of the present invention is to provide a novel electrode capable of producing an electrode having a good level of energy density characteristics, cycle capacity maintenance characteristics at high temperatures, input / output characteristics at low temperatures, and resistance to PC (propylene carbonate) electrolyte. It is to provide a graphitic carbon material.
  • the present invention includes the following aspects.
  • [1] In measurement of powder X-ray diffraction of graphitic carbon material, (1) The (002) plane average plane distance d 002 is 0.3354 nm or more and 0.3370 nm or less, (2) The crystallite size Lc 112 calculated from the (112) diffraction line is 3.0 nm or more and 6.0 nm or less, and (3) (110) diffraction with respect to the peak intensity I 004 of the (004) diffraction line.
  • the ratio I 110 / I 004 of the peak intensity I 110 of the line is 0.30 or more and 0.67 or less
  • area Da 90 when the 90% total area of isotropic domains is at 0.7 [mu] m 2 or more 30.0 2 below, and (3) cumulative from the smaller the area of each optically isotropic domain
  • the area Dc 10 when the cumulative total is 10% with respect to the total area of the optical isotropic domain is 0.5 ⁇ m 2 or more and 1.0 ⁇ m 2 or less
  • the area Dc 50 when the total is 50% of the total area of the optical isotropic domain is 0.6 ⁇ m 2 or more and 2.0 ⁇ m 2 or less
  • the total is optical or the like.
  • area Dc 90 when the 90% total area of isotropic domains is 0.7 [mu] m 2 or more 14.0 2 below, Graphite Carbon Material.
  • a multi-layer structure including a core layer made of a carbon material (a Carbon Material) and a skin layer made of another carbon material (another Carbon Material) covering the surface, [1] to [6 ]
  • the graphite carbon material as described in any one of.
  • a battery electrode material (Cell Electrode Material) containing particles containing the graphitic carbon material according to any one of [1] to [7].
  • Mean spacing d 002 contains a spherical natural graphite or artificial graphite 0.01-200 parts by weight or less 0.3370nm than 0.3354 nm, battery electrode material.
  • the total amount of asphaltene and resin is 20% by mass to 60% by mass, the amount of sulfur is 0.5% by mass to 6.0% by mass, and the amount of ash is 0.2% by mass.
  • % To 1.0% by mass, carbon source (Carbon Source) is subjected to delayed coking by controlling the furnace heater outlet temperature before the caulking drum to 550 ° C. to 580 ° C., and the micro strength is 20 mass.
  • % To 40% by mass of coke, Crush the obtained coke, Graphitizing the ground coke at a temperature of 2500-3600 ° C., [1] to [6] The method for producing a graphitic carbon material according to any one of [6].
  • the total amount of asphaltene and resin is 20% by mass or more and 60% by mass or less, the amount of sulfur is 0.5% by mass or more and 6.0% by mass or less, and the amount of ash is 0.2% by mass.
  • % To 1.0% by mass the carbon steel raw material is subjected to delayed coking by controlling the furnace heater outlet temperature before the coking drum to 550 ° C. to 580 ° C., and the micro strength is 20% by mass to 40% by mass. % Less coke, Crush the obtained coke, The ground coke is graphitized at a temperature of 2500 to 3600 ° C. to obtain a core layer made of a carbon material, and then the core layer is coated with a skin layer made of another carbon material.
  • a method for producing a graphitic carbon material is produced.
  • the graphitic carbon material of the present invention is suitable as a battery electrode material.
  • the battery electrode material containing particles containing the graphitic carbon material of the present invention is used, energy density characteristics, cycle capacity maintenance characteristics at high temperatures, input / output characteristics at low temperatures, and PC (propylene carbonate) electrolysis at low temperatures A battery having excellent liquid resistance can be obtained.
  • the graphitic carbon material of the present invention can be mass-produced economically.
  • the battery or lithium ion secondary battery of the present invention maintains high cycle characteristics for a long period of time, has excellent high-temperature cycle capacity maintainability, has input / output characteristics suitable for driving a high-power motor at low temperatures, and is high Since it has energy density, it is suitable not only for portable electronic devices but also as a power source for electric tools such as electric drills, battery electric vehicles (BEV), hybrid electric vehicles (HEV), and the like.
  • BEV battery electric vehicles
  • HEV hybrid electric vehicles
  • FIG. 2 is a diagram showing an example of a polarizing microscope image of the multilayer graphitic carbon material obtained in Example 1.
  • the graphitic carbon material of the present invention exhibits the following physical property values in powder X-ray diffraction measurement, Raman spectroscopy measurement and polarization microscope observation.
  • the lower limit of the average spacing d 002 of (002) plane 0.3354 nm, preferably 0.3358Nm, more preferably 0.3360 nm
  • the upper limit of d 002 is, 0.3370 nm, preferably 0.3369Nm, more preferably 0.3368Nm.
  • the lower limit of the crystallite size Lc 112 calculated from the (112) diffraction line is 3.0 nm, preferably 3.5 nm, more preferably The upper limit of Lc 112 is 6.0 nm, preferably 5.5 nm, and more preferably 5.0 nm.
  • the lower limit of the ratio I 110 / I 004 of the peak intensity I 110 of the (110) diffraction line to the peak intensity I 004 of the ( 004 ) diffraction line is 0 .30, preferably 0.35, more preferably 0.40, and the upper limit of the ratio I 110 / I 004 is 0.67.
  • I 004 is the maximum intensity in the range of diffraction angle (2 ⁇ ) from 54.0 degrees to 55.0 degrees
  • I 110 is the maximum in the range of diffraction angle (2 ⁇ ) from 76.5 degrees to 78.0 degrees. It is strength.
  • the lower limit of the crystallite size Lc 002 calculated from the (002) diffraction line is preferably 50 nm, more preferably 52 nm, still more preferably 54 nm.
  • the upper limit of Lc 002 is preferably 80 nm, more preferably 70 nm, and even more preferably 65 nm. As Lc 002 is in the above range, the discharge capacity tends to be higher and the input / output characteristics are better.
  • the powder X-ray diffraction is measured by a known method. Then, a diffraction peak derived from the crystal structure of graphite is extracted from the obtained X-ray diffraction data, and the average interplanar spacing d 002 of the (002) plane and the crystallite size Lc 112 are obtained by a method known to those skilled in the art. calculates a value of (004) the ratio I 110 / I 004 of the peak intensity I 110 of (110) diffraction line to the peak intensity I 004 of diffraction lines, and the crystallite size Lc 002. The calculation method is well known to those skilled in the art. For example, Michio Inagaki, “Carbon”, 1963, No.
  • Graphitic carbon material of the present invention in the measurement of Raman spectroscopy, 1570 the ratio I D / I of the peak intensity I D that exists in the region of ⁇ 1630 cm 1350 to the peak intensity I G existing in the region of -1 ⁇ 1370 cm -1
  • the lower limit of G is 0.05, preferably 0.10, more preferably 0.15
  • the upper limit of the ratio I D / I G is 0.30, preferably 0.25.
  • the measurement of Raman spectroscopy was performed using a laser Raman spectrometer such as JASCO Corporation with an excitation wavelength of 532 nm, an incident slit width of 200 ⁇ m, an exposure time of 3 seconds, an integration count of 2 times, and a diffraction grating of 1800 lines / mm. Perform under conditions. As the ratio I D / I G is smaller, the degree of graphitization tends to be higher.
  • the lower limit of the total area Da 100 of the optical anisotropy domain is the total area of the optical anisotropy domain Da 100 and the total area of the optical isotropic domain in the polarization microscope observation.
  • the total of the Dc 100 65.0% preferably 70.0%, more preferably 75.0% and the upper limit of the total Da 100 of the area of the optically anisotropic domains, optical anisotropy It is 90.0%, preferably 88.0%, more preferably 85.0% with respect to the sum of the total area Da 100 of domains and the total area Dc 100 of optical isotropic domains.
  • Graphitic carbon material of the present invention is the observation with a polarizing microscope, and accumulated from the smaller the area of each of the optical anisotropic domain, the cumulative total becomes 10% with respect to total Da 100 of the area of the optically anisotropic domain the area Da 10 when, 0.5 [mu] m 2 or more 2.0 .mu.m 2 or less, preferably 0.5 [mu] m 2 or more 1.2 [mu] m 2 or less, more preferably 0.5 [mu] m 2 or more 0.9 .mu.m 2 or less.
  • Graphitic carbon material of the present invention is the observation with a polarizing microscope, and accumulated from the smaller the area of each of the optical anisotropic domain, the cumulative total becomes 50% with respect to total Da 100 of the area of the optically anisotropic domain
  • the area Da 50 is 0.6 ⁇ m 2 or more and 4.0 ⁇ m 2 or less, preferably 0.6 ⁇ m 2 or more and 3.0 ⁇ m 2 or less, more preferably 0.6 ⁇ m 2 or more and 2.0 ⁇ m 2 or less.
  • Graphitic carbon material of the present invention is the observation with a polarizing microscope, and accumulated from the smaller the area of each of the optical anisotropic domain, the cumulative total is 90% with respect to total Da 100 of the area of the optically anisotropic domain the area Da 90 when, 0.7 [mu] m 2 or more 30.0 2 or less, preferably 0.7 [mu] m 2 or more 20.0 .mu.m 2 or less, more preferably 0.7 [mu] m 2 or more 10.0 [mu] m 2 or less.
  • the area of each optical isotropic domain is accumulated from the smaller one in the polarization microscope observation, and the total is 10% with respect to the total area Dc 100 of the optical isotropic domain.
  • the area Dc 10 is 0.5 ⁇ m 2 or more and 1.0 ⁇ m 2 or less, preferably 0.7 ⁇ m 2 or more and 0.8 ⁇ m 2 or less, more preferably 0.5 ⁇ m 2 or more and 0.6 ⁇ m 2 or less.
  • the area of each optical isotropic domain is accumulated from the smaller one in the polarization microscope observation, and the total is 50% with respect to the total area Dc 100 of the optical isotropic domain.
  • the area Dc 50 is 0.6 ⁇ m 2 or more and 2.0 ⁇ m 2 or less, preferably 0.6 ⁇ m 2 or more and 1.8 ⁇ m 2 or less, more preferably 0.6 ⁇ m 2 or more and 1.5 ⁇ m 2 or less.
  • the area of each optical isotropic domain is accumulated from the smaller one in the polarization microscope observation, and the total is 90% with respect to the total area Dc 100 of the optical isotropic domain.
  • the area Dc 90 when, 0.7 [mu] m 2 or more 14.0 2 or less, preferably 0.7 [mu] m 2 or more 10.0 [mu] m 2 or less, more preferably 0.7 [mu] m 2 or more 5.0 .mu.m 2 or less.
  • Graphite carbon material is an aggregate of graphite crystallites. Aggregation mode of graphite crystallites in graphitic carbon materials can be observed with a polarizing microscope (Mochida et al., “Structure Control of Carbon Materials”, Functional Materials Science Laboratory, Vol. 4, No. 2, PP 81-88 (1990) , “Latest carbon material experimental technique (analysis / analysis bias)”, Carbon Materials Society of Japan (2001), publication: see the method described in Cypec Corporation, pages 1-8, etc.).
  • the polarizing microscope observation in the present invention is performed as follows.
  • a double-sided adhesive tape is affixed to the bottom of a plastic container having an internal volume of 30 cm 3 , and two cups (about 2 g) of a spatula carbon material are placed thereon.
  • Cold embedding resin (trade name: cold embedding resin # 105, manufacturing company: Japan Composite Co., Ltd., sales company: Marumoto Struers Co., Ltd.) and curing agent (trade name: curing agent (M agent), Manufacturing company: Nippon Oil & Fat Co., Ltd., sales company: Marumoto Struers Co., Ltd.) is added and kneaded for 30 seconds.
  • the obtained kneaded material (about 5 ml) is slowly poured into the container until the height is about 1 cm.
  • the bottom surface of the cured product is polished at a polishing plate rotation speed of 1000 rpm using a polishing plate rotating type polishing machine.
  • the polishing plates are replaced in the order of # 500, # 1000, and # 2000 depending on the polishing degree.
  • it is mirror-polished using alumina (trade name: Baikalox (registered trademark) type 0.3CR, particle size 0.3 ⁇ m, manufacturer: Baikowski, sales company: Baikowski Japan) and carbonized. Take out a cross section of the material.
  • the mirror-polished cured product is fixed on a preparation with clay.
  • the polished surface is observed using a polarizing microscope (for example, OLYMPAS, BX51, etc.) with an objective lens of 50 and a pixel size of 0.5 ⁇ m.
  • a polarizing microscope for example, OLYMPAS, BX51, etc.
  • the optical isotropic domain is detected in a pure magenta image in a polarizing microscope even if the cured product is rotated.
  • the color of the optically anisotropic domain changes depending on the direction of the graphite mesh surface, and is detected in yellow, magenta, and blue images with a polarizing microscope.
  • the resin portion is detected by a black image in a polarizing microscope.
  • a digital camera for example, CAMEDIA C-5050 ZOOM digital camera made by OLYMPUS
  • Connect a digital camera for example, CAMEDIA C-5050 ZOOM digital camera made by OLYMPUS
  • a digital camera for example, CAMEDIA C-5050 ZOOM digital camera made by OLYMPUS
  • An image of 2560 pixels ⁇ 1920 pixels is captured.
  • the captured images are randomly trimmed to 10 squares of 100 ⁇ m ⁇ 100 ⁇ m at random, and these are subjected to image analysis.
  • Color extraction is performed using the three attributes shown in Table 1, luminance (Intensity), hue (Hue), and purity (Purity).
  • the color extraction can be performed using, for example, an image analysis apparatus LUZEX AP manufactured by Nireco Corporation.
  • an area of 1 dot or less is removed using the W-1 command of Eliminate 1 of the logical filter.
  • the area of one optically anisotropic domain is the average of the number of blue, yellow, or magenta pixels in that domain, counted from the respective polarization microscope observation images at rotation angles of 0, 45, and 90 degrees. Calculated from the values, the area of one optical isotropic domain is the number of pure magenta pixels in the domain, counted from the observation images of the respective polarization microscopes at rotation angles of 0, 45 and 90 degrees. Calculated from the average value of
  • the ratio of the total area of the optical anisotropy domain to the sum of the total area of the optical anisotropy domain and the total area of the optical isotropic domain is represented by rotation angles of 0 degrees, 45 degrees, and 90 degrees, respectively. Counted from the observation images of the respective polarization microscopes at the rotation angles of 0 degree, 45 degrees and 90 degrees with respect to the total number of pixels of blue, yellow, magenta and pure magenta, counted from the observation images of the polarization microscope. It can be represented by the ratio of the total number of pixels of blue, yellow and magenta. Similarly, Da 10 , Da 50 and Da 90 , and Dc 10 , Dc 50 and Dc 90 can also be calculated from the number of pixels in the corresponding domain.
  • the lower limit of the BET specific surface area S sa is preferably 1.5 m 2 / g, more preferably 1.7 m 2 / g, still more preferably 1.8 m 2 / g.
  • the upper limit of the specific surface area S sa is preferably 4.0 m 2 / g, more preferably 3.7 m 2 / g, still more preferably 3.5 m 2 / g.
  • the BET specific surface area is measured by a specific surface area measuring apparatus (NOVA 4200e) manufactured by Quantachrome INSTRUMENTS, heated to 300 ° C. as preliminary drying, and after flowing nitrogen gas for 15 minutes, measured by the BET three-point method by nitrogen gas adsorption. be able to.
  • NOVA 4200e specific surface area measuring apparatus manufactured by Quantachrome INSTRUMENTS
  • the lower limit of the volume-based 50% diameter D 50 by the laser diffraction method of the graphitic carbon material of the present invention is preferably 4.0 ⁇ m, more preferably 4.2 ⁇ m, and even more preferably 4.5 ⁇ m.
  • the upper limit of the volume-based 50% diameter D 50 is preferably 20.0 ⁇ m, more preferably 15.0 ⁇ m, and still more preferably 7.0 ⁇ m. As the 50% diameter is within the above range, the amount of side reaction during the initial charge / discharge is suppressed, and the resulting battery tends to have good initial Coulomb efficiency and good input / output characteristics.
  • the 50% diameter D 50 can be measured by, for example, a laser diffraction particle size distribution measuring device master sizer (manufactured by Malvern).
  • the graphitic carbon material of the present invention preferably contains as little secondary particles, that is, aggregates or aggregates of primary particles, from the viewpoint of cycle maintenance characteristics. Therefore, the graphitic carbon material of the present invention has a 50% diameter D p50 obtained by statistically processing the diameter of primary particles measured by electron microscope observation on a volume basis, and 50% of the volume basis by the laser diffraction method.
  • the diameter D 50 is preferably substantially the same.
  • the lower limit of the average circularity R av is preferably 0.86, more preferably 0.87, still more preferably 0.88, and the upper limit of the average circularity R av is preferably Is 0.95, more preferably 0.94, and still more preferably 0.93.
  • the average circularity is measured as follows. First, the graphite carbon material is passed through a 106 ⁇ m filter to remove fine dust.
  • 0.1 g of the graphitic carbon material is added to 20 ml of ion exchange water, 0.1 to 0.5% by mass of a surfactant is added to the ion exchange water, and an ultrasonic cleaner (for example, UT-105S (A sample solution for measurement is obtained by performing a dispersion process for 5 minutes using a sharp manufacturing system, etc.
  • the sample solution for measurement is put into a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation), and LPF
  • the average circularity was calculated from 10,000 particles in the mode, where the circularity is the area of the projected image of the single graphitic carbon material relative to the circumference of the projected image of the single graphitic carbon material. When the projected image of the graphitic carbon material is a perfect circle, the circularity is 1.00.
  • the lower limit of the tap density [rho T is preferably 0.55 g / cm 3, more preferably 0.65 g / cm 3, more preferably 0.68 g / cm 3, a tap density limit is preferably 1.30 g / cm 3, more preferably 1.10 g / cm 3, more preferably at 0.95 g / cm 3.
  • the tap density is a density obtained by measuring the volume and mass of 100 g of powder tapped 400 times using a cantachrome auto tap. These are measurement methods based on ASTM B527 and JIS K5101-12-2, but the drop height of the auto tap was 5 mm.
  • the graphitic carbon material of the present invention may be a single-layer graphitic carbon material (hereinafter referred to as a single-layer graphitic carbon material) or a multilayer as long as it exhibits the above physical properties. It may be a graphite carbon material having a structure (hereinafter referred to as a multilayer graphitic carbon material).
  • the multilayer graphitic carbon material of the present invention has a multilayer structure including a core layer made of a carbon material and a skin layer made of another carbon material covering the surface thereof, and exhibits the above physical property values.
  • the multilayer graphitic carbon material may further improve the characteristics of the battery depending on the type of carbon material constituting the core layer and the type of carbon material constituting the skin layer.
  • the lower limit of the amount of the skin layer is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and even more preferably 0.5 parts by weight with respect to 100 parts by weight of the multilayer graphitic carbon material.
  • the upper limit of the amount is preferably 3.0 parts by mass, more preferably 2.0 parts by mass, and even more preferably 1.5 parts by mass with respect to 100 parts by mass of the multilayer graphitic carbon material.
  • the lower limit of the amount of the skin layer can be set from the viewpoint of a good effect that is provided by providing the skin layer, and the upper limit of the amount of the skin layer can be set from the viewpoint of side effects caused by providing the skin layer.
  • Carbon materials constituting the core layer of the multilayer graphitic carbon material are d 002 , Lc 112 , I 110 / I 004 , I D / I G , Da 100 , Dc 100 , Da 10 , Dc 10 , Da 50 , Dc 50 , Da 90 , and Dc 90 , and preferably those in which S sa , D 50 , Lc 002 , R av , and ⁇ T are within the above ranges, for example, the single-layer graphitic carbon material of the present invention. It is preferable.
  • the carbon material constituting the skin layer of the multilayer graphitic carbon material has I D / I G in the above range.
  • the carbon material constituting the skin layer is preferably an optically isotropic carbon material from the viewpoint of input characteristics during charging and characteristics required for a large battery, and specifically, an optically anisotropic domain total Da 100 of area, the total of the sum Dc 100 of the area of the total Da 100 and optically isotropic domains in the area of the optically anisotropic domains, preferably 10% or less, more preferably 5% or less, More preferably, it is 0%.
  • the graphitic carbon material of the present invention is not particularly limited by its production method.
  • a preferred method for producing the graphitic carbon material of the present invention is to subject the carbon raw material (Carbon Source) to delayed coking to obtain coke, pulverize the obtained coke, and pulverize the coke to 2500-3600. Including graphitizing at a temperature of ° C.
  • the carbon raw material used in the production method of the present invention is preferably a crude oil distillation residue such as a crude oil atmospheric distillation residue or a crude oil vacuum distillation residue or a tar obtained by thermal decomposition of crude oil; more preferably a crude oil distillation residue Can be mentioned.
  • the crude oil that is the source of the carbon source is preferably one that contains a large amount of naphthenic hydrocarbons.
  • the carbon raw material (Carbon Source) used in the present invention has a lower limit of the total amount of asphaltenes and resins, preferably 20% by mass, more preferably 25% by mass, and even more preferably 30% by mass.
  • the upper limit of the total amount of the resin is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass.
  • the asphaltene content is a black-brown, brittle solid, a substance with a condensed polycyclic structure having a small H / C, soluble in benzene, carbon tetrachloride, etc., insoluble in pentane, alcohol, etc. and considered to have a molecular weight of 1000 or more. It is a substance.
  • the resin component is a brown resinous substance and is a compound having a large amount of oxygen and nitrogen.
  • the total amount of asphaltene and resin is measured based on “Asphalt composition analysis method by column chromatography (JPI-5S-22-83)” defined by JPI (Japan Petroleum Institute). Specifically, the carbon source (Carbon Source) is separated into a saturated component, an aromatic component, a resin component, and an asphaltene component and quantified in a column using alumina as a filler.
  • the carbon raw material used in the present invention has a lower limit of the sulfur content, preferably 0.5% by mass, more preferably 0.8% by mass, and still more preferably 1.0% by mass.
  • the upper limit of the amount of the minute is preferably 6.0% by mass, more preferably 4.5% by mass, and further preferably 3.0% by mass.
  • the amount of sulfur can be obtained by analyzing according to JISK2541.
  • the lower limit of the amount of ash is preferably 0.2% by mass, more preferably 0.3% by mass, and the upper limit of the amount of ash is preferably 1. It is 0 mass%, More preferably, it is 0.7 mass%, More preferably, it is 0.5 mass%.
  • the amount of ash is 0.2% by mass or more, crystal development is suppressed during the coking process by the delayed coker, and the optical isotropic domain is appropriately developed. When the optical isotropic domain develops, current input / output characteristics, cycle characteristics, and PC electrolyte resistance tend to be improved as characteristics of the negative electrode material after graphitization.
  • Ash is an oxide containing one or more metal components from magnesium, aluminum, titanium, manganese, cobalt, sodium, nickel, and the like.
  • the carbon raw material (Carbon Source) used in the present invention is preferably not added with FCC (fluid catalytic cracker) residual oil (FCC bottom oil).
  • FCC fluid catalytic cracker
  • the delayed coking process includes heating a carbon raw material in a heating furnace to cause a limited range of thermal decomposition, and then supplying the carbon raw material into a coking drum to generate a coking reaction therein.
  • the furnace heater outlet temperature before the coking drum is controlled to 480 to 500 ° C.
  • the internal pressure of the drum is usually controlled to 100 to 280 kPa (about 15 psig to 40 psig).
  • the furnace heater outlet temperature before the coking drum is controlled to 550 ° C. to 580 ° C.
  • the internal pressure of the drum is preferably 115 to 305 kPa (about 17 psig to 44 psig).
  • coke used for graphitization has the following micro strength.
  • the coke used for graphitization has a lower limit of micro strength of preferably 20% by mass, preferably 23% by mass, more preferably 25% by mass, and an upper limit of micro strength of preferably 40% by mass, more preferably 35%. It is 32 mass%, More preferably, it is 32 mass%.
  • delayed coking of carbon source with the total amount of asphaltene and resin, amount of sulfur and amount of ash within the above ranges is performed.
  • coke having a micro strength within the above range can be obtained, but if the coke obtained by delayed coking does not have a micro strength within the above range, coke having a high micro strength or a low micro strength can be obtained.
  • the microintensity can be adjusted within the above range.
  • the micro strength is an index indicating the bond strength between adjacent crystallites. It is said that unorganized carbon exists between adjacent crystallites, and the unorganized carbon has a function of bonding crystallites. Furthermore, it is said that unorganized carbon has a function of bonding even after graphitization.
  • microstrength When the microstrength is within the above range, it is easy to adjust to a predetermined particle size, the battery charge / discharge rate characteristics are improved, the expansion / contraction due to electrode charge / discharge is reduced, and the battery capacity maintenance characteristics are improved. Tend.
  • a steel cylinder (inner diameter: 25.4 mm, length: 304.8 mm) is charged with 2 g of 20-30 mesh coke and 12 steel balls with a diameter of 5/16 inch (7.9 mm), and both ends of the cylinder are covered with steel. Closed with.
  • the cylinder was attached to a rotating machine so that the rotation axis passed horizontally through the midpoint in the longitudinal direction of the cylinder, and was rotated 800 times at 25 rpm.
  • the lid was opened, the coke was taken out from the cylinder, and sieved with a 48 mesh sieve.
  • the percentage of the mass of coke on the sieve relative to the mass of coke subjected to sieving was defined as microintensity.
  • Coke can be pulverized using a known pulverizer such as a jet mill, a hammer mill, a roller mill, a pin mill, or a vibration mill.
  • a jet mill is preferable from the viewpoint of obtaining a product having an appropriate degree of circularity.
  • the edge portion may be exposed by pulverization, and the edge portion may cause a side reaction during charging and discharging. When pulverization is performed with a low heat history, the edge portion is repaired with high probability by subsequent heat treatment, and side reactions may be suppressed.
  • the pulverized coke may be fired at 500 to 1300 ° C. in a non-oxidizing atmosphere before graphitization. By firing, the gas generated during graphitization can be reduced. Moreover, since the bulk density is reduced by firing, the cost required for graphitization can be reduced.
  • Coke graphitization is performed by heat treatment at a temperature at which amorphous carbon in the coke can be crystallized.
  • the lower limit of the heat treatment temperature for graphitization is preferably 2500 ° C, more preferably 2900 ° C, still more preferably 3000 ° C, and the upper limit is preferably 3500 ° C.
  • a known furnace such as an Atchison furnace can be used.
  • Single layer graphitic carbon material is obtained by graphitization of coke.
  • the obtained single-layer graphitic carbon material has a smooth surface.
  • the single-layer graphitic carbon material is preferably not crushed and pulverized in order to maintain the smoothness of the surface.
  • the multilayer graphitic carbon material can be obtained by a known carbon coating method.
  • a multilayer graphitic carbon material including a core layer made of a single-layer graphitic carbon material and a skin layer made of an optically isotropic carbon material can be obtained as follows.
  • Coal tar pitch or a polymer-containing composition and a single layer graphitic carbon material are mixed and heated in a non-oxidizing atmosphere, preferably at 800 ° C. to 3300 ° C., more preferably at 800 ° C. to 1300 ° C.
  • a carbonaceous material can be obtained.
  • the coal tar pitch those having a volume-based 50% diameter D 50 by laser diffraction of 0.1 to 10 ⁇ m are preferably used.
  • the polymer-containing composition for example, a composition containing a drying oil or a fatty acid thereof and a phenol resin can be used (see Japanese Patent Application Laid-Open Nos. 2003-1000029 and 2005-019397).
  • the battery electrode material of the present invention contains particles containing the graphitic carbon material of the present invention.
  • the battery electrode material of the present invention can be preferably used, for example, as a negative electrode active material, a negative electrode conductivity-imparting material and the like of a lithium ion secondary battery.
  • the battery electrode material of the present invention comprises 100 parts by mass of the graphitic carbon material of the present invention and 0.01 to 200 parts by mass, preferably 0.01 to 100 parts by mass of spherical natural graphite or artificial graphite. Also good. Spherical natural graphite or artificial graphite preferably has an average spacing d 002 is less 0.3370nm than 0.3354 nm. A synergistic effect between the action caused by the graphitic carbon material of the present invention and the action caused by spherical natural graphite or artificial graphite can be expected. For example, when mesocarbon microbeads (MCMB) are used as artificial graphite, the electrode density can be increased and the volume energy density can be improved due to the crushability of MCMB.
  • MCMB mesocarbon microbeads
  • the battery electrode material of the present invention may further contain a conductive additive.
  • the conductive auxiliary agent can serve to impart conductivity to the electrode layer or a buffering action against a volume change upon insertion / extraction of lithium ions.
  • Examples of the conductive aid include carbon materials such as carbon black, carbon nanotube (CNT), carbon nanofiber, and vapor grown carbon fiber (VGCF (registered trademark)).
  • Examples of carbon black include ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black. You may use a conductive support agent individually by 1 type or in combination of 2 or more types.
  • the amount of the conductive assistant is preferably 0.5 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 0.5 to 25% by mass with respect to the mass of the battery electrode material.
  • the conductive aid used in preparing the battery electrode material of the present invention is preferably in the form of powder, paste or the like.
  • the battery electrode material of the present invention may further contain a binder.
  • the binder include fluorine polymers such as polyvinylidene fluoride and polytetrafluoroethylene, and rubber polymers such as SBR (styrene butadiene rubber).
  • the amount of the binder is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass in total of the graphitic carbon material of the present invention and spherical natural graphite or artificial graphite battery.
  • the binder used in the preparation of the battery electrode material of the present invention is preferably in the form of powder, solution, emulsion or dispersion.
  • the battery electrode material of the present invention may further contain a liquid medium and may be in the form of a paste.
  • the liquid medium may be derived from a conductive agent in a paste state; a binder in a solution, emulsion, or dispersion state.
  • the liquid medium include known materials suitable for each binder, such as toluene and N-methylpyrrolidone in the case of a fluorine-based polymer; water in the case of SBR; and dimethylformamide and isopropanol.
  • a binder that uses water as the liquid medium it is preferable to use a thickener together.
  • the thickener include polycarboxylic acid, polycarboxylate, carboxymethyl cellulose, carboxymethyl cellulose alkali metal salt and the like. The amount of the liquid medium is set so that the viscosity is easy to apply.
  • the battery electrode material of the present invention is obtained, for example, by supplying the kneaded carbonaceous material of the present invention and, if necessary, a binder, a conductive additive and / or other components simultaneously or in random order to a kneading apparatus and kneading. can get.
  • a kneading apparatus such as a ribbon mixer, a screw type kneader, a Spartan reuser, a Redige mixer, a planetary mixer, a universal mixer, or the like can be used.
  • the electrode of the present invention has a compact layer containing the battery electrode material of the present invention.
  • the compact layer is usually laminated to the current collector.
  • the current collector include foil, mesh, and the like such as aluminum, nickel, copper, and stainless steel.
  • the thickness of the layer of the molded body is preferably 50 to 200 ⁇ m.
  • the molded body layer can be obtained, for example, by applying a paste-like battery electrode material on a current collector, drying, and pressure-molding as necessary. When the paste battery electrode material is applied to the current collector, dried, and pressure-molded, a coating device such as a doctor blade or a bar coater, a drying device, and a press machine can be used.
  • the molded body layer can also be obtained, for example, by pressure molding a granular or powdered negative electrode material together with a current collector.
  • Examples of the pressure molding method include a pressure roll method and a pressure plate method.
  • the pressure during the pressure molding is preferably 1 to 3 t / cm 2 .
  • the density (electrode density) of the molded body layer is preferably 1.3 to 1.7 g / cm 3 .
  • the battery capacity per volume tends to increase, and when the electrode density is increased too much, the cycle characteristics tend to deteriorate.
  • the electrode of the present invention is suitable for a negative electrode of a battery or a negative electrode of a lithium ion secondary battery.
  • the battery or lithium ion secondary battery of the present invention includes the electrode of the present invention.
  • a battery or a lithium ion secondary battery usually includes a negative electrode, an electrolyte, and a positive electrode.
  • the electrode of the present invention is preferably used for the negative electrode.
  • the electrode of the present invention may be used for the positive electrode of the lithium ion secondary battery, but an electrode containing a positive electrode active material is preferably used.
  • the positive electrode active material include lithium-containing transition metal oxides, and preferably lithium and at least one transition metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Mo, and W.
  • the positive electrode active material may contain Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, or the like in a range of less than 30 mol% with respect to the transition metal element present.
  • Li a MO 2 (M is at least one element selected from the group consisting of Co, Ni, Fe, and Mn, 0 ⁇ a ⁇ 1.2), or Li b L 2 O 4 (L is an element containing at least Mn.
  • the volume-based 50% diameter D 50 of the positive electrode active material by laser diffraction is not particularly limited, but is preferably 0.1 to 50 ⁇ m.
  • the positive electrode active material has a volume occupied by a particle group having a particle size of 3 ⁇ m or less being 18% or less of the total volume, and a volume occupied by a particle group of 15 ⁇ m or more and 25 ⁇ m or less is the total volume. It is preferable that it is 18% or less.
  • the BET specific surface area of the positive electrode active material is not particularly limited, is preferably 0.01 ⁇ 50m 2 / g, more preferably 0.2m 2 /g ⁇ 1.0m 2 / g.
  • the pH of the supernatant liquid when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
  • a separator may be provided between the positive electrode and the negative electrode.
  • the separator include non-woven fabric, cloth, microporous film, or a combination thereof.
  • the separator is preferably made of a material mainly composed of polyolefin such as polyethylene or polypropylene.
  • organic electrolytes As the electrolyte and electrolyte constituting the lithium ion secondary battery of the present invention, known organic electrolytes, inorganic solid electrolytes, and polymer solid electrolytes can be used, but organic electrolytes are preferred from the viewpoint of electrical conductivity.
  • the organic electrolytic solution is obtained by dissolving an electrolyte in an organic solvent.
  • the organic solvent include diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl 5 glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol phenyl ether, Ethers such as 1,2-dimethoxyethane; formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N- Ethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, Amides such as samethyl phosphorylamide; sulfur-containing organic compounds such as dimethyl
  • carbonates such as ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, vinylene carbonate, esters such as ⁇ -butyrolactone, ethers such as diethyl ether and diethoxyethane, dimethyl sulfoxide, acetonitrile, Tetrahydrofuran and 1,3-dioxolane are preferred; carbonates such as ethylene carbonate and propylene carbonate are more preferred.
  • organic solvents can be used alone or in admixture of two or more.
  • Examples of the electrolyte used for the organic electrolyte include lithium salts.
  • Examples of the lithium salt as the electrolyte include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCl, LiCF 3 SO 3 , LiCF 3 CO 2 , and LiN (CF 3 SO 2 ) 2 .
  • polymer solid electrolyte examples include polyethylene oxide derivatives, polymers containing polyethylene oxide derivatives, polypropylene oxide derivatives, polymers containing polypropylene oxide derivatives, phosphate ester polymers, polycarbonate derivatives, polymers containing polycarbonate derivatives, and the like. . There are no restrictions on the selection of members other than those described above necessary for the battery configuration.
  • Viscosity is adjusted by appropriately adding 1.5 parts by mass of carboxymethyl cellulose and water to 100 parts by mass of the graphitic carbon material, and 3.8 parts by mass of an aqueous dispersion of styrene-butadiene rubber fine particles (solid content: 40% by mass).
  • a negative electrode material slurry having sufficient fluidity.
  • the negative electrode material slurry was applied to a high-purity copper foil at a thickness of 150 ⁇ m and vacuum-dried at 70 ° C. for 12 hours.
  • the copper foil on which the negative electrode material coating film was formed was punched out to obtain a rectangular piece of 20 cm 2 .
  • the small piece is sandwiched between super steel press plates and pressed at a pressing pressure of 1 ⁇ 10 2 to 3 ⁇ 10 2 N / mm 2 (1 ⁇ 10 3 to 3 ⁇ 10 3 kg / cm 2 ) to form a negative electrode molded body layer 1 was formed on a copper foil to obtain a negative electrode 1.
  • N-methyl-pyrrolidone is appropriately added to 90 g of Li 3 Ni 1/3 Mn 1/3 Co 1/3 O 2 (D50: 7 ⁇ m), 5 g of carbon black (manufactured by TIMCAL, C45), and 5 g of polyvinylidene fluoride (PVdF). The mixture was stirred while being added to prepare a positive electrode material slurry.
  • the positive electrode material slurry was applied in a uniform thickness on an aluminum foil having a thickness of 20 ⁇ m, and then dried. It was roll-pressed to form a positive electrode molded body layer on the aluminum foil. The aluminum foil on which the positive electrode molded body layer was formed was punched out to obtain a 20 cm 2 rectangular small piece (positive electrode).
  • a Ni tab was attached to the copper foil of the negative electrode 1.
  • An Al tab was attached to the Al foil of the positive electrode.
  • a polypropylene microporous membrane was laminated between the negative electrode molded body layer and the positive electrode molded body layer. This was packed with aluminum laminate leaving one opening.
  • An electrolytic solution (formed by dissolving 1 mol / liter of LiPF 6 in a mixed solution of 2 parts by mass of ethylene carbonate and 3 parts by mass of ethyl methyl carbonate) is injected into the opening, and then the opening is heat-sealed. Was sealed to obtain a bipolar cell.
  • constant voltage charging is performed at 4.15 V until the current value reaches 1.25 mA. It was.
  • Electrolytic solution A LiPF 6 dissolved at 1 mol / liter in a mixed solution consisting of 2 parts by mass of ethylene carbonate and 3 parts by mass of ethyl methyl carbonate was injected into it and sealed with a screw-in type lid. Lithium cell A was obtained.
  • the counter electrode lithium cell A was charged with a constant current from the rest potential to 0.002 V at 0.2 mA. After reaching 0.002 V, constant voltage charging was performed at 0.002 V until 25.4 ⁇ A. The amount of charge A was measured. Thereafter, constant current discharge was performed at 0.2 mA until 1.5 V was reached, and the discharge capacity A was measured. The ratio of the discharge capacity A to the charge amount A was defined as the initial coulomb efficiency [%].
  • Electrolyte B LiPF 6 was dissolved in 1 mol / liter in a mixed solution consisting of 1 part by mass of ethylene carbonate, 3 parts by mass of ethyl methyl carbonate and 1 part by mass of propylene carbonate was poured into the screw-type lid. And the counter electrode lithium cell B was obtained.
  • the counter lithium cell B was charged at a constant current of 0.2 mA from the rest potential to 0.002 V. After reaching 0.002 V, constant voltage charging was performed at 0.002 V until 25.4 ⁇ A. The amount of charged electricity B was measured. Thereafter, constant current discharge was performed at 0.2 mA until 1.5 V was reached, and the discharge capacity B was measured. The ratio of the discharge capacity B to the amount of charge B was defined as PC electrolyte resistance [%].
  • the copper foil on which the negative electrode material coating film was formed was punched out to obtain a round piece of 16 mm ⁇ .
  • the small piece is sandwiched between press plates made of super steel, pressed at a pressing pressure of 2 ⁇ 10 2 N / mm 2 (2 ⁇ 10 3 kg / cm 2 ), and a negative electrode molded body layer 2 is formed on the copper foil.
  • a negative electrode 3 was obtained.
  • the thickness of the negative electrode 3 was measured using a film thickness meter (SMD-565, TECLOCK Co., Ltd.), and the electrode density was calculated from the mass of the negative electrode material coating film.
  • the product of the calculated electrode density and discharge capacity A was defined as the volume energy density.
  • Example 1 A Brazilian crude oil vacuum distillation residue having a specific gravity of 4.2 ° API, an asphaltene content of 17% by mass, a resin content of 21% by mass, a sulfur content of 2.1% by mass, and an ash content of 0.3% by mass is put into a delayed coking apparatus.
  • the furnace heater outlet temperature before the caulking drum was controlled to 570 ° C., and the internal pressure was controlled to about 138 kPa (35 psig) to perform delayed coking.
  • Granular coke having a diameter of about 3 to 8 mm was obtained. This was cooled with water and discharged from the caulking drum. This was heated at 120 ° C. and dried to a moisture content of 0.5% by mass or less.
  • the obtained coke having a micro strength of 30% was pulverized with a bantam mill manufactured by Hosokawa Micron. Subsequently, airflow classification was performed with a turbo classifier TC-15N manufactured by Nisshin Engineering, and coke having a D 50 of 15.5 ⁇ m was obtained. This was pulverized with a jet mill manufactured by Seishin Corporation to obtain coke having a D 50 of 6.6 ⁇ m. Coke having a D 50 of 6.6 ⁇ m was filled into a graphite crucible with a screw lid, and heat-treated at 3100 ° C. in an Atchison furnace to obtain powder of particles containing a single-layer graphitic carbon material. Table 2 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • Example 2 To 100 parts by mass of the powder of particles containing the single-layer graphitic carbon material obtained in Example 1, 1.0 part by mass of a powdery isotropic petroleum pitch was added and dry mixed. Subsequently, it heated at 1100 degreeC under argon atmosphere for 1 hour, and obtained the powder of the particle
  • Example 3 Crude oil produced in Brazil in Xinjiang Uygur Autonomous Region with a specific gravity of 3.1 ° API, an asphaltene content of 17% by mass, a resin content of 20% by mass, a sulfur content of 0.8% by mass, and an ash content of 0.4% by mass
  • a powder of particles containing a single layer graphitic carbon material is obtained by the same method as in Example 1 except that the residue is changed to a vacuum distillation residue, and a powder of particles containing a multilayer graphitic carbon material is obtained by using the same method as in Example 2.
  • Got. The powder had no aggregation and consisted only of primary particles.
  • Table 2 shows the physical properties of the multilayer graphitic carbon material and the evaluation results of the battery obtained using the multilayer graphitic carbon material.
  • Example 4 Brazilian crude oil produced in Liaoning Republic has a specific gravity of 5.2 ° API, an asphaltene content of 22% by mass, a resin content of 17% by mass, a sulfur content of 1.2% by mass, and an ash content of 0.6% by mass.
  • a powder of particles containing a single layer graphitic carbon material is obtained by the same method as in Example 1 except that the residue is changed to a vacuum distillation residue, and a powder of particles containing a multilayer graphitic carbon material is obtained by using the same method as in Example 2.
  • Got. The powder was not aggregated and consisted only of primary particles.
  • Table 2 shows the physical properties of the multilayer graphitic carbon material and the evaluation results of the battery obtained using the multilayer graphitic carbon material.
  • Example 5 D 50 is obtained coke 5.8 ⁇ m in air classification, to obtain a powder of particles including the single-layer graphitic carbon material in the same manner as in Example 1, except that the supplied directly to the graphitization without jet milling it Using this, a powder of particles containing a multilayer graphitic carbon material was obtained in the same manner as in Example 2. The powder was not aggregated and consisted only of primary particles. Table 2 shows the physical properties of the multilayer graphitic carbon material and the evaluation results of the battery obtained using the multilayer graphitic carbon material.
  • Example 6 Chopper rotation for 2 minutes with a Henschel mixer using 70 parts by mass of particles containing the single-layer graphitic carbon material obtained in Example 2 and 30 parts by mass of artificial graphite MCMB2528 (graphitization temperature: 2800 ° C.) manufactured by Osaka Gas Co., Ltd. The mixture was stirred at several 2000 rpm to obtain a mixed graphitic carbon material. Table 2 shows the evaluation results of the battery obtained using the mixed graphitic carbon material.
  • Example 7 D 50 is obtained coke 15.5 ⁇ m in air classification, to obtain a powder of particles including the single-layer graphitic carbon material in the same manner as in Example 1, except that the supplied directly to the graphitization without jet milling it It was. The powder was not aggregated and consisted only of primary particles.
  • Table 2 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • Example 8 Brazilian crude oil produced in Liaoning Republic has a specific gravity of 5.2 ° API, an asphaltene content of 22% by mass, a resin content of 17% by mass, a sulfur content of 1.2% by mass, and an ash content of 0.6% by mass.
  • a powder of particles containing a single-layer graphitic carbon material was obtained in the same manner as in Example 7 except that the residue was changed to a vacuum distillation residue. The powder was not aggregated and consisted only of primary particles.
  • Table 2 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • a Brazilian crude oil vacuum distillation residue has a specific gravity of 3.4 ° API, an asphaltene content of 21% by mass, a resin content of 11% by mass, a sulfur content of 3.3% by mass, and an ash content of 0.2% by mass.
  • a powder of particles containing a single layer graphitic carbon material was obtained in the same manner as in Example 7 except that the residue was changed to a residue. The powder was not aggregated and consisted only of primary particles.
  • Table 3 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • a Brazilian crude oil vacuum distillation residue has a specific gravity of 3.0 ° API, an asphaltene content of 28% by mass, a resin content of 11% by mass, a sulfur content of 3.5% by mass, and an ash content of 0.1% by mass.
  • a powder of particles containing a single layer graphitic carbon material was obtained in the same manner as in Example 7 except that the residue was changed to a residue. The powder was not aggregated and consisted only of primary particles.
  • Table 3 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • Comparative Example 4 70 parts by mass of particles containing the single-layered graphitic carbon material obtained in Comparative Example 3 and 30 parts by mass of Osaka Gas Artificial Graphite MCMB2528 (graphitization temperature: 2800 ° C.) for 2 minutes using a Henschel mixer, chopper rotation speed The mixture was stirred at 2000 rpm to obtain a mixed graphitic carbon material.
  • Table 3 shows the evaluation results of the battery obtained using the mixed graphitic carbon material.
  • Comparative Example 5 5 parts by mass of coal tar pitch (average particle diameter: 0.5 ⁇ m) is added to 93 parts by mass of the powder of particles containing the single-layer graphitic carbon material obtained in Comparative Example 3, and gas phase method carbon fiber manufactured by Showa Denko KK 2 parts by mass of (VGCF (registered trademark)) was added, and the mixture was stirred for 5 minutes at Hosokawa Micron Mechanofusion at a chopper rotation speed of 2000 rpm to obtain a mixture. This mixture was heat-treated at 1200 ° C. in an argon atmosphere to obtain particles of powder containing the composite graphitic carbon material. The powder was not aggregated and consisted only of primary particles. Table 3 shows the physical properties of the composite graphitic carbon material and the evaluation results of the battery obtained using the composite graphitic carbon material.
  • Comparative Example 6 A phenol resin (“Bellpearl® C-800”; manufactured by Kanebo Co., Ltd.) was heated at 170 ° C. for 3 minutes and then heated at 130 ° C. for 8 hours to be cured. Thereafter, the temperature was raised to 1200 ° C. at a rate of 250 ° C./h in a nitrogen atmosphere and held at 1200 ° C. for 1 hour. Then, it cooled to room temperature and obtained the powder of the particle
  • Table 4 shows the evaluation results of the battery obtained using artificial graphite MCMB (registered trademark) 2528 (graphitization temperature 2800 ° C.) manufactured by Osaka Gas Co., Ltd.
  • the artificial graphite MCMB (registered trademark) 2528 manufactured by Osaka Gas Co., Ltd. had no aggregation and consisted only of primary particles.
  • Comparative Example 8 A crude oil from Brazil, which has a specific gravity of 3.4 ° API, an asphaltene content of 7% by mass, a resin content of 7% by mass, a sulfur content of 0.2% by mass, and an ash content of 0.0% by weight.
  • a powder of particles containing a single-layer graphitic carbon material was obtained in the same manner as in Example 7 except that the residue was changed to a vacuum distillation residue. The powder was not aggregated and consisted only of primary particles.
  • Table 4 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.
  • Comparative Example 9 600 g of Chinese natural graphite having a D 50 of 7 ⁇ m was put into a hybridizer NHS1 type manufactured by Nara Machinery, and treated for 3 minutes at a rotor peripheral speed of 60 / m / sec to obtain spherical graphite particles. This operation was repeated to prepare 3 kg of spherical graphite particles. The spherical graphite particles were agglomerated and their D 50 was 15 ⁇ m. 3 kg of spherical graphite particles and 1 kg of petroleum-based tar were put into an M20-type readyge mixer (internal volume 20 liters) manufactured by Matsubo Co., Ltd. and kneaded.
  • M20-type readyge mixer internal volume 20 liters
  • Comparative Example 11 Texas crude oil normal pressure having a specific gravity of 17.0 ° API, an asphaltene content of 8% by mass, a resin content of 6% by mass, a sulfur content of 6.3% by mass and an ash content of 0.1% by mass.
  • a powder of particles containing a single layer graphitic carbon material is obtained by the same method as in Example 1 except that the residue is changed to a distillation residue, and a powder of particles containing a multilayer graphitic carbon material is obtained by using the same method as in Example 2. Obtained. The powder was not aggregated and consisted only of primary particles.
  • Table 4 shows the physical properties of the multilayer graphitic carbon material and the evaluation results of the battery obtained using the multilayer graphitic carbon material.
  • Comparative Example 12 Brazilian crude oil vacuum distillation residue, Indonesian crude oil atmospheric pressure with specific gravity 5.0 ° API, asphaltene content 12% by mass, resin content 9% by mass, sulfur content 0.7% by mass, and ash content 0.1% by mass
  • a powder of particles containing a single layer graphitic carbon material was obtained in the same manner as in Example 7 except that the residue was changed to a distillation residue. The powder was not aggregated and consisted only of primary particles.
  • Table 4 shows the physical properties of the single-layer graphitic carbon material and the evaluation results of the battery obtained using the single-layer graphitic carbon material.

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PCT/JP2019/002854 2018-01-30 2019-01-29 黒鉛材料、その製造方法及びその用途 WO2019151201A1 (ja)

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WO2020137909A1 (ja) * 2018-12-26 2020-07-02 昭和電工株式会社 リチウムイオン二次電池負極用黒鉛材料
CN112930610A (zh) * 2020-02-19 2021-06-08 杰富意化学株式会社 锂离子二次电池的负极用碳材料及其制造方法以及使用该碳材料的负极和锂离子二次电池
WO2021166359A1 (ja) * 2020-02-19 2021-08-26 Ｊｆｅケミカル株式会社 リチウムイオン二次電池の負極用炭素材料およびその製造方法並びにそれを用いた負極およびリチウムイオン二次電池

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CN114702316B (zh) * 2022-03-23 2023-05-30 湖南大学 一种低成本高纯石墨材料的制备方法及应用
WO2024195012A1 (ja) * 2023-03-20 2024-09-26 株式会社レゾナック リチウムイオン二次電池負極用黒鉛質炭素材、リチウムイオン二次電池用負極材、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
WO2024195011A1 (ja) * 2023-03-20 2024-09-26 株式会社レゾナック リチウムイオン二次電池負極用黒鉛質炭素材、リチウムイオン二次電池用負極材、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
CN116314612B (zh) * 2023-05-11 2023-08-18 中创新航科技集团股份有限公司 一种负极极片及其应用

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WO2020137909A1 (ja) * 2018-12-26 2020-07-02 昭和電工株式会社 リチウムイオン二次電池負極用黒鉛材料
CN112930610A (zh) * 2020-02-19 2021-06-08 杰富意化学株式会社 锂离子二次电池的负极用碳材料及其制造方法以及使用该碳材料的负极和锂离子二次电池
JP6924917B1 (ja) * 2020-02-19 2021-08-25 Ｊｆｅケミカル株式会社 リチウムイオン二次電池の負極用炭素材料およびその製造方法並びにそれを用いた負極およびリチウムイオン二次電池
WO2021166359A1 (ja) * 2020-02-19 2021-08-26 Ｊｆｅケミカル株式会社 リチウムイオン二次電池の負極用炭素材料およびその製造方法並びにそれを用いた負極およびリチウムイオン二次電池
JP2021180186A (ja) * 2020-02-19 2021-11-18 Ｊｆｅケミカル株式会社 リチウムイオン二次電池の負極用炭素材料およびその製造方法並びにそれを用いた負極およびリチウムイオン二次電池
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CN112930610B (zh) * 2020-02-19 2024-08-23 杰富意化学株式会社 锂离子二次电池的负极用碳材料及其制造方法以及使用该碳材料的负极和锂离子二次电池

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