WO2012133788A1 - Particules de graphite pour batterie rechargeable non aqueuse et leur procédé de production, électrode négative et batterie rechargeable non aqueuse - Google Patents

Particules de graphite pour batterie rechargeable non aqueuse et leur procédé de production, électrode négative et batterie rechargeable non aqueuse Download PDF

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WO2012133788A1
WO2012133788A1 PCT/JP2012/058611 JP2012058611W WO2012133788A1 WO 2012133788 A1 WO2012133788 A1 WO 2012133788A1 JP 2012058611 W JP2012058611 W JP 2012058611W WO 2012133788 A1 WO2012133788 A1 WO 2012133788A1
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graphite
secondary battery
negative electrode
less
aqueous secondary
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PCT/JP2012/058611
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English (en)
Japanese (ja)
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布施　亨
宇尾野　宏之
哲 赤坂
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三菱化学株式会社
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Priority to CN201280015723.8A priority Critical patent/CN103443977B/zh
Priority to KR1020137026385A priority patent/KR20140016925A/ko
Publication of WO2012133788A1 publication Critical patent/WO2012133788A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 graphite particles used in a non-aqueous secondary battery, a negative electrode formed using the graphite particles, and a non-aqueous secondary battery having the negative electrode.
  • lithium ion secondary batteries having higher energy density and excellent large current charge / discharge characteristics have attracted attention as compared to nickel / cadmium batteries and nickel / hydrogen batteries.
  • higher capacity of lithium ion secondary batteries has been widely studied, but in recent years, due to the increasing demand for higher performance of lithium ion secondary batteries, further increase in capacity, large current charge / discharge characteristics, high temperature storage characteristics, It is required to satisfy high cycle characteristics.
  • a negative electrode material of a lithium ion secondary battery graphite material and amorphous carbon are often used in terms of cost and durability.
  • the amorphous carbon material has a problem that the reversible capacity in a material range that can be put into practical use is small, and it is difficult to increase the density of the active material layer, so that the capacity cannot be increased.
  • a graphite material has a capacity close to 372 mAh / g, which is the theoretical capacity of lithium storage, and is preferable as an active material.
  • a carbon material for example, a high density isotropic graphite powder having a specific range of oil absorption, powder bulk density, particle size distribution, and specific resistance in Patent Document 1 is used. It is disclosed that a carbon material for a negative electrode of a lithium secondary battery can be obtained that has excellent properties, excellent adhesion with copper foil, large discharge capacity, small initial irreversible capacity, and excellent cycle characteristics.
  • Patent Document 2 by mixing two types of graphite powders that are equally crushed and have different oil absorption and circularity, the secondary lithium is excellent in liquid immersion and high cycle characteristics. It is disclosed that a carbon material for a battery negative electrode can be obtained.
  • the present invention has been made in view of the background art, and the problem is that, even when the density of the negative electrode active material layer is increased, the initial efficiency is high, and lithium ions are excellent in cycle characteristics even during large current charge / discharge.
  • An object of the present invention is to provide a negative electrode material for producing a secondary battery and, as a result, to provide a lithium ion secondary battery having high capacity, high input / output characteristics, and high cycle characteristics.
  • the inventors of the present invention use graphite particles that are composites of graphite, and use a negative electrode material that satisfies specific conditions such as DBP oil absorption, specific surface area, and Raman R value. Therefore, even when the negative electrode active material layer is densified, the initial efficiency is high, and it is possible to satisfy the high cycle characteristics even during large current charge / discharge. As a result, the high capacity and high cycle characteristics are achieved.
  • the present inventors have found that a lithium ion secondary battery can be obtained, and have reached the present invention.
  • the gist of the present invention resides in a negative electrode material for a non-aqueous secondary battery that is graphite particles and satisfies the following three requirements (A), (B), and (C).
  • A DBP oil absorption is 0.42 mL / g or more and 0.85 mL / g or less.
  • B The specific surface area is 0.5 m 2 / g or more and 6.5 m 2 / g or less.
  • Raman R value is 0.03 or more and 0.19 or less.
  • the negative electrode material of the present invention as a negative electrode material for non-aqueous secondary batteries, a non-aqueous secondary battery having high capacity, high input / output characteristics, high-temperature storage characteristics, and high cycle characteristics can be provided. Moreover, according to the manufacturing method of the negative electrode material for non-aqueous secondary batteries of this invention, it becomes possible to manufacture the negative electrode material which has the above-mentioned advantage.
  • the DBP oil absorption of the graphite particles of the present invention is 0.42 mL / g or more, preferably 0.45 mL / g or more, more preferably 0.50 mL / g or more. Moreover, it is 0.85 mL / g or less, Preferably it is 0.80 mL / g or less, More preferably, it is 0.76 mL / g or less.
  • DBP oil absorption is less than this range, there will be less voids that can be infiltrated by the non-aqueous electrolyte solution, so lithium ion insertion / desorption will not be in time when rapid charge / discharge is performed, and lithium metal will be deposited accordingly. Cycle characteristics tend to deteriorate.
  • the binder is likely to be absorbed into the gap during electrode plate production, and accordingly, the electrode plate strength and initial efficiency tend to be reduced.
  • DBP dibutyl phthalate
  • the measurement of DBP (dibutyl phthalate) oil absorption can be performed by the following procedure using a negative electrode material.
  • DBP oil absorption is measured in accordance with JIS K6217, 40 g of measurement material is added, dripping speed is 4 ml / min, rotation speed is 125 rpm, and measurement is performed until the maximum value of torque is confirmed. It is defined by the value (DBP dripping oil amount per 1 g of negative electrode material) calculated from the dripping oil amount when showing a torque of 70% of the maximum torque in the range shown.
  • the specific surface area of the graphite particles of the present invention is a value of the specific surface area measured using the BET method, and is 0.5 m 2 ⁇ g ⁇ 1 or more, preferably 1.0 m 2 ⁇ g ⁇ 1 or more, more preferably 1 .3m 2 ⁇ g -1 or more, particularly preferably at 1.5 m 2 ⁇ g -1 or more,, 6.5m 2 ⁇ g -1 or less, preferably 6.0 m 2 ⁇ g -1 or less, more preferably Is 5.5 m 2 ⁇ g ⁇ 1 or less, particularly preferably 5.0 m 2 ⁇ g ⁇ 1 or less.
  • the value of the specific surface area is less than this range, the acceptability of lithium tends to deteriorate during charging when used as a negative electrode material, and lithium metal tends to precipitate on the electrode surface, which tends to deteriorate the cycle characteristics.
  • the reactivity with the non-aqueous electrolyte increases, the initial efficiency tends to decrease, and a preferable battery is difficult to obtain.
  • the specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately adjusted so that the value of the relative pressure becomes 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used.
  • the specific surface area obtained by the measurement is defined as the specific surface area of the negative electrode material of the present invention.
  • the Raman R value of the graphite particles of the present invention is a value measured using an argon ion laser Raman spectrum method, and is 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more, It is 0.19 or less, preferably 0.18 or less, more preferably 0.16 or less, and particularly preferably 0.14 or less.
  • the Raman R value is less than the above range, the crystallinity of the particle surface becomes too high, and there are cases where the sites where lithium enters between layers are decreased along with charge / discharge. That is, the charge acceptance may be reduced and the cycle characteristics may be deteriorated.
  • the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • the above range is exceeded, the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the initial efficiency may be lowered and the gas generation may be increased.
  • a material having high lithium acceptability is a material having a wide contact area with the electrolyte, a large reaction area, and low crystallinity on the surface of the negative electrode particles (wide graphite layer, low La ⁇ Lc). It is considered that a material having a high DBP oil absorption, a large specific surface area, and a high Raman R value has a high lithium acceptability.
  • the material having low reactivity with the electrolytic solution is a material having a small contact area with the electrolytic solution, a small reaction area, and high crystallinity on the surface of the negative electrode material particles (the graphite layer is narrow, La ⁇ Lc is considered to be a material having a low DBP oil absorption, a specific surface area is small, and a material having a low Raman R value is considered to have a low reactivity with the electrolytic solution. This is considered to be a tendency to
  • both the cycle characteristics and the initial efficiency can be achieved by setting the contact area with the electrolytic solution to a certain extent, the reaction area to a certain extent, and the crystallinity of the negative electrode material particle surface within a certain range. That is, the present invention suppresses the specific surface area in a low range while maintaining the DBP oil absorption amount of the negative electrode material in a high range, and makes the Raman R value in a specific range, thereby quickly inserting and desorbing lithium ions. In addition, the reactivity with the non-aqueous electrolyte can be suppressed, and a negative electrode material having excellent cycle characteristics and high initial efficiency can be obtained.
  • the measurement of the Raman spectrum using a Raman spectrometer (manufactured by JASCO Corporation Raman spectrometer), the sample is naturally dropped into the measurement cell and filled, and while irradiating the sample surface in the cell with argon ion laser light, This is done by rotating the cell in a plane perpendicular to the laser beam.
  • the resulting Raman spectrum, the intensity I A of the peak P A in the vicinity of 1580 cm -1, and measuring the intensity I B of a peak P B in the vicinity of 1360 cm -1, the intensity ratio R (R I B / I A) Is calculated.
  • the Raman R value calculated by the measurement is defined as the Raman R value of the negative electrode active material of the present invention.
  • said Raman measurement conditions are as follows. Argon ion laser wavelength: 514.5nm ⁇ Laser power on the sample: 15-25mW ⁇ Resolution: 10-20cm -1 Measurement range: 1100 cm -1 to 1730 cm -1 -Raman R value, Raman half-value analysis: Background treatment-Smoothing treatment: Simple average, 5 points of convolution As other physical properties of the graphite particles of the present invention, it is desirable to have the following physical properties.
  • the Raman half-width in the vicinity of 1580 cm ⁇ 1 of the graphite particles of the present invention is not particularly limited, but is usually 10 cm ⁇ 1 or more, preferably 15 cm ⁇ 1 or more, and is usually 100 cm ⁇ 1 or less, preferably 80 cm ⁇ 1 or less. More preferably, it is 60 cm ⁇ 1 or less, and particularly preferably 40 cm ⁇ 1 or less. If the Raman half width is less than the above range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge and discharge. That is, the charge acceptance may be reduced and the cycle characteristics may be reduced.
  • the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.
  • the resulting measured half width of the peak P A in the vicinity of 1580 cm -1 of the Raman spectrum which is defined as the Raman half-value width of the negative electrode active material of the present invention.
  • the surface functional group O / C of the graphite particles of the present invention is represented by the following formula 1, and the O / C is usually 0.1% or more, preferably 0.2% or more, more preferably 0.3% or more. Yes, particularly preferably 0.5 or more, usually 2.0% or less, preferably 1.4% or less, more preferably 1.0% or less. If the surface functional group O / C is too small, the reactivity with the electrolytic solution is poor, and stable SEI formation cannot be performed and the cycle characteristics may be deteriorated. On the other hand, if the surface functional group O / C is too large, the crystal on the particle surface is disturbed, the reactivity with the electrolytic solution is increased, and there is a risk of increasing the irreversible capacity and increasing gas generation.
  • O / C (%) O atom concentration obtained based on the peak area of the O1s spectrum in X-ray photoelectron spectroscopy (XPS) analysis ⁇ 100 / C atom obtained based on the peak area of the C1s spectrum in XPS analysis Concentration
  • the surface functional group O / C of the graphite particles of the present invention can be measured using X-ray photoelectron spectroscopy (XPS).
  • the surface functional group O / C uses an X-ray photoelectron spectrometer as an X-ray photoelectron spectroscopic measurement, mounts the measurement target on a sample stage so that the surface is flat, and uses aluminum K ⁇ rays as an X-ray source.
  • the spectra of C1s (280 to 300 eV) and O1s (525 to 545 eV) are measured.
  • the obtained C1s peak top is corrected to be 284.3 eV, the peak areas of the C1s and O1s spectra are obtained, and the device sensitivity coefficient is multiplied to calculate the surface atomic concentrations of C and O, respectively.
  • the obtained atomic concentration ratio O / C of O and C (O atomic concentration / C atomic concentration) is defined as the surface functional group O / C of the graphite particles of the present invention.
  • the pore volume Vi of the graphite particles of the present invention is a value measured using a mercury intrusion method (mercury porosimetry), and is usually 0.10 mL / g or more, preferably 0.12 mL / g or more, more preferably 0. .14 mL / g or more, usually 0.30 mL / g or less, preferably 0.28 mL / g or less, more preferably 0.25 mL / g or less.
  • the pore volume Vi When the pore volume Vi is less than the above range, the number of voids into which the nonaqueous electrolyte solution can enter decreases, so that when lithium ion is rapidly charged / discharged, lithium ion insertion / desorption is not in time, and lithium metal is deposited accordingly. Characteristics tend to deteriorate. On the other hand, when it exceeds the above range, the binder is easily absorbed into the gap during electrode plate production, and accordingly, the electrode plate strength and initial efficiency tend to decrease.
  • a mercury porosimeter Autopore 9520 manufactured by Micromeritex Co., Ltd.
  • a sample negative electrode material
  • room temperature and vacuum 50 ⁇ mHg or less
  • the pressure was reduced in steps to 4 psia
  • mercury was introduced
  • the pressure was increased in steps from 4 psia to 40000 psia
  • the pressure was further decreased to 25 psia.
  • the pore distribution was calculated from the obtained mercury intrusion curve using the Washburn equation. Note that the surface tension of mercury was calculated as 485 dyne / cm and the contact angle was 140 °.
  • the total pore volume i of the graphite particles of the present invention is a value measured using the mercury intrusion method (mercury porosimetry), and is usually 0.48 mL / g or more, preferably 0.50 mL / g or more, more preferably. Is 0.52 mL / g or more, and usually 0.95 mL / g or less, preferably 0.93 mL / g or less, more preferably 0.90 mL / g or less.
  • the total pore volume is below the above range, the number of voids that can be infiltrated by the non-aqueous electrolyte solution tends to be small, and when lithium ions are rapidly charged and discharged, lithium ions are not inserted and released in time, and lithium metal is deposited accordingly. Characteristics tend to deteriorate. On the other hand, when it exceeds the above range, the binder is easily absorbed into the gap during electrode plate production, and accordingly, the electrode plate strength and initial efficiency tend to decrease.
  • the tap density of the graphite particles of the present invention is usually 0.70 g ⁇ cm ⁇ 3 or more, preferably 0.80 g ⁇ cm ⁇ 3 or more, more preferably 0.90 g ⁇ cm ⁇ 3 or more. 25 g ⁇ cm -3 or less, preferably 1.20 g ⁇ cm -3 or less, more preferably 1.18 g ⁇ cm -3 or less, particularly preferably not more than 1.15 g ⁇ cm -3.
  • the tap density is below the above range, the packing density is difficult to increase when used as a negative electrode, and a high-capacity battery may not be obtained.
  • the above range is exceeded, there are too few voids between particles in the electrode, it is difficult to ensure conductivity between the particles, and it may be difficult to obtain preferable battery characteristics.
  • the tap density is measured by passing a sieve having a mesh opening of 300 ⁇ m, dropping the sample onto a 20 cm 3 tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring instrument (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated from the volume at that time and the mass of the sample. The tap density calculated by the measurement is defined as the tap density of the negative electrode active material of the present invention.
  • the volume-based average particle diameter of the graphite particles of the present invention is such that the volume-based average particle diameter (median diameter) determined by the laser diffraction / scattering method is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably. Is 7 ⁇ m or more, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the volume-based average particle size is measured by dispersing the carbon powder in a 0.2% by mass aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. This is carried out using a total (LA-700 manufactured by Horiba Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the negative electrode material of the present invention.
  • the crystallite size (Lc) and (La) of the carbonaceous material obtained by X-ray diffraction by the Gakushin method of the graphite particles of the present invention is preferably 30 nm or more, and more preferably 100 nm or more. . If the crystallite size is in this range, the amount of lithium that can be charged in the negative electrode material is increased, and a high capacity is easily obtained, which is preferable.
  • the orientation ratio of the graphite particle powder of the present invention is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less, preferably 0.5 or less. More preferably, it is 0.4 or less.
  • the normal upper limit of the said range is a theoretical upper limit of the orientation ratio of a carbonaceous material.
  • the orientation ratio is measured by X-ray diffraction after pressure-molding the sample.
  • Set the molded body obtained by filling 0.47 g of the sample into a molding machine with a diameter of 17 mm and compressing it with 58.8 MN ⁇ m -2 so that it is flush with the surface of the sample holder for measurement.
  • X-ray diffraction is measured.
  • From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.
  • the orientation ratio calculated by the measurement is defined as the orientation ratio of the negative electrode material of the present invention.
  • the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
  • ⁇ Target Cu (K ⁇ ray) graphite monochromator
  • Light receiving slit 0.15
  • Scattering slit 0.5 degree / measurement range and step angle / measurement time: (110) plane: 75 degrees ⁇ 2 ⁇ ⁇ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ⁇ 2 ⁇ ⁇ 57 degrees 1 degree / 60 seconds
  • the form of the graphite particle of the present invention is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a massive shape, a plate shape, and a polygonal shape. It is preferable because the property can be improved.
  • the surface morphology of the graphite particles of the present invention is not particularly limited, but preferably has a concavo-convex structure as shown in the SEM photograph of FIG.
  • the concavo-convex structure include (1) a concave structure in which a hole is formed on the particle surface such as a sphere or an ellipse, and (2) a convex structure in which fine particles are bound on the particle surface such as a sphere or an ellipse. It is done.
  • the particle surface has a concavo-convex structure, even when a high-density negative electrode is formed, a void into which a nonaqueous electrolytic solution can enter can be secured, so that improvement in cycle characteristics can be expected.
  • the size of the concavo-convex structure is not particularly limited, but preferably corresponds to a diameter of about 0.1 ⁇ m to 4 ⁇ m when converted into a circular area.
  • the size of the concavo-convex structure is within this range, even when the negative electrode has a high density, it is possible to secure a void into which the non-aqueous electrolyte solution can enter, so that improvement in cycle characteristics can be expected.
  • the manufacturing method of the graphite particle of this invention is not specifically limited, The method shown to following (I) and (II) etc. are mentioned.
  • the graphite particles of the present invention are not particularly limited, but are graphite particles coated with a carbonaceous material. Among them, graphite particles coated with amorphous carbon, graphite particles coated with a graphite material are preferable, and more preferable. Is a graphite particle coated with amorphous carbon obtained by mixing and firing raw graphite and carbon precursor, and a graphite material obtained by mixing and firing raw graphite and carbon precursor. Graphite particles are preferred.
  • a convex structure is formed by binding to the surface of the core particles such as a spherical shape or an elliptical shape and the core particles such as a plate shape or a scale shape.
  • a production method comprising a step of mixing at least raw material graphite and a raw material organic material and a step of firing at a temperature of 2300 ° C. or higher using two or more kinds of raw material graphite (mixture) composed of fine particles.
  • the manufacturing method (I) is preferable because it can easily form an uneven structure.
  • the raw graphite is not particularly limited as long as it is graphitized (or graphitized by firing at a temperature of 2300 ° C. or higher), but natural graphite, artificial graphite, coke powder, and needle coke powder. And graphitized resin (or graphitizable carbon) powder. Of these, natural graphite is preferable because it is easy to process.
  • the form of the raw material graphite particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a lump shape, a plate shape, a scale shape, and a polygonal shape.
  • the spherical and elliptical shapes used in the production methods (I) and (II) are exemplified.
  • the shape, lump, or polygonal shape is a graphite particle, the particle filling property can be improved, which is preferable.
  • an apparatus for obtaining spherical and elliptical graphite used in the production methods (I) and (II) for example, mechanical force such as compression, friction, shear force including particle interaction mainly including impact force.
  • An apparatus that repeatedly gives action to particles can be used. Specifically, it has a rotor with a large number of blades installed inside the casing, and when the rotor rotates at high speed, mechanical action such as impact compression, friction, shearing force, etc. is applied to the carbon material introduced inside.
  • An apparatus that provides a surface treatment is preferable.
  • Preferred devices include, for example, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron (manufactured by Earth Technica), a CF mill (manufactured by Ube Industries), a mechano-fusion system (manufactured by Hosokawa Micron), and a theta composer (Tokuju Kosakusho). Etc.).
  • a hybridization system manufactured by Nara Machinery Co., Ltd. is preferable.
  • Spherical or elliptical graphite is pulverized into base particles that have been made spherical by spheroidizing the scale-like natural graphite by folding the flaky natural graphite by applying the spheroidization step by the above surface treatment.
  • a condition in which fine particles of 5 ⁇ m or less produced mainly due to adhesion are attached, and the surface functional group O / C of the graphite particles after the surface treatment is usually 0.5% to 10%, preferably 1% to 4%. Thus, it is manufactured by performing a spheroidizing process.
  • the peripheral speed of the rotating rotor is usually 30 to 100 m / sec, preferably 40 to 100 m / sec, and more preferably 50 to 100 m / sec.
  • the treatment can be performed by simply passing a carbonaceous material, but it is preferable to circulate or stay in the apparatus for 30 seconds or longer, and it is preferable to circulate or stay in the apparatus for 1 minute or longer. More preferred.
  • a device for feeding particles can be used. Specific examples include a jet mill, a hammer mill, a pin mill, a turbo mill, and a pulverizer.
  • the volume-based average particle diameter of the raw graphite is not particularly limited, but is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably 7 ⁇ m or more, and usually 100 ⁇ m or less, preferably 50 ⁇ m or less. More preferably, it is 40 ⁇ m or less, particularly preferably 30 ⁇ m or less.
  • the volume-based average particle diameter is usually 5 ⁇ m or more, preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more. Usually, it is 50 micrometers or less, Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. Further, in the case of fine particles such as plate, scale, and lump used in the method (II) for producing graphite particles, the volume-based average particle size is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 20 ⁇ m.
  • the particle size of the raw material graphite is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less. If the particle size of the raw material graphite is within this range, it is preferable to form a concavo-convex structure on the particle surface when the graphite particles are used.
  • the roughening step of the raw material graphite refers to a step of imparting an uneven structure to the surface of the raw material graphite.
  • the method used in the roughening step is not particularly limited as long as the surface of the raw graphite is provided with a concavo-convex structure.
  • mechanical energy for example, pulverization
  • compression, friction, and shear force is applied to the raw graphite.
  • there is a method of imparting a concavo-convex structure to the surface and it may be performed in a dry state or a wet state.
  • methods for imparting a concavo-convex structure to the surface of raw graphite are listed.
  • the pulverization speed in the dry state varies depending on the apparatus to be used, but when the raw material graphite is spherical or elliptical, select the shape and rotation speed of the rotor of the pulverizer to be used as appropriate, and
  • the calculated rotor circumferential speed is preferably set to 50 m / sec or more, more preferably set to 80 m / sec or more, and further preferably set to 100 m / sec or more.
  • the upper limit is usually 300 m / sec or less.
  • Peripheral speed (m / sec) diameter of rotor of roughening device ⁇ 3.14 ⁇ rotational speed
  • the specific shape of the rotor and / or stator of the grinding device to be used can be set as long as the peripheral speed can be set. Although there is no particular limitation, it is preferable that the rotor has a blade and the stator has a groove.
  • the pulverization speed is too high, a lot of fine powder may be generated. Even if the roughened raw material graphite and the raw material organic material are mixed and fired at a temperature of 2300 ° C. or higher, the specific surface area of the obtained graphite particles is large. The reactivity with the electrolytic solution cannot be suppressed, and the initial efficiency and cycle characteristics may be deteriorated. On the other hand, if it is slower than this pulverization rate, the effect of roughening hardly appears, and it tends to be difficult to improve the initial efficiency and cycle characteristics.
  • the raw material charging speed at the time of pulverization is usually 10 kg / hr or more, preferably 50 kg / hr or more, more preferably 100 kg / hr or more, and further preferably 200 kg / hr or more. Moreover, it is 1000 kg / hr or less normally, Preferably it is 700 kg / hr or less, More preferably, it is 500 kg / hr or less. If the charging speed is too high, mechanical energy is hardly imparted to the raw material graphite, the effect of roughening is difficult to appear, and the initial efficiency and cycle characteristics tend to be difficult to improve. Further, if it is slower than the charging speed, the productivity may be lowered.
  • an ultrasonic cleaner when used, it is performed as follows. After mixing raw material graphite and ion exchange water at a predetermined mass ratio, the mixture is stirred and then subjected to ultrasonic irradiation and then dried. When ultrasonic irradiation is performed, it is preferable to generate and disappear bubbles in a short time.
  • the frequency is usually 10 Hz to 50000 Hz, preferably 20 Hz to 40000 Hz, and more preferably 30 Hz to 30000 Hz.
  • the output is generally 10 W to 30000 W, preferably 20 W to 20000 W, more preferably 30 W to 16000 W.
  • the ultrasonic irradiation time is usually from 30 seconds to 20 hours, preferably from 60 seconds to 10 hours, more preferably from 120 seconds to 3 hours. If this time is short, the treatment effect tends to be insufficient. If the length is too long, particle breakage is promoted, battery characteristics are remarkably lowered, and mass productivity tends to be lowered.
  • a mass ratio of 1: 1.1 to 1:30 is preferable. Preferably it is 1:20, More preferably, it is 1:10. When it becomes thinner than 1:30, the productivity tends to decrease. Conversely, when it becomes a concentrated liquid of 1: 1.1 or less, it is difficult to stir.
  • a surfactant can be used. As the surfactant, a general commercial product can be selected. It is also effective for improving dispersibility to mix carbon after wetting it with alcohols such as ethanol or isopropyl alcohol.
  • shelf drying is simple, but a model that can be dried while stirring or a baking furnace can also be used.
  • the drying temperature should just be 110 degreeC or more, and can be selected as needed.
  • the raw organic material is not particularly limited as long as it is carbonaceous that can be graphitized by firing, coal-based heavy oil, DC heavy oil, cracked heavy oil, aromatic hydrocarbon, N-ring compound, Examples thereof include carbonizable organic substances selected from the group consisting of S ring compounds, polyphenylene, organic synthetic polymers, natural polymers, thermoplastic resins, and thermosetting resins. Moreover, in order to adjust the viscosity at the time of mixing, a raw material organic substance may be used by dissolving in a low molecular organic solvent.
  • coal-based heavy oil coal tar pitch from dry pitch to hard pitch, dry distillation liquefied oil, etc. are preferable, and as DC heavy oil, normal pressure residual oil, reduced pressure residual oil, etc. are preferable, cracked petroleum heavy oil, etc.
  • the crude oil is preferably ethylene tar or the like by-produced during thermal decomposition of crude oil, naphtha, etc.
  • the aromatic hydrocarbon is preferably acenaphthylene, decacyclene, anthracene, phenanthrene, etc.
  • the N-ring compound is phenazine, acridine, etc.
  • the S ring compound is preferably thiophene, bithiophene, etc.
  • the polyphenylene is preferably biphenyl, terphenyl, etc.
  • the organic synthetic polymer is polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, insolubilization treatment thereof.
  • Products, polyacrylonitrile, polypyrrole, polythiophene Polystyrene, etc. are preferred
  • natural polymers are preferably polysaccharides such as cellulose, lignin, mannan, polygalacturonic acid, chitosan, saccharose, etc.
  • thermoplastic resins are preferably polyphenylene sulfide, polyphenylene oxide, etc.
  • the curable resin furfuryl alcohol resin, phenol-formaldehyde resin, imide resin and the like are preferable. Further, as the low molecular organic solvent, benzene, toluene, xylene, quinoline, n-hexane and the like are preferable.
  • the method of mixing the raw material graphite and the raw material organic material in the manufacturing method is not particularly limited, but a general mixing device can be used. Specific examples include a mixer, a kneader, and a twin-screw kneader.
  • a raw material organic material dissolved or diluted with a low molecular organic solvent may be used, or the viscosity of the raw material organic material may be adjusted by heating. .
  • the mixing ratio (mass ratio) of the raw material graphite and the raw material organic material is appropriately selected depending on the type of the raw material graphite and the raw material organic material to be used, and the amount of the raw material organic material with respect to 100 parts by mass of the raw material graphite is not particularly limited. Usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and usually 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 35 parts by mass or less.
  • the method for firing the mixture of the raw material graphite and the raw material organic material in the production method is not particularly limited, and includes a carbonization step for removing volatile components and a graphitization step at a temperature of 2300 ° C. or higher.
  • the carbonization step for removing volatile components is usually performed at a temperature of 600 ° C. or higher, preferably 650 ° C. or higher, usually 1300 ° C. or lower, preferably 1100 ° C. or lower, usually for 0.1 to 10 hours.
  • heating is usually performed in a non-oxidizing atmosphere in which an inert gas such as nitrogen or argon is circulated or a granular carbon material such as breeze or packing coke is filled in the gap.
  • the equipment used for the carbonization process to remove volatiles is, for example, a shuttle furnace, a tunnel furnace, a lead hammer furnace, a rotary kiln, an autoclave, a reaction tank, a coker (heat treatment tank for coke production), an electric furnace, a gas furnace, etc.
  • the heating rate during heating is desirably a low speed for removing volatile components. Normally, from about 200 ° C. where volatilization of low-boiling components starts to around 700 ° C. where only hydrogen is generated, 3 to 100 ° C.
  • the temperature is raised at / hr. During the treatment, stirring may be performed as necessary.
  • the carbide obtained by the carbonization step is then graphitized by heating at a high temperature.
  • the heating temperature at the time of graphitization is 2300 ° C or higher, preferably 2600 ° C or higher, more preferably 2800 ° C or higher. Moreover, since the sublimation of graphite will become remarkable when heating temperature is too high, 3300 degrees C or less is preferable.
  • the heating time may be performed until the binder and the carbonaceous particles become graphite, and is usually 1 to 24 hours.
  • the atmosphere during graphitization is performed under a non-oxidizing atmosphere in which an inert gas such as nitrogen or argon is circulated or a granular carbon material such as breeze or packing coke is filled in the gap.
  • the equipment used for graphitization is not particularly limited as long as it meets the above purpose, such as an electric furnace, a gas furnace, an electrode material Atchison furnace, etc.
  • the heating rate, cooling rate, heat treatment time, etc. are acceptable for the equipment used. It can be set arbitrarily within the range.
  • the fired product is subjected to powder processing such as pulverization, pulverization, grinding, and classification as required.
  • powder processing such as pulverization, pulverization, grinding, and classification as required.
  • the coarse pulverizer includes a shearing mill, jaw crusher, impact crusher, cone crusher, etc.
  • the intermediate pulverizer includes a roll crusher, hammer mill, etc.
  • the fine pulverizer include a ball mill, a vibration mill, a pin mill, a stirring mill, and a jet mill.
  • the above-described graphite particles for non-aqueous secondary batteries of the present invention are suitably used as a negative electrode material for lithium ion secondary batteries, either alone or in combination of two or more in any composition and combination.
  • one or two or more kinds may be mixed with another kind or two or more other carbon materials, and this may be used as a negative electrode material for non-aqueous secondary batteries, preferably lithium ion secondary batteries. .
  • the mixing ratio of the negative electrode material for the non-aqueous secondary battery to the total amount of the negative electrode material for the non-aqueous secondary battery and the other carbon material is usually 10 masses. % Or more, preferably 20% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less.
  • the mixing ratio of other carbon materials is less than the above range, the added effect tends to hardly appear.
  • the above range is exceeded, the characteristics of the negative electrode material for non-aqueous secondary batteries tend to hardly appear.
  • a material selected from natural graphite, artificial graphite, amorphous coated graphite, and amorphous carbon is used as the other carbon material. Any one of these materials may be used alone, or two or more of these materials may be used in any combination and composition.
  • natural graphite for example, highly purified flaky graphite or spheroidized graphite can be used as natural graphite.
  • the volume-based average particle diameter of natural graphite is usually 8 ⁇ m or more, preferably 12 ⁇ m or more, and usually 60 ⁇ m or less, preferably 40 ⁇ m or less.
  • the natural graphite has a BET specific surface area of usually 3.5 m 2 / g or more, preferably 4.5 m 2 / g or more, and usually 8 m 2 / g or less, preferably 6 m 2 / g or less.
  • Examples of the artificial graphite include particles obtained by graphitizing a carbon material.
  • particles obtained by firing and graphitizing a single graphite precursor particle while it is powdered can be used.
  • amorphous-coated graphite for example, natural graphite or artificial graphite coated with an amorphous precursor pair and fired, or natural graphite or artificial graphite coated with amorphous by CVD can be used.
  • amorphous carbon for example, particles obtained by firing a bulk mesophase, or particles obtained by firing an infusible carbonized pitch or the like can be used.
  • the device used for mixing the negative electrode material for non-aqueous secondary batteries and other carbon materials for example, in the case of a rotary mixer: a cylindrical mixer, a twin cylinder mixer, a double cone Type mixer, regular cubic mixer, vertical mixer, stationary mixer: spiral mixer, ribbon mixer, Muller mixer, Helical Flyt mixer, Pugmill mixer, fluidized mixer A mixer or the like can be used.
  • a negative electrode for a non-aqueous secondary battery of the present invention (hereinafter also referred to as an “electrode sheet” as appropriate) includes a current collector and an active material layer formed on the current collector, and the active material layer is at least the present material layer. It contains the negative electrode material for non-aqueous secondary batteries of the invention. More preferably, it contains a binder.
  • the binder here means a binder added for the purpose of binding active materials and holding the active material layer on a current collector when producing a negative electrode for a non-aqueous secondary battery. It is different from the binder that can be converted.
  • the binder one having an olefinically unsaturated bond in the molecule is used.
  • the type is not particularly limited, and specific examples include styrene-butadiene rubber, styrene / isoprene / styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene / propylene / diene copolymer.
  • styrene-butadiene rubber is preferred because of its availability.
  • the strength of the negative electrode plate can be increased.
  • the strength of the negative electrode is high, deterioration of the negative electrode due to charge / discharge is suppressed, and the cycle life can be extended.
  • the negative electrode according to the present invention since the adhesive strength between the active material layer and the current collector is high, even when the binder content in the active material layer is reduced, the negative electrode is wound to produce a battery. It is speculated that the problem that the active material layer peels from the current collector does not occur.
  • the binder having an olefinically unsaturated bond in the molecule one having a large molecular weight or one having a large proportion of unsaturated bonds is desirable.
  • the weight average molecular weight is usually 10,000 or more, preferably 50,000 or more, and usually 1,000,000 or less, preferably 300,000 or less.
  • the number of moles of olefinically unsaturated bonds per gram of all binders is usually 2.5 ⁇ 10 ⁇ 7 or more, preferably 8 ⁇ 10 ⁇ 7 or more.
  • the binder only needs to satisfy at least one of these regulations regarding molecular weight and regulations regarding the proportion of unsaturated bonds, but it is more preferable to satisfy both regulations simultaneously.
  • the molecular weight of the binder having an olefinically unsaturated bond is too small, the mechanical strength is inferior, and when it is too large, the flexibility is inferior.
  • the ratio of the olefinic unsaturated bond in a binder is too small, the strength improvement effect will fade, and when too large, it will be inferior to flexibility.
  • the binder having an olefinically unsaturated bond has a degree of unsaturation of usually 15% or more, preferably 20% or more, more preferably 40% or more, and usually 90% or less, preferably 80% or less. Is desirable.
  • the degree of unsaturation represents the ratio (%) of the double bond to the repeating unit of the polymer.
  • a binder having no olefinically unsaturated bond can also be used in combination with the above-mentioned binder having an olefinically unsaturated bond as long as the effects of the present invention are not lost.
  • the mixing ratio of the binder having no olefinically unsaturated bond to the binder having an olefinically unsaturated bond is usually 150% by mass or less, preferably 120% by mass or less.
  • binders having no olefinic unsaturated bond include thickening polysaccharides such as methylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum (xanthan gum), polyethers such as polyethylene oxide and polypropylene oxide, Vinyl alcohols such as polyvinyl alcohol and polyvinyl butyral, polyacids such as polyacrylic acid and polymethacrylic acid, or metal salts of these polymers, fluorine-containing polymers such as polyvinylidene fluoride, alkane polymers such as polyethylene and polypropylene, and these A copolymer etc. are mentioned.
  • the negative electrode of the present invention is formed by dispersing the above-described negative electrode material of the present invention and a binder in a dispersion medium to form a slurry, which is applied to a current collector.
  • a dispersion medium an organic solvent such as alcohol or water can be used.
  • a conductive agent may be added to the slurry.
  • the conductive agent include carbon black such as acetylene black, ketjen black, and furnace black, and fine powder made of Cu, Ni having an average particle diameter of 1 ⁇ m or less, or an alloy thereof.
  • the addition amount of the conductive agent is usually about 10% by mass or less with respect to the negative electrode material of the present invention.
  • a conventionally well-known thing can be used as a collector which apply
  • Specific examples include metal thin films such as rolled copper foil, electrolytic copper foil, and stainless steel foil.
  • the thickness of the current collector is usually 4 ⁇ m or more, preferably 6 ⁇ m or more, and usually 30 ⁇ m or less, preferably 20 ⁇ m or less.
  • This slurry was applied to a width of 5 cm using a doctor blade so that the negative electrode material was 14.5 ⁇ 0.3 mg / cm 2 on a 18 ⁇ m-thick copper foil as a current collector, and air-dried at room temperature. Went. Further, after drying at 110 ° C. for 30 minutes, roll pressing was performed using a roller having a diameter of 20 cm, and the density of the active material layer was adjusted to 1.70 ⁇ 0.03 g / cm 3 to obtain an electrode sheet.
  • the slurry After applying the slurry on the current collector, the slurry is usually dried at a temperature of 60 ° C. or higher, preferably 80 ° C. or higher, and usually 200 ° C. or lower, preferably 195 ° C. or lower, in dry air or an inert atmosphere. A physical layer is formed.
  • the thickness of the active material layer obtained by applying and drying the slurry is usually 5 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and usually 200 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less. .
  • the active material layer is too thin, it is not practical as a negative electrode because of the balance with the particle size of the active material, and if it is too thick, it is difficult to obtain a sufficient Li occlusion / release function for high-density current values.
  • Density of the negative electrode material for nonaqueous secondary battery in the active material layer varies depending on the application, the application that emphasizes capacity, preferably 1.55 g / cm 3 or more, especially 1.60 g / cm 3 or more, further 1. 65 g / cm 3 or more, particularly 1.70 g / cm 3 or more is preferable. If the density is too low, the capacity of the battery per unit volume is not always sufficient. Moreover, since a rate characteristic will fall when a density is too high, 1.9 g / cm ⁇ 3 > or less is preferable.
  • the method and selection of other materials are not particularly limited.
  • the selection of members necessary for the battery configuration such as the positive electrode and the electrolytic solution constituting the lithium ion secondary battery.
  • the details of the negative electrode for lithium ion secondary batteries and the lithium ion secondary battery using the negative electrode material of the present invention will be exemplified, but the materials that can be used and the method of production are not limited to the following specific examples. Absent.
  • Non-aqueous secondary battery of the present invention is the same as that of a conventionally known lithium ion secondary battery, and usually includes a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte. Is provided.
  • the negative electrode of the present invention described above is used as the negative electrode.
  • the positive electrode is obtained by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector.
  • Examples of the positive electrode active material include metal chalcogen compounds that can occlude and release alkali metal cations such as lithium ions during charge and discharge.
  • metal chalcogen compounds include vanadium oxide, molybdenum oxide, manganese oxide, chromium oxide, titanium oxide, tungsten oxide and other transition metal oxides, vanadium sulfide, molybdenum sulfide.
  • Transition metal sulfides such as NiPS 3 and FePS 3 , selenium compounds of transition metals such as VSe 2 and NbSe 3 , Fe 0.25 V 0.75 S 2 , Na0.1CrS 2 composite oxide of a transition metal such as, LiCoS 2, LiNiS 2 composite sulfide of a transition metal, such as and the like.
  • V 2 O 5 , V 5 O 13 , VO 2 , Cr 2 O 5 , MnO 2 , TiO, MoV 2 O 8 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , TiS 2 , V 2 S 5 , Cr 0.25 V 0.75 S 2 , Cr 0.5 V 0.5 S 2, etc. are preferable.
  • LiCoO 2 , LiNiO 2 , LiMn 2 O 4, and lithium transitions in which some of these transition metals are replaced with other metals are particularly preferable. It is a metal complex oxide.
  • These positive electrode active materials may be used alone or in combination.
  • binders can be arbitrarily selected and used. Examples include inorganic compounds such as silicate and water glass, and resins having no unsaturated bond such as Teflon (registered trademark) and polyvinylidene fluoride. Among these, a resin having no unsaturated bond is preferable. If a resin having an unsaturated bond is used as the resin for binding the positive electrode active material, the resin may be decomposed during the oxidation reaction.
  • the weight average molecular weight of these resins is usually 10,000 or more, preferably 100,000 or more, and usually 3 million or less, preferably 1 million or less.
  • the positive electrode active material layer may contain a conductive material in order to improve the conductivity of the electrode.
  • the conductive agent is not particularly limited as long as it can be mixed with an active material in an appropriate amount to impart conductivity, but is usually carbon powder such as acetylene black, carbon black, and graphite, various metal fibers, powder, and foil. Etc.
  • the positive electrode plate is formed by slurrying a positive electrode active material and a binder with a solvent in the same manner as in the production of the negative electrode as described above, and applying and drying on a current collector.
  • As the current collector of the positive electrode aluminum, nickel, SUS, or the like is used, but is not limited at all.
  • a non-aqueous electrolyte obtained by dissolving a lithium salt in a non-aqueous solvent, or a gel, rubber, or solid sheet obtained by using an organic polymer compound or the like from the non-aqueous electrolyte is used.
  • the non-aqueous solvent used in the non-aqueous electrolyte is not particularly limited, and can be appropriately selected from known non-aqueous solvents that have been conventionally proposed as solvents for non-aqueous electrolytes.
  • chain carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate
  • cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate
  • chain ethers such as 1,2-dimethoxyethane
  • tetrahydrofuran 2-methyl
  • chain ethers such as tetrahydrofuran, sulfolane, and 1,3-dioxolane
  • chain esters such as methyl formate, methyl acetate, and methyl propionate
  • cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone.
  • non-aqueous solvents may be used alone or in a combination of two or more.
  • a mixed solvent a combination of a mixed solvent containing a cyclic carbonate and a chain carbonate is preferable, and the cyclic carbonate is a mixed solvent of ethylene carbonate and propylene carbonate.
  • propylene carbonate is preferably in the range of 2 wt% to 80 wt%, more preferably in the range of 5 wt% to 70 wt%, and still more preferably in the range of 10 wt% to 60 wt% with respect to the entire non-aqueous solvent.
  • the lithium salt used in the non-aqueous electrolytic solution is not particularly limited, and can be appropriately selected from known lithium salts that can be used for this purpose.
  • halides such as LiCl and LiBr
  • perhalogenates such as LiClO 4 , LiBrO 4 and LiClO 4
  • inorganic lithium salts such as inorganic fluoride salts such as LiPF 6 , LiBF 4 and LiAsF 6 , LiCF 3 SO 3
  • Fluorine-containing organic lithium salts such as perfluoroalkanesulfonic acid salts such as LiC 4 F 9 SO 3 and perfluoroalkanesulfonic acid imide salts such as Li trifluorosulfonimide ((CF 3 SO 2 ) 2 NLi)
  • LiClO 4 , LiPF 6 , and LiBF 4 are preferable.
  • Lithium salts may be used alone or in combination of two or more.
  • concentration of the lithium salt in the non-aqueous electrolyte is usually in the range of 0.5M to 2.0M.
  • organic polymer compound when an organic polymer compound is included in the above non-aqueous electrolyte and used in the form of a gel, rubber, or solid sheet, specific examples of the organic polymer compound include polyethylene oxide, polypropylene oxide, and the like.
  • Polyether polymer compounds ; Cross-linked polymers of polyether polymer compounds; Vinyl alcohol polymer compounds such as polyvinyl alcohol and polyvinyl butyral; Insolubilized vinyl alcohol polymer compounds; Polyepichlorohydrin; Polyphosphazene; Siloxane; vinyl polymer compounds such as polyvinylpyrrolidone, polyvinylidene carbonate, polyacrylonitrile; poly ( ⁇ -methoxyoligooxyethylene methacrylate), poly ( ⁇ -methoxyoligooxyethylene methacrylate-co-methyl methacrylate) Rate) and polymer copolymers such as poly (hexafluoropropylene-vinylidene fluoride).
  • Vinyl alcohol polymer compounds such as polyvinyl alcohol and polyvinyl butyral
  • Insolubilized vinyl alcohol polymer compounds Polyepichlorohydrin; Polyphosphazene; Siloxane
  • vinyl polymer compounds such as polyvinylpyrrolidone, polyvinylidene carbonate
  • the above non-aqueous electrolyte may further contain a film forming agent.
  • the film forming agent include carbonate compounds such as vinylene carbonate, vinylethyl carbonate, and methylphenyl carbonate; alken sulfides such as ethylene sulfide and propylene sulfide; sultone compounds such as 1,3-propane sultone and 1,4-butane sultone And acid anhydrides such as maleic acid anhydride and succinic acid anhydride.
  • an overcharge inhibitor such as diphenyl ether or cyclohexylbenzene may be added.
  • the content is usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. If the content of the additive is too large, other battery characteristics such as an increase in initial irreversible capacity, low temperature characteristics, and deterioration in rate characteristics may be adversely affected.
  • a polymer solid electrolyte which is a conductor of an alkali metal cation such as lithium ion can be used.
  • the polymer solid electrolyte include a polymer in which a salt of Li is dissolved in the aforementioned polyether polymer compound, and a polymer in which the terminal hydroxyl group of the polyether is substituted with an alkoxide.
  • a porous separator such as a porous film or a nonwoven fabric is usually interposed between the positive electrode and the negative electrode.
  • the nonaqueous electrolytic solution is used by impregnating a porous separator.
  • polyolefin such as polyethylene and polypropylene, polyethersulfone, and the like are used, and polyolefin is preferable.
  • the form of the lithium ion secondary battery of the present invention is not particularly limited. Examples include a cylinder type in which a sheet electrode and a separator are spiral, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, a coin type in which a pellet electrode and a separator are stacked, and the like.
  • the battery can be used in an arbitrary shape such as a coin shape, a cylindrical shape, or a square shape.
  • the procedure for assembling the lithium ion secondary battery of the present invention is not particularly limited, and may be assembled by an appropriate procedure according to the structure of the battery.
  • the negative electrode is placed on the outer case, and the electrolytic solution is placed thereon.
  • a separator is provided, and a positive electrode is placed so as to face the negative electrode, and it is caulked together with a gasket and a sealing plate to form a battery.
  • the initial efficiency during battery charging / discharging was measured by the following measurement method. After charging to 5 mV with respect to the lithium counter electrode at a current density of 0.16 mA / cm 2 , and further charging until the charge capacity value becomes 350 mAh / g at a constant voltage of 5 mV, after doping lithium in the negative electrode, 0 The battery was discharged to 1.5 V with respect to the lithium counter electrode at a current density of .33 mA / cm 2 .
  • the second and third times were charged at 10 mV and 0.005 Ccut with cc-cv charge at the same current density, and discharged at all times with 0.04 C to 1.5 V.
  • the sum of the difference between the charge capacity and discharge capacity for a total of three cycles was calculated as an irreversible capacity.
  • the discharge capacity at the third cycle was defined as the discharge capacity of the material, the discharge capacity at the third cycle / (the discharge capacity at the third cycle + the sum of the difference between the charge capacity and the discharge capacity at the third cycle).
  • an electrode plate having an active material layer density of 1.70 ⁇ 0.03 g / cm 3 was prepared. Specifically, 20.00 ⁇ 0.02 g of negative electrode material 20.00 ⁇ 0.02 g of a 1% by mass aqueous solution of sodium carboxymethylcellulose (0.200 g in terms of solid content), and styrene having a weight average molecular weight of 270,000 -Aqueous dispersion of butadiene rubber 0.50 ⁇ 0.05 g (0.2 g in terms of solid content) was stirred for 5 minutes with a hybrid mixer manufactured by Keyence, and defoamed for 30 seconds to obtain a slurry.
  • This slurry was applied to a width of 5 cm using a doctor blade so that the negative electrode material was 14.5 ⁇ 0.3 mg / cm 2 on a 18 ⁇ m-thick copper foil as a current collector, and air-dried at room temperature. Went. Further, after drying at 110 ° C. for 30 minutes, roll pressing was performed using a roller having a diameter of 20 cm, and the density of the active material layer was adjusted to 1.70 ⁇ 0.03 g / cm 3 to obtain an electrode sheet.
  • B ethylene carbonate and propylene carbonate
  • Electrolyte solution in which LiPF 6 was dissolved in a mixed solvent of 1 and diethyl carbonate (volume ratio 2: 4: 4) to a concentration of 1 mol / L
  • a separator made of a porous polyethylene film impregnated with an electrolytic solution in which LiPF 6 was dissolved to 1 mol / L (represented in the table as electrolytic solutions A, B, and C, respectively) )
  • 2016 coin type batteries using the AC electrolytes were produced.
  • the negative electrode sheet produced by the above method was cut into a square of 4 cm ⁇ 3 cm to form a negative electrode, and a positive electrode made of LiCoO 2 was cut out with the same area and combined.
  • a separator (made of a porous polyethylene film) impregnated with 2% by volume of an electrolytic solution was placed and a laminate type battery was produced.
  • Example 1 Spherical natural graphite having a volume-based average particle diameter of 17 ⁇ m is used as raw material graphite, and a grinding device comprising a rotor and a stator is used as a roughening process, and the rotor is ground at a peripheral speed of 145 m / sec and an input speed of 200 kg / hr. A graphite having an uneven structure was obtained.
  • the pitch of the raw material organic matter was mixed at a ratio of 30 parts by mass with 100 parts by mass of the obtained graphite using a kneader. After the resulting mixture was molded, it was fired and carbonized at 1000 ° C. in an inert atmosphere, and further graphitized at 3000 ° C.
  • the obtained graphite compact was roughly crushed and pulverized to obtain a powder sample made of graphite particles.
  • the DBP oil absorption, specific surface area, Raman R value, pore volume Vi, total pore volume, O / C, tap density, and average particle diameter were measured by the above measurement methods. Moreover, the presence or absence of the uneven structure was judged from SEM observation of the particle surface.
  • FIG. 2 shows an example of a SEM observation photograph. As a result of SEM observation, it was observed that an uneven structure was formed on the particle surface.
  • Example 2 A powder sample made of graphite particles was obtained in the same manner as in Example 1 except that the circumferential speed of the rotor was changed to 145 m / sec as the roughening step. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Example 3 A powder sample made of graphite particles was obtained in the same manner as in Example 1 except that the circumferential speed of the rotor was changed to 130 m / sec as the roughening step. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Comparative Example 1 A powder sample made of graphite particles was obtained in the same manner as in Example 1 except that the roughening step was not performed. About this, the physical property and the battery characteristic were evaluated by the same method as Example 1. The results are shown in Table 1.
  • FIG. 3 shows an example of an SEM observation photograph. As a result of SEM observation, an uneven structure was not observed on the particle surface.
  • Comparative Example 2 A powder sample made of graphite particles was obtained in the same manner as in Example 1 except that the peripheral speed of the rotor was 48 m / sec. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Comparative Example 3 The roughened graphite used in Example 1 was used as a sample as it was. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Comparative Example 4 The roughened graphite used in Example 3 was used as a sample as it was. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Comparative Example 5 Spherical natural graphite having a volume-based average particle diameter of 21 ⁇ m was used as a sample as it was. About this, the physical property, the evaluation of battery characteristics, and SEM observation were performed by the same method as Example 1. The results are shown in Table 1.
  • Comparative Example 1 the raw graphite was not roughened, and (B) specific surface area and (C) Raman R value were within the scope of the present invention, but (A) DBP oil absorption was 0.00. 37 mL / g and out of the specified range of the present invention, and as a result, a high cycle maintenance rate was not obtained.
  • the comparative example 2 is performing the process of roughening raw material graphite, the circumferential speed is smaller than 50 m / sec, and (B) specific surface area and (C) Raman R value of the present invention.
  • Comparative Example 3 does not perform the step of mixing the roughened raw material graphite and the organic material and the step of firing the mixture, and (A) the DBP oil absorption is within the scope of the present invention.
  • B) Specific surface area and (C) Raman R value were outside the specified range of the present invention, and as a result, high initial efficiency could not be obtained.
  • the comparative example 4 is not performing the process of mixing the raw material graphite and organic substance which roughened, and the process of baking a mixture, (A) DBP oil absorption, (B) specific surface area, and (C) Raman. All the requirements for the R value were outside the specified range of the present invention, and as a result, high initial efficiency could not be obtained.
  • the negative electrode materials of the present invention of Examples 1 to 3 satisfy all the requirements of (A) DBP oil absorption, (B) specific surface area, and (C) Raman R value.
  • a high-performance battery having excellent cycle characteristics and high initial efficiency can be obtained.
  • the negative electrode material of the present invention as a negative electrode material for a non-aqueous secondary battery, a negative electrode material for a non-aqueous secondary battery having high initial efficiency and good cycle characteristics can be provided. Moreover, according to the manufacturing method of the said material, since there are few processes, it can manufacture stably and efficiently and cheaply.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un matériau d'électrode négative pour une batterie rechargeable non aqueuse qui possède une capacité élevée et de bonnes caractéristiques de cycle charge/décharge. Le matériau d'électrode négative pour une batterie rechargeable non aqueuse est constitué de particules de graphite qui satisfont les trois conditions A, B et C suivantes: (A) l'absorption d'huile de phtalate de dibutyle est comprise entre 0,42 mL/g et 0,85 mL/g ; (B) la surface spécifique est comprise entre 0,5 m2/g et 6,5 m2/g ; (C) la valeur de résistance thermique de Raman est comprise entre 0,03 et 0,19.
PCT/JP2012/058611 2011-03-30 2012-03-30 Particules de graphite pour batterie rechargeable non aqueuse et leur procédé de production, électrode négative et batterie rechargeable non aqueuse WO2012133788A1 (fr)

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JP7178270B2 (ja) * 2019-01-15 2022-11-25 Ｅｎｅｏｓ株式会社 人造黒鉛材料、人造黒鉛材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP7178271B2 (ja) * 2019-01-15 2022-11-25 Ｅｎｅｏｓ株式会社 人造黒鉛材料、人造黒鉛材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池
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